KR102181114B1 - Positive photosensitive resin composition and titanium black dispersion - Google Patents

Abstract

For example, there is provided a positive photosensitive resin composition that is highly sensitive and satisfies the characteristics of developability, resolution, and heat resistance that can be used to form a black partition material of an organic EL display device. The positive photosensitive resin composition comprises (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH/g or less, an acid value of 20 to 200 mgKOH/g, (C) a solvent having a solubility parameter of 10.5 or more, (D) a binder resin, and ( E) A quinone diazide compound is included.

Description

Positive photosensitive resin composition and titanium black dispersion

The present invention relates to a positive photosensitive resin composition, a method for producing the same, a titanium black dispersion used in the production thereof, and a partition wall and an insulating film of an organic EL display device.

In a display device such as an organic EL display, in order to improve display characteristics, a partition material is used for the spaced portion of the colored pattern in the display area or the edge of the peripheral portion of the display area. In the manufacture of an organic EL display device, in order to prevent the pixels of organic material from contacting each other, barrier ribs are first formed, and pixels of organic material are formed between the barrier ribs. This partition wall is generally formed by photolithography using a photosensitive resin composition, and has insulating properties. Specifically, a photosensitive resin composition is applied on a substrate using a coating device, and the volatile component is removed by means of heating or the like, and then exposed through a mask. Then, in the case of a negative type, the unexposed portion is removed from the positive type. In this case, the exposed portion is developed by removing it with a developer such as an aqueous alkali solution, and the obtained pattern is subjected to heat treatment to form a partition wall (insulating film). Subsequently, an organic material that generates light in three colors of red, green, and blue by an ink jet method or the like is deposited between the partition walls to form pixels of the organic EL display device.

In the above field, in recent years, due to the miniaturization of display devices and the diversification of displayed content, high performance and high definition of pixels are required. In order to increase the contrast in the display device and improve the visibility, attempts have been made to blacken the partition material using a colorant to provide light-shielding properties. However, even if it has light-shielding property, it becomes important that it is high sensitivity because if it is low with respect to light for reaction, exposure time becomes long and productivity falls. In order to meet the demand for high definition, it is required that the pattern shape is excellent and the pattern surface is smooth in order to cope with the narrow pitch of the pattern. In order to improve visibility, it is required to make the blackened partition material closer to black, and since various processes are performed after the partition material is formed, it is required to have excellent heat resistance so as not to affect peripheral members.

For example, in Patent Document 1, a method of blackening a partition wall material using carbon black is proposed. However, in these radiation-sensitive resin compositions, the light-shielding property of the cured film is insufficient, and an improvement in contrast cannot be expected.

On the other hand, as a radiation-sensitive resin composition that has high resolution and exhibits high light-shielding property by heat treatment after exposure, titanium is a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound as in Patent Document 2 A composition in which black is added has been proposed. Although these compositions have sufficient sensitivity and light-shielding properties, they are heated at a high temperature under air in order to increase light-shielding properties, and use coloring with oxidation deterioration of the resin. In this case, since the outgas due to deterioration of the resin increases, heat resistance is poor, and it is not suitable for manufacturing and stable driving of an organic EL display device. It is difficult to say that the properties of titanium black are not in conflict and that the surface smoothness is sufficiently produced.

As the partition material, generally, a polyimide resin having excellent insulating properties is used, but in order to make it light-shielding, it is necessary to blacken. However, it is difficult to form a blackened polyimide resin by a lithography method in terms of storage stability and cost of the photosensitive polyimide, and good resolution is difficult to obtain. Therefore, it has not yet been obtained that the partition material is blackened and the sensitivity, developability, resolution, and heat resistance are satisfied.

Japanese Patent Laid-Open No. 2002-116536 Japanese Patent Laid-Open No. 2001-281440

In order to increase the contrast of the organic EL display device, attempts have been made to blacken the barrier material, but a positive photosensitive resin composition having high sensitivity and satisfying all characteristics of developability, resolution, and heat resistance, and a method of manufacturing the same, have been known so far. Not.

The present invention has been made on the basis of the above circumstances, and its object is to provide a positive photosensitive resin composition and a method for producing the same, which is highly sensitive in a blackened partition material and satisfies the characteristics of developability, resolution, and heat resistance. will be.

As a result of intensive examination, the present inventors found that titanium black, a dispersant having an amine value of 5 mgKOH/g or less and an acid value of 20 to 200 mgKOH/g, a solvent having a solubility parameter (SP value) of 10.5 or more, a binder resin, and a quinone diazide compound It has been found that the positive photosensitive resin composition containing is high sensitivity in the blackened partition wall material and satisfies the characteristics of developability, resolution, and heat resistance.

That is, the present invention includes the following aspects.

[1] (A) titanium black,

(B) a dispersant having an amine value of 5 mgKOH/g or less and an acid value of 20 to 200 mgKOH/g,

(C) a solvent having a solubility parameter of 10.5 or more,

(D) binder resin, and

(E) Quinone diazide compound

Positive photosensitive resin composition comprising a.

[2] The composition according to [1], wherein the solvent (C) is γ-butyrolactone or n-methyl-2-pyrrolidone.

[3] The composition according to [1] or [2], wherein the dispersant (B) is 1 to 40 parts by mass and the solvent (C) is 250 to 600 parts by mass based on 100 parts by mass of titanium black (A).

[4] Any one of [1] to [3] in which 3 to 30 parts by mass of titanium black (A) and 3 to 20 parts by mass of the quinone diazide compound (E) are based on 100 parts by mass of the binder resin (D). The composition described in.

[5] The binder resin (D),

(d1) an alkali-soluble copolymer having an alkali-soluble group,

(d2) an alkali-soluble resin having an epoxy group and a phenolic hydroxyl group, and

(d3) polyalkenylphenol resin

The composition according to any one of [1] to [4] containing at least one selected from the group consisting of.

[6] (A) titanium black,

(B) a dispersant having an amine value of 5 mgKOH/g or less and an acid value of 20 to 200 mgKOH/g, and

(C) a solvent with a solubility parameter of 10.5 or more

Titanium black dispersion comprising a.

[7] (1) (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH/g or less, an acid value of 20 to 200 mgKOH/g, and (C) a solvent having a solubility parameter of 10.5 or more to prepare a titanium black dispersion The process of doing, and

(2) The process of mixing the titanium black dispersion, (D) binder resin and (E) quinone diazide compound

A method for producing a positive photosensitive resin composition comprising in this order.

[8] A cured product of the composition according to any one of [1] to [5].

[9] (I) a coating step of applying the positive photosensitive resin composition according to any one of [1] to [5] to a substrate,

(II) drying step of removing the solvent in the applied positive photosensitive resin composition,

(III) exposure process in which radiation is irradiated over a photomask,

(IV) a developing step of forming a pattern by alkali development, and

(V) Heat treatment step of heating at a temperature of 100 to 350°C

Method of manufacturing a radiation lithographic structure comprising a.

[10] A partition wall of an organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [5].

[11] An insulating film for an organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [5].

[12] An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [5].

(Effects of the Invention)

Advantageous Effects of Invention According to the present invention, it is possible to provide a positive photosensitive resin composition that is highly sensitive in a blackened partition material and satisfies the characteristics of developability, resolution, and heat resistance.

