TW201635033A - Positive photosensitive resin composition - Google Patents

Abstract

An object of the present invention is to provide a positive photosensitive resin composition which can be formed directly in a high-sensitivity pattern while maintaining the adhesion during development, and can form a cured film having a small amount of residue in the pattern. The solution of the present invention is a positive photosensitive resin composition containing the following components (A), (B), (C), and (D) a solvent. (A) component: an alkali-soluble acrylic copolymer (A1) obtained by copolymerizing the following (A1) to (A4), an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (A2) having a phenolic hydroxyl group and polymerizability a monomer having an unsaturated group, (A3) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A4)N-substituted maleimide compound; (B) a component: 1,2-quinonediazide ( Quinonediazide) compound, (C) component: crosslinking agent (D) solvent.

Description

Positive photosensitive resin composition

The present invention relates to a positive photosensitive resin composition and a cured film obtained from the composition. More specifically, the present invention relates to a positive photosensitive resin composition suitable for use in a display material, a cured film thereof, and various materials using the cured film.

In general, a display element such as a thin film transistor (TFT) type liquid crystal display element or an organic EL (electroluminescent) element is provided with an electrode protective film, a planarization film, an insulating film, or the like which is formed by a pattern. Among the photosensitive resin compositions, the photosensitive resin composition having a feature that the number of steps for obtaining a necessary pattern shape is small and having sufficient flatness is more widely used than in the past. use.

Further, in the above-mentioned films, it is required to have excellent process resistance such as heat resistance, solvent resistance, long-time firing resistance, and metal plating resistance, and good adhesion to the substrate, and various types which can be used together. The process conditions form a wide range of process margins, and in addition, require high sensitivity and high transparency, and less film unevenness after development. And many other features. Therefore, from the viewpoint of the required characteristics, a resin containing a naphthoquinonediazide compound has been conventionally used as the above-mentioned photosensitive resin composition.

It is proposed that such a material is cured by adding an epoxy crosslinking agent or by forming a pattern in which a carboxyl group and an epoxy group are thermally crosslinked in an acrylic resin (Patent Documents 1 and 2). However, the use of such a resin does not provide sufficient sensitivity and is associated with a decrease in throughput during the manufacture of the display. Moreover, the shape of the pattern is easily changed by the baking temperature at the time of post-baking, so that precise temperature regulation is required.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-103937

[Patent Document 2] Japanese Patent Laid-Open No. 4-352101

In view of the above, the present invention provides a positive photosensitive resin composition which can be formed directly in a high-sensitivity pattern while maintaining the adhesion during development, and can form a cured film having a small amount of residue in the pattern.

The inventors of the present invention have made an effort to solve the above problems. As a result, the invention was discovered. That is, the present invention relates to the following.

A positive photosensitive resin composition comprising the following components (A), (B), (C), and (D) a solvent, and component (A): (A1) to (A1) A4) an alkali-soluble acrylic copolymer (A1) obtained by copolymerization, an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, and (A3) having a hydroxyalkane a monomer with a polymerizable unsaturated group, (A4)N substituted maleimide compound; (B) component: 1,2-quinonediazide compound, (C) component: crosslinking agent (D) solvent .

2. The positive photosensitive resin composition according to the above 1, wherein the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group in (A2) is p-hydroxyphenyl (meth) acrylate.

3. The positive photosensitive resin composition according to the above 1 or 2, wherein the number average molecular weight of the alkali-soluble acrylic polymer of the component (A) is 2,000 to 30,000 in terms of polystyrene.

4. The positive photosensitive resin composition of the above-mentioned 1 to 3, wherein the component (B) is 5 to 100 parts by mass based on 100 parts by mass of the component (A).

The positive photosensitive resin composition of any one of the above-mentioned items 1 to 4, wherein the component (C) is 5 to 50 parts by mass based on 100 parts by mass of the component (A).

6. The positive photosensitive resin composition according to any one of the above items 1 to 5, wherein the component (E) is bound to 100 parts by mass of the component (A) The surfactant further contains 0.01 to 1.0 part by mass.

7. The positive-type photosensitive resin composition according to any one of the above-mentioned items 1 to 6, wherein the adhesion promoter further contains 0.1 to 20 masses as the component (F), based on 100 parts by mass of the component (A). Share.

A cured film obtained by curing the positive photosensitive resin composition according to any one of the above 1 to 7.

A display member having a cured film as described above.

A display element comprising the cured film of the above 8 as an array flattening film for a display.

A display element having a cured film as described above as an interlayer insulating film.

The positive photosensitive resin composition of the present invention can be formed directly in a high-sensitivity pattern while maintaining the adhesion during development, and can form a cured film having less residue in the pattern.

