KR20170092542A - Positive-acting photosensitive resin composition - Google Patents

Abstract

[PROBLEMS] To provide a positive photosensitive resin composition capable of forming a pattern with high sensitivity while maintaining the adhesiveness at the time of development, and capable of forming a cured film having little residue in the pattern.
[Solution] A positive photosensitive resin composition comprising the following components (A), (B), (C), and (D)
(A): an alkali-soluble acrylic copolymer (A1) obtained by copolymerizing the following (A1) to (A4): unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, (A3) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A4) an N-substituted maleimide compound; (B): 1,2-quinonediazide compound, (C) component: crosslinking agent; (D) Solvent.

Description

[0001] POSITIVE-ACTING PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a positive photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a positive-working photosensitive resin composition and a cured film thereof, which are suitable for use as a display material, and various materials using the cured film.

Generally, in a display element such as a thin film transistor (TFT) type liquid crystal display element or an organic EL (electroluminescent) element, a patterned electrode protecting film, a planarizing film, an insulating film and the like are provided. As a material for forming these films, a photosensitive resin composition having a feature that not only the number of steps (steps) for obtaining a required pattern shape is small, but also has sufficient flatness is widely used in the photosensitive resin composition.

The above-mentioned films are required to have good process resistance such as heat resistance, solvent resistance, long time firing resistance and metal sputter resistance, good adhesion to the base (undercoat), and various process conditions It is required to have a large process margin capable of forming a pattern, and furthermore, various characteristics such as high sensitivity, high transparency, and small film unevenness after development are required. From the viewpoint of such required characteristics, up to now, a resin containing a naphthoquinone diazide compound has been widely used as the above-mentioned photosensitive resin composition.

These materials have been proposed to thermally crosslink the formed pattern by adding an epoxy crosslinking agent or by containing a carboxyl group and an epoxy group in the acrylic resin and curing them (Patent Documents 1 and 2). However, when such a resin is used, sufficient sensitivity can not be obtained, leading to deterioration of the throughput (throw-away) in the manufacture of a display. Further, the pattern shape easily changes due to the bake temperature at the time of post-baking, and precise temperature control is required.

Japanese Patent Application Laid-Open No. 2000-103937 Japanese Patent Application Laid-Open No. H4-352101

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a positive photosensitive resin composition capable of forming a pattern with high sensitivity while maintaining adhesion at the time of development, and capable of forming a cured film with little residue in the pattern.

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, they have found the present invention. That is, the present invention relates to the following.

1. A positive-working photosensitive resin composition comprising a component (A), a component (B), a component (C), and a solvent (D).

(A): An alkali-soluble acrylic copolymer obtained by copolymerizing the following (A1) to (A4)

(A1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, (A3) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A4) ;

Component (B): 1,2-quinonediazide compound,

Component (C): Crosslinking agent

(D) Solvent.

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

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

4. The positive photosensitive resin composition as described in any one of 1 to 3 above, wherein the amount of the component (B) is 5 to 100 parts by mass based on 100 parts by mass of the component (A).

5. The positive photosensitive resin composition as described in any one of 1 to 4 above, wherein the amount of 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 as described in any one of 1 to 5 above, which further contains, as a component (E), a surfactant in an amount of 0.01 to 1.0 part by mass per 100 parts by mass of the component (A).

7. The positive photosensitive resin composition as described in any one of 1 to 6 above, which contains, as the component (F), an adhesion promoter in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A).

(8) A cured film obtained by curing the positive photosensitive resin composition as described in any one of (1) to (7) above.

9. A display element having the cured film described in 8 above.

10. A display element having the cured film as described in 8 above as an array planarizing film for display.

11. A display element having the cured film as described in 8 above as an interlayer insulating film.

The positive photosensitive resin composition of the present invention can form a pattern with high sensitivity while maintaining the adhesiveness at the time of development, and can form a cured film having less pattern residue.