Hereinafter, the present invention will be described in detail.

The titanium black dispersion of the present invention contains (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH/g or less, an acid value of 20 to 200 mgKOH/g, and (C) a solvent having a solubility parameter of 10.5 or more.

The positive photosensitive resin composition of the present invention includes (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH/g or less, an acid value of 20 to 200 mgKOH/g, (C) a solvent having a solubility parameter of 10.5 or more, and (D) a binder resin. , And (E) a quinone diazide compound.

(A) Titanium black

As the titanium black used in the present invention, a method of reducing a mixture of titanium dioxide and titanium metal by heating in a reducing atmosphere (Japanese Patent Laid-Open Publication No. 49-5432), ultrafine dioxide obtained from high-temperature hydrolysis of titanium tetrachloride A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open Publication No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open Publication No. 60-65069, Japan Patent Laid-Open Publication No. 61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing at high temperature in the presence of ammonia (Japanese Patent Laid-Open Publication No. 61-201610), etc., but these It is not limited to. Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13-MT, 16M, UF-8, Tilack D manufactured by Akokasei, etc., manufactured by Mitsubishi Matterial Co., Ltd. Can be lifted. These titanium blacks may be used alone or in combination of two or more.

The titanium black (A) is preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 8 to 15 parts by mass based on 100 parts by mass of the binder resin (D). If the content of the titanium black (A) is 3 to 30 parts by mass based on 100 parts by mass of the binder resin (D), the target OD value (optical concentration) is obtained.

The average particle diameter D50 (volume basis) of the titanium black (A) in the dispersion is preferably 5 to 100 nm. When the average particle diameter D50 is 5 to 100 nm, high light-shielding property is obtained. The average particle diameter D50 can be measured using a laser diffraction/scattering particle diameter distribution measuring device Microtrac wave (Nikiso Corporation).

(B) A dispersant having an amine value of 5 mgKOH/g or less and an acid value of 20 to 200 mgKOH/g

A known dispersant having an amine value of 5 mgKOH/g or less and an acid value of 20 to 200 mgKOH/g used for dispersion of the titanium black of the present invention can be used. For example, phosphate esters such as brand names DISPERBYK110, DISPERBYK111 (made by Big Chemical Japan Co., Ltd.), brand names Disparon PW-36, Disparon DA-375 (made by Kusumoto Kasei Co., Ltd.), poly Phosphoric acid-based dispersants such as phosphate esters, phosphate polyesters, polyether phosphate esters, brand names Floren G-700, Floren G-900, Floren GW-1500 (Kyoeisha Chemical Co., Ltd. product), etc. And higher fatty acid ester-based dispersants such as a carboxyl group-containing polymer-based dispersant of Azisper PN411 and Azisper PA111 (manufactured by Ajinomoto Fine Techno Co., Ltd.). Among them, dispersants that do not have a graft chain in the skeleton, such as brand names DISPERBYK110, DISPERBYK111 (product of BIC Chemie Japan Co., Ltd.), and the like are preferably used.

The acid value of the dispersant is 20 to 200 mgKOH/g, preferably 30 to 180 mgKOH/g, and more preferably 40 to 150 mgKOH/g. The amine value of the dispersant is 5 mgKOH/g or less, preferably 4 mgKOH/g or less, more preferably 3 mgKOH/g or less, and most preferably 0 mgKOH/g. When the acid value is 20 to 200 mgKOH/g and the amine value is 5 mgKOH/g or less, it is easy to obtain a good dispersion having an appropriate bond with titanium black. These dispersants may be used alone or in combination of two or more.

To the extent that the effects of the present invention are not impaired, a dispersant having a salt structure, a dispersant having an ester or ether structure, a dispersant having a pigment affinity group, and the like can be used in combination. For the purpose of improving compatibility with the binder resin, storage stability, and various physical properties or properties, a resin component having a functional group such as a hydroxyl group, a carboxyl group, an amino group, and a sulfo group may be used in combination.

The dispersant (B) preferably contains 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and still more preferably 3 to 20 parts by mass based on 100 parts by mass of the titanium black (A). If the dispersant is 1 to 40 parts by mass per 100 parts by mass of titanium black (A), the particles can be satisfactorily dispersed.

The amine value refers to the number of mg of perchloric acid and equivalent potassium hydroxide required to neutralize the total basic nitrogen contained in 1 g of a sample, and the measurement method is as follows. The sample is dissolved in a mixed solvent of o-nitrotoluene and acetic acid, and titrated with 0.1 mol/L perchloric acid acetic acid solution using a glass electrode and a comparative electrode. The relationship between the reading of the potentiometer or the pH meter and the appropriate amount of the 0.1 mol/L perchloric acid acetic acid solution corresponding thereto is drawn, and the inflection point obtained in the titration curve is taken as the end point. The total amine number is calculated by the amount of 0.1 mol/L perchloric acid acetic acid solution consumed.

The acid value refers to the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of a sample, and the measurement methods include neutralization titration and potential difference titration. In the case of the neutralization titration method, a sample is dissolved in a solvent, phenolphthalein is added as an indicator, and the acid value is determined by titration with a potassium hydroxide ethanol solution.

(C) Solvent with a solubility parameter (SP value) of 10.5 or more

As the dispersion solvent of the titanium black of the present invention, the SP value is 10.5 to 15.0, preferably 10.5 to 13.0. It is more preferable not to contain a hydroxyl group. As a solvent having an SP value of 10.5 or more, specifically, γ-butyrolactone (12.6), N-methyl-2-pyrrolidone (11.3), N,N-dimethylformamide (12.1), and N,N-dimethylacet Although amide (10.8) and the like are mentioned, among them, N-methyl-2-pyrrolidone or γ-butyrolactone is more preferable, and γ-butyrolactone is still more preferable. Titanium black (A) can be uniformly dispersed by using a solvent having an SP value of 10.5 or more. These solvents may be used alone or in combination of two or more.

The solvent (C) preferably contains 250 to 600 parts by mass, more preferably 300 to 500 parts by mass, and still more preferably 350 to 450 parts by mass based on 100 parts by mass of the titanium black (A). If the solvent is 250 to 600 parts by mass per 100 parts by mass of titanium black (A), appropriate fluidity is obtained and the dispersion state is likely to be favorable.

The solubility parameter is defined by the square root of the cohesive energy density of the material, and can be used as a measure to predict the thermodynamic properties of the sample mixture. It is possible to use the numerical values described in the Application of Chemistry Handbook (Revised 3rd Edition, Maruzen, 1980) or the 4th Edition Experimental Chemistry Course (Maruzen, 1990, p.186).

(D) Binder resin

Although it does not specifically limit as a binder resin (D) used in the positive photosensitive resin composition of this invention, It is preferable that it has an alkali-soluble group and is alkali-soluble.

The alkali-soluble group of the binder resin is not particularly limited, but includes a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group, and the like. A resin having two or more alkali-soluble groups may be used. good. In addition, in the present invention, alkali-soluble means that it is soluble in an alkali solution, for example, an aqueous solution of 2.38 mass% tetramethylammonium hydroxide.

Examples of the binder resin include acrylic resins, styrene resins, epoxy resins, amide resins, phenol resins, polyamic acid resins, and those in which an alkali-soluble group is added to these resins. These can be used alone or in combination of two or more types of resins.