The photosensitive resin composition of the present invention contains the following (A) component, (B) component, (C) component, and (D) solvent positive photosensitive resin composition, and (A) component: the following ( A1)~(A4) an alkali-soluble acrylic copolymer (A1) obtained by copolymerization of an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (A2) having a phenolic hydroxyl group a monomer having a radical and a polymerizable unsaturated group, (A3) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A4)N-substituted maleimide compound; (B) component: 1,2-anthracene Diazide compound, (C) component: crosslinking agent (D) solvent.

Hereinafter, the details of each component will be described.

<(A) component>

The component (A) is a copolymerized (A1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, and (A3) has a hydroxyalkyl group and a polymerizable property. An alkali-soluble acrylic polymer obtained by substituting a monomer of a saturated group with (A4)N for a maleimide compound.

In the present invention, the term "acrylic polymer" means a polymerizable unsaturated group such as acrylate, methacrylate, styrene or maleimide, that is, a polymerization having a C=C double bond in its structure. A polymer derived from a monomer.

The alkali-soluble acrylic polymer of the component (A) is not particularly limited as long as it is an alkali-soluble acrylic polymer, and the type of the skeleton and the side chain of the polymer main chain constituting the acrylic polymer.

When the number average molecular weight of the component (A) is more than 30,000, the flatness of the step is lowered, and when the number average molecular weight is less than 2,000, the heat hardening is insufficient. Reduce solvent resistance. Accordingly, the number average molecular weight is in the range of 2,000 to 30,000.

As described above, the synthesis method of the alkali-soluble acrylic polymer of the component (A) is a copolymerization of (A1) a monomer having a carboxyl group and/or an acid anhydride group, and (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group. The method of (A3) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A4) a monomer mixture containing N-substituted maleimide is simple.

Hereinafter, specific examples of the constituent monomers of the component (A) are listed, but they are not limited thereto.

Examples of the monomer having an unsaturated carboxylic acid as the component (A1) include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl)phthalate, and mono-( 2-(Methethyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxybenzene Further, as the monomer having an unsaturated carboxylic anhydride, acrylamide or the like may, for example, be maleic anhydride or itaconic anhydride.

Examples of the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group as the component (A2) include, for example, p-hydroxystyrene, α-methyl-p-hydroxystyrene, and N-hydroxyphenylmaleimide. , N-hydroxyphenyl acrylamide, N-hydroxyphenyl methacrylamide, p-hydroxyphenyl acrylate, p-hydroxyphenyl methacrylate, etc., these may be used alone or in combination of two or more. . Among them, a monomer selected from the group consisting of p-hydroxyphenyl acrylate and p-hydroxyphenyl methacrylate is preferred.

Examples of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in (A3) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 2,3-di. Hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxyl Butyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, 5-propenyloxy-6-hydroxynordecene-2-carboxylic acid group (Carboxylic)-6 - lactones, etc.

Examples of the (A4)N-substituted maleimide compound include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

Further, in the present invention, when the acrylic polymer of the component (A) is obtained, other monomers copolymerizable with the above monomers (A1) to (A4) may be used in combination. Specific examples of such a monomer include an acrylate compound, a methacrylate compound, a maleimide, an acrylamide compound, an acrylonitrile, a styrene compound, and a vinyl compound. Hereinafter, specific examples of the other monomer are listed, but are not limited thereto.

Examples of the acrylate compound include methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl methacrylate, and phenyl acrylate. Ester, epoxy propyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isodecyl acrylate, 2- Methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy butyl Acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl -8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, and the like.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and fluorenyl group. Acrylate, mercaptomethyl methacrylate, phenyl methacrylate, propylene methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl Acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, 2-methoxyethyl methacrylate, methoxy triethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-gold Alkyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloxy)ethyl ester , poly(ethylene glycol) ethyl ether methacrylate, and the like.

Examples of the acrylamide compound include N-methyl acrylamide, N-methyl methacrylamide, N,N-dimethyl decylamine, and N,N-dimethyl methacrylate. Amine, N-methoxymethylpropenylamine, N-methoxymethylmethacrylamide, N-butoxymethylpropenylamine, N-butoxymethylmethacrylamide, etc. .

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl epoxypropyl ether, and 3-vinyl group. -7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxy Compounds, etc.

The styrene compound is a styrene having no hydroxyl group, and examples thereof include styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

The method for obtaining the alkali-soluble acrylic polymer used in the present invention is not particularly limited, and for example, the alkali-soluble monomers (A1) to (A4), other monomers which are copolymerizable, and the desired polymerization are used. The solvent in which the initiator or the like is present is obtained by polymerization at a temperature of 50 to 110 ° C. In this case, the solvent to be used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. Specific examples thereof include the solvents described in the solvent (D) described later.

The acrylic polymer having a specific functional group thus obtained is usually in a state of being dissolved in a solvent.

