WO2022255171A1

WO2022255171A1 - Positive photosensitive resin composition and organic el element partition

Info

Publication number: WO2022255171A1
Application number: PCT/JP2022/021293
Authority: WO
Inventors: 由起宮石
Original assignee: 昭和電工株式会社
Priority date: 2021-06-02
Filing date: 2022-05-24
Publication date: 2022-12-08
Also published as: TW202311322A; JPWO2022255171A1; TWI809906B; CN117480451A; KR20230162069A

Abstract

Provided is a highly sensitive chemical amplification photosensitive resin composition containing a metal complex dye. This positive photosensitive resin composition contains: (A) a first resin having multiple alkali-soluble functional groups in which at least a portion of the multiple alkali-soluble functional groups is protected by acid-decomposable groups, (B) a photoacid generator, and (C) a metal complex dye, wherein the metal complex dye (C) contains 50 to 94 mass% metal complex ions.

Description

Positive type photosensitive resin composition and organic EL element partition

The present invention relates to a positive photosensitive resin composition, an organic EL element partition wall, an organic EL element insulating film, and an organic EL element using the same. More specifically, the present invention relates to a positive photosensitive resin composition containing a metal complex dye, an organic EL element partition wall, an organic EL element insulating film, and an organic EL element using the same.

In a display device such as an organic EL display (OLED), in order to improve display characteristics, a partition material is used in the gap between the colored patterns in the display area or the edge of the display area peripheral portion. In the manufacture of an organic EL display device, partition walls are first formed, and organic pixels are formed between the partition walls in order to prevent organic substance pixels from coming into contact with each other. This partition is generally formed by photolithography using a photosensitive resin composition and has insulating properties. Specifically, a photosensitive resin composition is applied onto a substrate using a coating device, volatile components are removed by means of heating or the like, and then exposed through a mask. In the case of the positive type, the exposed portion is developed by removing it with a developing solution such as an alkaline aqueous solution, and the resulting pattern is heat-treated to form a partition wall (insulating film). Next, by an ink jet method or the like, an organic substance emitting three colors of red, green, and blue is deposited between the barrier ribs to form the pixels of the organic EL display device.

In this field, in recent years, due to the miniaturization of display devices and the diversification of content to be displayed, there is a demand for higher performance and higher definition of pixels. Attempts have been made to impart a light-shielding property to the partition wall material by using a coloring agent for the purpose of increasing the contrast in the display device and improving the visibility. However, when the partition wall material is provided with a light-shielding property, the sensitivity of the photosensitive resin composition tends to be low, and as a result, the exposure time becomes long, which may reduce productivity. Therefore, the photosensitive resin composition used for forming the partition wall material containing the colorant is required to have higher sensitivity.

Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2001-281440) discloses a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition exhibiting high light-shielding properties by heat treatment after exposure. describes a composition to which titanium black is added.

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

Patent Document 3 (Japanese Patent Application Laid-Open No. 2010-237310) describes a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition that exhibits light-shielding properties by heat treatment after exposure. Compositions with added thermal dyes are described.

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

Japanese Patent Application Laid-Open No. 2001-281440 JP-A-2002-116536 Japanese Patent Application Laid-Open No. 2010-237310 WO2017/069172

In the photosensitive resin composition used to form a colored partition wall material, it is necessary to use a considerable amount of a coloring agent in order to sufficiently enhance 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 that the effective intensity of the radiation in the film is reduced, and the photosensitive resin composition is not sufficiently exposed, resulting in poor patternability.

In the formation of partition walls in organic EL elements, it is important from the viewpoint of productivity that the material forming the partition walls has high sensitivity.

As a method for increasing the sensitivity of a photosensitive resin composition, it is widely known to make the photosensitive resin composition a chemically amplified system. A chemically amplified photosensitive resin composition generally contains a resin in which an alkali-soluble functional group is protected with an acid-decomposable group, and a photoacid generator. The acid generated from the photoacid generator during exposure promotes decomposition (deprotection) of the acid-decomposable group to regenerate the alkali-soluble functional group. This promotes alkali dissolution of the resin in the exposed areas during development. The acid derived from the photoacid generator is regenerated after decomposing a certain acid-decomposable group and participates in the decomposition of another acid-decomposable group. The apparent quantum efficiency of the chemical amplification system based on the above reaction mechanism is expressed as the product of the quantum efficiency of acid generation and the reaction chain, so high sensitivity is achieved by using a photosensitive resin composition as a chemical amplification system. can do.

However, the present inventors have found that the use of a metal complex dye as a colorant in a chemically amplified photosensitive resin composition may reduce the sensitivity of the photosensitive resin composition. A metal complex dye is a soluble azo dye composed of an azo dye molecule, a metal complex ion (anion) composed of a metal such as chromium, and a counter cation.

An object of the present invention is to provide a highly sensitive chemically amplified photosensitive resin composition containing a metal complex dye.

The present inventors have found that the sensitivity of the chemically amplified photosensitive resin composition can be increased by setting the content of the metal complex ions constituting the metal complex dye within a predetermined range.

That is, the present invention includes the following aspects.
[1]
a first resin (A) having a plurality of alkali-soluble functional groups, at least a portion of which is protected with an acid-decomposable group;
a photoacid generator (B);
A positive photosensitive resin composition containing a metal complex dye (C), wherein the metal complex dye (C) contains 50 to 94% by mass of metal complex ions.
[2]
The positive type according to [1], wherein the metal element forming the metal complex ion contained in the metal complex dye (C) is at least one selected from the group consisting of chromium, copper, cobalt, and iron. A photosensitive resin composition.
[3]
The positive photosensitivity according to [1] or [2], wherein the metal complex dye (C) is at least one of black dyes defined by a color index (C.I.) of Solvent Black 22 to 47. elastic resin composition.
[4]
[1] to [3], wherein the first resin (A) is a resin having a plurality of phenolic hydroxyl groups, and at least a portion of the plurality of phenolic hydroxyl groups are protected with the acid-decomposable groups. The positive photosensitive resin composition according to any one of .
[5]
a polymerizable monomer having a phenolic hydroxyl group in which the first resin (A) has a plurality of phenolic hydroxyl groups, at least a portion of which is protected by the acid-decomposable group; The positive photosensitive resin composition according to [4], which is a copolymer with another polymerizable monomer.
[6]
The first resin (A) has the formula (3)

(In formula (3), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is the acid-decomposable group, r is an integer of 0 to 5, and s is 0 to is an integer of 5, provided that r+s is an integer of 1 to 5.)
The positive photosensitive resin composition according to [5], which has at least one structural unit represented by formula (3), wherein s is an integer of 1 or more.
[7]
The first resin (A) has the formula (2)

(In Formula (2), R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms. , or a halogen atom, and R ⁴ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, or a 1 to 6 carbon atom is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.)
The positive photosensitive resin composition according to [5] or [6], which has a structural unit represented by:
[8]
The positive photosensitive resin composition further includes a second resin (D), and the second resin (D) is a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group, or an epoxy The positive photosensitive resin composition according to any one of [1] to [7], which is a resin having a group and a phenolic hydroxyl group.
[9]
The positive photosensitive resin composition according to any one of [1] to [8], comprising 10 parts by mass to 150 parts by mass of the metal complex dye (C) based on a total of 100 parts by mass of the resin components.
[10]
The positive photosensitive resin composition according to any one of [1] to [9], wherein the photoacid generator (B) is contained in an amount of 0.1 parts by mass to 85 parts by mass based on a total of 100 parts by mass of the resin components. thing.
[11]
The positive photosensitive resin composition according to any one of [1] to [10], wherein the cured film of the positive photosensitive resin composition has an optical density (OD value) of 0.5 or more per 1 μm of film thickness. .
[12]
[1] An organic EL element partition comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [11].
[13]
An organic EL element insulating film comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [11].
[14]
An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [11].

According to the present invention, it is possible to provide a highly sensitive chemically amplified photosensitive resin composition containing a metal complex dye.

The present invention will be described in detail below.

In the present disclosure, "alkali-soluble" and "alkali aqueous solution-soluble" mean that the positive photosensitive resin composition or its components, or the coating or cured coating of the positive photosensitive resin composition is an alkaline aqueous solution, for example, 2.38 mass. % tetramethylammonium hydroxide aqueous solution. The “alkali-soluble functional group” means a group that imparts such alkali-solubility to a positive photosensitive resin composition or a component thereof, or a coating or cured coating of a positive photosensitive resin composition. Alkali-soluble functional groups include, for example, a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group, and a mercapto group.

In the present disclosure, "acid-decomposable group" means a group that is decomposed (deprotected) by heating in the presence of an acid as necessary to generate an alkali-soluble functional group.

