KR20190034262A - The positive photosensitive resin composition and the titanium black dispersion - Google Patents

Abstract

For example, there is provided a positive photosensitive resin composition which can be used for forming a black partition wall material of an organic EL display element and which has high sensitivity and satisfies the properties of developing property, resolution and heat resistance. (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) a binder resin, and E) quinone diazide compounds.

Description

The positive photosensitive resin composition and the titanium black dispersion

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

In a display device such as an organic EL display, a barrier rib material is used for the interval portion of the coloring pattern in the display region or the edge of the peripheral portion of the display region in order to improve display characteristics. In the production of the organic EL display device, in order to prevent the pixels of the organic material from coming into contact with each other, barrier ribs are first formed, and pixels of organic material are formed between the barrier ribs. This partition is generally formed by photolithography using a photosensitive resin composition and has insulating properties. Specifically, a photosensitive resin composition is coated on a substrate using a coating apparatus, the volatile components are removed by means of heating and then exposed through a mask. Subsequently, in the case of a negative type, the unexposed portion is replaced with a positive type , The exposed portion is removed by developing with a developing solution such as an aqueous alkaline solution, and the resulting pattern is heat-treated to form a partition (insulating film). Subsequently, an organic material that generates light of three colors of red, green, and blue is formed between the barrier ribs by an ink-jet method or the like to form pixels of the organic EL display device.

In recent years, with the miniaturization of display devices and the diversification of contents to be displayed, high performance and high definition of pixels have been demanded. Attempts have been made to make the barrier rib material blackish by using a coloring agent for the purpose of enhancing the contrast in the display device and improving the visibility. Even if the light has a light shielding property, it is important that the sensitivity is low because the exposure time is long and the productivity is deteriorated. In order to meet the demand for high definition, it is required that the pattern shape is excellent and the surface of the pattern is smooth in order to cope with the narrow pitch of the pattern. In order to improve the visibility, it is required to make the blackened barrier rib material closer to black. Since the barrier rib material is subjected to various processes after the barrier rib material is formed, excellent heat resistance is required so as not to affect peripheral members.

For example, Patent Document 1 proposes a method of blackening a barrier rib material using carbon black. However, in these radiation-sensitive resin compositions, the light shielding property of the cured film is insufficient and the improvement of the contrast can not be expected.

On the other hand, as a radiation-sensitive resin composition which is high in resolution and exhibits high light-shielding properties by heat treatment after exposure, a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound as in Patent Document 2 A black added composition has been proposed. These compositions have sufficient sensitivity and light shielding property, but are heated at high temperature under air to improve light shielding property, and coloring accompanied by oxidation deterioration of the resin is used. In this case, the outgassing due to the deterioration of the resin is increased, so the heat resistance is lowered, which is not suitable for manufacturing and stable driving of the organic EL display device. The properties of the titanium black are not in conflict with each other, and it is difficult to say that the surface smoothness is sufficient.

As the barrier rib material, a polyimide resin which is generally excellent in insulating property is used, but it is necessary to make it black to obtain a light shielding property. However, forming the blackened polyimide resin by the lithography method is difficult in terms of storage stability and cost of the photosensitive polyimide, and it is difficult to obtain good resolution. For this reason, it has not yet been obtained that the barrier rib material is made black to satisfy sensitivity, developability, resolution and heat resistance.

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

Attempts have been made to blacken the barrier rib material to increase the contrast of the organic EL display element. However, a positive photosensitive resin composition that satisfies all the characteristics of high sensitivity, developability, resolution, and heat resistance and a method for manufacturing the same are heretofore known It is not.

Disclosure of the Invention The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a positive photosensitive resin composition and a method for producing the positive photosensitive resin composition which satisfy high developing sensitivity, resolution and heat resistance characteristics in a blackened barrier rib material will be.

As a result of intensive studies, the present inventors have 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 Of the present invention satisfies the characteristics of developing property, resolution, and heat resistance in a blackened barrier rib material with high sensitivity.

That is, the present invention includes the following modes.

[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) a binder resin, and

(E) quinone diazide compound

Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

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

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

[4] The toner according to any one of [1] to [3], wherein the titanium black (A) is 3 to 30 parts by mass and the quinone diazide compound (E) is 3 to 20 parts by mass based on 100 parts by mass of the binder resin (D) ≪ / RTI >

[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

[4] The composition according to any one of [1] to [4], wherein the composition comprises at least one member selected from the group consisting of

[6] A process for producing a titanium-

(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 having a solubility parameter of 10.5 or more

≪ / RTI >

[7] A method for producing a titanium black dispersion, which comprises mixing (1) a titanium black (A), (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 having a solubility parameter of 10.5 or more, , And

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

In the above-described order.

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

[9] A method for producing a positive photosensitive resin composition, comprising the steps of: (I) applying a positive photosensitive resin composition according to any one of [1] to [5]

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

(III) an exposure process for irradiating radiation over a photomask,

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

(V) a heat treatment step of heating at a temperature of 100 to 350 캜

≪ / RTI >

[10] A barrier rib 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 of 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)

According to the present invention, it is possible to provide a positive-working photosensitive resin composition which has high sensitivity in a blackened barrier rib material and satisfies properties of developability, resolution, and heat resistance.

Hereinafter, the present invention will be described in detail.

(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 having a solubility parameter of 10.5 or more.

(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) a binder resin , And (E) quinone diazide compounds.