The photosensitive resin composition of the present invention is a positive photosensitive resin composition containing the following components (A), (B), (C), and (D)

(A): An alkali-soluble acrylic copolymer obtained by copolymerizing the following (A1) to (A4)

(A1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, (A3) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A4) ;

Component (B): 1,2-quinonediazide compound,

Component (C): Crosslinking agent

(D) Solvent.

Hereinafter, each component will be described in detail.

≪ Component (A) >

(A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, (A3) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A4) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A4) ) N-substituted maleimide compound.

In the present invention, the acrylic polymer is a polymer obtained by using a polymerizable unsaturated group such as an acrylate ester, a methacrylate ester, styrene, or maleimide, that is, a monomer having a polymerizable group having a C = C double bond in its structure It says.

The alkali-soluble acrylic polymer as the component (A) may be an alkali-soluble acrylic polymer, and is not particularly limited as to the skeleton of the main chain of the polymer constituting the acrylic polymer and the kind of the side chain.

If the number average molecular weight of the alkali-soluble acrylic polymer as the component (A) is excessively larger than 30,000, the planarization performance to the step is lowered, while if the number average molecular weight is less than 2,000, And the solvent resistance may be lowered. Therefore, the number average molecular weight is in the range of 2,000 to 30,000.

(A1) a monomer having a carboxyl group and / or an acid anhydride group, (A2) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, (A3) a monomer having a hydroxyl group and a polymerizable unsaturated group, A monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A4) a monomer mixture containing an N-substituted maleimide.

Specific examples of the constituent monomers of the component (A) are shown below, but the present invention is 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- (acryloyloxy) ethyl) phthalate, mono- (2- Examples of monomers having an unsaturated carboxylic acid anhydride such as roloyloxyethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, Acid, itaconic anhydride, and the like.

Examples of the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group of the component (A2) include p-hydroxystyrene,? -Methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N- Phenylacrylamide, N-hydroxyphenylmethacrylamide, p-hydroxyphenyl acrylate, and p-hydroxyphenyl methacrylate. These may be used alone or in combination of two or more. Of these, monomers selected from p-hydroxyphenyl acrylate and p-hydroxyphenyl methacrylate are preferable.

Examples of the monomer (A3) having a hydroxyalkyl group and a polymerizable unsaturated group include, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, Hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, 5-acryloyloxy-6-hydroxy norbornene-2-carboxy-6-lactone, and the like.

(A4) N-substituted maleimide compounds include, for example, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

In the present invention, other monomers copolymerizable with the above monomers (A1) to (A4) can be used in combination with the acrylic polymer of component (A). Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide, acrylamide compounds, acrylonitrile, styrene compounds and vinyl compounds. Specific examples of the other monomers include, but are not limited to, the following.

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, Dodecyl acrylate, dodecyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2- methoxyethyl acrylate, methoxy tri Acrylates such as ethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2- Adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacryl Sites, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) and the like ether acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate Methyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, Methoxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3- Methyl-2-adamantyl methacrylate,? -Butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclo Dehermesse (Ethylene glycol) ethyl ether methacrylate, poly (ethylene glycol) ethyl ether methacrylate, and poly (ethylene glycol) ethyl methacrylate, And the like.

Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methoxymethylacrylamide, N -Methoxymethyl methacrylamide, N-butoxymethylacrylamide, N-butoxymethyl methacrylamide and the like.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [ 4.1.0] heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

Examples of the styrene compound include styrene having no hydroxy group such as styrene,? -Methylstyrene, chlorostyrene, and bromostyrene.

The method for obtaining the alkali-soluble acrylic polymer to be used in the present invention is not particularly limited. For example, a method in which the alkali-soluble monomers (A1) to (A4), the other copolymerizable monomers and the polymerization initiator , And polymerizing at a temperature of 50 to 110 캜. Here, 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 the specific functional group. Specific examples include the solvents described in the solvent (D) described later.