In the present disclosure, "radical polymerizable functional group" refers to one or more ethylenically unsaturated groups, and "radical polymerizable compound" refers to compounds having one or more ethylenically unsaturated groups.

In the present disclosure, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl.

In the present disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a resin or polymer mean standard polystyrene equivalent values measured by gel permeation chromatography (GPC).

In the present disclosure, the "resin component" means the total component of the first resin (A) and the second resin (D).

In the present disclosure, "solid content" means the first resin (A), the photoacid generator (B), the metal complex dye (C), the second resin (D), the dissolution accelerator (E) and the optional component (F ) and excluding the solvent (G).

[Positive photosensitive resin composition]
A positive photosensitive resin composition of one embodiment includes a first resin (A) having a plurality of alkali-soluble functional groups, at least a portion of which is protected with an acid-decomposable group; It contains a photoacid generator (B) and a metal complex dye (C).

<First resin (A)>
The first resin (A) is not particularly limited as long as it has a plurality of alkali-soluble functional groups and at least part of the plurality of alkali-soluble functional groups are protected with an acid-decomposable group. Alkali-soluble functional groups include a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group, and a mercapto group. Among them, the alkali-soluble functional group is preferably a carboxy group or a phenolic hydroxyl group, more preferably a phenolic hydroxyl group. By protecting a part of the alkali-soluble functional groups with the acid-decomposable groups, the alkali-solubility of the first resin (A) before exposure is suppressed. The first resin (A) may have an alkali-soluble functional group other than the alkali-soluble functional group protected with an acid-decomposable group. Post-exposure baking (PEB) is optionally performed in the presence of an acid generated during exposure to promote decomposition (deprotection) of the acid-decomposable groups and regenerate the alkali-soluble functional groups. This promotes alkali dissolution of the first resin (A) in the exposed areas during development. A 1st resin (A) can be used individually or in combination of 2 or more types. For example, the first resin (A) may be a combination of two or more resins differing in polymer constitutional units, acid-decomposable groups, protection rates of alkali-soluble functional groups, or combinations thereof.

<Protection of alkali-soluble functional group by acid-decomposable group>
The first resin (A) can be obtained by protecting some of the alkali-soluble functional groups of the base resin (a) having multiple alkali-soluble functional groups with acid-decomposable groups. For example, when the alkali-soluble functional group is a phenolic hydroxyl group, the first resin (A) having a phenolic hydroxyl group protected with an acid-decomposable group has a partial structure of Ar—O—R ⁵ , and Ar is phenol and R ⁵ represents an acid-decomposable group.

The acid-decomposable group is a group that is decomposed (deprotected) by heating in the presence of an acid, if necessary, to generate an alkali-soluble functional group. Specifically, for example, tert-butyl group, 1,1-dimethyl-propyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-methyladamantyl group , 1-ethyladamantyl group, tert-butoxycarbonyl group, group having a tertiary alkyl group such as 1,1-dimethyl-propoxycarbonyl group; trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, triisopropylsilyl group , a silyl group such as a tert-butyldiphenylsilyl group; and formula (4)
—CR ⁶ R ⁷ —OR ⁸ (4)
(In formula (4), R ⁶ and R ⁷ are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R ⁸ is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a carbon atom an alkenyl group having a number of 2 to 12, and one of R ⁶ or R 7 and R ⁸ may combine to form a ring structure ^having 3 to 10 ring members, and R ⁶ , R ⁷ and R ⁸ are optionally substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine). When the alkali-soluble functional group is an alcoholic hydroxyl group or a phenolic hydroxyl group, the group represented by formula (4) forms an acetal structure or ketal structure together with an oxygen atom derived from the alkali-soluble functional group. These acid-decomposable groups can be used alone or in combination of two or more.

The acid-decomposable group is preferably a group represented by formula (4), since a highly sensitive photosensitive resin composition can be obtained even with a low exposure dose. R ⁶ and R ⁷ are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R ⁸ is fluorine, chlorine, bromine and optionally substituted with a halogen atom selected from the group consisting of iodine, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or having 3 to 12 carbon atoms A cyclic alkyl group is more preferred. Examples of such acid-decomposable groups include 1-alkoxyalkyl groups. 1-alkoxyalkyl groups include, for example, methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1 -(2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group; - n-propoxyethyl groups are preferred. As the acid-decomposable group, a group represented by formula (4) in which one of R ⁶ or R ⁷ and R ⁸ are bonded to form a ring structure having 3 to 10 ring members is also preferably used. can do. At this time, ^R6 or ^R7 that does not participate in the formation of the ring structure is preferably a hydrogen atom. Examples of such acid-decomposable groups include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, with a 2-tetrahydrofuranyl group being preferred.

The protective reaction of the alkali-soluble functional group can be carried out under known conditions using a general protective agent. For example, by reacting the base resin (a) of the first resin (A) with a protective agent in the absence of solvent or in a solvent such as toluene or hexane in the presence of an acid or base at a reaction temperature of -20 to 50°C. , the first resin (A) can be obtained.

As a protective agent, a known protective agent capable of protecting an alkali-soluble functional group can be used. Examples of protective agents that can be used include isobutene when the acid-decomposable group is a tert-butyl group and di-tert-butyl dicarbonate when the acid-decomposable group is a tert-butoxycarbonyl group. When the acid-decomposable group is a silyl group such as trimethylsilyl group and triethylsilyl group, silicon-containing chlorides such as trimethylsilyl chloride and triethylsilyl chloride, or silicon-containing triflate compounds such as trimethylsilyl triflate and triethylsilyl triflate can be used. . Chloromethyl methyl ether when the acid-decomposable group is a methoxymethyl group, ethyl vinyl ether when it is a 1-ethoxyethyl group, n-propyl vinyl ether when it is a 1-n-propoxyethyl group, and 2-tetrahydrofuranyl group when it is a 2-tetrahydrofuranyl group. In the case of 2,3-dihydrofuran and 2-tetrahydropyranyl groups, 3,4-dihydro-2H-pyran and the like 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 acid sources. Examples of the base include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, potassium carbonate and cesium carbonate, inorganic hydrogen carbonates such as sodium hydrogen carbonate, and metals such as sodium hydride. hydrides and amine compounds such as pyridine, N,N-dimethyl-4-aminopyridine, imidazole, triethylamine and diisopropylethylamine;

In another embodiment, after protecting the alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group with an acid-decomposable group, the polymerizable monomer having an alkali-soluble functional group protected with an acid-decomposable group The first resin (A) can also be obtained by polymerizing or copolymerizing the polymer and optionally other polymerizable monomers. Protection of the alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group can be carried out in the same manner as the protection of the alkali-soluble functional group of the base resin (a).

(Base resin (a))
Examples of the base resin (a) of the first resin (A) include polystyrene resins, epoxy resins, polyamide resins, phenol resins, polyimide resins, polyamic acid resins, polybenzoxazole resins having a plurality of alkali-soluble functional groups, Polybenzoxazole resin precursors, silicone resins, cyclic olefin polymers, cardo resins, and derivatives of these resins. For example, phenol resin derivatives include polyalkenylphenol resins in which alkenyl groups are bonded to benzene rings, and polystyrene resin derivatives include hydroxypolystyrene resin derivatives in which phenolic hydroxyl groups and hydroxyalkyl groups or alkoxy groups are bonded to benzene rings. be done. A homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group can also be used as the base resin (a). These base resins (a) can be used alone or in combination of two or more.

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

(Copolymer (a1) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer)
In one embodiment, the base resin (a) of the first resin (A) is a copolymer (a1) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer, Polymer (a1) has a plurality of alkali-soluble functional groups. In this embodiment, the first resin (A) is obtained by protecting at least part of the multiple alkali-soluble functional groups of the copolymer (a1) with an acid-decomposable group. The copolymer (a1) may have two or more types of alkali-soluble functional groups. Examples of the polymerizable functional group possessed by the polymerizable monomer include radically polymerizable functional groups such as CH ₂ ═CH—, CH ₂ ═C(CH ₃ )—, CH ₂ ═CHCO—, CH ₂ =C(CH ₃ )CO-, -OC-CH=CH-CO- and the like.