(A) Titanium black

Examples of the titanium black used in the present invention include a method of heating and reducing a mixture of titanium dioxide and titanium metal in a reducing atmosphere (Japanese Patent Application Laid-Open No. 49-5432), ultrafine oxidation of titanium tetrachloride obtained by high temperature hydrolysis of titanium tetrachloride A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Application Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (JP 60-65069 A, JP-A-61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide, and a method in which the mixture is subjected to high-temperature reduction in the presence of ammonia (JP-A-61-201610) . Titanium black 10S, 12S, 13R, 13M, 13M-C, 13-MT, 16M, UF-8 manufactured by Mitsubishi Materials Corporation, Tilack D manufactured by Akiko Seiki Co., . 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). When 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 desired OD value (optical density) 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, a high light shielding property can be obtained. The average particle diameter D50 can be measured using a laser diffraction / scattering type particle size distribution measuring apparatus Microtrac wave (Nikkiso Co., Ltd.).

(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, which is used for dispersing the titanium black of the present invention, may be used. Examples thereof include phosphoric acid esters such as DISPARON PW-36 and DISPARON DA-375 (manufactured by Cusmotocase Co., Ltd.) such as DISPERBYK110 and DISPERBYK111 (manufactured by Big Chemical Japan K.K.), poly (Trade name: Floren G-700, Floren G-900, Floren GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), etc.) such as phosphoric acid esters, phosphoric acid polyesters and polyether phosphate esters , And higher fatty acid ester dispersants such as Ajisper PN411 and Ajisper PA111 (manufactured by Ajinomoto Fine Techno Co., Ltd.). Among them, a dispersant having no graft chain in the skeleton such as DISPERBYK110, DISPERBYK111 (manufactured by Big Chem Japan Japan K.K.) is preferably used.

The dispersant has an acid value of 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, a good dispersion is easily obtained with proper bonding with titanium black. These dispersants may be used singly or in combination of two or more.

A dispersant having a salt structure, a dispersant having an ester or ether structure, a dispersant having a pigment-affinitive group, or the like can be used in combination to the extent that the effect of the present invention is not impaired. 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 for the purpose of improving compatibility with a binder resin, storage stability, and various physical properties or properties.

The dispersant (B) is preferably contained in an amount of 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and still more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the titanium black (A). When the dispersant is 1 to 40 parts by mass based on 100 parts by mass of the (A) titanium black, the particles can be dispersed well.

The number of mg of perchloric acid and equivalent amount of potassium hydroxide required to neutralize the total basic nitrogen contained in 1 g of the amine gas sample is expressed as follows. The sample is dissolved in a mixed solvent of o-nitrotoluene and acetic acid, and titrated with a 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 plotted, and the inflection point obtained in the titration curve is set as the end point. The total amine value is calculated by the amount of 0.1 mol / L perchloric acid acetic acid solution consumed.

The number of milligrams of potassium hydroxide required to neutralize the free fatty acid and the resin acid contained in 1 g of the acid-laden sample is referred to as a neutralization titration method and a potentiometric titration method. In the case of the neutralization titration method, the sample is dissolved in a solvent, phenolphthalein is added as an indicator, and the resultant is titrated with a potassium hydroxide ethanol solution to obtain an acid value.

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

The dispersion solvent of the titanium black of the present invention has an SP value of 10.5 to 15.0, preferably 10.5 to 13.0. And it is more preferable that it does not contain a hydroxyl group. Specific examples of the solvent having an SP value of 10.5 or more include γ-butyrolactone (12.6), N-methyl-2-pyrrolidone (11.3), N, N-dimethylformamide (12.1) Amide (10.8), etc. Among them, N-methyl-2-pyrrolidone or? -Butyrolactone is more preferable, and? -Butyrolactone is more preferable. By using a solvent having an SP value of 10.5 or more, the titanium black (A) can be uniformly dispersed. These solvents may be used alone or in combination of two or more.

The solvent (C) is preferably contained in an amount of 250 to 600 parts by mass, more preferably 300 to 500 parts by mass, and still more preferably 350 to 450 parts by mass with respect to 100 parts by mass of the titanium black (A). When the solvent is 250 to 600 parts by mass based on 100 parts by mass of the titanium black (A), a suitable fluidity is obtained and the dispersion state tends 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 of the thermodynamic properties of the sample during mixing. It is possible to use the numerical values described in the application manual of the chemical manual (revised 3rd edition, Maruzen, 1980) or the fourth edition experimental chemistry lecture (Maruzen, 1990, p.186).

(D) binder resin

The binder resin (D) used in the positive photosensitive resin composition of the present invention is not particularly limited, but it is preferable that the binder resin (D) has an alkali-soluble group and is alkali-soluble.

The alkali-soluble group of the binder resin is not particularly limited, and examples thereof include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, and an acid anhydride group, and even when a resin having two or more alkali- good. Further, in the present invention, alkali solubility means that it is soluble in an alkaline solution, for example, an aqueous solution of 2.38 mass% of tetramethylammonium hydroxide.

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

Examples of the binder resin having a phenolic hydroxyl group include phenol novolak resins, cresol novolak resins, triphenylmethane type phenol resins, phenol aralkyl resins, biphenylaralkylphenol resins, phenol-dicyclopentadiene copolymer resins And the like.

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

(d1) an 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. The alkali-soluble resin comprising a copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer can be prepared by, for example, reacting a polymerizable monomer having an alkali-soluble group and other polymerizable monomers with a polymerization initiator and a RAFT agent (Reversible Addition Fragmentation Transfer ; A reversible adduct 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 synthesizing a copolymer by radical polymerization and then adding an alkali-soluble group.