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

The solution of the specific copolymer thus obtained may be re-precipitated by the addition of diethyl ether, water or the like with stirring, and the resultant precipitate may be filtered and washed and then dried at room temperature or under reduced pressure or by heating and drying, It can be a powder of a specific copolymer. Through such operations, the polymerization initiator coexisting with the specific copolymer and the unreacted monomer can be removed, and as a result, the purified specific copolymer powder can be obtained. When the powder can not be sufficiently purified by 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 may be used as it is, or the powder may be used as a solution state by, for example, reusing it in a solvent (D) described later.

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

≪ Component (B) >

The 1,2-quinonediazide compound as the component (B) is a compound having either a hydroxyl group or an amino group or a compound having both a hydroxyl group and an amino group. The hydroxyl group or the amino group (when both of the hydroxyl group and the amino group are present, The total amount thereof), preferably 10 to 100 mol%, particularly preferably 20 to 95 mol%, is esterified or amidated with 1,2-quinonediazide sulfonic acid.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxyphenylsulfone, (4-hydroxyphenyl) ethane, hexafluoroisopropylidene diphenol, 1,1,1-tris (4-hydroxyphenyl) Methylethyl] phenyl] ethylidene] bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2 ', 3,4,4'-pentahydroxybenzophenone, 2,5-bis (2-hydroxy-5-methylbenzyl) Phenol compounds, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol , There may be mentioned the 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, aliphatic alcohols such as 2-butoxy-propanol, ethyl lactate, lactic acid butyl.

Examples of the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m- p-phenylenediamine, 4,4'-diaminophenylmethane, 4,4'-diaminodiphenyl ether, and aminocyclohexane.

Furthermore, examples of the compound containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, Diaminophenol, 4,4'-diamino-4''-hydroxytriphenylmethane, 4-amino-4 ', 4 "-dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2 , 2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane and the like, alkanolamines such as 2-aminoethanol, 3-aminopropanol and 4-aminocyclohexanol .

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

The content of the component (B) in 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, more preferably 5 to 100 parts by mass, And preferably 10 to 40 parts by mass. When the amount is less than 5 parts by mass, the difference in dissolution rate between the exposed portion of the positive photosensitive resin composition and the developing solution of the unexposed portion becomes small, and patterning due to development may be difficult. On the other hand, when the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time, so that the sensitivity is lowered, or when the component (B) absorbs light and the transparency of the cured film is lowered .

≪ Component (C) >

The component (C) is a crosslinking agent, and more specifically, a compound having a structure capable of forming a crosslinking structure by thermal reaction with the component (A). Hereinafter, the present invention is not limited to these specific examples. The thermal crosslinking agent is preferably selected from, for example, a crosslinkable compound having at least two substituents selected from (C1) an alkoxymethyl group and a hydroxymethyl group, and (C2) a crosslinkable compound represented by the following formula (2) Do. These crosslinking agents may be used alone or in combination of two or more.

When a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group of the component (C1) is exposed to a high temperature during thermal curing, the crosslinking reaction proceeds by a dehydration condensation reaction. Such compounds include, for example, compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast-based compounds.

Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) (Methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis ) -4,5-dimethoxy-2-imidazolidinone. As a commercial product, a compound such as a glycoluril compound (trade name: Cymel (registered trademark) 1170 and Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., a methylation urea resin (trade name: UFR (registered trademark) 65) (Trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), a urea / formaldehyde resin J-300S, P-955, N).

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. (Trade name: Nikarac (registered trademark) BX-4000, copper BX-37, copper BL-60, manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) BX-55H), and the like.

Specific examples of the alkoxymethylated melamine include, for example, hexamethoxymethylmelamine and the like. As a commercial product, a methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, Copper 301, Copper 303, Copper 350) manufactured by Mitsui Cytec Ltd., a butoxymethyl type melamine compound (trade name: 506 and 508 manufactured by Nippon Denshoku Industries Co., Ltd.), a methoxymethyl type melamine compound (trade name: NIKARAK (registered trademark) MW-30, copper MW-22, copper MW-11, copper MW-100LM, copper MS- (Trade name: NIKARAK (registered trademark) MX-45, MX-410, MX-302) and the like .

A compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound prepared from a melamine compound and a benzoguanamine compound described in U.S. Patent 6,323,310 can be mentioned. Commercially available products of the above-mentioned melamine compounds include trade names: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec) and the like. Commercially available products of the benzoguanamine compound include Cymel (registered trademark) 1123 (Manufactured by Mitsui Cytec Co., Ltd.).

Specific examples of the phenoplast compound include, for example, 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, 2,6- 4-methoxyphenol, 3,3 ', 5,5'-tetrakis (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy- Methyl-6-hydroxymethylphenol], 4,4'- (1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol] Bis (hydroxymethyl) phenol], 4,4'- (1-methylethylidene) bis [2,6-bis Bis (methoxymethyl) cresol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 3,3 ', 5,5'- (Methoxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-methoxy-5-methylbenzene methanol), 4,4 '- (1-methylethylidene) Bis [2-methyl-6-methoxymethylphenol], 4,4'-methylenebis [2-methyl-6-methoxymethylphenol] Ethylidene) bis [2,6-bis (methoxymethyl) phenol] and 4,4'-methylenebis [2,6-bis (methoxymethyl) phenol]. DM-BIPC-F, DM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (hereinafter referred to as " Manufactured by Asahi Organic Materials Industry Co., Ltd.).

Furthermore, examples of the component (C1) include hydroxymethyl groups such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide and N-butoxymethylmethacrylamide, or alkoxymethyl groups Or a polymer prepared by using a methacrylamide compound may also be used.

Such polymers include, for example, poly (N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate, A copolymer of N-ethoxymethylmethacrylamide and benzylmethacrylate, and a copolymer of N-butoxymethylacrylamide and benzylmethacrylate and 2-hydroxypropylmethacrylate. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

These crosslinkable compounds may be used alone or in combination of two or more.

When the component (C1) is selected as the crosslinking agent in the positive photosensitive resin composition of the present invention, the content is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the component (A) 40 parts by mass. If the amount is less than 5 parts by mass, the heat resistance after the metal sputtering may be lowered or the stepwise planarization property may be lowered. If it exceeds 50 parts by mass, there is a possibility that the adhesion at the time of development is lowered and the sensitivity is lowered.

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

[Chemical Formula 1]

(Wherein k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R ¹ represents a k-valent organic group)

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

(2)

(3)

Examples of commercially available products include EPOLED GT-401, GT-403, GT-301, GT-302, Celloxide 2021 and Celllock 3000 (trade names, manufactured by Daicel Chemical Industries, (Commercially available from CIBA-GEIGY AG), Araldite CY-182, CY-192 and CY-184 (trade names, manufactured by Nagase ChemteX Corporation), CY175, CY177 and CY179 (Trade name, manufactured by CIBA-GEIGY AG), Epiclon 200, and EP-400 (manufactured by DIC Corporation), Epikote 871 and Epikote 872 -5662 (trade name, manufactured by Selenium Coatings Co., Ltd.). These crosslinkable compounds may be used alone or in combination of two or more.

Among them, from the viewpoints of the process resistance and transparency such as heat resistance, solvent resistance, internal time-plastic resistance and the like, the compounds represented by the above formulas C2-1 and C2-2 having a cyclohexene oxide structure, 401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 are preferable.

When the component (C2) is selected as the crosslinking agent, the content is 3 to 50 parts by mass, preferably 7 to 40 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the component (A). When the content of the crosslinking compound is small, the crosslinking density formed by the crosslinking compound is insufficient, so that the effect of improving the heat resistance, solvent resistance, resistance to firing for a long time after pattern formation can not be obtained have. On the other hand, when the amount is more than 50 parts by mass, uncrosslinked crosslinkable compounds are present to reduce heat resistance, solvent resistance, resistance to firing for a long time after pattern formation, and the storage stability of the photosensitive resin composition deteriorates .

≪ (D) Solvent >

The solvent (D) used in the present invention is obtained by dissolving the components (A), (B) and (C) and dissolving the components (E) to , And the type and structure of the solvent are not particularly limited as long as they have such solubility.