The 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, an alkali-soluble functional group may be added to the copolymer. Examples of the polymerizable monomer having an alkali-soluble functional group include maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; (meth)acrylic acid, α-bromo(meth)acrylic acid, α - acrylic acid derivatives such as chloro (meth)acrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid; and maleic acid, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid , crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, unsaturated carboxylic acid compounds such as 6-maleimidohexanoic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Polymerizable monomers having an alcoholic hydroxyl group such as hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; 4-hydroxystyrene, 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4 -Polymerizable monomers having a phenolic hydroxyl group such as hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide; (meth)allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, Polymerizable monomers having a sulfo group such as styrenesulfonic acid; Polymerizable monomers having a phosphoric acid group such as mono (2-(meth)acryloyloxyethyl) phosphate; and itaconic anhydride, citraconic anhydride, Examples thereof include polymerizable monomers having an acid anhydride group such as maleic anhydride. Other polymerizable monomers include, for example, styrene; styrene derivatives such as α-methylstyrene, p-methylstyrene and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2 , 2,3,3-tetrafluoropropyl (meth)acrylate and isobornyl (meth)acrylate; and N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide. From the viewpoint of heat resistance, etc., the copolymer (a1) has one or more cyclic structures such as an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure. It is preferable to have From the viewpoint of sensitivity, the polymerizable monomer having an alkali-soluble functional group is preferably a polymerizable monomer having an acrylic acid derivative or a phenolic hydroxyl group, and is a polymerizable monomer having a phenolic hydroxyl group. is more preferred.

As a polymerizable monomer having a phenolic hydroxyl group, the formula (1) after polymerization

Those forming the structural unit represented by are preferable. 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. a is preferably an integer of 1 to 3, more preferably 1; 4-Hydroxyphenyl methacrylate is particularly preferred as such a polymerizable monomer having a phenolic hydroxyl group.

As other polymerizable monomers, formula (2) after polymerization

Those forming the structural unit represented by are preferable. In formula (2), R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom, and R ⁴ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, or a A phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms. R ² and R ³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom. R ⁴ is at least one 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; A phenyl group substituted with a species is preferable, and a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group is more preferable. Phenylmaleimide and N-cyclohexylmaleimide are particularly preferred as such other polymerizable monomers.

In one embodiment, copolymer (a1) has the 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.)
A structural unit represented by the formula (2)

(In Formula (2), R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms. , or a halogen atom, and R ⁴ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, or a 1 to 6 carbon atom is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.)
It has a structural unit represented by

In the copolymer (a1), the molar ratio of the structural unit represented by formula (1) and the structural unit represented by formula (2) is formula (1): formula (2) = 70 to 95: 30 to 5, and more preferably formula (1): formula (2) = 75-90: 25-10.

It is particularly preferable to use 4-hydroxyphenyl methacrylate as a polymerizable monomer having a phenolic hydroxyl group and phenylmaleimide or N-cyclohexylmaleimide as another polymerizable monomer. By using a resin obtained by radically polymerizing these polymerizable monomers, it is possible to improve shape retention and developability and reduce outgassing.

Polymerization initiators for producing the base resin (a) or copolymer (a1) by radical polymerization include, but are not limited to, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2,4- Azo polymerization initiators such as dimethylvaleronitrile) (AVN); dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert- butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, or a peroxide polymerization initiator having a 10-hour half-life temperature of 100 to 170°C; or benzoyl peroxide, peroxide Peroxide polymerization initiators such as lauroyl, 1,1′-di(tert-butylperoxy)cyclohexane, tert-butylperoxypivalate and the like can be used. 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 and 40 parts by mass or less, or 20 parts by mass or more with respect to a total of 100 parts by mass of the polymerizable monomers. It is preferably 15 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 the polymerization initiator. Thiocarbonylthio compounds such as, but not limited to, dithioesters, dithiocarbamates, trithiocarbonates, and xanthates can be used as RAFT agents. The RAFT agent can be used in the range of 0.005 to 20 parts by weight, preferably in the range of 0.01 to 10 parts by weight, per 100 parts by weight of the total polymerizable monomers.

The weight average molecular weight (Mw) of the base resin (a) or 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 from 1,000 to 30,000, preferably from 1,500 to 25,000, more preferably from 2,000 to 20,000. The polydispersity (Mw/Mn) can be from 1.0 to 3.5, preferably from 1.1 to 3.0, more preferably from 1.2 to 2.8. By setting the weight average molecular weight, number average molecular weight and polydispersity within the above ranges, a positive photosensitive resin composition having excellent alkali solubility and developability can be obtained.

In one embodiment, 1 mol% to 99 mol%, preferably 5 mol% to 98 mol%, more preferably 10 mol% to 97 mol% of the alkali-soluble functional groups of the first resin (A) are acid-decomposable groups. protected by In the first resin (A), by setting the ratio of the alkali-soluble functional group protected by the acid-decomposable group to 1 mol% or more, a chemical amplification function is imparted to the photosensitive resin composition to achieve high sensitivity. can do. By keeping the ratio of alkali-soluble functional groups protected by acid-decomposable groups to 99 mol% or less, the residual amount of acid-decomposable groups that do not react during exposure is reduced, and the solubility of exposed areas is increased, resulting in high sensitivity. can be realized. The proportion of alkali-soluble functional groups protected by acid-decomposable groups is calculated from the weight loss rate (%) of the first resin (A) measured by a thermogravimetric differential thermal analyzer (TG/DTA). In the present disclosure, when the first resin (A) is a combination of two or more resins with different protection rates, the protection rate of the alkali-soluble functional groups of the first resin (A) is the two or more resins as a whole. It is a numerical value when regarded as one first resin (A).

The first resin (A) is represented by formula (3)

(In formula (3), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is an acid-decomposable group, r is an integer of 0 to 5, s is 0 to 5 where r + s is an integer of 1 to 5.) and has at least one structural unit represented by formula (3) where s is an integer of 1 or more is preferred. The acid-labile group of R ⁵ is represented by formula (4)
—CR ⁶ R ⁷ —OR ⁸ (4)
is preferably a group represented by In formula (4), R ⁶ and R ⁷ are each independently more preferably a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms. . R ⁸ is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or More preferably, it is an alkenyl group having 2 to 12 carbon atoms, or one of R ⁶ or R ⁷ and R ⁸ combine to form a ring structure having 3 to 10 ring members. 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. Examples of such acid-decomposable groups include 1-alkoxyalkyl groups. 1-alkoxyalkyl groups include, for example, methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1 -(2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group; - n-propoxyethyl groups are preferred. Examples of the acid-decomposable group in which one of R ⁶ or R 7 and R ⁸ are bonded to form ^a ring structure having 3 to 10 ring members include 2-tetrahydrofuranyl and 2-tetrahydropyranyl. and the 2-tetrahydrofuranyl group is preferred. In formula (3), the acid-decomposable group for R ⁵ is, for example, tert-butyl, 1,1-dimethyl-propyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1 Groups having a tertiary alkyl group such as -ethylcyclohexyl group, 1-methyladamantyl group, 1-ethyladamantyl group, tert-butoxycarbonyl group, 1,1-dimethyl-propoxycarbonyl group; trimethylsilyl group, triethylsilyl group, tert -Butyldimethylsilyl group, triisopropylsilyl group, tert-butyldiphenylsilyl group, and other silyl groups.

The first resin (A) has the formula (2)

(In Formula (2), R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms. , or a halogen atom, and R ⁴ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, or a 1 to 6 carbon atom is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.). R ² and R ³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom. R ⁴ is at least one 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; A phenyl group substituted with a species is preferable, and a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group is more preferable.

In one embodiment, a structural unit represented by formula (3) and s is an integer of 1 or more, i.e., represented by formula (3) in which at least one alkali-soluble functional group is protected with an acid-decomposable group is 5% to 95%, preferably 15% to 90%, more preferably 25% to 85% of the total number of structural units in the first resin (A). By setting the ratio of the structural unit to 5% or more, a chemical amplification function can be imparted to the photosensitive resin composition to realize high sensitivity. By setting the ratio of the structural unit to 95% or less, the residual amount of unreacted acid-decomposable groups can be reduced, the solubility of the exposed area can be improved, and high sensitivity can be realized.

In one embodiment, the positive photosensitive resin composition contains 0.5% to 80% by mass, preferably 1% to 65% by mass, of the first resin (A) based on 100% by mass of solid content, More preferably, it contains 2% by mass to 50% by mass. When the content of the first resin (A) is 0.5% by mass or more based on the solid content of 100% by mass, a chemical amplification function can be imparted to the photosensitive resin composition to achieve high sensitivity. . When the content of the first resin (A) is 80% by mass or less based on the solid content of 100% by mass, the residual amount of unreacted acid-decomposable groups is reduced, and the solubility of the exposed area is increased to increase the Sensitivity can be achieved.

<Photoacid generator (B)>
The positive photosensitive resin composition contains a photoacid generator (B). The photoacid generator (B) is a compound that generates an acid when exposed to radiation such as visible light, ultraviolet light, γ-rays and electron beams. The photoacid generator (B) accelerates the decomposition of the acid-decomposable groups of the first resin (A) to regenerate the alkali-soluble functional groups and increases the alkali-solubility of the first resin (A). In addition, since the acid generated from the photoacid generator (B) is present in the portion irradiated with radiation, the resin in that portion is easily dissolved in the alkaline aqueous solution together with the acid. As a result, a pattern with high sensitivity and high resolution can be formed even with a low exposure dose. Photoacid generator (B) can be used individually or in combination of 2 or more types.