The polymerizable functional group of the polymerizable monomer includes a radically polymerizable functional group. _{Specifically, CH 2 = CH-, CH 2} = C (CH 3) -, CH 2 = CHCO-, CH 2 = C (CH 3) be mentioned, such as CO-, -OC-CH = CH- CO- . Examples of the polymerizable monomer having an alkali-soluble group include 4-hydroxystyrene, (meth) acrylic acid, alpha -bromo (meth) acrylic acid, alpha -chloro (meth) acrylic acid, (Meth) acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, cinnamic acid,? -Cyanosinic acid, itaconic acid, crotonic acid, propiolic acid , 4-hydroxyphenylmethacrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide, 3-maleimidopropionic acid, 4-maleimide Butyric acid, and 6-maleimide hexanoic acid.

Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene,? -Methylstyrene, p-methylstyrene and p-ethylstyrene, acrylamide, acrylonitrile, vinyl-n- (Meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, diethylaminoethyl (meth) acrylate, glycidyl (Meth) acrylate such as 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, isobornyl Maleic anhydride, phenylmaleimide, cyclohexylmaleimide, and the like. Here, "(meth) acrylic" represents "acryl" and "methacryl".

It is particularly preferable to use 4-hydroxyphenyl methacrylate as the polymerizable monomer having an alkali-soluble group and at least one member 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, shape retentivity and developability can be improved, and also outgas can be reduced.

The polymerization initiator in the case of producing an alkali-soluble copolymer of an alkali-soluble group-containing polymerizable monomer and other polymerizable monomers by radical polymerization is not limited to the following, and examples thereof include 2,2'-azobisisobutylonitrile, 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) A peroxide polymerization initiator having a 10-hour half-life temperature of 100 to 170 DEG C such as butyl cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethyl butyl hydroperoxide or cumene hydroperoxide, Peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di (t-butylperoxy) cyclohexane and t-butyl peroxypivalate, 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, relative to 100 parts by mass of the mixture of polymerizable monomers .

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 an amount of 0.005 to 20 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomers, and is preferably used in a 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 copolymer of 4-hydroxyphenylmethacrylate, a radical copolymer of phenylmaleimide and cyclohexylmaleimide, or a copolymer of 4-hydroxyphenylmethacrylate and cyclohexyl When a maleic anhydride radical copolymer is used, the number average molecular weight thereof is preferably in the range of 1,000 to 30,000, more preferably in the range of 3,000 to 20,000, and still more preferably in the range of 10,000 to 15,000. When the molecular weight is 1000 or more, it is suitable as a resin of a photosensitive material since alkali solubility is suitable. When the molecular weight is 30,000 or less, developability is good.

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

The alkali-soluble resin of (d2) can be prepared by, for example, reacting an epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as "epoxy compound") with a carboxyl group of hydroxybenzoates 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, it has an advantage that it reacts with the phenolic hydroxyl group upon heating and crosslinks to improve chemical resistance, heat resistance, etc. By having a phenolic hydroxyl group There is an advantage that it is soluble in an aqueous alkaline solution.

An example of a reaction in which one of the epoxy groups of the epoxy compound reacts with the carboxyl group of the hydroxybenzoates to form a compound having a phenolic hydroxyl group is shown in the following Reaction Scheme 1.

Examples of the compound having at least two epoxy groups in one molecule include phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, naphthalene skeleton containing epoxy resin, alicyclic epoxy resin , Heterocyclic epoxy resins, and the like. These epoxy compounds may have two or more epoxy groups in one molecule and may be used alone or in combination of two or more. Further, since these compounds are thermosetting, they can not be uniquely described as the common sense of those skilled in the art based on differences in the presence or absence of epoxy groups, kinds of functional groups, degree of polymerization, and the like. An example of the structure of the novolak type epoxy resin is shown in Formula (1). In the formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 50.

Examples of the phenol novolak type epoxy resin include EPICLON (registered trademark) N-770 (manufactured by DIC Corporation) and jER (registered trademark) -152 (manufactured by Mitsubishi Chemical Corporation).

Examples of the cresol novolak type epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation) and EOCN (registered trademark) -102S (manufactured by Nippon Kayaku Corporation).

Examples of the bisphenol-type epoxy resin include epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), YD-128 (trade name, manufactured by Shinnitetsu Sumikin Kagaku Kogyo Co., Ltd.) Bisphenol F type epoxy resins such as bisphenol A type epoxy resin, jER (registered trademark) 806 (manufactured by Mitsubishi Chemical Corp.) and YDF-170 (trade name, manufactured by Shinnitetsu Sumikin Kagaku Kogyo Co., Ltd.) .

Examples of the biphenol type epoxy resin include jER (registered trademark) YX-4000, jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation) and the like.

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

Examples of the alicyclic epoxy resin include EHPE (registered trademark) -3150 (available from Daicel Chemical Industries, Ltd.).

As the heterocyclic epoxy resin, for example, TEPIC (registered trademark), TEPIC (registered trademark) -L, TEPIC (registered trademark) -H, TEPIC (registered trademark) -S (manufactured by Nissan Kagaku Kogyo K.K.) .

Refers to a compound in which at least one of the 2 to 6 positions of benzoic acid is substituted with a hydroxyl group, and examples thereof include 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- , 3-hydroxy-4-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid and the like, but dihydroxybenzoic acids are preferred from the standpoint of enhancing alkali developability. These hydroxybenzoates may be used alone or in combination of two or more.

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

A catalyst may be used to promote the reaction. The amount of the catalyst to be 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 hydroxybenzoates. The reaction temperature is 60 to 150 占 폚, and the reaction time is 3 to 30 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, and zirconium octanoate. .

The number average molecular weight of the alkali-soluble resin (d2) having an epoxy group and the phenolic hydroxyl group is preferably in the range of 500 to 8000, more preferably in the range of 1,500 to 5,000, and still more preferably in the range of 2,000 to 3,500 . When the molecular weight is 500 or more, the resin is good as a resin for a photosensitive material because of its good solubility in an aqueous alkali solution. When the molecular weight is 8,000 or less, the coatability and developability are good.