Further, a solution of the specific copolymer obtained as described above is placed under stirring with diethyl ether or water, and reprecipitated and filtered. After washing the resulting precipitate, it can be a powder of a specific copolymer by normal temperature or under reduced pressure at normal temperature or under reduced pressure. By such an operation, the polymerization initiator or the unreacted monomer which coexists with the specific copolymer can be removed, and as a result, the powder of the purified specific copolymer can be obtained. In the case where the purification cannot be sufficiently performed in one operation, the obtained powder may be redissolved in a solvent, and the above operation may be repeated.

In the present invention, the powder of the specific copolymer described above may be used as it is, or the powder may be redissolved, for example, in the solvent (D) described later as a solution. Can also be used.

Further, in the present invention, the acrylic polymer of the component (A) may be a mixture of a plurality of specific copolymers.

<(B) component>

The 1,2-quinonediazide compound as the component (B) is a compound having either a hydroxyl group or an amine group or a hydroxyl group or an amine group, and these hydroxyl groups or amine groups (having both a hydroxyl group and an amine group) In the total amount of the above, it is preferably used in an amount of 10 to 100 mol%, particularly preferably 20 to 95 mol%, esterified with 1,2-quinonediazidesulfonic acid, or decylamine. Compound.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcin, catechol, methyl gallate, and gallic acid. Ethyl acetate, 1,3,3-cis (4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane , 4,4'-dihydroxyphenyl hydrazine, 4,4-hexafluoroisopropylidene diol, 1,1,1-cis (4-hydroxyphenyl)ethane, 4,4'-[1- [4-[1-(4-Hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxyl Benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'- Phenolic compound such as pentahydroxybenzophenone, 2,5-bis(2-hydroxy-5-methylbenzyl)methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol , propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate, etc. Aliphatic alcohols.

Further, examples of the compound containing an amine group include benzene. Amine, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-benzene Amine, 4,4'-diaminophenylmethane, 4,4'-diaminodiphenyl ether, aniline or the like, aminocyclohexane.

Further, examples of the compound containing both a hydroxyl group and an amine group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcin, and 2,3-diaminophenol. , 2,4-diaminophenol, 4,4'-diamino-4"-hydroxytriphenylmethane, 4-amino-4',4"-dihydroxytriphenylmethane, bis(4- Amino-3-carboxy-5-hydroxyphenyl)ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5 Aminophenols such as -hydroxyphenyl)propane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane, 2-aminoethanol, 3-aminopropanol An alkanolamine such as 4-aminocyclohexanol.

These 1,2-quinonediazide compounds may be used singly or in combination of two or more.

The content of the component (B) of the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, even more preferably 100 parts by mass of the component (A). Good for 10~40 parts by mass. When the amount is less than 5 parts by mass, the difference in the dissolution rate of the developing portion from the exposed portion and the unexposed portion of the positive photosensitive resin composition is reduced, and the patterning by development is difficult. In addition, when the amount is more than 100 parts by mass, the sensitivity of the 1,2-quinonediazide compound may not be sufficiently decomposed by exposure for a short period of time, or the transparency of the cured film may be lowered by absorption of light by the component (B). .

<(C) component>

The component (C) is a crosslinking agent, and more specifically, a compound having a structure in which a crosslinking structure can be formed by thermal reaction with the component (A). Although specific examples are given below, they are not limited thereto. The thermal crosslinking agent is preferably, for example, a crosslinkable compound selected from (C1) having two or more substituents selected from the group consisting of an alkoxymethyl group and a hydroxymethyl group, or (C2) represented by the formula (2) described later. Associated compounds. These crosslinking agents may be used singly or in combination of two or more.

The crosslinkable compound having two or more substituents selected from the group consisting of an alkoxymethyl group and a hydroxymethyl group (C1) is a cross-linking reaction which is subjected to a dehydration condensation reaction when exposed to a high temperature at the time of thermal curing. Examples of such a compound include a compound such as alkoxymethylated acetylene urea, alkoxymethylated benzene melamine, and alkoxymethylated melamine, and a phenol resin (Phenoplast) compound.

Specific examples of the alkoxymethylated acetylene urea include 1,3,4,6-fluorene (methoxymethyl)acetylene urea and 1,3,4,6-fluorene (butoxymethyl). Ethylene acetylene, 1,3,4,6-indole (hydroxymethyl) acetylene urea, 1,3-bis(hydroxymethyl) urea, 1,1,3,3-indole (butoxymethyl) urea 1,1,3,3-肆(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidinone, and 1,3-double ( Methoxymethyl)-4,5-dimethoxy-2-imidazolidinone and the like. As a commercial product, a compound such as an acetylene urea compound (trade name: Cymel (registered trademark) 1170, Powder link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., and a methylated urea resin (trade name: UFR (trade name: UFR) Registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (stock) urea / formamide resin (high condensation Type, trade name: BECKAMINE (registrar Standard) J-300S, same as P-955, same as N).