In one embodiment, the positive photosensitive resin composition contains 0.1 parts by mass to 85 parts by mass, preferably 10 parts by mass to 60 parts by mass of the photoacid generator (B) based on a total of 100 parts by mass of the resin components. Parts by weight, more preferably 15 to 42 parts by weight. High sensitivity can be achieved when the content of the photoacid generator (B) is 0.1 parts by mass or more based on the above total of 100 parts by mass. When the content of the photoacid generator (B) is 85 parts by mass or less based on the above total of 100 parts by mass, the alkali developability is good.

In one embodiment, the positive photosensitive resin composition contains a quinonediazide compound as the photoacid generator (B). A quinonediazide compound produces an alkali-soluble carboxylic acid compound through the reaction shown in Reaction Formula 1 below when irradiated with radiation such as visible light, ultraviolet light, γ-rays, and electron beams. The produced carboxylic acid compound accelerates the decomposition of the acid-decomposable groups of the first resin (A), regenerates the alkali-soluble functional groups, and increases the alkali-solubility of the first resin (A). The quinonediazide compound interacts (for example, forms hydrogen bonds) with the functional groups of a binder resin such as a novolak resin before exposure to make the binder resin insoluble in an alkaline aqueous solution. On the other hand, the presence of the alkali-soluble carboxylic acid compound in the irradiated portion makes it easier for the resin in that portion to dissolve in the alkaline aqueous solution together with the carboxylic acid compound. Furthermore, 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 diffuse in the coating. hard to do. As a result of the synergistic action of these, the difference in alkali solubility between the unexposed area and the exposed area can be increased, so that a pattern with high sensitivity and high resolution can be formed even with a low exposure dose. A quinonediazide compound can be used individually or in combination of 2 or more types.

In one embodiment, high-resolution patterns can be formed without the post-exposure bake (PEB) required for typical chemically amplified resists. A quinonediazide compound has a relatively high quantum yield, and a carboxylic acid compound is efficiently produced in an exposed area. When an acid-decomposable group that can be decomposed by a carboxylic acid compound is present in the surroundings, the generated carboxylic acid compound causes decomposition of the acid-decomposable group even at room temperature to regenerate the alkali-soluble functional group. It is possible to increase the difference in alkali solubility of the exposed areas. By omitting PEB, it is possible to suppress deterioration in pattern formability due to excessive diffusion of acid generated from the photo-acid generator into unexposed areas in a high-temperature environment during PEB. Further, when a resin having an epoxy group and a phenolic hydroxyl group, which will be described later, is used as an optional component, if PEB is omitted, the ring-opening polymerization of the epoxy group of the resin having an epoxy group and a phenolic hydroxyl group does not proceed. And the alkali solubility of the resin having a phenolic hydroxyl group can be maintained.

The quinonediazide compounds include those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound via an ester bond, the sulfonic acid of quinonediazide to a polyamino compound in a sulfonamide bond, and the sulfonic acid of quinonediazide to a polyhydroxypolyamino compound in an ester bond or a sulfonamide bond. and the like. From the viewpoint of the contrast between the exposed and unexposed areas, it is preferable that 20 mol % or more of all the functional groups of the polyhydroxy compound, polyamino compound or polyhydroxypolyamino compound are substituted with quinonediazide.

Examples of polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, 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 (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR- PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), Tetra Hydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.) and the like, but not limited thereto.

Polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diamino Examples include, but are not limited to, diphenyl sulfide and the like.

Examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

The quinonediazide compound is preferably 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate of a polyhydroxy compound.

In one embodiment, the positive photosensitive resin composition contains 5 parts by mass to 60 parts by mass, preferably 10 parts by mass to 50 parts by mass, more preferably 15 parts by mass of a quinonediazide compound based on a total of 100 parts by mass of the resin components. Contains parts by mass to 42 parts by mass. When the content of the quinonediazide compound is 5 parts by mass or more based on the above total of 100 parts by mass, high sensitivity can be achieved. When the content of the quinonediazide compound is 60 parts by mass or less based on the above total of 100 parts by mass, the alkali developability is good.

The photoacid generator (B) other than the quinonediazide compound is preferably one that generates an acid with a pKa of 4 or less upon exposure to radiation, more preferably one that generates an acid with a pKa of 3 or less. Such a photoacid generator (B) can generate an acid capable of decomposing an acid-decomposable group.

As the photoacid generator (B) other than the quinonediazide compound, those that generate an acid with a pKa of -15 or more upon exposure to radiation are preferable, and those that generate an acid with a pKa of -5 or more are more preferable. Such a photoacid generator (B) excessively promotes the ring-opening polymerization of the epoxy group of the resin having an epoxy group and a phenolic hydroxyl group, which will be described later, during exposure and post-exposure heat treatment (PEB). However, the alkali solubility of the resin having epoxy groups and phenolic hydroxyl groups can be maintained during development.

Examples of such photoacid generators (B) include trichloromethyl-s-triazine compounds, onium salts such as sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts, quaternary ammonium salts, diazomethane compounds, and imidosulfonate compounds. , and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound because of its high sensitivity and high insulating properties.

Examples of oxime sulfonate compounds include compounds represented by Formula (5).

In formula (5), R ⁹ is a substituted or unsubstituted alkyl group, alkoxy group, aryl group, or halogen atom, and R ¹⁰ and R ¹¹ are each independently a substituted or unsubstituted aryl group, substituted or an unsubstituted heterocyclic group, cyano group, acyloxy group, carboxy group, alkoxycarbonyl group, or fluoroalkyl group. R ¹⁰ and R ¹¹ may combine to form a ring structure. The number of ring members in the ring structure is preferably 3-10.

The substituted or unsubstituted alkyl group for R ⁹ includes, for example, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, a methyl group, an ethyl group, or An n-propyl group is preferred. The substituted or unsubstituted alkoxy group for R ⁹ includes, for example, a linear alkoxy group having 1 to 5 carbon atoms or a branched alkoxy group having 3 to 5 carbon atoms, such as a methoxy group or an ethoxy group. is preferred. Examples of substituents of the alkyl group and alkoxy group of R ⁹ include halogen atoms (fluorine, chlorine, bromine and iodine atoms), cyano groups, nitro groups, aryl groups having 6 to 20 carbon atoms, carbon Alkoxy groups of 1 to 10 atoms and cycloalkyl groups of 3 to 10 carbon atoms are included. The substituted alkyl group for R ⁹ is preferably a fluoroalkyl group, more preferably a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group, even more preferably a trifluoromethyl group. . The substituted or unsubstituted aryl group for R ⁹ includes, for example, an aryl group having 6 to 20 carbon atoms, preferably a phenyl group, a 4-methylphenyl group or a naphthyl group. Examples of substituents of the aryl group of R ⁹ include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and halogen atoms (fluorine, chlorine, bromine, and iodine atoms). is mentioned. Halogen atoms for ^R9 include fluorine, chlorine, bromine and iodine atoms.

The substituted or unsubstituted aryl group for R ¹⁰ and R ¹¹ includes, for example, an aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group. Examples of substituted or unsubstituted heterocyclic groups for R ¹⁰ and R ¹¹ include 2-benzofuranyl, 3-benzofuranyl, 2-benzimidazolyl, 2-benzoxazolyl, 2-benzothiazolyl and 2-indolyl. 3-coumarinyl, 4-coumarinyl, 3-isocoumarinyl, and 4-isocoumarinyl groups. Examples of substituents of the aryl group and heterocyclic group of R ¹⁰ and R ¹¹ include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, and halogen atoms (fluorine, chlorine, bromine, and iodine atoms). Acyloxy groups for R ¹⁰ and R ¹¹ include, for example, an acetoxy group and a benzoyloxy group. Examples of alkoxycarbonyl groups for R ¹⁰ and R ¹¹ include ethoxycarbonyl groups. Examples of fluoroalkyl groups for R ¹⁰ and R ¹¹ include trifluoromethyl, pentafluoroethyl and heptafluoropropyl groups. R ¹⁰ is preferably a cyano group, a carboxy group, an alkoxycarbonyl group or a fluoroalkyl group, more preferably a cyano group or a trifluoromethyl group. R ¹¹ is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, a 4-methoxyphenyl group, a substituted or unsubstituted 2-benzofuranyl group, a 3-benzofuranyl group, a 3- A coumarinyl group, a 4-coumarinyl group, a 3-isocoumarinyl group, or a 4-isocoumarinyl group is preferred.

Examples of the oxime sulfonate compound having a ring structure formed by combining R ¹⁰ and R ¹¹ include an oxime sulfonate compound represented by formula (5a).