(d3) polyalkenylphenol resin

The polyalkenylphenol resin is obtained by alkenyl etherating the hydroxyl group of a known phenolic resin, and also by subjecting an alkenyl ether group to the crazene potential. The polyalkenyl phenol resin preferably has a structure represented by formula (2). By containing such a resin, it is possible to improve the developing property of the obtained photosensitive resin composition and to contribute to the reduction of outgas.

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,

(Wherein 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, And * in the formula (3) represents a bonding site with a carbon atom constituting an aromatic ring.

, An alkoxy group having ¹ to 2 carbon atoms or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by the 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 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 the formula (2) are present in one molecule, the structure of each formula (2) may be the same or different.

R ¹ , R ² and R ³ in the 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, ¹ , at least one of R ² and R ³ is an alkenyl group represented by the formula (3).

Specific examples of the alkyl group having 1 to 5 carbon atoms in R ¹ , R ² and R ³ in the formula (2) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, -Butyl group, n-pentyl group and the like. Specific examples of the alkoxy group having 1 to 2 carbon atoms include a methoxy group and an ethoxy group.

R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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, and specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- n-pentyl group, and the like. 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 an aryl group having 6 to 12 carbon atoms Specific examples thereof include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, and a naphthyl group. 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. Preferred examples of the alkenyl group represented by the formula (3) include an allyl group and a methacryl group from the viewpoint of reactivity, and more preferably an allyl group. It is most preferable that any one of R ¹ , R ² and R ³ is an allyl group or methacryl group and the other two are hydrogen atoms.

Q in the 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 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, ≪ / RTI > Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl and n-pentyl. Specific examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group and a 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 a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom.

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. Specific examples of the divalent organic group having an aromatic ring include a phenylene group, a tolylene group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthracenylene group, a xylylene group, a 4,4'- 4), and the like.

As a specific example of the divalent organic group having an alicyclic condensed ring, dicyclopentadienylene group and the like can be given.

When a polyalkenylphenol resin is used as the binder resin (D) used in the photosensitive resin composition of the present invention, particularly preferably a polyalkenylphenol resin from the viewpoint of alkali developability and outgas, Q in the formula (2) -CH ₂ -, that is, those having a structure represented by the formula (5).

In the formula (5), R ¹ , R ² and R ³ are as shown in the 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 the formula (2) or (5) is preferably from 50 to 100 mol%, more preferably from 70 to 100 mol%, and still more preferably from 85 to 100 mol% in the polyalkenylphenol resin Mol%. When the structural unit represented by the formula (2) or (5) is 50 mol% or more in the polyalkenyl phenol resin, the heat resistance is preferably improved. Since the phenolic hydroxyl group in the polyalkenyl phenol resin can be ionized in the presence of a basic compound and dissolved in water, it is necessary that the phenolic hydroxyl group is present in a certain amount or more from the viewpoint of alkali developability. Therefore, the polyalkenylphenol resin containing the structure of the formula (5) is particularly preferably a polyalkenylphenol resin having the structural unit represented by the formula (5) and the structural unit represented by the formula (6) .

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

In the polyalkenylphenol resin having the structural unit represented by the formula (5) and the structural unit represented by the formula (6), the number of the structural units represented by the formula (5) is x, Y / (x + y)? 0.5, (x + y) is preferably 2 to 3,000, and the number of structural units represented by y is 0.5? X / More preferably 2 to 2,000, and still more preferably 2 to 1,000.

When a polyalkenyl phenol resin is used as the binder resin (D), the number average molecular weight is preferably 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 developing rate of the alkali is adequate, the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, and the resolution is good.

As the binder resin, one type of resin may be used alone, or two or more kinds of resins may be used in combination. Among them, it is preferable to include at least one kind selected from the resin components (d1) to (d3), and it is more preferable to include at least (d1) and (d2). The total amount of one or more kinds of components selected from (d1) to (d3) relative to 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, Preferably 30 to 100 parts by mass. When the total amount of one kind or plural kinds selected from (d1) to (d3) relative to 100 parts by mass of the binder resin (D) is 1 to 100 parts by mass, the heat resistance of the resin composition is good.

As the binder resin (D), for example, any combination of resin components (d1) and (d2) may be used in combination, and a plurality of components (d1) to (d3) may be used in combination.

For example, three types of the alkali-soluble copolymer (d1) having an alkali-soluble group, the alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group, and the polyalkenylphenol resin (d3) may be used in combination. The ratio of the alkali-soluble copolymer (d1) having an alkali-soluble group in the binder resin (D) is 5 to 60 mass%, the ratio of the alkali-soluble resin (d2) having an epoxy group and the phenolic hydroxyl group is 35 To 90 mass% and the polyalkenyl phenol resin (d3) is preferably 5 to 60 mass%.

When the alkali-soluble copolymer (d1) having an alkali-soluble group also corresponds to an alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group, it is regarded 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 regarded as an alkali-soluble copolymer (d1) having an alkali-soluble group. That is, the alkali-soluble resin (d2) having an epoxy group and the phenolic hydroxyl group and the polyalkenylphenol resin (d3) are not to be regarded as 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. Examples of the quinone diazide compound include a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxy compound with an ester, a compound in which a sulfonic acid of quinone diazide is sulfonamide bonded to a polyamino compound, a compound in which a sulfonic acid in quinone diazide is esterified with a 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 functional groups of the polyhydroxy compound or the polyamino compound are substituted with quinone diazide. By using such a quinone diazide compound, it is possible to obtain a positive type photosensitive resin composition which is sensitized to i-line (365 nm), h-line (405 nm) and g-line (436 nm) of a general ultraviolet ray.