As a binder resin having a phenolic hydroxyl group, for example, a phenol novolak resin, a cresol novolak resin, a triphenylmethane type phenol resin, a phenol aralkyl resin, a biphenyl aralkyl phenol resin, a phenol-dicyclopentadiene copolymer resin Well-known phenol resins, such as are mentioned.

In the present invention, it is preferable that the binder resin (D) contains at least one selected from the following components (d1) to (d3).

(d1) alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble group and other polymerizable monomers

Examples of the alkali-soluble group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, and an acid anhydride group. Alkali-soluble resin composed of a copolymer of a polymerizable monomer having an alkali-soluble group and other polymerizable monomers is, for example, a polymerizable monomer having an alkali-soluble group and other polymerizable monomers as a polymerization initiator and a RAFT agent (Reversible Addition Fractionation Transfer). ; Can be produced by radical polymerization with a reversible addition cleavage type chain transfer agent) or the like. The alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer may be obtained by adding an alkali-soluble group after synthesizing the copolymer by radical polymerization.

A radical polymerizable functional group is mentioned as a polymerizable functional group which the polymerizable monomer has. Specifically, CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CHCO-, CH ₂ =C(CH ₃ )CO-, -OC-CH=CH-CO-, etc. I can. As a polymerizable monomer having an alkali-soluble group, for example, 4-hydroxystyrene, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, β- Styryl (meth)acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid , 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide, 3-maleimidepropionic acid, 4-maleimide Butyric acid, 6-maleimidehexanoic acid, etc. are mentioned.

Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene, acrylamide, acrylonitrile, vinyl-n-butyl ether, etc. Ethers of vinyl alcohol, (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid glycidyl ester (Meth)acrylic esters such as esters, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, isobornyl (meth)acrylic And N-substituted maleimides such as late, maleic anhydride, phenylmaleimide, and cyclohexylmaleimide. Here, "(meth)acryl" represents "acrylic" and "methacryl."

It is particularly preferable to use 4-hydroxyphenyl methacrylate as the polymerizable monomer having an alkali-soluble group, and to use at least one selected from the group consisting of phenylmaleimide and cyclohexylmaleimide as other polymerizable monomers. . By using a resin obtained by radical polymerization of these polymerizable monomers, it is possible to improve shape retention and developability and contribute to reduction of outgassing.

The polymerization initiator in the preparation of an alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer by radical polymerization is not limited to the following, but 2,2'-azobisisobutylonitrile, 2,2'-azobis (2-methylbutylonitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2 Azo polymerization initiators such as ,2'-azobis (2,4-dimethylvaleronitrile) (AVN), dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert -Peroxide polymerization initiator with a 10-hour half-life temperature of 100 to 170°C, such as butyl cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide, or Peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(t-butylperoxy)cyclohexane, and t-butylperoxypivalate can be used. The amount of the polymerization initiator to be used is generally 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, based on 100 parts by mass of the polymerizable monomer mixture. .

The RAFT agent is not limited to the following, but thiocarbonylthio compounds such as dithioester, dithiocarbamate, trithiocarbonate, and xanthate can be used. The RAFT agent can be used in the range of 0.005 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer, and is preferably used in the range of 0.01 to 10 parts by mass.

As the binder resin (D) of the positive photosensitive resin composition of the present invention, a radical copolymer of 4-hydroxyphenyl methacrylate and phenylmaleimide and cyclohexylmaleimide, or 4-hydroxyphenylmethacrylate and cyclohexyl When using a radical copolymer of maleimide, the number average molecular weight is preferably in the range of 1000 to 30000, more preferably in the range of 3000 to 20000, and even more preferably in the range of 10000 to 15000. When the molecular weight is 1000 or more, it is suitable as a resin for a photosensitive material because alkali solubility is appropriate, and when the molecular weight is 30000 or less, developability is good.

(d2) alkali-soluble resin having an epoxy group and a phenolic hydroxyl group

The alkali-soluble resin of (d2) is, for example, reacted with an epoxy group of a compound having at least two epoxy groups per molecule (hereinafter sometimes referred to as "epoxy compound") and a carboxyl group of hydroxybenzoic acids. Can be obtained. However, the reaction rate is adjusted so that the epoxy group remains.

In the positive photosensitive resin composition of the present invention, since the alkali-soluble resin has an epoxy group, there is an advantage that it reacts with a phenolic hydroxyl group and crosslinks when heated to improve chemical resistance, heat resistance, etc., and by having a phenolic hydroxyl group There is an advantage of being soluble in an aqueous alkali solution.

An example of the reaction of one of the epoxy groups of the epoxy compound with the carboxyl group of hydroxybenzoic acids to form a compound having a phenolic hydroxyl group is shown in Scheme 1 below.

As a compound having at least two epoxy groups in one molecule, for example, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol type epoxy resin, a biphenol type epoxy resin, a naphthalene skeleton-containing epoxy resin, an alicyclic epoxy resin And heterocyclic epoxy resins. These epoxy compounds need only have two or more epoxy groups in one molecule, and may be used only with one type, but may be used in combination of two or more. In addition, since these compounds are of a thermosetting type, it cannot be uniquely described from the difference in the presence or absence of an epoxy group, the kind of functional group, the degree of polymerization, etc. as a common knowledge for those skilled in the art. An example of the structure of a novolac-type epoxy resin is shown in Formula (1). In addition, R in formula (1) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 50.

As a phenol novolak type epoxy resin, EPICLON (registered trademark) N-770 (made by DIC Corporation), jER (registered trademark)-152 (made by Mitsubishi Chemical Corporation), etc. are mentioned, for example.

As a cresol novolak type epoxy resin, EPICLON (registered trademark) N-695 (made by DIC Corporation), EOCN (registered trademark)-102S (made by Nippon Kayaku Corporation), etc. are mentioned, for example.

Examples of bisphenol-type epoxy resins include jER (registered trademark) 828, jER (registered trademark) 1001 (made by Mitsubishi Chemical Co., Ltd.), YD-128 (brand name, manufactured by Shinnittetsu Sumikin Kagaku Co., Ltd.), etc. Bisphenol A type epoxy resins, bisphenol F type epoxy resins such as jER (registered trademark) 806 (manufactured by Mitsubishi Chemical Co., Ltd.), and YDF-170 (brand name, manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), and the like. .

Examples of the non-phenolic epoxy resin include jER (registered trademark) YX-4000, jER (registered trademark) YL-6121H (made by Mitsubishi Chemical Co., Ltd.) and the like.

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (brand name, manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (brand name, manufactured by DIC Corporation), and the like.

As an alicyclic epoxy resin, EHPE (registered trademark)-3150 (made by Daicel Chemical Industries, Ltd.), etc. are mentioned, for example.

As the heterocyclic epoxy resin, for example, TEPIC (registered trademark), TEPIC (registered trademark)-L, TEPIC (registered trademark)-H, TEPIC (registered trademark)-S (made by Nissan Chemical Industries, Ltd.), etc. Can be lifted.

"Hydroxybenzoic acid" refers to a compound in which at least one of the 2 to 6 positions of benzoic acid is substituted with a hydroxyl group, for example, salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 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-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid, and the like, but dihydroxybenzoic acids are preferred from the viewpoint of enhancing alkali developability. These hydroxybenzoic acids may be used alone, but may be used in combination of two or more.