In formula (5a), R ⁹ is as described for formula (5), each R ¹² is independently an alkyl group, an alkoxy group, or a halogen atom, and m represents an integer of 0 to 5. .

The alkyl group for R ¹² includes, for example, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and a methyl group, an ethyl group or an n-propyl group. Preferably. The alkoxy group for R ¹² includes, for example, a linear alkoxy group having 1 to 5 carbon atoms or a branched alkoxy group having 3 to 5 carbon atoms, preferably a methoxy group or an ethoxy group. The halogen atom for R ¹² includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a fluorine atom. Preferably, m is 0 or 1.

Examples of oximesulfonate compounds include (Z,E)-2-(4-methoxyphenyl)([(4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 2-[2-(propylsulfonyloxyimino)thiophene -3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile, 2-[2-(4-methylphenylsulfonyloxyimino)thiophene-3(2H)-ylidene]-2-(2-methylphenyl ) acetonitrile and the like.

In one embodiment, the positive photosensitive resin composition contains 0.5 parts by mass to 60 parts by mass, preferably 5 parts by mass of a photoacid generator (B) other than a quinonediazide compound, based on a total of 100 parts by mass of the resin components. Parts by weight to 50 parts by weight, more preferably 10 parts by weight to 45 parts by weight. High sensitivity can be achieved when the content of the photoacid generator (B) other than the quinonediazide compound is 0.5 parts by mass or more based on the above total of 100 parts by mass. When the content of the photoacid generator (B) other than the quinonediazide compound is 60 parts by mass or less based on the above total of 100 parts by mass, the alkali developability is good.

<Metal complex dye (C)>
A positive photosensitive resin composition contains a metal complex dye (C). A typical metal complex dye (C) is a monoazo dye having a coordinating functional group such as a hydroxy group, a carboxyl group or an amino group, to metal ions such as chromium, copper, cobalt, iron and nickel. It is composed of a metal complex ion (anion) and a counter cation coordinated together. Metal complex dyes (C) are generally of two classes: 1:1 type metal complex dyes (1 molecule of monoazo dye coordinated to 1 atom of metal) and 1:2 type metal complex dyes (monoazo dye to 1 atom of metal). two molecules of the dye are coordinated). Monoazo dyes generally have either o,o'-dihydroxyazo, o-hydroxy-o'-aminoazo, or o-hydroxy-o'-carboxazo structures. The metal complex dye (C) leaves less residue during development than pigments, and can form a highly precise pattern on the film. In addition, the metal complex dye (C) is easily dissolved in an organic solvent and hardly precipitates in the solution even when mixed at a high concentration. Furthermore, since it is difficult to fade during heat treatment after exposure, the optical density (OD value) of the cured film can be efficiently increased. Metal complex dye (C) can be used individually or in combination of 2 or more types.

The metal complex dye (C) contains 50 to 94% by mass of metal complex ions. Although not bound by any theory, the degree of interaction between the metal complex ion and the resin, for example, the degree of interaction between the metal complex ion and the alkali-soluble functional group of the resin, affects the solubility of the unexposed area and the exposed area. considered to have an impact. Specifically, the metal complex dye (C) containing 50% by mass or more of metal complex ions releases the entanglement between the polymer chains of the resin, and the alkali-soluble functional groups of the resin effectively interact with the alkali component of the developer. Any operable amount of metal complex ions can be provided. Thereby, the solubility of the exposed area can be enhanced, and the sensitivity of the positive photosensitive resin composition can be enhanced. On the other hand, the metal complex dye (C) containing 94% by mass or less of the metal complex ions moderately maintains the entanglement between the polymer chains of the resin and imparts the degree of insolubility necessary for pattern formation to the unexposed areas. can be done. Thus, by setting the metal complex ion content of the metal complex dye (C) to 50 to 94% by mass, it is possible to provide a highly sensitive positive photosensitive resin composition.

The metal complex ion content (% by mass) in the metal complex dye (C) is determined by the following procedure. A sample is prepared by adding methyl benzoate as an internal standard substance and diethyl carbonate as a dilution solvent to the metal complex dye (C) and, if necessary, adding a pretreatment agent for gas chromatography. After stirring the obtained sample, it is analyzed by GC or GC-MS using an internal standard method, and the metal complex ion content (% by mass) is calculated from the following formula.
Content of metal complex ions (% by mass) = 100-Total content of each substance detected by GC (% by mass)
When two or more metal complex dyes (C) are combined, the metal complex ion content of the metal complex dye (C) is the total mass of the metal complex ions of the two or more metal complex dyes (C). Determined by dividing by the total mass of one or more metal complex dyes (C).

The metal complex dye (C) preferably contains 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more of metal complex ions. The metal complex dye (C) preferably contains 93% by mass or less, more preferably 92% by mass or less of metal complex ions. The metal complex dye (C) preferably contains 60 to 94% by mass, more preferably 80 to 94% by mass or 60 to 92% by mass, still more preferably 80 to 92% by mass of metal complex ions.

The metal element forming the metal complex ion contained in the metal complex dye (C) is preferably at least one selected from the group consisting of chromium, copper, cobalt, and iron, and more preferably chromium. .

Counter cations contained in the metal complex dye (C) include Na ⁺ , Li ⁺ , K ⁺ , H ⁺ , NH ₄ ⁺ , primary ammonium cations, secondary ammonium cations, tertiary ammonium cations, quaternary ammonium cations, and the like.

As the metal complex dye (C), for example, a black dye defined by the color index (C.I.) of Solvent Black 22 to 47, C.I. of Solvent Blue 137, I. C.I. of Solvent Yellow 13, 19, 21, 25, 25:1, 62, 79, 81, 82, 83, 83:1, 88, 89, 90, 151, 161; I. and solvent orange 5, 11, 20, 40:1, 41, 45, 54, 56, 58, 62, 70, 81, 99 C.I. I. Solvent Red 8, 35, 83:1, 84:1, 90, 90:1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; I. red dyes defined in Solvent Violet 2, 21, 21:1, 46, 49, 58, 6 C.I. I. and C.I. of Solvent Brown 28, 42, 43, 44, 53, 62, 63. I. Brown dyes defined in , Acid Yellow 59, 121, Acid Orange 74, 162, Acid Red 211 C.I. I. Dyes defined in and the like. The metal complex dye (C) is preferably Solvent Black 22-47 C.I. I. and more preferably Solvent Black 27, 29 or 34 C.I. I. At least one of the black dyes defined in When the metal complex dye (C) is used, the light-shielding property of the film of the positive photosensitive resin composition after baking can be maintained.

In one embodiment, the positive photosensitive resin composition contains 10 parts by mass to 150 parts by mass, preferably 30 parts by mass to 100 parts by mass of the metal complex dye (C) based on a total of 100 parts by mass of the resin components. More preferably, it contains 40 parts by mass to 60 parts by mass. When the content of the metal complex dye (C) is 10 parts by mass or more based on the above total of 100 parts by mass, the light-shielding properties of the baked film can be maintained. When the content of the metal complex dye (C) is 150 parts by mass or less based on the above total of 100 parts by mass, the coating can be colored without impairing the alkali developability.

<Second resin (D)>
The positive photosensitive resin composition may further contain a second resin (D). The second resin (D) is a resin different from the first resin (A). Although the second resin (D) is not particularly limited, it preferably has an alkali-soluble functional group and is alkali-soluble. Alkali-soluble functional groups include, but are not particularly limited to, carboxy groups, phenolic hydroxyl groups, sulfo groups, phosphoric acid groups, and mercapto groups. A second resin (D) having two or more alkali-soluble functional groups may be used. However, the second resin (D) does not have an alkali-soluble functional group protected by an acid-decomposable group.

Examples of the second resin (D) include homopolymers or copolymers of polymerizable monomers having alkali-soluble functional groups, and resins having epoxy groups and phenolic hydroxyl groups. Other second resins (D) include, for example, acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenol resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, silicone resins, Cyclic olefin polymers, cardo resins, derivatives of these resins, and alkali-soluble functional groups bonded to these resins can be mentioned. For example, phenol resin derivatives include polyalkenylphenol resins in which alkenyl groups are bonded to benzene rings, and polystyrene resin derivatives include hydroxypolystyrene resin derivatives in which phenolic hydroxyl groups and hydroxyalkyl groups or alkoxy groups are bonded to benzene rings. be done. These resins can be used alone or in combination of two or more.

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

In one embodiment, the second resin (D) is the polymerizable monomer having a phenolic hydroxyl group and other polymerizable monomers that can be used as the base resin (a) of the first resin (A). including the copolymer (a1) with the The copolymer (a1) as the second resin (D) and the copolymer (a1) as the base resin (a) of the first resin (A) have a number average molecular weight Mn and a weight average molecular weight Mw , and polydispersity Mw/Mn, and types and mass ratios of polymerizable monomers constituting them, may be the same or different.