Examples of the solvent (D) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl- 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxynaphthoate, Methyl 3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, And the like can be set acid ethyl acetate, butyl acetate, ethyl lactate, lactic acid butyl, N, N- dimethylformamide, N, N- dimethylacetamide and N- methylpyrrolidone.

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

Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate and butyl lactate are preferable because of good film properties and safety Is high. These solvents are generally used as a solvent for a photoresist material.

≪ Component (E) >

Component (E) is a surfactant. In the positive photosensitive resin composition of the present invention, a surfactant may be further contained so long as the effect of the present invention is not impaired for the purpose of improving its coatability.

The surfactant of the component (E) is not particularly limited, and examples thereof include a fluorine surfactant, a silicone surfactant, and a nonionic surfactant. As such a surfactant, for example, commercially available products such as those available from Sumitomo 3M Ltd., DIC Ltd. or AGC Seimei Chemical Co., Ltd. can be used. These commercially available products are suitable because they are readily available. Specific examples thereof include polypox PF-136A, 151, 156A, 154N, 159, 636, 6320, 656 and 6520 (manufactured by Omnova), Megapark R30, R08, R40, R41, R43, F251, F477, F552 and F553 , F554, F555, F556, F557, F558, F559, F560, F561, F562, F563, F565, F567, F570 (manufactured by DIC), FC4430, FC4432 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, (Manufactured by NEOS), Saffron S-386, S-611, S-651, AGC Seiyaku Chemical Co., Ltd., Fructose FTX-218, DFX-18, 220P, 251, 212M, 300, 302, 306, 307, 310, 313, 315, 320, 322, 323, 325, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, KF-351, KF-352, and KF-357 (manufactured by Dow Corning Toray Silicone Co., Ltd.), 377, 378, 3455 (manufactured by Big Chemie Japan K.K.), SH3746, SH3749, SH3771, SH8400, SH8410, SH8700, SF8428 Silicone surfactants such as KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011 and KF-6015 (manufactured by Shinetsu Kagaku Kogyo K.K.) .

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

When a surfactant is used, its content 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 when the amount of the surfactant (E) used is set to an amount exceeding 1.0 part by mass, the effect of improving the coating property becomes dull and uneconomical. When the amount is 0.01 parts by mass or less, the effect of improving the coating property may not be exhibited.

≪ Component (F) >

Component (F) is an adhesion promoter. The positive photosensitive resin composition of the present invention may be added with an adhesion promoter for the purpose of improving the adhesion with the substrate after development. Specific examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, Dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, vinyl trichlorosilane,? -Aminopropyltriethoxysilane,? -Methacryloyloxypropyltriethoxysilane,? -Methacryloxy (N-piperidinyl) propyltriethoxysilane, 3-ureide propyltriethoxysilane, 3-ureide propyltriethoxysilane, 3-mercaptopropyltriethoxysilane, Silane residues such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine and trimethylsilylimidazole, benzotriazole, benzimidazole, Indazole, A heterocyclic compound such as mercapto benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, uraazole, thiouracil, mercaptoimidazole and mercaptopyrimidine , 1,1-dimethylurea, and 1,3-dimethylurea, and thiourea compounds.

The adhesion promoter may be a commercially available compound such as, for example, Shin-Etsu Chemical Co., Ltd., Momentive Performance Materials Worldwide Inc., Jenna Toray, Dow Corning Silicone Co., .

As the component (F), one kind or two or more kinds of the above adhesion promoters may be used in combination.

Of these components (F), alkoxysilanes (that is, a silane coupling agent) are preferable in that good adhesion is obtained.

The amount of the adhesion promoter to be 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). If the amount is more than 20 parts by mass, the sensitivity may be lowered. If the amount is less than 0.1 part by mass, sufficient effect of the adhesion promoter may not be obtained.

<Other additives>

Further, the positive-working photosensitive resin composition of the present invention can be dissolved in a rheology modifier, a pigment, a dye, a storage stabilizer, a defoaming agent, or a polyhydric phenol, a polyvalent carboxylic acid or the like Accelerators and the like.