Specific examples of the alkoxymethylated benzene melamine include tetramethoxymethylbenzene melamine and the like. As a commercial item, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), (share), and chemical industry (trade name: NIKALAC (registered trademark) BX-4000, same as BX-37, Same as BL-60, same as BX-55H).

Specific examples of the alkoxymethylated melamine include hexamethoxymethylmelamine and the like. As a commercial item, a methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, the same 301, the same 303, the same 350) manufactured by Mitsui Cytec Co., Ltd., and a butoxymethyl type melamine compound are mentioned. (trade name: My coat (registered trademark) 506, 508), methoxymethyl melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade name: NIKALAC (registered trademark) MW-30, same MW-22, same MW-11 , the same MW-100LM, with MS-001, with MX-002, with MX-730, with MX-750, with MX-035), butoxymethyl melamine compound (trade name: NIKALAC (registered trademark) MX -45, same as MX-410, with MX-302).

Further, it may be a compound obtained by condensing a melamine compound, a urea compound, an acetylene urea compound, and a benzene melamine compound in which a hydrogen atom of such an amine group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound produced from the melamine compound and the benzene melamine compound described in U.S. Patent No. 6,323,310 can be cited. As a commercial item of the above-mentioned melamine compound, Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.) or the like can be cited as the aforementioned benzoguanamine compound. Commercially available products include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

Specific examples of the phenol resin-based compound include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, and 2,6-bis(hydroxymethyl)-4-. Methoxyphenol, 3,3',5,5'-indole (hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methyl-bis(2-hydroxy-5-- Benzomethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methyl-bis[2-methyl-6 -hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-extended methyl bis[2,6- Bis(hydroxymethyl)phenol], 2,6-bis(methoxymethyl)phenol, 2,6-bis(methoxymethyl)cresol, 2,6-bis(methoxymethyl) 4-methoxyphenol, 3,3',5,5'-fluorene (methoxymethyl)biphenyl-4,4'-diol, 3,3'-methyl-bis(2- Methoxy-5-methylbenzyl alcohol), 4,4'-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4'-extension Bis[2-methyl-6-methoxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], 4 , 4'-methyl bis[2,6-bis(methoxymethyl)phenol] and the like. It can also be obtained as a commercial item, and as a specific example, 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (above) For Asahi Organic Materials Industry Co., Ltd.).

Further, as the component (C1), N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butyl may also be used. A polymer produced by a hydroxymethyl group such as oxymethylmethacrylamide or an alkoxymethyl group substituted with an acrylamide compound or a methacrylamide compound.

Examples of such a polymer include poly(N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, and N-hydroxymethyl methacrylamide. Copolymer with methyl methacrylate, copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and N-butoxymethyl acrylamide and benzyl methyl a copolymer of acrylate and 2-hydroxypropyl methacrylate, and the like. Such a polymer has a weight average molecular weight of 1,000 to 50,000, preferably 1,500 to 20,000, more preferably 2,000 to 10,000.

These crosslinkable compounds can be used individually or in combination of 2 or more types.

The content of the component (C1) in the crosslinking agent of the positive photosensitive resin composition of the present invention is preferably 5 to 50 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the component (A). 10 to 40 parts by mass. When the amount is less than 5 parts by mass, the heat resistance after metal sputtering may be lowered or the step flatness may be lowered. Moreover, when it exceeds 50 mass parts, there exists a possibility that the adhesiveness at the time of image development may fall, or the sensitivity may fall.

Further, the positive photosensitive resin composition of the present invention may contain a crosslinkable compound represented by the formula (2) as the component (C2).

(wherein k represents an integer from 2 to 10, m represents an integer from 0 to 4, and R ¹ represents an organic group of k valence).

The component (C2) is not particularly limited as long as it is a compound having a cycloolefin oxide structure represented by the formula (2). Specific examples thereof include commercially available products represented by the following formulas C2-1 and C2-2, or the following.

As a commercial item, Epolead GT-401, GT-403, GT-301, GT-302, CELLOXIDE 2021, CELLOXIDE 3000 (product name of Daicel Chemical Industry Co., Ltd.), and alicyclic epoxy resin are mentioned. Namely, Denacol EX-252 (trade name manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179 (above, trade name of CIBA-GEIGY AG), Araldite CY-182, same CY-192, and CY-184 (above, CIBA-GEIGY AG product name), Epiclon 200, same 400 (above, DIC (product) product name), Epikote 871, same 872 (above, oiled shell epoxy (stock) product name), ED-5661 ED-5662 (above, product name of Celanese coating). Again, this cross-linking The compounds may be used alone or in combination of two or more.

Among these, from the viewpoints of process resistance and transparency of heat resistance, solvent resistance, long-time baking resistance, and the like, the above formula C2-1 and formula having a cyclohexene oxide structure are preferred. Compound represented by C2-2, Epolead GT-401, same GT-403, same GT-301, same GT-302, CELLOXIDE 2021, CELLOXIDE 3000.