In one embodiment, the second resin (D) has formula (1)

(In Formula (2), R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms. , or a halogen atom, and R ⁴ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, or a 1 to 6 carbon atom is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.)
It is a copolymer (a1) having a structural unit represented by

In one embodiment, the second resin (D) contains a resin having epoxy groups and phenolic hydroxyl groups. A resin having an epoxy group and a phenolic hydroxyl group is an alkaline aqueous solution-soluble resin. A resin having an epoxy group and a phenolic hydroxyl group may have an alkali-soluble functional group other than the phenolic hydroxyl group. A resin having an epoxy group and a phenolic hydroxyl group is, for example, a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as an "epoxy compound"), a part of the epoxy group and a hydroxyl It can be obtained by reacting the carboxy group of a benzoic acid compound. Epoxy groups of resins containing epoxy groups and phenolic hydroxyl groups form crosslinks by reacting with phenolic hydroxyl groups during heat treatment (post-baking) after development, thereby improving the chemical resistance and heat resistance of the film. be able to. Since the phenolic hydroxyl group contributes to the solubility in an alkaline aqueous solution during development, the resin having an epoxy group and a phenolic hydroxyl group is not sufficiently decomposed (deprotected) of the acid-decomposable group when exposed to light at a low exposure dose. It also functions as a dissolution accelerator for the first resin (A), thereby making the photosensitive resin composition highly sensitive.

An example of the reaction in which one of the epoxy groups of the epoxy compound reacts with the carboxyl group of the hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group is shown in Reaction Formula 2 below.

Examples of compounds having at least two epoxy groups in one molecule include phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol type epoxy resins, biphenol type epoxy resins, naphthalene skeleton-containing epoxy resins, and alicyclic epoxy resins. , heterocyclic epoxy resins, and the like. These epoxy compounds need only have two or more epoxy groups in one molecule, and may be used alone or in combination of two or more. Since these compounds are thermosetting, it is common knowledge for those skilled in the art that their structures cannot be uniquely described due to differences in the presence or absence of epoxy groups, types of functional groups, degrees of polymerization, and the like. An example of the structure of the novolak type epoxy resin is shown in formula (6). In formula (6), for example, R ¹³ is a hydrogen atom, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-2 carbon atoms or a hydroxyl group, and n is an integer of 1-50.

Examples of phenolic novolak-type epoxy resins include EPICLON (registered trademark) N-770 (manufactured by DIC Corporation) and JER (registered trademark)-152 (manufactured by Mitsubishi Chemical Corporation). Examples of cresol novolac type epoxy resins include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation) and EOCN (registered trademark)-102S (manufactured by Nippon Kayaku Co., Ltd.). Bisphenol-type epoxy resins include, for example, jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), YD-128 (trade name, manufactured by Nippon Steel Chemical & Materials Co., Ltd.) and other bisphenol A types. Bisphenol F-type epoxy resins such as epoxy resins, jER (registered trademark) 806 (manufactured by Mitsubishi Chemical Corporation) and YDF-170 (trade name, manufactured by Nippon Steel Chemical & Materials Co., Ltd.). Examples of biphenol-type epoxy resins 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 Co., Ltd.) and EXA-4750 (trade name, manufactured by DIC Corporation). Alicyclic epoxy resins include, for example, EHPE (registered trademark)-3150 (manufactured by Daicel Chemical Industries, 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, more preferably at least one selected from the group consisting of phenol novolak type epoxy resins and cresol novolak type epoxy resins. preferable. A positive photosensitive resin composition containing a resin having an epoxy group derived from a novolak-type epoxy resin and a phenolic hydroxyl group has excellent pattern formability, easy adjustment of alkali solubility, and little outgassing.

A hydroxybenzoic acid compound is a compound in which at least one of the 2-6 positions of benzoic acid is substituted with a hydroxyl group, such as salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, and 2,4-dihydroxybenzoic acid. , 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4-nitro Benzoic acid, 4-hydroxy-3-nitrobenzoic acid and the like can be mentioned, and dihydroxybenzoic acid compounds are preferred from the viewpoint of enhancing alkali developability. A hydroxybenzoic acid compound can be used individually or in combination of 2 or more types.

In one embodiment, 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, represented by formula (7)

has the structure 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 a resin having an epoxy group and a phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid compound, it is possible to use 0.2 to 0.95 equivalents of the hydroxybenzoic acid compound with respect to 1 equivalent of the epoxy group of the epoxy compound. preferably 0.3 to 0.9 equivalents, more preferably 0.4 to 0.8 equivalents. If the amount of the hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and if the amount is 0.95 equivalents 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 the catalyst used can be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture comprising the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature can be 60-150° C., and the reaction time can be 3-30 hours. Examples of catalysts used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, and zirconium octanoate.

The number average molecular weight (Mn) of the resin having an epoxy group and a phenolic hydroxyl group is preferably 500-8000, more preferably 800-6000, even more preferably 1000-5000. If the number-average molecular weight is 500 or more, the alkali solubility is appropriate, so it is good as a resin for a photosensitive material.

In one embodiment, the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300-7000, preferably 400-6000, more preferably 500-5000. If the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300 or more, the resin having an epoxy group and a phenolic hydroxyl group can develop sufficient alkali solubility. If the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 7000 or less, the strength and heat resistance of the cured coating film can be enhanced. Epoxy equivalent is determined by JIS K 7236:2009.

In one embodiment, the hydroxyl equivalent weight of the resin having an epoxy group and a phenolic hydroxyl group is 160-500, preferably 170-400, more preferably 180-300. If the hydroxyl group equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 160 or more, the strength and heat resistance of the cured coating film can be enhanced. When the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 500 or less, the resin having epoxy groups and phenolic hydroxyl groups can exhibit sufficient alkali solubility. The hydroxyl equivalent is determined according to JIS K 0070:1992.

In one embodiment, the positive photosensitive resin composition contains 5% by mass to 80% by mass, preferably 10% by mass to 75% by mass, more preferably 10% by mass to 75% by mass of the second resin (D) based on the solid content of 100% by mass. contains 15% by mass to 70% by mass. When the content of the second resin (D) is 5% by mass or more based on the solid content of 100% by mass, the dissolution of the exposed area can be promoted to achieve high sensitivity, and the coating after heat curing can be improved. Stability and durability can be ensured. When the content of the second resin (D) is 80% by mass or less based on 100% by mass of the solid content, the solubility of the unexposed areas can be kept low and the residual film rate can be kept high.

<Solubilizer (E)>
The positive photosensitive resin composition may further contain a dissolution accelerator (E) for improving the solubility of the alkali-soluble portion in the developer during development. Examples of the dissolution accelerator (E) include organic low-molecular-weight compounds selected from the group consisting of compounds having a carboxyl group and compounds having a phenolic hydroxyl group. The dissolution accelerator (E) can be used alone or in combination of two or more.

In the present disclosure, "low-molecular-weight compounds" refer to compounds with a molecular weight of 1000 or less. The organic low-molecular compound has a carboxyl group or a plurality of phenolic hydroxyl groups and is alkali-soluble.

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; 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, citraconic acid, etc. Aliphatic dicarboxylic acids; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid and mesitylene acid; Aromatic polycarboxylic acids such as mellitic acid, trimesic acid, melophanic acid, pyromellitic acid and hemimellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid and gallic acid; phenylacetic acid, hydroatropic acid, hydrosilicone Other carboxylic acids such as mic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umberic acid; catechol, resorcinol, hydroquinone, 1, Aromatic polyols such as 2,4-benzenetriol, pyrogallol, phloroglucinol, bisphenol and the like are included.

The content of the dissolution accelerator (E) in the positive photosensitive resin composition can be 0.1 parts by mass to 50 parts by mass, preferably 1 part by mass, based on the total of 100 parts by mass of the resin components. parts to 35 parts by mass, more preferably 2 parts to 20 parts by mass. If the content of the dissolution accelerator (E) is 0.1 parts by mass or more based on the above total of 100 parts by mass, the 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 can be suppressed, and the pattern formability, surface quality, etc. of the film can be improved.

<Optional component (F)>
The positive photosensitive resin composition can contain, as an optional component (F), a thermosetting agent, a surfactant, a coloring agent other than the component (C), and the like. For purposes of this disclosure, optional component (F) is defined as none of (A)-(E).

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

The content of the heat curing 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 the total 100 parts by mass of solid content excluding the heat curing agent. .

The positive photosensitive resin composition can contain a surfactant, for example, to improve coatability, to improve the smoothness of the film, or to improve the developability of the film. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Oxyethylene aryl ethers; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Megafac (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, Trade name, manufactured by DIC Corporation), Surflon (registered trademark) S-242, S-243, S-386, S-420, S-611 (trade name, manufactured by AGC Seimi Chemical Co., Ltd.) fluorine-based surfactants such as; A surfactant can be used individually or in combination of 2 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 the total 100 parts by mass of the solid content excluding the surfactant. is.