BisP-PZ, BisP-IPZ, BisOCP, BisP-ZZ, BisP-ZZ, BisP-EZ, DML-PCP, DML-PC, DML-PCP, DIP-DIP, bisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris- PML, TML-BP, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BISOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML- , BIR-OC, BIP-PC, BIR-PC, TML-BP-BPF, TML-BPA, TMOM-BP, HML-TPPHBA and HML-TPHAP (all trade names, manufactured by Honshu Kagaku Kogyo K.K.) BIP-A (trade name, manufactured by Asahi Yuki Kagaku Kogyo Co., Ltd.), BIP-BIP-B, BIP-BIP-B, BIP- , 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, Acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Although the like Chemical Industries products manufactured by or wrong), but are not limited to these.

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

The quinone diazide compound generates a carboxyl group through the reaction shown in the following reaction formula 2 when ultraviolet light or the like is exposed. As the carboxyl group is generated, the exposed part (coating film) can be dissolved in the alkali solution, so that the alkali developing property is expressed.

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) 5 to 15 parts by mass, more preferably 7 to 10 parts by mass. When the amount is 3 parts by mass or more based on 100 parts by mass of the binder resin (D), the alkali developability is good. When the amount is less than 20 parts by mass, the heating reduction rate at 300 DEG C or more is unlikely to increase.

(F) Optional ingredients

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

(F1) Thermal curing agent

As the heat curing agent, a thermal radical generator may be used. Preferred examples of the thermal radical generator include organic peroxides, and specific examples thereof include dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl cumyl peroxide, -Butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and the like, and organic peroxides having a 10-hour half-life temperature of 100 to 170 占 폚.

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

(F2) Surfactant

The positive-working photosensitive resin composition of the present invention may further contain, as optional components, a surfactant, for example, in order to improve the coating property or to improve the developability of the 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 dilaurate and polyoxyethylene distearate; F-554, F-555, F-556, F-555, F-554, S-243, S-385, S-386, S-420 (trade name, , S-611 (trade name, product of ACG Seiyam Chemical Co., Ltd.), and the like; And organosiloxane polymers KP323, KP326 and KP341 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or in combination of two or more.

Such a surfactant is incorporated in an amount of not more than 2 parts by mass, more preferably not more than 1 part by mass, more preferably not more than 0.5 parts by mass, 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, as an optional component, a colorant other than the titanium black (A). Such colorants include dyes, organic pigments and inorganic pigments, but they can be used in accordance with the purpose. Incidentally, the content of the colorant other than the titanium black (A) is within the range that does not impair the effect of the present invention.

Specific examples of the dye include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, melocyanine dyes, stilbene dyes, diphenylmethane dyes, , Fluororan dye, spiropyran dye, phthalocyanine dye, indigo dye, fulgide dye, nickel complex dye, and azulene dye.

Examples of pigments include black pigments such as carbon black, carbon nanotubes, acetylene black, graphite, iron black, and aniline black; 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 and the like.

(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 coating methods depending on the amount of the solvent. Depending on the purpose of use, a suitable solid content concentration can be adopted, and for example, the solid content concentration can be 1 to 60 mass%, preferably 3 to 50%, and 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 another solvent to 5% by mass or less of the total solvent.

Examples of the other solvent 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, di Diethylene glycol such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether, propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate, and toluene and xylene. Aromatic ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy- , Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyacetic acid Methyl 2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate And the like. These solvents may be used alone or in combination of two or more.

[Production method of titanium black dispersion]

(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 having a solubility parameter of 10.5 or more as essential components to prepare a titanium black dispersion can do.

The dispersing machine for crushing and dispersing the titanium black is not particularly limited and may be a ball type such as a ball mill, a sand mill, a bead mill, a paint shaker and a locking mill, a blade type such as a kneader, a paddle mixer, a planetary mixer or a Henschel mixer , A roll type mixer such as a three-roll mixer, and the like; and a Leica mixer, a colloid mill, an ultrasonic mixer, a homogenizer, and a rotary mixer. Among these, a ball type in which fine dispersion can be stably performed in a short time is preferable. Examples of the material of the ball used in this ball type include glass, silicon nitride, alumina, zircon, zirconia, and steel. 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 refinement.

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

First, the solvent (C) and the dispersant (B) are uniformly dispersed. When the solvent and the dispersant are not uniformly dispersed in advance, there is a region where the concentration of the dispersant is high partially, which tends to cause problems such as agglomeration of the particles. Then, the required amount of titanium black (A) is put into a solution prepared first, and finally, beads are added. When coagulation 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 inhibition of re-aggregation of titanium black.

[Method of producing positive-type photosensitive resin composition]

The positive photosensitive resin composition of the present invention is obtained by first preparing a titanium black dispersion by mixing titanium black (A), dispersant (B) and solvent (C), and then mixing the binder resin (D), quinone diazide compound ), And optional component (F). The method of preparing the titanium black dispersion is as described above.

The order of mixing the titanium black dispersion with the binder resin, the quinone diazide compound, and optional components is not particularly limited. For example, the binder resin may be dissolved in a solvent other than the solvent (C) or (C) A positive type photosensitive resin composition in a solution state can be prepared by mixing an additive such as a quinone diazide compound, a titanium black dispersion, a heat curing agent and a surfactant, if necessary, in a predetermined ratio.