The content of the component (C2) is 3 to 50 parts by mass, preferably 7 to 40 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the component (A). . When the content of the crosslinkable compound is small, the crosslinking density formed by the crosslinkable compound is insufficient, and heat resistance, solvent resistance, resistance to long-time firing, and the like after formation of the pattern are not obtained. The situation of the effect of the promotion. In addition, when it is more than 50 parts by mass, there is a crosslinkable compound which is not crosslinked, and the heat resistance, solvent resistance, resistance to long-time baking, and the like after formation of the pattern are lowered, and the photosensitive resin composition is preserved. The situation of deterioration in stability.

<(D) Solvent>

The solvent (D) used in the present invention dissolves the component (A), the component (B), and the component (C), and dissolves the component (E) to the component (F) described later as desired. The type and structure of the solvent which dissolves the energy are not particularly limited.

Examples of such a solvent (D) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol alone. Methyl ether, diethylene glycol monoethyl ether, propane Alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3 -methyl-2-pentanone, 2-pentanone, 2-hexanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl ester, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Ester, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N , N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used singly or in combination of two or more.

Among these (D) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. It is more preferable from the viewpoint of good coating properties and high safety. These solvents are generally used as solvents for photoresist materials.

<(E) component>

The component (E) is a surfactant. In the positive photosensitive resin composition of the present invention, for the purpose of improving the coatability, the surfactant may be further contained in a range that does not impair the effects of the present invention.

The surfactant of the component (E) is not particularly limited, and examples thereof include a fluorine-based surfactant, a ruthenium-based surfactant, and a nonionic surfactant. As such a surfactant, for example, Commercial products such as Sumitomo 3M (share), DIC (share) or AGC Qingmei Chemical (share). These commercial products are convenient because they are easy to obtain. Specific examples thereof include Poly Fox PF-136A, 151, 156A, 154N, 159, 636, 6320, 656, 6520 (manufactured by Omnova), Megafac R30, R08, R40, R41, R43, F251, F477, and F552. , F553, F554, F555, F556, F557, F558, F559, F560, F561, F562, F563, F565, F567, F570 (DIC (share) system), FC4430, FC4432 (Sumitomo 3M (share) system), Asahi guard Fluorine such as AG710, Surflon S-386, S-611, S-651, (AGC Qingmei Chemical Co., Ltd.), Ftergent FTX-218, DFX-18, 220P, 251, 212M, 215M (manufactured by Neos) Surfactant, BYK-300, 302, 306, 307, 310, 313, 315, 320, 322, 323, 325, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377 , 378, 3455 (BYK Chemie Japan (stock) system), SH3746, SH3749, SH3771, SH8400, SH8410, SH8700, SF8428 (Toray Dow Corning. Oxygen (manufactured by the company), KF-351, KF-352, KF- 353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011, KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.) and other oxime-based surfactants.

The surfactant of the component (E) may be used singly or in combination of two or more.

When the surfactant is used, the content thereof is usually 0.01 to 1.0 part by mass, preferably 0.02 to 0.8 part by mass, based on 100 parts by mass of the component (A). Even if the amount of surfactant used in component (E) is set to exceed 1.0 The amount of the mass fraction, the improvement effect of the above coating property becomes dull, and it becomes uneconomical. When it is 0.01 part by mass or less, there is a case where the effect of improving the coating property is not exhibited.

<(F) component>

The component (F) is a adhesion promoter. The positive photosensitive resin composition of the present invention may have an adhesion promoter added for the purpose of improving the adhesion to the substrate after development. Specific examples of such a adhesion promoter include chlorodecanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane. Methyl methoxy decane, dimethyl diethoxy decane, methyl dimethoxy decane, dimethyl vinyl ethoxy decane, diphenyl dimethoxy decane, phenyl triethoxy decane , vinyl trichloromethane, γ-aminopropyl triethoxy decane, γ-methyl propylene methoxy propyl triethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, Γ-glycidoxypropyltriethoxydecane, γ-(N-piperidinyl)propyltriethoxydecane, 3-ureidopropyltriethoxydecane, 3-ureidopropyltrimethoxy Alkoxy decanes such as decane, hexamethyldioxane, N,N'-bis(trimethyldecyl)urea, dimethyltrimethyldecylamine, trimethyldecyl imidazole, etc. Azapines, benzotriazoles, benzimidazoles, oxazoles, imidazoles, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, urazoles, thiouracils, thiol groups Imidazole Heterocyclic compound pyridine, etc., or 1,1-dimethyl urea, 1,3-dimethyl urea, urea, etc., or thiourea compounds.

The above adhesion promoter, for example, Shin-Etsu Chemical Industrial (stock) system, made by Momentive Performance Materials Worldwide Inc. or Toray Dow Corning. A commercially available product such as a oxime (share) system, such a commercially available product can be easily obtained.

The component (F) may be used alone or in combination of two or more kinds of the above-mentioned adhesion promoters.