The method of obtaining a compound having an alkali-soluble phenolic hydroxyl group from the epoxy compound and hydroxybenzoic acids is 0.2 to 0.9 equivalents, more preferably 0.4 to 0.8 equivalents of hydroxybenzoic acids per equivalent of the epoxy group of the epoxy compound, More preferably, 0.5 to 0.7 equivalents are used. When the amount of hydroxybenzoic acid is 0.2 equivalent or more, sufficient alkali solubility is expressed, and when it is 0.9 equivalent or less, an increase in molecular weight due to side reactions can be suppressed.

A catalyst may be used to accelerate the reaction. The amount of the catalyst used is 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture in which the epoxy compound is composed of hydroxybenzoic acids. The reaction temperature is 60 to 150°C, and the reaction time is 3 to 30 hours. As a catalyst used in this reaction, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, zirconium octanoate, etc. Can be lifted.

The number average molecular weight of the alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group is preferably in the range of 500 to 8000, more preferably in the range of 1500 to 5000, and even more preferably in the range of 2000 to 3500. . When the molecular weight is 500 or more, the solubility in an aqueous alkali solution is appropriate, so that it is good as a resin for the photosensitive material, and when the molecular weight is 8000 or less, the coatability and developability are good.

(d3) polyalkenylphenol resin

The polyalkenylphenol resin is obtained by alkenyl etherification of a hydroxyl group of a known phenolic resin, and Klaigen dislocation of the alkenyl ether group. It is preferable that the polyalkenylphenol resin has the structure of formula (2). By containing such a resin, while improving the developing characteristics of the resulting photosensitive resin composition, it can also contribute to reduction of outgassing.

In formula (2), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, formula (3)

(In formula (3), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a 6 to carbon atom Represents an aryl group of 12. * in formula (3) represents a bonding portion with a carbon atom constituting an aromatic ring.)

An alkenyl group represented by, an alkoxy group having ¹ to 2 carbon atoms, or a hydroxyl group is represented, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by formula (3). Q is an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a combination thereof. And R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. do. When two or more structures of formula (2) exist in one molecule, the structures of each formula (2) may be the same or different.

R ¹ , R ² and R ³ in formula (2) represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by formula (3), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and R At least one of ¹ , R ² and R ³ is an alkenyl group represented by formula (3).

In R ¹ , R ² and R ³ of formula (2), examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t -Butyl group, n-pentyl group, etc. are mentioned. Specific examples of the alkoxy group having 1 to 2 carbon atoms include a methoxy group and an ethoxy group.

In the alkenyl group represented by formula (3), R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms Or an aryl group having 6 to 12 carbon atoms, but specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and the like, and examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cycloheptyl group, and the aryl group having 6 to 12 carbon atoms As a specific example, a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, a naphthyl group, etc. are mentioned. R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As a preferable alkenyl group represented by formula (3), an allyl group and a methacryl group are mentioned from a reactive point, More preferably, it is an allyl group. And, it is most preferable that any one of R ¹ , R ² and R ³ is an allyl group or a methacryl group, and the other two are hydrogen atoms.

Q in formula (2) is an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or These are a combination of divalent groups, and R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to carbon atoms. It represents 12 aryl groups. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group and n-pentyl group. Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group. Examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cycloheptyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, and a naphthyl group. R ⁴ and R ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably all of them are hydrogen atoms.

Here, specific examples of the cycloalkylene group having 5 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, and a cycloheptylene group. As specific examples of the divalent organic group having an aromatic ring, a phenylene group, tolylene group, naphthylene group, biphenylene group, fluorenylene group, anthracenylene group, xylylene group, 4,4'-methylenediphenyl group, formula ( The group represented by 4), etc. are mentioned.

As a specific example of the divalent organic group which has an alicyclic condensed ring, a dicyclopentadienylene group etc. are mentioned.

In the case of using a polyalkenylphenol resin in the binder resin (D) used in the photosensitive resin composition of the present invention, in terms of alkali developability and outgassing, as a particularly preferred polyalkenylphenol resin, Q in formula (2) is What is -CH ₂ -, that is, what has a structure represented by Formula (5) is mentioned.

In formula (5), R ¹ , R ² and R ³ are the same as in formula (2).

Preferred R ^1, R ² and R ³ is the same as the preferred R ^1, R ² and R ³ in the formula (2).

The structural unit represented by formula (2) or formula (5) is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and still more preferably 85 to 100 mol% in the polyalkenylphenol resin. It is mole percent. When the structural unit represented by the formula (2) or the formula (5) is 50 mol% or more in the polyalkenylphenol resin, heat resistance is improved, and therefore it is preferable. Since the phenolic hydroxyl group in the polyalkenylphenol resin is ionized in the presence of a basic compound and can be dissolved in water, it is necessary to have a phenolic hydroxyl group in a certain amount or more from the viewpoint of alkali developability. Therefore, it is particularly preferable that the polyalkenylphenol resin containing the structure of formula (5) is a polyalkenylphenol resin having a structural unit represented by formula (5) and a structural unit represented by formula (6). .

In formula (6), R ^1a , R ^2a and R ^3a each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In a polyalkenylphenol resin having a structural unit represented by formula (5) and a structural unit represented by formula (6), the number of structural units represented by formula (5) is denoted by x, and by formula (6) If the number of structural units represented is y, 0.5≦x/(x+y)<1, 0<y/(x+y)≦0.5, and (x+y) is preferably 2 to 3000, More preferably, it is 2 to 2000, and still more preferably, it is 2 to 1000.

When a polyalkenylphenol resin is used as the binder resin (D), the preferred number average molecular weight is 500 to 5000, more preferably 800 to 3000, and still more preferably 1000 to 1500. When the number average molecular weight is 500 or more, the alkali development rate is appropriate, the resolution is good because the difference in dissolution rate of the exposed portion and the unexposed portion is sufficient, and when it is 5000 or less, the alkali developability is good.

As the binder resin, one type of resin may be used alone, or two or more types of resin may be used in combination. Especially, it is preferable to contain at least 1 type selected from resin components (d1)-(d3), and it is more preferable to contain at least (d1) and (d2). The total amount of components selected from (d1) to (d3) per 100 parts by mass of the binder resin (D) is preferably 1 to 100 parts by mass, more preferably 10 to 100 parts by mass, further It is preferably 30 to 100 parts by mass. The heat resistance of the resin composition is good when the total amount of components selected from (d1) to (d3) is 1 to 100 parts by mass relative to 100 parts by mass of the binder resin (D).

The binder resin (D) can be any combination, such as using resin components (d1) and (d2) together, and it is also possible to use a plurality of components (d1) to (d3).

For example, three types of alkali-soluble copolymer (d1) having an alkali-soluble group, alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group, and polyalkenylphenol resin (d3) may be used in combination. When three types are used together, the ratio of the alkali-soluble copolymer (d1) having an alkali-soluble group in the binder resin (D) is 5 to 60% by mass, and the ratio of the alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group is 35 It is preferable that the ratio of -90 mass% and the polyalkenylphenol resin (d3) is 5-60 mass %.