The stirrer for mixing the titanium black dispersion with the binder resin, the quinone diazide compound, and optional components is not particularly limited and may be any of a ball, a kneader, a paddle mixer such as a ball mill, a sand mill, a bead mill, a paint shaker, A planetary mixer, a Henschel mixer, and the like, a roll type such as a three-roll mixer, a Leica, a Colloid mill, an ultrasonic wave, a homogenizer, a rotary mixer, and a mechanical stirrer. When used at a lab level, mechanical stirrers are preferable because they are stable and can be mixed in a short time. The stirring blades used at the time of stirring may be suitably selected from a fan, a propeller, a crucible, a turbine, a dragonfly type, and the like. A titanium black dispersion or a binder resin solution or the like is mixed and stirred at room temperature for 1 to 10 minutes at a rotation number of 10 to 1000 rpm to obtain a resin composition.

It is preferable that the composition liquid prepared as described above is filtered before use. As a filtration means, for example, a Millipore filter having a pore diameter of 0.05 to 1.0 mu m can be cited.

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

[Pattern formation and hardening 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 substrate surface, 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 substrate surface is not particularly limited, and various methods such as a spray method, a roll coating method, a slit method, and a spin coating method can be employed.

After applying the positive photosensitive resin composition of the present invention to the substrate surface, the solvent is usually dried by heating (prebaking) to form a coating film. The heating conditions vary depending on the kind of each component, blending ratio, etc., but usually the coating film is obtained by heat treatment at 70 to 130 캜 for a predetermined time, for example, 1 to 20 minutes in a hot plate and 3 to 60 minutes in an oven .

Subsequently, the prebaked coating film is irradiated (exposed) with radiation (e.g., visible light, ultraviolet light, far ultraviolet light, etc.) through a mask of a predetermined pattern and then developed with a developing solution to remove unnecessary portions, Thereby forming a coating film (developing step). When naphthoquinonediazidesulfonic acid ester is used as a positive photosensitive compound, preferable radiation is ultraviolet to visible light having a wavelength of 250 to 450 nm.

Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; Primary amines such as ethylamine, n-propylamine and the like; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alcohol amines such as dimethylethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline; Cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] Can be used. The concentration is not particularly limited, but is preferably 0.5 to 5.0 mass%. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. is added to the aqueous alkaline solution may be used as a developer. The developing time is usually 30 to 180 seconds, and the developing method may be any of a puddle method, a shower method, and a dipping method. After development, water washing is carried out for 30 to 90 seconds to remove unnecessary portions, and the pattern is formed by air-blowing with compressed air or compressed nitrogen. Thereafter, this pattern is subjected to heat treatment at a predetermined temperature, for example, 120 to 350 캜 for 20 to 200 minutes by a heating apparatus such as a hot plate or an oven, but the temperature may be increased stepwise Treatment process).

(II) a drying step of removing the solvent in the applied positive photosensitive resin composition; (III) a step of irradiating the radiation onto a photomask (IV) a development step of forming a pattern by an alkali development, and (V) a heat treatment step of heating at a temperature of 100 to 350 캜. This method can be used for forming barrier ribs and insulating films of organic EL elements.

The present invention can provide a barrier rib of an organic EL device comprising a cured product of the above positive photosensitive resin composition.

The present invention can provide an insulating film of an organic EL device comprising a cured product of the above positive photosensitive resin composition.

The present invention can provide an organic EL device including a cured product of the above positive photosensitive resin composition.

(Example)

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

(1) Synthesis of binder resin

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

, 76.8 g of 4-hydroxyphenyl methacrylate ("PQMA", manufactured by Showa Denko K.K.), 14.4 g of N-phenylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), N-cyclohexylmaleimide (Product of Nippon Shokubai Co., Ltd.), 1.80 g of V-601 (produced by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, 1.5 g of S-dodecyl-S '- ) Was dissolved completely in 180 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.). The resulting solution was added to a 500 mL three-necked Methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) heated to 85 ° C in a nitrogen gas atmosphere over 1 hour, and then reacted at 85 ° C for 3 hours. One reaction solution was added dropwise to 1200 g of toluene, The precipitated polymer was recovered by filtration and vacuum-dried at 80 DEG C for 7 hours to recover 104.4 g of a white powder which was dissolved in? -Butyrolactone to obtain a resin liquid having a solid content of 20 mass% 1). The obtained reaction product had a number average molecular weight of 14,100 and a weight average molecular weight of 24,900.

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

60 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent and EPICLON (registered trademark) N-695 (manufactured by DIC Corporation) were added to a 300 mL three-necked flask, 42 g of epoxy resin having an epoxy equivalent of 210) was charged and dissolved at 60 캜 in a nitrogen atmosphere. 15.5 g (0.10 mol, 0.5 equivalents based on 1 equivalent of epoxy) of 3,5-dihydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the hydroxybenzoates, and triphenylphosphine (0.76 mmol) was added, and the mixture was allowed to react at 110 占 폚 for 12 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20 mass%, and the solution was filtrated to recover 260 g (resin liquid 2). The number average molecular weight of the obtained reaction product was 2,400 and the weight average molecular weight was 5,600.