Among these (F) components, alkoxy decane (i.e., a decane coupling agent) is preferred because it can provide good adhesion.

The amount of the adhesion promoter added is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component (A). When the amount is 20 parts by mass or more, the sensitivity may be lowered. When the amount is less than 0.1 part by mass, the effect of the adhesion promoter may not be obtained.

<Other additives>

Further, the positive photosensitive resin composition of the present invention may contain a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, or a polyhydric phenol or a polycarboxylic acid, if necessary, without impairing the effects of the present invention. Such as a dissolution promoter and the like.

<Positive Photosensitive Resin Composition>

The positive photosensitive resin composition of the present invention is a copolymer obtained by copolymerizing (A1) to (A4) of the component (A), and a 1,2-quinonediazide compound of the component (B), (C) The crosslinking agent of the component is dissolved in the solvent (D), and each of them may further contain the surfactant of the component (E) and the adhesion of the component (F). One or more of the accelerators and other additives.

Among them, preferred examples of the positive photosensitive resin composition of the present invention are as follows.

[1]: According to 100 parts by mass of the component (A), it contains 5 to 100 parts by mass of the component (B) and 5 to 50 parts by mass of the component (C), and these components are dissolved in the positive photosensitive property of the solvent (D). Resin composition.

[2]: The composition of the above [1] further contains 0.01 to 1.0 part by mass of the positive photosensitive resin composition of the component (E), based on 100 parts by mass of the component (A).

[3] The composition of the above [1] or [2] further contains 0.1 to 20 parts by mass of the positive photosensitive resin composition of the component (F), based on 100 parts by mass of the component (A).

The ratio of the solid content of the positive photosensitive resin composition of the present invention is not particularly limited as long as the components are uniformly dissolved in the solvent, but it is, for example, 1 to 80% by mass, for example, 5 to 60% by mass. Or 10~50% by mass. The solid content herein refers to a solvent (D) which is removed from the entire composition of the positive photosensitive resin composition.

The preparation method of the positive photosensitive resin composition of the present invention is not particularly limited. However, as a preparation method, for example, the component (A) (alkali-soluble resin) is dissolved in the solvent (D), and the solution is B) The 1,2-quinonediazide compound of the component and the crosslinking agent of the component (C) are mixed in a specific ratio to form a homogeneous solution, or at an appropriate stage of the preparation method, and may be further added if necessary ( A method of mixing the components (surfactant), (F) component (adhesion promoter), and other additives.

In the preparation of the positive photosensitive resin composition of the present invention, a solution of a copolymer obtained by polymerization in a solvent (D) may be used as it is. In this case, the solution of the component (A) is as described above. When the (B) component, the component (C), and the like are added in the same manner to form a homogeneous solution, the concentration adjustment may be further added, and the (D) solvent may be further added. In this case, the solvent (D) used in the formation of the specific copolymer and the (D) solvent used for the concentration adjustment in the preparation of the positive photosensitive resin composition may be the same or different.

Further, the solution of the prepared positive photosensitive resin composition is preferably filtered using a filter having a pore diameter of about 0.2 μm or the like.

<Coating film and hardened film>

The positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a ruthenium/yttrium oxide-coated substrate, a tantalum nitride substrate, a coated metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, or the like). The coating is performed by spin coating, flow coating, roll coating, crack coating, crack followed by spin coating, inkjet coating, or the like. Thereafter, a coating film can be formed by preliminary drying by a hot plate or an oven. Thereafter, the coating film is subjected to heat treatment to form a positive photosensitive resin film.

As conditions for the heat treatment, for example, a heating temperature and a heating time which are appropriately selected from a temperature of 70 ° C to 160 ° C and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably from 80 ° C to 140 ° C for 0.5 to 10 minutes.

In addition, the film thickness of the positive photosensitive resin film formed of the positive photosensitive resin composition is, for example, 0.1 to 30 μm, for example, 0.2 to 10 μm, and further, for example, 0.3 to 8 μm.

The coating film obtained as described above is irradiated with ultraviolet light or the like by a mask having a specific pattern, and is developed by an alkali developing solution to wash out the exposed portion to obtain a relief pattern having a sharp end surface.

Examples of the alkaline developing solution that can be used include an aqueous solution of an alkali metal hydroxide such as potassium carbonate, sodium carbonate, potassium hydroxide or sodium hydroxide, tetramethylammonium hydroxide or tetraethylammonium hydroxide. An aqueous solution of a fourth-order ammonium hydroxide such as choline or an aqueous solution of an amine such as ethanolamine, propylamine or ethylenediamine. Further, a surfactant or the like may be added to the developer such as this.

In the above, the tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developing solution, and even if the photosensitive developer composition of the present invention is used, the alkaline developing solution does not cause swelling or the like. The problem can be a good development.

Further, as the developing method, a liquid pool method, a dip coating method, a shaking dipping method, or the like can be used. The development time at this time is usually 15 to 180 seconds.