[Coating composition]
<Solvent (G)>
The positive photosensitive resin composition can be dissolved in the solvent (G) and used as a solution state coating composition. For example, a photoacid generator (B), a metal complex dye (C), and a A coating composition containing a positive photosensitive resin composition is prepared by mixing an optional component (F) such as a dissolution accelerator (E), a thermosetting agent, and a surfactant as required in a predetermined ratio. be able to. The coating composition can be adjusted to a viscosity suitable for the coating method used by varying the amount of solvent (G).

Examples of the solvent (G) 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; and diethylene glycol. diethylene glycol compounds such as 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 alkyl ether acetate compounds such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; toluene; Aromatic hydrocarbons such as xylene, ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate , ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, esters such as γ-butyrolactone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Amide compounds are mentioned. A solvent can be used individually or in combination of 2 or more types.

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

The prepared coating composition is usually filtered before use. Filtration means include, for example, a Millipore filter with a pore size of 0.05 to 1.0 μm.

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

[How to use the positive photosensitive resin composition]
When a positive photosensitive resin composition is used in radiation lithography, first, a coating composition is prepared by dissolving or dispersing the positive photosensitive resin composition in a solvent. The coating composition can then be applied to the substrate surface and the solvent removed by means such as heating to form a coating. The method of applying the coating composition to the substrate surface is not particularly limited, and for example, a spray method, a roll coating method, a slit method, a spin coating method, or the like can be used.

After applying the coating composition to the substrate surface, the solvent is usually removed by heating to form a film (pre-bake). The heating conditions vary depending on the type of each component, the mixing ratio, etc., but usually at 70 to 130 ° C., for example, 30 seconds to 20 minutes on a hot plate, 1 to 60 minutes in an oven to obtain a coating. be able to.

Next, the pre-baked film is irradiated with radiation (for example, visible light, ultraviolet light, deep ultraviolet light, X-rays, electron beams, gamma rays, synchrotron radiation, etc.) through a photomask having a predetermined pattern (exposure step). Preferred radiation is ultraviolet to visible light having a wavelength of 250-450 nm. In one embodiment, the radiation is i-line. In another embodiment, the radiation is ghi rays.

After the exposure process, heat treatment (PEB) can be performed to promote decomposition of the acid-decomposable groups. PEB promotes the deprotection of the protected alkali-soluble functional groups in the first resin (A) in the exposed area, and can further increase the alkali-solubility. The heating conditions vary depending on the type of each component, the mixing ratio, etc., but usually PEB is performed by heating at 70 to 140° C., for example, for 30 seconds to 20 minutes on a hot plate and 1 to 60 minutes in an oven. be able to. In one embodiment, the PEB after the exposure step can be omitted.

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

Thereafter, the film having the pattern formed thereon is subjected to heat treatment at 100 to 350° C. for 20 to 200 minutes using a heating device such as a hot plate or oven to obtain a cured film (post-baking, heat treatment process). In the heat treatment, the temperature may be maintained constant, may be increased continuously, or may be increased stepwise. Heat treatment is preferably performed in a nitrogen atmosphere.

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

A method for producing an organic EL element partition wall or an insulating film of one embodiment includes dissolving or dispersing a positive photosensitive resin composition in a solvent to prepare a coating composition, applying the coating composition to a substrate to form a film. forming, drying the coating by removing the solvent contained in the coating, exposing the coating by irradiating the dried coating with radiation through a photomask, and contacting the exposed coating with a developer to form a pattern on the film, and heat treatment of the patterned film at a temperature of 100° C. to 350° C. to form an organic EL element partition wall or an insulating film. The above PEB can also be performed after exposure and before development.

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

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

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

The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.

(1) Raw Materials 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 the first resin (A) and the second resin (D) were calculated using a calibration curve prepared using polystyrene standard substances under the following measurement conditions.
Apparatus name: Shodex (registered trademark) GPC-101
Column: Shodex® LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL/min Detector: Shodex (registered trademark) RI-71
Temperature: 40°C

[Production Example 1] Production of a copolymer (PCX-02e) of a polymerizable monomer having an alkali-soluble functional group (phenolic hydroxyl group) and another polymerizable monomer 4-hydroxyphenyl methacrylate (Showa Denko K.K. 25.5 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and 4.50 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) were added to 77.1 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) to initiate polymerization. As an agent, 3.66 g of V-601 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation). The two solutions obtained were simultaneously added to 61.2 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) heated to 85° C. in a 300 mL three-necked flask under a nitrogen gas atmosphere for 2 hours. It was added dropwise and then reacted at 85° C. for 3 hours. The reaction solution cooled to room temperature was dropped into 815 g of toluene to precipitate a copolymer. The precipitated copolymer was collected by filtration and vacuum-dried at 90° C. for 4 hours to collect 32.4 g of white powder. The obtained PCX-02e had a number average molecular weight of 3,100 and a weight average molecular weight of 6,600.

[Production Example 2] Production of the first resin (A) (PCX-02e-THF97) in which the alkali-soluble functional group (phenolic hydroxyl group) is protected with a 2-tetrahydrofuranyl group In a 100 mL three-necked flask, phenol 10.00 g of a copolymer of a polymerizable monomer having a hydroxyl group and another polymerizable monomer (PCX-02e), and a pyridinium salt of p-toluenesulfonic acid as an acid catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.60 g was dissolved in 50.00 g of tetrahydrofuran (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). Thereafter, the mixture was ice-cooled in a nitrogen gas atmosphere, and 6.68 g of 2,3-dihydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. After that, the mixture was stirred at room temperature for 4 hours. After neutralizing the acid catalyst with saturated sodium bicarbonate aqueous solution, the water layer was removed. Furthermore, the organic layer was washed twice with water. The tetrahydrofuran was then distilled off. The resulting solid was dissolved in 50.0 g of ethyl acetate and added dropwise to 200 g of hexane to precipitate the product. The precipitate was recovered by filtration and vacuum dried at 80° C. for 4 hours to recover 9.86 g of white powder. The obtained powder was dissolved in propylene glycol monomethyl ether acetate to obtain a 20 mass% solids solution of the first resin (A) (PCX-02e-THF97) in which the phenolic hydroxyl group was protected with a 2-tetrahydrofuranyl group. rice field. The resulting PCX-02e-THF97 had a number average molecular weight of 3098, a weight average molecular weight of 5958, a proportion of phenolic hydroxyl groups protected with acid-decomposable groups of 97 mol%, and at least one phenolic hydroxyl group being acid-decomposable. The number of structural units represented by formula (3) protected by groups was 77% of the total number of structural units in the first resin (A). The proportion of phenolic hydroxyl groups protected with acid-decomposable groups was determined using a thermogravimetric differential thermal analyzer (TG/DTA6200, manufactured by Hitachi High-Tech Science Co., Ltd.) in a nitrogen gas stream at a temperature elevation rate of 10°C/min. The weight loss rate of the first resin (A) at 260°C when the temperature is raised from room temperature to 250°C under the conditions, held for 10 minutes, and further heated to 400°C at a temperature increase rate of 10°C/min. (%).

[Production Example 3] Production of the first resin (A) (PCX-02e-TBMA50) in which the alkali-soluble functional group (carboxy group) is protected with a tert-butyl group 4-hydroxyphenyl methacrylate (manufactured by Showa Denko K.K. ”) 17.3 g, tert-butyl methacrylate (manufactured by Mitsubishi Chemical Corporation “Acrylic ester TB”) 13.8 g, and N-cyclohexylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.15 g, isopropyl acetate as a solvent ( Shinko Organic Chemical Industry Co., Ltd.) 56.0 g, V-601 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 2.69 g as a polymerization initiator, isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.)4. 05 g each completely dissolved. The resulting two solutions were added dropwise to 90.4 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89° C. in a 300 mL three-necked flask under a nitrogen gas atmosphere over 2 hours. , and then reacted at 89° C. for 4 hours. 50 g of the reaction solution cooled to room temperature was dropped into a mixed solvent of 50 g of toluene and 200 g of hexane to precipitate a copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80° C. for 5 hours to recover 8.98 g of white powder. The obtained PCX-02e-TBMA50 had a number average molecular weight of 4,122, a weight average molecular weight of 7,583, and a ratio of carboxy groups protected with acid-decomposable groups of 50 mol %.

PCX-02e-THF97 and PCX-02e-TBMA50 were used as the first resin (A).