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

A solution obtained by dissolving 201 g (1.45 mol) of potassium carbonate (manufactured by Nippon Soda Co., Ltd.) in 100 g of pure water, a solution obtained by dissolving phenol novolak resin "SCONOL (registered trademark) BRN-5834Y" (AICA SDK Phenol Co., Ltd.) and 16 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, the reactor was purged with nitrogen gas and heated to 85 캜. 84 g (0.84 mol) of allyl acetate (manufactured by Showa Denko K.K.) and 50% aqueous solution of 5% -Pd / C-STD type (metal palladium was dispersed in the activated carbon in an amount of 5 mass% 0.40 g (palladium: 0.188 mmol) of a catalyst for allylation reaction, which is stabilized by adding water so that the amount of the activated carbon in which the metal palladium is dispersed is 50% by mass, manufactured by NIKKE KEMPO Co., Ltd.) and triphenylphosphine 2.45 g (9.4 mmol) of an activating agent for an allylation reaction catalyst (product of Hokkou Kagaku Kogyo K.K.) was added, and the mixture was heated to 105 DEG C in a nitrogen atmosphere and reacted for 4 hours. Then, 14 g ) Was further added, and heating was continued for 10 hours while confirming the formation of allyl ether groups by ¹ H-NMR. Thereafter, stirring was stopped and the mixture was allowed to stand to separate into two layers, an organic layer and an aqueous layer. After adding 200 g of pure water until the precipitated salt dissolved, 200 g of toluene was added, and it was confirmed that a white precipitate was not precipitated by keeping at a temperature of 80 캜 or higher. Then, Pd / C was filtered (0.3 MPa) using a membrane filter (KST-142-JA manufactured by Advantech Co., Ltd.) .The filtration residue was washed with 100 g of toluene and the aqueous layer was separated. The organic layer was separated and concentrated under reduced pressure to obtain a phenol novolak-type polyallyl ether resin as a brown oil.

Subsequently, 125 g of a phenol novolak type polyallyl ether resin was placed in a 500 mL flask in which a mechanical stirrer was set and diluted with 130 g of? -Butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.). The mixture was heated to 170 ° C with stirring at 300 rpm, and subjected to Clizer potential reaction for 30 hours while confirming reduction of allyl ether groups by ¹ H-NMR. After the reaction, the solution was returned to room temperature and diluted with 20% by mass of solid content with? -Butyrolactone to obtain a phenol novolak type polyallylphenol resin solution (resin solution 3). The polyarylphenol resin had a hydroxyl group equivalent of 132, a number average molecular weight of 1100, and a weight average molecular weight of 9900 as solids.

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

The weight average molecular weight and the number average molecular weight were calculated using a calibration curve prepared using standard materials of polystyrene under the following measurement conditions.

Device name: Shodex (registered trademark) GPC-101

Column: Shodex (R) LF-804

Mobile phase: tetrahydrofuran

Flow rate: 1.0 mL / min

Detector: Shodex (R) RI-71

Temperature: 40 ° C

(2) raw materials

(D) As the binder resin, the resin liquids 1 to 3 synthesized in Production Examples 1 to 3 and the novolak phenol resin BRM-595M (manufactured by Aika SDK Phenol Corporation) were subjected to reprecipitation to remove low molecular weight components, and resin liquid 4 prepared by using? -butyrolactone to have a solid content of 20 mass%.

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

(3) Preparation of titanium black dispersion

[Example 1]

39 g of? -butyrolactone and 1 g of dispersant DISPERBYK-111 were added to 150 cc of a total throttle screw type storage container (made of stainless steel) and mixed. Thereafter, 10 g of titanium black UF-8 having a primary particle diameter of 20 nm was added and mixed, and then 200 g of a zirconia bead (trade name: YTZ ball, manufactured by Nikkato K.K.) for diameter reduction of Φ0.3 mm was added Sealed to prevent leakage, and this was set on a paint shaker (manufactured by Asada Teco Co., Ltd.) and dispersed for 10 hours. The obtained dispersion was filtered with a Millipore filter having pore diameters of 0.45 mu m and 0.22 mu m to obtain a titanium black dispersion. The obtained titanium black dispersion is hereinafter referred to as dispersion 1.

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

A titanium black dispersion was obtained in the same manner as in Example 1 according to the blend shown in Table 2 and the diameter of the zirconia beads. 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 referred to as dispersions C1 to C5 hereinafter.

(4) Preparation of Positive Photosensitive Resin Composition

[Example 6]

50 parts by mass of the resin solution 1 obtained in Production Examples 1 and 2, 125 parts by mass of the resin solution 2, 15 parts by mass of TS-130A as the quinone diazide compound, and 100 parts by mass of the titanium black dispersion 1 obtained in Example 1 And 7.5 parts by mass of a 1% by mass solution (diluted with? -Butyrolactone) of Surplon S-386 as a surfactant were added and further mixed. The resulting mixture was visually observed and then filtered through a Millipore filter having a pore diameter of 0.22 탆 to prepare a positive photosensitive resin composition having a solid content concentration of 24%.

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

A positive photosensitive resin composition was prepared in the same manner as in Example 6,

(5) Evaluation

The titanium black dispersions prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated for the average particle diameter of titanium black. However, the titanium black dispersions of Comparative Example 1 and Comparative Example 5 were not subjected to measurement because aggregation could be confirmed visually. The results are shown in Table 2.

[Average particle size of titanium black]

20 g of? -butyrolactone was weighed and one drop of the dispersion was added thereto and mixed by ultrasonic wave for 1 minute. Thereafter, a laser diffraction / scattering particle size distribution analyzer Nanotrac wave (Ex) (Nikkiso Co., Ltd.) And the average particle diameter D50 of the titanium black after the dispersion was measured.

Pattern formation properties, pattern linearity, light shielding property (OD value), appearance after pre-baking, surface roughness Ra, and surface roughness Ra of the positive photosensitive resin composition prepared in Examples 6 to 12 and Comparative Examples 6 to 8 Heat resistance (weight reduction rate) was evaluated. The results are shown in Table 3. The evaluation method is as follows.