After development, the positive photosensitive resin film is washed by running water, for example, for 20 to 120 seconds, and then air-dried by using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate. A film formed by a pattern.

Next, the film is formed for the pattern, and is subjected to post-baking for thermal hardening, specifically, by using a hot plate, an oven, or the like. It is excellent in heat resistance, transparency, flatness, low water absorption, chemical resistance, and the like, and has a film having a good relief pattern.

As the post-baking, a heating temperature in a range selected from the range of 140 ° C to 270 ° C is generally employed, and the case is 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven.

Then, by this post-baking, a cured film which is a target and has a good pattern shape can be obtained.

As described above, the positive-type photosensitive resin composition of the present invention can form a coating film having a high-preservation property and a sufficiently high sensitivity, and having a very small film thickness in the unexposed portion during development, and having a fine pattern.

Further, the cured film obtained from the coating film has a feature that the pattern residue is small. Therefore, it can be suitably used for various films of a liquid crystal display or an organic EL display, for example, it is suitable for use with an interlayer insulating film, a protective film, an insulating film, etc., and is used for an array planarizing film of a TFT type liquid crystal element.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

[Abbreviation used in the embodiment]

The meanings of the abbreviations used in the following examples are as follows.

MAA: Methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

PQMA: 4-hydroxyphenyl methacrylate

CHMI: N-cyclohexylmaleimide

AIBN: azobisisobutyronitrile

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

QD: 1 mol of α,α,α'-parade (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 1,2-naphthoquinone-2-diazide-5-sulfonate Compound synthesized by condensation reaction of mercapto chloride 1.5 mol

CEL-2021P: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate

GT-401: Butane tetracarboxylic acid Tetrakis(3,4-epoxycyclohexylmethyl) modified ε-caprolactone

MPTS: γ-methacryloxypropyltrimethoxydecane

R30: DIC (share) system Megafac R-30 (trade name)

[Determination of number average molecular weight and weight average molecular weight]

The number average molecular weight and the weight average molecular weight of the specific copolymer and the specific crosslinked body obtained by the following synthesis examples were determined by using a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation. Tetrahydrofuran was measured by flowing into the column at a flow rate of 1 ml/min (column temperature: 40 ° C) to dissolve it. In addition, the following average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>

As a monomer component constituting the specific copolymer, 12.0 g of MAA, 21.0 g of CHMI, 27.0 g of MMA, and 3.8 g of AIBN were used as a radical polymerization initiator, and these were used in the solvent PGMEA 95.8 g by The polymerization was carried out at a temperature of 60 ° C to 100 ° C to obtain a solution of a base-soluble acrylic polymer component (specific copolymer) of Mn 4,500 and Mw 7,800 (specific copolymer concentration: 40.0% by mass). (P1)

<Synthesis Example 2>

As the monomer component constituting the specific copolymer, MAA 4.2 g, CHMI 21.0 g, HEMA 27.6 g, MMA 7.2 g were used, and AIBN 3.8 g was used as a radical polymerization initiator, and this was used in the solvent PGME 95.8 g. The solution was subjected to a polymerization reaction at a temperature of 60 ° C to 100 ° C to obtain a solution of a base-soluble acrylic polymer component (specific copolymer) of Mn 4,200 and Mw 7,500 (specific copolymer concentration: 40.0% by mass). (P2)

<Synthesis Example 3>

As a monomer component constituting the specific copolymer, MAA 11.0 g, CHMI 20.9 g, PQMA 15.0 g, MMA 12.9 g, and AIBN 2.9 g as a radical polymerization initiator were used, and the solvent was PGMEA 95.4 g. By carrying out a polymerization reaction at a temperature of 60 ° C to 100 ° C to obtain a solution of an alkali-soluble acrylic polymer component (specific copolymer) of Mn 5,400 and Mw 10,000 (specific copolymer concentration: 40.0 mass) %). (P3)

<Synthesis Example 4>

As a monomer component constituting the specific copolymer, 7.8 g of MAA, 21.0 g of CHMI, 15.0 g of HEMA, 1.2 g of PQMA, and 15.0 g of MMA were used, and AIBN 3.8 g was used as a radical polymerization initiator. In a solvent PGMEA 95.8g, a solution of an alkali-soluble acrylic polymer component (specific copolymer) of Mn4, 100, Mw7, 600 is obtained by polymerization at a temperature of 60 ° C to 100 ° C (specific copolymer concentration: 40.0% by mass). (P4)

<Example 1>

As the alkali-soluble resin solution, QD (hereinafter referred to as sensitizer), a crosslinkable compound, a surfactant, a adhesion aid, and a solvent are added to the specific copolymer solution (P4) obtained in the above Synthesis Example 4, and then The positive photosensitive composition of the composition shown in Table 1 was prepared by stirring at room temperature for 8 hours.