In addition, when the alkali-soluble copolymer (d1) having an alkali-soluble group also corresponds to the alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group, it is treated as an alkali-soluble copolymer (d1) having an alkali-soluble group. When the alkali-soluble copolymer (d1) having an alkali-soluble group also corresponds to the polyalkenylphenol resin (d3), it is treated as an alkali-soluble copolymer (d1) having an alkali-soluble group. That is, the alkali-soluble resin (d2) and polyalkenylphenol resin (d3) having an epoxy group and a phenolic hydroxyl group are excluded from those corresponding to the alkali-soluble copolymer (d1) having an alkali-soluble group.

(E) Quinone diazide compound

The positive photosensitive resin composition of the present invention contains a quinone diazide compound as a radiation-sensitive compound. As quinonediazide compounds, those in which the sulfonic acid of quinonediazide is bonded to the polyhydroxy compound as an ester, the sulfonic acid of quinonediazide is bonded to the sulfonamide of the polyamino compound, and the sulfonic acid of quinonediazide is bonded to the polyhydroxypolyamine compound , A sulfonamide bond, or an ester bond and a sulfonamide bond. From the viewpoint of the contrast between the exposed portion and the unexposed portion, it is preferable that 20 to 100 mol% of the total functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of a mercury lamp, which are general ultraviolet rays.

As a polyhydroxy compound, 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 (above, brand name, 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 (above, brand name, product of Asahi Yukizai High School Co., Ltd.) , 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic Acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and the like, but are not limited to these.

Specific examples of the quinone diazide compound include 1,2-naphthoquinone diazide-4-sulfonic acid ester or 1,2-naphthoquinone diazide-5-sulfonic acid ester of the polyhydroxy compound.

When the quinone diazide compound is exposed to ultraviolet light or the like, a carboxyl group is generated through the reaction shown in Scheme 2 below. As the carboxyl group is generated, the exposed portion (film) can be dissolved in an alkaline solution, thereby expressing alkali developability.

The content of the quinone diazide compound in the photosensitive resin composition in the present invention varies depending on the quinone diazide compound to be used, but is preferably 3 to 20 parts by mass based on 100 parts by mass of the binder resin (D), more preferably 5 to 15 parts by mass, more preferably 7 to 10 parts by mass. Alkali developability is good when it is 3 mass parts or more based on 100 mass parts of binder resin (D). If it is 20 parts by mass or less, the reduction rate of heating at 300°C or higher is difficult to increase.

(F) Optional ingredient

In the positive photosensitive resin composition of the present invention, as optional components, a thermosetting agent, a surfactant, a coloring agent other than (A), a solvent other than (C), and the like can be added. In addition, the optional component (F) is defined as not suitable for any of (A) to (E).

(F1) Heat curing agent

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

The content of the thermosetting agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less based on 100 parts by mass of the binder resin (D).

(F2) Surfactant

The positive photosensitive resin composition of the present invention may further contain a surfactant as an optional component, for example, to improve coating properties or to improve developability of a coating film.

Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene diraulate and polyoxyethylene distearate; Megapack (registered trademark) F-251, F-281, F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558 (above, brand name, manufactured by DIC Corporation), Sufflon (registered trademark) S-242, S-243, S-385, S-386, S-420 And fluorine-based surfactants such as S-611 (above, brand name, manufactured by ACG Semichemical Co., Ltd.); Organosiloxane polymers KP323, KP326, KP341 (above, brand name, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. These may be used alone or in combination of two or more.

These surfactants are blended in an amount of 2 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.5 parts by mass or less based on 100 parts by mass of the binder resin (D).

(F3) Other colorants

The positive photosensitive resin composition of the present invention may further contain a coloring agent other than titanium black (A) as an optional component. Such colorants include dyes, organic pigments, and inorganic pigments, but can be used according to the purpose. However, the content of the coloring agent other than titanium black (A) is in a range that does not impair the effect of the present invention.

Specific examples of dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, melocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes , A fluorane dye, a spiropyran dye, a phthalocyanine dye, an indigo dye, a pulzide dye, a nickel complex dye, and an azulene dye.

As pigments, black pigments such as carbon black, carbon nanotubes, acetylene black, graphite, iron black, and aniline black, or C.I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. Pigment Green 7, C.I. Pigment Brown 23, 25, 26, etc. are mentioned.

(F4) other solvents

The positive photosensitive resin composition of the present invention is dissolved in a solvent and used in a solution state. The positive photosensitive resin composition of the present invention can be adjusted to a viscosity suitable for various application methods depending on the amount of the solvent. Depending on the purpose of use, a suitable solid content concentration may be adopted, but for example, the solid content concentration may be 1 to 60% by mass, preferably 3 to 50%, more preferably 5 to 40%. In addition to the solvent (C) having a solubility parameter (SP value) of 10.5 or more, it is also possible to add other solvents at 5% by mass or less of the total solvent.

Examples of other solvents include glycol ethers such as ethylene glycol dimethyl ether and ethylene glycol methyl ethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, diethylene glycol monomethyl ether, and diethylene glycol. Diethylene glycols such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, propylene glycol alkyl ether acetates such as propylene glycol ethyl ether acetate, toluene, xylene, etc. Aromatic hydrocarbons, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, ketones such as 4-hydroxy-4-methyl-2-pentanone, 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, 3- Esters, such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, and methyl lactate, are mentioned. These solvents may be used alone or in combination of two or more.

[Method of preparing titanium black dispersion]

The titanium black dispersion of the present invention is prepared by mixing (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH/g or less, an acid value of 20 to 200 mgKOH/g, and (C) a solvent having a solubility parameter of 10.5 or more as essential components. can do.

Dispersers for crushing and dispersing titanium black are not particularly limited, and ball types such as ball mills, sand mills, bead mills, paint shakers, rocking mills, kneaders, paddle mixers, planetary mixers, Henschel mixers, etc. , A roll type such as a three-roll mixer, and other examples include a Leica machine, a colloid mill, an ultrasonic wave, a homogenizer, and a rotation/revolution mixer. Among these, a ball type that can be stably finely dispersed in a short time is preferable. As a material of the ball used for this ball shape, glass, silicon nitride, alumina, zircon, zirconia, steel, etc. are mentioned. As the bead diameter, a general shape having a diameter of 0.03 to 25 mm can be used, but a small diameter of 5 mm or less is preferable from the viewpoint of miniaturization.

The order of addition when preparing the dispersion is not particularly limited, but the following procedure is preferable to obtain a good dispersion.

First, the solvent (C) and the dispersant (B) are uniformly dispersed. In the case where the solvent and the dispersant are not uniformly dispersed in advance, a region in which the concentration of the dispersant is partly high is likely to cause problems such as aggregation of particles. Subsequently, a required amount of titanium black (A) is added to the solution prepared first, and a bead is added at the end. When agglomeration is observed in the titanium black, preliminary dispersion may be performed. A binder resin or other resin component may be used for the purpose of compatibility with resin and suppression of re-aggregation of titanium black.

[Method for producing positive photosensitive resin composition]

In the positive photosensitive resin composition of the present invention, first, titanium black (A), a dispersant (B), and a solvent (C) are mixed to prepare a titanium black dispersion, and then a binder resin (D) and a quinone diazide compound (E ), and the optional component (F) are preferably further mixed and prepared. The method of preparing the titanium black dispersion is as described above.