TS-150A and TS-200A (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene] which are quinonediazide compounds as photoacid generators (B) Ester of bisphenol (TrisP-PA) and 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid (1,2-naphthoquinonediazide-5-sulfonic acid), manufactured by Toyo Gosei Co., Ltd.) It was used. The structures of TS-150A and TS-200A are shown below. TS-150A has a quinonediazide structure in an average of 1.5 R out of 3 R per molecule. TS-200A has a quinonediazide structure for an average of 2.0 R out of 3 R per molecule.

PAG-103 (2-[2-(propylsulfonyloxyimino)thiophene-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile which is an oxime photoacid generator as the photoacid generator (B) , BASF, CAS No. 852246-55-0) and PAG-169 (BASF) were used. PAG-103 generates 1-propanesulfonic acid (pKa=-2.8) upon irradiation with light. PAG-169 generates trifluoromethanesulfonic acid (pKa=-13) upon irradiation with light.

C-1 to C-5 shown in Table 1 were used as metal complex dyes (C). In C-1 to C-5, the metal element forming metal complex ions is chromium. C-1, C-3, and C-5 are Solvent Black 27 from different lots. The metal complex ion content (% by mass) of metal complex dyes C-1 to C-5 was determined by the following procedure. 0.1 g of metal complex dye is weighed, 0.1 g of methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.0 g of diethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) are added, and if necessary, gas chromatography Samples were prepared with the addition of pretreatment agents. After stirring the obtained sample with a mix rotor (VMR-5 manufactured by AS ONE) for 30 minutes to 1 day, it was analyzed by GC (GC6850 series manufactured by Agilent) or GC-MS (7890A manufactured by Agilent, Q-1000 manufactured by JEOL) and analyzed as follows. The metal complex ion content (% by mass) was calculated from the formula.
Content of metal complex ions (% by mass) = 100-Total content of each substance detected by GC (% by mass)

PCX-02e was used as the second resin (D).

Phloroglucinol was used as a dissolution accelerator (E).

As an optional component (F), Megafac (registered trademark) F-559 (fluorosurfactant, manufactured by DIC Corporation), which is a surfactant (leveling agent), was used.

A mixed solvent of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) (GBL:PGMEA=40:60 (mass ratio)) was used as the solvent (G).

(2) Evaluation methods Evaluation methods used in Examples and Comparative Examples are as follows.

[Unexposed area solubility]
A glass substrate (size 100 mm × 100 mm × 1 mm) was bar-coated with a positive photosensitive resin composition so that the dry film thickness was 2.6 µm, dried in vacuum at room temperature for 60 seconds, and placed on a hot plate with a lid at 100 °C. was heated for 100 seconds for pre-baking. Further, PEB was performed by heating at 115° C. for 200 seconds on a hot plate with a lid. After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Co., Ltd.), a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.) was used to obtain 2.38% by mass hydroxylation. Alkaline development was carried out for 80 seconds with a tetramethylammonium aqueous solution. The film thickness after alkali development was measured again using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Co., Ltd.), and the dissolved film thickness (μm) before and after development was taken as an index of the unexposed area solubility. did. The positive photosensitive resin composition in which the film thickness dissolved before and after development was in the range of 0.3 to 1.9 μm has high alkali solubility resistance in the unexposed area, and the difference in film thickness between the unexposed area and the exposed area is It was judged to have high sensitivity because it was easy to attach.

[Hole diameter]
A glass substrate (size 100 mm × 100 mm × 1 mm) was bar-coated with a positive photosensitive resin composition to a dry film thickness of 2.6 μm, vacuum dried for 90 seconds, and then placed on a hot plate with a lid at 100 ° C. It was pre-baked by heating for 100 seconds. Exposure was performed at 150 mJ/cm ² through a quartz photomask (having a φ10 μm pattern) with an exposure apparatus (trade name: Multilight ML-251A/B, manufactured by Ushio Inc.) incorporating an ultra-high pressure mercury lamp. The amount of exposure was measured using an ultraviolet integrating photometer (trade name: UIT-150 light receiving unit UVD-S365, manufactured by Ushio Inc.). After the exposure, PEB was performed by heating at 115° C. for 200 seconds on a hot plate with a lid. After that, using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), alkali development was carried out for 60 seconds with a 2.38% by mass tetramethylammonium hydroxide aqueous solution. Further, the coating was cured by heating at 250° C. for 60 minutes in an inert oven (DN411I, manufactured by Yamato Scientific Co., Ltd.). The hole diameter (μm) obtained by observing the holes formed in the coating film after curing with a microscope (VHX-6000, manufactured by Keyence Corporation) was used as an index of sensitivity. A positive photosensitive resin composition having a hole diameter in the range of 9.0 to 11.0 μm was judged to have good pattern formability.

[OD value of cured film]
A glass substrate (size 100 mm × 100 mm × 1 mm) was spin-coated with a positive photosensitive resin composition to a dry film thickness of about 1.5 µm, and heated on a hot plate at 120°C for 80 seconds to dry the solvent. . After that, the coating 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, manufactured by Sakata Inx Engineering Co., Ltd.), corrected with the OD value of the glass alone, and converted to an OD value per 1 μm of film thickness. The thickness of the coating was measured using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Co., Ltd.).

(3) Preparation and evaluation of positive photosensitive resin composition [Examples 1 to 5, Comparative Examples 1 to 3]
The first resin (A) and the second resin (D) are mixed and dissolved with the composition shown in Table 2, and the resulting solution is added to the photoacid generator (B) shown in Table 2 and the metal complex dye. (C), dissolution enhancer (E), surfactant (F) and GBL/PGMEA mixed solvent (G) were added and further mixed. After visually confirming that the components had dissolved, the mixture was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a positive photosensitive resin composition with a solid content concentration of 12% by mass. The mass parts of the compositions in Table 2 are solid content conversion values. Table 2 shows the evaluation results of the positive photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3.

The positive photosensitive resin composition according to the present disclosure can be suitably used for radiation lithography for forming partition walls or insulating films of organic EL elements. An organic EL element provided with a partition wall or an insulating film formed from the positive photosensitive resin composition according to the present disclosure is suitably used as an electronic component of a display device exhibiting good contrast.

Claims

a first resin (A) having a plurality of alkali-soluble functional groups, at least a portion of which is protected with an acid-decomposable group;
a photoacid generator (B);
A positive photosensitive resin composition containing a metal complex dye (C), wherein the metal complex dye (C) contains 50 to 94% by mass of metal complex ions.
The positive type according to claim 1, wherein the metal element forming the metal complex ion contained in the metal complex dye (C) is at least one selected from the group consisting of chromium, copper, cobalt, and iron. A photosensitive resin composition.
The positive photosensitive resin composition according to claim 1, wherein the metal complex dye (C) is at least one of black dyes defined by color indexes (C.I.) of Solvent Black 22 to 47. .
4. Any one of claims 1 to 3, wherein the first resin (A) is a resin having a plurality of phenolic hydroxyl groups, and at least a portion of the plurality of phenolic hydroxyl groups are protected with the acid-decomposable groups. The positive photosensitive resin composition according to claim 1.
a polymerizable monomer having a phenolic hydroxyl group in which the first resin (A) has a plurality of phenolic hydroxyl groups, at least a portion of which is protected by the acid-decomposable group; 5. The positive photosensitive resin composition according to claim 4, which is a copolymer with other polymerizable monomers.
The first resin (A) has the formula (3)

(In formula (3), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 5 is the acid-decomposable group, r is an integer of 0 to 5, and s is 0 to is an integer of 5, provided that r+s is an integer of 1 to 5.)
The positive photosensitive resin composition according to claim 5, which has at least one structural unit represented by formula (3), wherein s is an integer of 1 or more.
The first resin (A) has the formula (2)

(In Formula (2), R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms. , or a halogen atom, and R 4 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, or a 1 to 6 carbon atom is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.)
The positive photosensitive resin composition according to claim 5, which has a structural unit represented by:
The positive photosensitive resin composition further includes a second resin (D), and the second resin (D) is a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group, or an epoxy The positive photosensitive resin composition according to any one of claims 1 to 3, which is a resin having a group and a phenolic hydroxyl group.
The positive photosensitive resin composition according to any one of claims 1 to 3, comprising 10 to 150 parts by mass of the metal complex dye (C) based on a total of 100 parts by mass of the resin components.
The positive photosensitive resin composition according to any one of claims 1 to 3, comprising 0.1 to 85 parts by mass of the photoacid generator (B) based on a total of 100 parts by mass of the resin components. thing.
The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the cured film of the positive photosensitive resin composition has an optical density (OD value) of 0.5 or more per 1 µm of film thickness. .
An organic EL element partition containing a cured product of the positive photosensitive resin composition according to any one of claims 1 to 3.
An organic EL element insulating film containing a cured product of the positive photosensitive resin composition according to any one of claims 1 to 3.
An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 3.