[Alkali developing property, pattern forming property, pattern linearity]

The positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were spin-coated on a glass substrate (size 100 mm x 100 mm x 1 mm) so as to have a dry film thickness of about 1.5 mu m, The supernatant was dried. Further, a photomask (5 占 퐉, 10 占 퐉, 20 占 퐉, 50 占 퐉, 100 占 퐉, and 200 占 퐉 made of quartz) was used with an exposure apparatus (trade name: Multilight ML-251A / B, manufactured by Ushio Denki Kabushiki Kaisha) equipped with an ultra- , 500 mu m line & space patterned). The amount of exposure was measured using an ultraviolet ray counting light meter (trade name UIT-150 light receiving unit UVD-S365, manufactured by Ushio DENKI K.K.). The exposed coating film was subjected to alkali development for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide by using a spin developing apparatus (AD-1200, manufactured by Takizawa Sangyo K.K.), and the alkali developability was evaluated. In the observation using an optical microscope (VH-Z250, manufactured by Guisens), it was judged as good when there was no residue after alkali development, and when the residue was found to be defective.

The evaluation of pattern formability was carried out by measuring the line width of the pattern after alkali development. (VH-Z250, manufactured by Guennec Co., Ltd.) was used to confirm a line-and-space pattern line width of 10 m each in a photomask with a microscope having a magnification of 1000 times. When the line width of the line and space pattern of the pattern after the alkali development was 1: 1, the line width of the line portion was within ± 10%. Otherwise, the pattern formation property was evaluated as defective.

The evaluation of the linearity of the pattern was made such that the pattern was linear and the wave was good.

[OD value]

The positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were spin-coated on a glass substrate (size 100 mm x 100 mm x 1 mm) so as to have a thickness of about 1.5 탆 and heated on a hot plate at 120 캜 for 80 seconds The solvent was dried. Thereafter, the coating film was cured at 250 DEG C for 60 minutes in a nitrogen gas atmosphere. The glass coating film after curing was measured with a transmission densitometer (BMT-1, manufactured by Sakata Ink Engineering Co., Ltd.) and corrected to the OD value of glass only, and converted into the OD value per 1 mu m of the thickness of the coating film. The thickness of the coating film was measured using a surface roughness meter (Surfcom 130A, manufactured by Tokyo Seimitsu Co., Ltd.).

[Appearance after pre-baking]

The positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were spin-coated on a glass substrate (size 100 mm x 100 mm x 1 mm) so as to have a thickness of about 1.5 탆 and heated on a hot plate at 120 캜 for 80 seconds The solvent was dried. The appearance evaluation after pre-baking showed that the surface of the coated film after drying was visually observed, and those having a uniform gloss surface were satisfactory, those having a variation in gloss were possible, and those having holes through which light was transmitted were evaluated as defective.

[Surface roughness Ra]

The positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were spin-coated on a glass substrate (size 100 mm x 100 mm x 1 mm) so that the dry film thickness became about 1.5 mu m, The solvent was dried. And exposed at 100 mJ / cm 2 through a quartz photomask with an exposure apparatus (trade name: Multilight ML-251A / B, manufactured by Ushio DENKI K.K.) equipped with an ultra-high pressure mercury lamp. The amount of exposure was measured using an ultraviolet ray counting light meter (trade name UIT-150 light receiving unit UVD-S365, manufactured by Ushio DENKI K.K.). The exposed coating film was subjected to alkali development with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds using a spin developing apparatus (AD-1200, manufactured by Takizawa Sangyo K.K.). Thereafter, it was cured at 250 DEG C for 60 minutes in a nitrogen gas atmosphere to obtain a patterned coating film. The surface roughness of the 10 탆 -thick pattern of the coated film after curing was measured using a surface roughness meter (Surfcom 130A, manufactured by Tokyo Seimitsu Kabushiki Kaisha).

[Weight reduction rate]

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

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

Examples 6 to 12, which are positive-working photosensitive resin compositions using the titanium black dispersions of Examples 1 to 5, show that all points of appearance after baking, alkali developability, pattern forming property, pattern linearity, surface roughness Ra, I was able to find good balance and excellent.

On the other hand, a 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, Comparative Example 5 using no dispersant, and Comparative Examples 6 to 8 It has been found that it is difficult to apply the positive-type photosensitive resin composition to a blackened barrier rib material which requires development and high resolution.

(Industrial availability)

The black positive photosensitive resin composition of the present invention can be suitably used for positive type radiation lithography. The organic EL element having the partition wall and the insulating film formed from the black positive photosensitive resin composition of the present invention is suitably used as an electronic part of a display device showing a 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) a binder resin, and
(E) quinone diazide compound
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. The method according to claim 1,
Wherein the solvent (C) is? -Butyrolactone or n-methyl-2-pyrrolidone. 3. The method according to claim 1 or 2,
Wherein the dispersant (B) is from 1 to 40 parts by mass and the solvent (C) is from 250 to 600 parts by mass based on 100 parts by mass of the titanium black (A). 4. The method according to any one of claims 1 to 3,
Wherein the titanium black (A) is 3 to 30 parts by mass and the quinone diazide compound (E) is 3 to 20 parts by mass based on 100 parts by mass of the binder resin (D). 5. The method according to any one of claims 1 to 4,
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
And at least one member 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 having a solubility parameter of 10.5 or more
≪ / RTI > (1) A process for producing a titanium black dispersion by mixing (A) 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 having a solubility parameter of 10.5 or more, And
(2) the step of mixing the titanium black dispersion, (D) the binder resin and (E) the quinone diazide compound
In the above-described order. A cured product of the composition according to any one of claims 1 to 5. (I) a step of applying the positive photosensitive resin composition according to any one of claims 1 to 5 to a substrate,
(II) a drying step of removing the solvent in the applied positive-working photosensitive resin composition,
(III) an exposure process for irradiating radiation over a photomask,
(IV) a developing step of forming a pattern by an alkali development, and
(V) a heat treatment step of heating at a temperature of 100 to 350 캜
≪ / RTI > A barrier rib of an organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 5. An insulating film of an organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 5. An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 5.