There is no particular limitation on the order of mixing the titanium black dispersion with the binder resin, the quinone diazide compound, and any components, but for example, the binder resin is dissolved in a solvent other than the solvent (C) or (C), and this solution A positive photosensitive resin composition in a solution state can be prepared by mixing additives such as an quinonediazide compound, a titanium black dispersion, and optionally a thermosetting agent and a surfactant in a predetermined ratio.

The stirrer for mixing the titanium black dispersion with the binder resin, quinone diazide compound, and optional components is not particularly limited, and ball-types such as ball mill, sand mill, bead mill, paint shaker, rocking mill, kneader, paddle mixer, etc. , A blade type such as a planetary mixer and a Henschel mixer, a roll type such as a three-roll mixer, a Leica machine, a collolead mill, an ultrasonic wave, a homogenizer, a rotating/revolving mixer, and a mechanical stirrer. When used at the laboratory level, it is preferable because the mechanical stirrer is stable and can be mixed in a short time. The stirring blade used for stirring can be appropriately selected from a fan, a propeller, a cross, a turbine, and a dragonfly type. A resin composition can be obtained by mixing a titanium black dispersion liquid or a binder resin solution, etc., and stirring at room temperature for 1 to 10 minutes at a rotation speed of 10 to 1000 rpm.

The composition liquid prepared as described above is preferably filtered before use. As a means of filtration, for example, a millipore filter having a pore diameter of 0.05 to 1.0 µm or the like can be mentioned.

The positive photosensitive resin composition of the present invention prepared as described above is also excellent in long-term storage stability.

[Pattern formation and curing method]

When the positive photosensitive resin composition of the present invention is used for radiation lithography, first, the positive photosensitive resin composition of the present invention is applied to the surface of a substrate, and the solvent is removed by means such as heating to form a coating film. The method of applying the positive photosensitive resin composition to the surface of the substrate is not particularly limited, and various methods, such as a spray method, a roll coating method, a slit method, and a rotation coating method, can be employed.

After applying the positive photosensitive resin composition of the present invention to the surface of a substrate, usually, the solvent is dried by heating (prebaking) to obtain a coating film. The heating conditions vary depending on the type of each component, the mixing ratio, etc., but it is usually heat treated at 70 to 130°C for a predetermined time, for example, 1 to 20 minutes on a hot plate, and 3 to 60 minutes in an oven to obtain a coating film. I can.

Subsequently, the prebaked coating film is irradiated with radiation (e.g., visible light, ultraviolet rays, far ultraviolet rays, etc.) through a mask of a predetermined pattern (exposure process) and developed with a developer, and unnecessary portions are removed to form a predetermined pattern. A coating film is formed (development process). When naphthoquinone diazide sulfonic acid ester is used as the positive photosensitive compound, preferred radiation is ultraviolet to visible light having a wavelength of 250 to 450 nm.

Examples of the developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alcohol amines such as dimethyl ethanol amine and triethanol amine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; Aqueous solutions of alkalis such as cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. You can use Although there is no restriction|limiting in particular in concentration, 0.5-5.0 mass% is preferable. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol to the alkaline aqueous solution, and a surfactant may be used as a developer. The developing time is usually 30 to 180 seconds, and the developing method may be any method such as a puddle method, a shower method, or a dipping method. After development, running water washing is performed for 30 to 90 seconds to remove unnecessary portions, and the pattern is formed by air drying with compressed air or compressed nitrogen. Thereafter, the pattern is heat-treated at a predetermined temperature, for example, 120 to 350°C for 20 to 200 minutes by a heating device such as a hot plate or an oven, to obtain a coating film, but the temperature may be increased step by step (heating Treatment process).

The present invention includes (I) a coating step of applying the positive photosensitive resin composition to a substrate, (II) a drying step of removing the solvent in the applied positive photosensitive resin composition, and (III) exposure of irradiating radiation through a photomask. A method for producing a radiation lithographic structure including a step, (IV) a developing step of forming a pattern by alkali development, and (V) a heat treatment step of heating at a temperature of 100 to 350°C can be employed. This method can be used for formation of partition walls and insulating films of organic EL elements.

In the present invention, a partition wall of an organic EL device made of a cured product of the positive photosensitive resin composition can be obtained.

The present invention can obtain an insulating film for an organic EL device made of a cured product of the positive photosensitive resin composition.

The present invention can obtain an organic EL device comprising a cured product of the positive photosensitive resin composition.

(Example)

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

(1) Synthesis of binder resin

[Production Example 1] Preparation of alkali-soluble copolymer (d1) having an alkali-soluble group

4-hydroxyphenyl methacrylate (Showa Denko Co., Ltd. "PQMA") 76.8 g, N-phenyl maleimide (Nippon Shokubai Co., Ltd. product) 14.4 g, N-cyclohexyl maleimide (Co., Ltd. product) Nippon Shokubai) 14.4g, V-601 as a polymerization initiator (made by Wako Pure Chemical Industries, Ltd.) 1.80g, S-dodecyl-S'-(α,α'-dimethyl-α"-acetic acid as a RAFT agent) ) 1.95 g of trithiocarbonate ("723010" manufactured by Sigma-Aldrich) was completely dissolved in 180 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation) The resulting solution was dissolved in 500 mL of 3-spherical shape. In a flask, 180 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) heated to 85° C. in a nitrogen gas atmosphere was added dropwise over 1 hour, and then reacted at 85° C. for 3 hours. One reaction solution was added dropwise to 1200 g of toluene to precipitate a polymer The precipitated polymer was collected by filtration and vacuum-dried at 80 DEG C for 7 hours to recover 104.4 g of white powder, which was dissolved in γ-butyrolactone. Thus, a resin liquid having a solid content of 20% by mass was obtained (resin liquid 1) The number average molecular weight of the obtained reaction product was 14100, and the weight average molecular weight was 24900.

[Production Example 2] Preparation of alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group

In a 300 mL three-necked flask, γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) 60g as a solvent, EPICLON (registered trademark) N-695 (Cresolno manufactured by DIC Corporation) as a compound having at least two epoxy groups per molecule. 42 g of rock-type epoxy resin, epoxy equivalent 210) were added, and dissolved at 60°C under a nitrogen atmosphere. In addition, 15.5 g (0.10 mol, 0.5 equivalent to 1 equivalent of epoxy) of 3,5-dihydroxybenzoic acid (made by Wako Pure Chemical Industries, Ltd.) as hydroxybenzoic acids, and triphenylphosphine (Hoku Add 0.2 g (0.76 mmol) of Ko Chemical Industries, Ltd. product), and it was made to react at 110 degreeC for 12 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to 20% by mass of solid content, and 260 g of the solution was filtered and recovered (resin solution 2). The number average molecular weight of the obtained reactant was 2400, and the weight average molecular weight was 5600.