<Comparative Example 1 to Comparative Example 3>

The alkali-soluble resin solution was added to the specific copolymer solution (P1 to P3) obtained in the above Synthesis Examples 1 to 3 by adding a photosensitizer, a crosslinkable compound, a surfactant, a adhesion aid, and a solvent at room temperature. After stirring for 8 hours, a positive photosensitive composition of the composition shown in Table 1 was prepared.

In each of the positive photosensitive resin compositions of the obtained Example 1 and Comparative Example 1 to Comparative Example 3, the sensitivity, the adhesion at the time of development, and the evaluation of the residue in the pattern at the time of thermal curing were evaluated as follows. The method is carried out.

[Evaluation of Sensitivity]

The positive photosensitive resin composition was applied onto a tantalum wafer by a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film having a film thickness of 4.0 μm. The film thickness was measured using F20 by FILMETRICS. The coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW/cm ² at 365 nm for a predetermined period of time by a UV irradiation apparatus PLA-600FA manufactured by Canon. Thereafter, the solution was immersed in an aqueous solution of 0.4% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 90 seconds, and then developed, and then washed with ultrapure water for 20 seconds. The minimum exposure amount (mJ/cm ² ) at which the dissolution residue was exhausted in the exposed portion was taken as the sensitivity.

[Evaluation of adhesion]

The positive photosensitive resin composition was applied onto a tantalum wafer by a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film. The coating film was irradiated with ultraviolet rays having a light intensity of 5.5 mW/cm ² at 365 nm for a predetermined period of time through a mask. A pattern in which contact holes of 10 μm × 10 μm were arranged at intervals of 130 μm was prepared. Thereafter, the solution was immersed in an aqueous solution of 0.4% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 90 seconds, and then washed with ultrapure water for 90 seconds. Thereafter, CLEANOVENPVHC-210 manufactured by ESPEC Co., Ltd. was baked at 230 ° C for 30 minutes to form a cured film having a film thickness of about 4.0 μm. Thereafter, the adhesion of the produced open pattern of 10 μm × 10 μm was evaluated using a day stand-emission type scanning electron microscope S-4100. It is judged as good (○) for the open pattern without the skirt floating completely, and the float is judged to be poor (×).

[Evaluation of residue in the pattern]

As described above, the residue in the 10 μm × 10 μm open pattern prepared by the evaluation of the adhesion was confirmed by a Japanese-based emission-emitting scanning electron microscope S-4100. At this time, the residue in the open pattern was judged to be good (○), and the remaining one was judged to be inferior (×).

[Results of the assessment]

The results of the above evaluations are shown in Table 2 below.

It can be judged from the results shown in Table 2 that the positive of the embodiment 1 The photosensitive resin composition is high in sensitivity and has sufficient adhesion during development. Further, it is shown that the residue in the pattern after the formation of the pattern has no excellent characteristics at all.

[Industrial availability]

The positive-type photosensitive resin composition of the present invention is suitable as a cured film of a protective film, a flattening film, an insulating film, or the like which is formed on various displays such as a thin film transistor (TFT) liquid crystal display device or an organic EL device. The material is particularly suitable as an interlayer insulating film for forming a TFT-type liquid crystal element, a protective film for a color filter, an array flattening film, an uneven film on the lower side of a reflective film of a reflective display, an insulating film of an organic EL element, or the like. The material is further suitable as a variety of electronic materials such as microlens materials.

Claims (11)

A positive photosensitive resin composition containing the following components (A), (B), (C), and (D) a solvent, and component (A): (A1) to (A4) An alkali-soluble acrylic copolymer (A1) obtained by copolymerization, an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, and (A3) having a hydroxyalkyl group and Monomer of polymerizable unsaturated group, (A4)N substituted maleimide compound; (B) component: 1,2-quinonediazide (Quinonediazide) compound, (C) component: crosslinker (D) Solvent. The positive photosensitive resin composition of claim 1, wherein (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group is p-hydroxyphenyl (meth) acrylate. The positive photosensitive resin composition of claim 1 or 2, wherein the number average molecular weight of the alkali-soluble acrylic polymer of the component (A) is 2,000 to 30,000 in terms of polystyrene. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the component (B) is 5 to 100 parts by mass based on 100 parts by mass of the component (A). The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the component (C) is 5 to 50 parts by mass based on 100 parts by mass of the component (A). A positive photosensitive resin composition according to any one of claims 1 to 5 In the component (E), the surfactant is further contained in an amount of 0.01 to 1.0 part by mass based on 100 parts by mass of the component (A). The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the adhesion promoter further contains 0.1 to 20 masses as the component (F), based on 100 parts by mass of the component (A). Share. A cured film obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 7. A display element having a cured film as claimed in claim 8. A display element having the cured film of claim 8 as an array flattening film for a display. A display element having a cured film as claimed in claim 8 as an interlayer insulating film.