[Production Example 3] Preparation of polyallylphenol resin (d3)

A solution in which 201 g (1.45 mol) of potassium carbonate (manufactured by Nippon Soda Corporation) is dissolved in 100 g of pure water in a 1000 mL three-necked flask, a phenol novolac resin "Shonol (registered trademark) BRN-5834Y" (Aika SDK Phenolic Co., Ltd.) Product) 100.0 g and 16 g of isopropyl alcohol (made by Wako Pure Chemical Industries, Ltd.) were added, and the reactor was replaced with nitrogen gas and heated to 85°C. Under nitrogen gas stream, allyl acetate (made by Showa Denko Corporation) 84 g (0.84 mol), 50% water content 5%-Pd/C-STD type (metal palladium is dispersed in the activated carbon in a content of 5% by mass, and further The catalyst for the allylation reaction stabilized by mixing water to make 50% by mass of the activated carbon in which the metallic palladium is dispersed, manufactured by EN Chemket Co., Ltd.0.40 g (palladium: 0.188 mmol) and triphenylphosphine (the palladium 2.45g (9.4mmol) of the activator of the contained allylation reaction catalyst, manufactured by Hokuko Chemical Industries, Ltd.) was added, the temperature was raised to 105°C and reacted for 4 hours in a nitrogen atmosphere, and then 14 g (0.14 mol) of allyl acetate ) Was added, and heating was continued for 10 hours while confirming the generation of allyl ether groups by ¹ H-NMR. After that, stirring was stopped and left to stand to separate into two layers, an organic layer and an aqueous layer. Pure water (200 g) was added until the precipitated salt was dissolved, then 200 g of toluene was added and maintained at a temperature of 80°C or higher to confirm that no white precipitate was precipitated, and then Pd/C was filtered (1 μm A membrane filter (pressurized (0.3 MPa) using Advantech KST-142-JA) was collected, and the filter residue was washed with 100 g of toluene and the aqueous layer was separated. After washing twice, it was confirmed that the aqueous layer was neutral The organic layer was separated and concentrated under reduced pressure to obtain a brown oily phenol novolak type polyallyl ether resin.

Subsequently, 125 g of a phenol novolak-type polyallyl ether resin was placed in a 500 mL flask set with a mechanical stirrer, and diluted with 130 g of γ-butyrolactone (made by Wako Pure Chemical Industries, Ltd.). While stirring at 300 rpm, the temperature was raised to 170° C., and a Klaigen potential reaction was carried out for 30 hours while confirming the decrease of allyl ether groups by ¹ H-NMR. After the reaction, the solution was returned to room temperature and diluted with γ-butyrolactone to a solid content of 20% by mass to obtain a phenol novolak type polyallylphenol resin solution (resin solution 3). The hydroxyl group equivalent of the solid content of this polyallylphenol resin was 132, the number average molecular weight was 1100, and the weight average molecular weight was 9900.

This resin is a polyalkenylphenol resin having a structural unit represented by formula (5) and a structural unit represented by formula (6), and in formula (5), one of R ¹ , R ² , and R ³ is allyl The other is a hydrogen atom, and in formula (6), R ^1a , R ^2a , and R ^3a are hydrogen atoms, x/(x+y is 0.85, y/(x+y) is 0.15.

In addition, the weight average molecular weight and the number average molecular weight were calculated using a calibration curve prepared using a standard material of polystyrene under the following measurement conditions.

Device name: Shodex (registered trademark) GPC-101

Column: Shodex (registered trademark) LF-804

Mobile phase: tetrahydrofuran

Flow rate: 1.0 mL/min

Detector: Shodex (registered trademark) RI-71

Temperature: 40℃

(2) Raw materials

(D) As a binder resin, resin solutions 1 to 3 synthesized according to Preparation Examples 1 to 3, and novolacphenol resin BRM-595M (manufactured by Aica SDK Phenol Co., Ltd.) were removed by a reprecipitation method to remove low molecular weight components, Resin solution 4 prepared with γ-butyrolactone to a solid content of 20% by mass was used.

(D) Table 1 shows materials other than the binder resin.

(3) Preparation of titanium black dispersion

[Example 1]

39 g of γ-butyrolactone and the dispersant DISPERBYK-111 were added to 1 g and 150 cc of a total throttle screw storage container (made of stainless steel) and mixed. Then, 10 g of titanium black UF-8 with a primary particle diameter of 20 nm was added and mixed, and then 200 g of zirconia beads for disintegration and dispersion treatment with a diameter of Φ 0.3 mm (brand name YTZ ball, manufactured by Nikkato Corporation) were added. It was sealed so as not to leak, and this was set in a paint shaker (manufactured by Asada Tekko Co., Ltd.) and dispersed for 10 hours. The obtained dispersion was filtered through a Millipore filter having a pore diameter of 0.45 µm and 0.22 µm to obtain a titanium black dispersion. The obtained titanium black dispersion is hereinafter referred to as dispersion liquid 1.

[Examples 2 to 5, Comparative Examples 1 to 5]

According to the formulation shown in Table 2 and the diameter of the zirconia beads, a titanium black dispersion was obtained in the same procedure as in Example 1. The titanium black dispersions obtained in Examples 2 to 5 are hereinafter referred to as dispersions 2 to 5, and the titanium black dispersions obtained in Comparative Examples 1 to 5 are hereinafter referred to as dispersions C1 to C5.

(4) Preparation of positive photosensitive resin composition

[Example 6]

50 parts by mass of the resin solution 1 obtained in Preparation Examples 1 to 2, 125 parts by mass of the resin solution 2, 15 parts by mass of TS-130A as a quinone diazide compound, and 100 parts by mass of the titanium black dispersion 1 obtained in Example 1 , 7.5 parts by mass of a 1% by mass solution (diluted with γ-butyrolactone) of Suflon S-386 as a surfactant was added, and mixing was further performed. After visually confirming that it became uniform, it filtered with a Millipore filter with a pore diameter of 0.22 micrometers, and the positive photosensitive resin composition with a solid content concentration of 24% was prepared.

[Examples 7 to 12 and Comparative Examples 6 to 8]

In the same manner as in Table 3, a positive photosensitive resin composition was prepared in the same procedure as in Example 6.

(5) Evaluation

For the titanium black dispersions prepared in Examples 1 to 5 and Comparative Examples 1 to 5, the average particle diameter of titanium black was evaluated. However, the titanium black dispersions of Comparative Examples 1 and 5 were not measured because aggregation was confirmed visually. The results are shown in Table 2.

[Average particle diameter of titanium black]

Weigh 20 g of γ-butyrolactone, add 1 drop of dispersion thereto, mix for 1 minute by ultrasonication, and then use a laser diffraction/scattering particle diameter distribution measuring device Nanotrac wave (Ex) (Nikiso Corporation) cell And the average particle size D50 of the dispersed titanium black was measured.

For the positive photosensitive resin compositions prepared in Examples 6 to 12 and Comparative Examples 6 to 8, alkali developability, pattern formation, pattern linearity, light-shielding property (OD value), appearance after prebaking, surface roughness Ra, and Heat resistance (weight reduction rate) was evaluated. Table 3 shows the results. The evaluation method is as follows.

[Alkaline developability, pattern formation, pattern linearity]

The positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were spin-coated to a dry film thickness of about 1.5 µm on a glass substrate (100 mm × 100 mm × 1 mm in size), and 80 at 120°C. The second solvent was dried. In addition, a quartz photomask (5µm, 10µm, 20µm, 50µm, 100µm, 200µm) with an exposure device equipped with an ultra-high pressure mercury lamp (brand name Multilite ML-251A/B, manufactured by Ushio Denki Co., Ltd.) , 500 µm of lines & spaces were patterned) through 100 mJ/cm 2 exposure. The exposure amount was measured using an ultraviolet ray integrating meter (brand name UIT-150 light receiving part UVD-S365, Ushio Denki Co., Ltd. product). The exposed coating film was subjected to alkali development for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), and alkali developability was evaluated. In observation using an optical microscope (VH-Z250, manufactured by Giens Co., Ltd.), the case where there was no residue after alkali development was judged as good, and the case where there was residue was judged as bad.

The evaluation of pattern formation was performed by measuring the line width of the pattern after alkali development. Using an optical microscope (VH-Z250, manufactured by Giens Co., Ltd.), a location where the line width of the line & space pattern of the photomask was 10 µm, respectively, was confirmed with a microscope having a magnification of 1000 times. It is satisfactory if the line width of the pattern line & space pattern after alkali development is 1:1, the line width of the line portion can be within ±10%, and other than that, the pattern formation property was evaluated as defective.

In the evaluation of the linearity of the pattern, it was good that the pattern was in a linear shape, it was possible that it was wavy, and other than that was considered as bad.

[OD value]

Spin coat the positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 to about 1.5 μm on a glass substrate (size 100 mm×100 mm×1 mm), and heated at 120° C. for 80 seconds on a hot plate. And dried the solvent. After that, the coating film was obtained by curing at 250° C. for 60 minutes in a nitrogen gas atmosphere. The cured glass coating film was measured with a transmission densitometer (BMT-1, manufactured by Sakata Ink Engineering Co., Ltd.), corrected by the OD value of only glass, and converted into an OD value per 1 µm of the thickness of the coating film. In addition, the thickness of the coating film was measured using a surface roughness meter (Surcom 130A, manufactured by Tokyo Seimits Co., Ltd.).

[Appearance after pre-baking]

Spin coat the positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 to about 1.5 μm on a glass substrate (size 100 mm×100 mm×1 mm), and heated at 120° C. for 80 seconds on a hot plate. And dried the solvent. In the evaluation of the appearance after prebaking, the surface of the coated film after drying was visually observed, and the uniform gloss surface was good, the gloss could be varied, and the hole through which light was present was determined as a defect.

[Surface roughness Ra]

The positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were spin-coated to a dry film thickness of about 1.5 μm on a glass substrate (size 100 mm×100 mm×1 mm), and at 120°C for 80 seconds. The solvent was dried. In addition, 100 mJ/cm 2 was exposed through a quartz photomask with an exposure apparatus equipped with an ultra-high pressure mercury lamp (brand name Multilite ML-251A/B, manufactured by Ushio Denki Co., Ltd.). The exposure amount was measured using an ultraviolet ray integrating meter (brand name UIT-150 light receiving part UVD-S365, Ushio Denki Co., Ltd. product). The exposed coating film was subjected to alkali development for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution using a spin developing apparatus (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). After that, curing was performed at 250° C. for 60 minutes in a nitrogen gas atmosphere to obtain a patterned coating film. The surface roughness of the 10 µm-wide pattern of the cured coating film was measured using a surface roughness meter (Surcom 130A, manufactured by Tokyo Seimits Co., Ltd.).

[Weight reduction rate]

The positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were put in an aluminum cup, dried at 60°C for 30 minutes in a nitrogen gas atmosphere, and then cured by heating at 250°C for 60 minutes in a nitrogen gas atmosphere. When the cured product is heated from room temperature to 300°C under the conditions of a temperature increase rate of 10°C/min in a nitrogen gas stream using TG/DTA7200 (manufactured by Hitachi High-Tech Science), and maintained at 300°C for 90 minutes The weight reduction rate (%) was measured.

From Examples 1 to 5 in Table 2, titanium black dispersions using a dispersant having an amine value of 5 mgKOH/g or less, an acid value of 20 to 200 mgKOH/g, and a solvent having a solubility parameter (SP value) of 10.5 or more are average particle diameter after dispersion treatment. D50 was 100 nm or less, and dispersibility was good.

In Examples 6 to 12, which are positive photosensitive resin compositions using the titanium black dispersion of Examples 1 to 5, the appearance after prebaking, alkali developability, pattern formation, pattern linearity, surface roughness Ra, and weight reduction ratio It was found that the balance was good and excellent.

On the other hand, the titanium black dispersion of Comparative Examples 1 to 4 using a dispersant having an amine value of 5 mgKOH/g or more, or a solvent having a solubility parameter (SP value) of less than 10.5, and Comparative Examples 5 and 6 to 8 without using a dispersant It was found that the positive photosensitive resin composition was difficult to apply to a blackened partition wall material requiring developability and high resolution.

(Industrial availability)

The black positive photosensitive resin composition of the present invention can be suitably used for positive radiation lithography. An organic EL element provided with a partition wall and an insulating film formed of the black positive photosensitive resin composition of the present invention is suitably used as an electronic component of a display device exhibiting good contrast.

Claims (12)

(A) titanium black,
(B) a dispersant having an amine value of 5 mgKOH/g or less and an acid value of 20 to 200 mgKOH/g,
(C) a solvent having a solubility parameter of 10.5 or more,
(D) binder resin, and
(E) Quinone diazide compound
Positive photosensitive resin composition comprising a. The method of claim 1,
The composition in which the solvent (C) is γ-butyrolactone or n-methyl-2-pyrrolidone. The method according to claim 1 or 2,
A composition in which the dispersant (B) is 1 to 40 parts by mass and the solvent (C) is 250 to 600 parts by mass based on 100 parts by mass of titanium black (A). The method according to claim 1 or 2,
A composition comprising 3 to 30 parts by mass of titanium black (A) and 3 to 20 parts by mass of a quinone diazide compound (E) based on 100 parts by mass of the binder resin (D). The method according to claim 1 or 2,
Binder resin (D),
(d1) an alkali-soluble copolymer having an alkali-soluble group,
(d2) an alkali-soluble resin having an epoxy group and a phenolic hydroxyl group, and
(d3) polyalkenylphenol resin
A composition comprising at least one selected from the group consisting of. (A) titanium black,
(B) a dispersant having an amine value of 5 mgKOH/g or less and an acid value of 20 to 200 mgKOH/g, and
(C) a solvent with a solubility parameter of 10.5 or more
Titanium black dispersion comprising a. (1) (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH/g or less, an acid value of 20 to 200 mgKOH/g, and (C) a solvent having a solubility parameter of 10.5 or more to prepare a titanium black dispersion, And
(2) The process of mixing the titanium black dispersion, (D) binder resin and (E) quinone diazide compound
A method for producing a positive photosensitive resin composition comprising in this order. A cured product of the composition according to claim 1 or 2. (I) a coating step of applying the positive photosensitive resin composition according to claim 1 or 2 to a substrate,
(II) drying step of removing the solvent in the applied positive photosensitive resin composition,
(III) exposure process in which radiation is irradiated over a photomask,
(IV) a developing step of forming a pattern by alkali development, and
(V) Heat treatment step of heating at a temperature of 100 to 350°C
Method of manufacturing a radiation lithographic structure comprising a. A partition wall of an organic EL device comprising a cured product of the positive photosensitive resin composition according to claim 1 or 2. An insulating film for an organic EL device comprising a cured product of the positive photosensitive resin composition according to claim 1 or 2. An organic EL device comprising a cured product of the positive photosensitive resin composition according to claim 1 or 2.