&Lt; Positive photosensitive resin composition >

The positive photosensitive resin composition of the present invention comprises a copolymer obtained by copolymerizing components (A1) to (A4) of component (A), a 1,2-quinonediazide compound of component (B), and a crosslinking agent of component (D) a solvent, and, if necessary, may further contain at least one of surfactant (E), adhesion promoter of component (F), and other additives.

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

(B) and 5 to 50 parts by mass of a component (C) based on 100 parts by mass of the component (A), wherein the component (D) is a positive Sensitive resin composition.

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

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

The proportion of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in a solvent, and is, for example, 1 to 80 mass% 60% by mass or 10% by mass to 50% by mass. Here, the solid content means that the solvent (D) is excluded from the total components of the positive photosensitive resin composition.

(A) (alkali-soluble resin) is dissolved in a solvent (D), and a solution of (B) is added to this solution, ) Or a crosslinking agent of the component (C) at a predetermined ratio to prepare a homogeneous solution, or a method in which, in an appropriate step of this preparation method, the component (E) (Surfactant), component (F) (adhesion promoter) and other additives are added and mixed.

When the positive photosensitive resin composition of the present invention is prepared, the solution of the copolymer obtained by the polymerization reaction in the solvent (D) can be used as it is. In this case, the solution of the component (A) (D) solvent may be further added for the purpose of adjusting the concentration when the components (B) and (C) are added to a uniform solution. Here, the solvent (D) used in the formation of the specific copolymer and the solvent (D) used for adjusting the concentration at the time of preparing the positive photosensitive resin composition may be the same or different.

Thus, the solution of the prepared positive-working photosensitive resin composition is preferably filtered after using a filter having a pore diameter of about 0.2 mu m or the like.

&Lt; Coating film and cured film &

The positive photosensitive resin composition of the present invention may be applied to a semiconductor substrate (e.g., a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum or chromium, a glass substrate, A substrate, or the like) by spin coating, flow coating, roll coating, slit coating, rotary coating followed by slit, inkjet coating, and the like, and thereafter preliminarily drying in a hot plate or oven. Thereafter, this coating film is subjected to heat treatment to form a positive photosensitive resin film.

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

The thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, from 0.1 to 30 占 퐉, for example, from 0.2 to 10 占 퐉, and further, for example, from 0.3 to 8 占 퐉.

A mask having a predetermined pattern is mounted on the coating film obtained above, and light such as ultraviolet rays is irradiated and developed with an alkali developing solution, whereby the exposed portion is washed to obtain a relief pattern having a sharp end face.

Examples of the alkaline developer which can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxide of tetraethylammonium hydroxide, tetraethylammonium hydroxide, , An aqueous solution of an amine such as ethanolamine, propylamine or ethylenediamine, and the like. Further, a surfactant or the like may be added to these developers.

The above aqueous solution of 0.1 to 2.38 mass% of tetraethylammonium hydroxide is generally used as a developer for a photoresist. Even in the photosensitive resin composition of the present invention, the alkaline developer can be used for the development of a good .

As the developing method, a liquid method, a dipping method, a calendering method, or the like can be used. The developing time at this time is usually 15 to 180 seconds.

After the development, the positive-type photosensitive resin film is washed with water by, for example, 20 to 120 seconds, then air-dried by using compressed air, compressed nitrogen, or spinning to remove moisture on the substrate, Then, a patterned film is obtained.

Then, the pattern-formed film is subjected to post-baking for thermal curing, specifically by heating using a hot plate, an oven, or the like to obtain a pattern-forming film having excellent heat resistance, transparency, flatness, low water- A film having a good relief pattern is obtained.

The post bake process is generally carried out at a heating temperature selected from the range of 140 ° C to 270 ° C, for 5 to 30 minutes in the case of a hot plate, and for 30 to 90 minutes in the case of an oven.

Thus, by the post-baking, a cured film having a desired pattern shape can be obtained.

As described above, the positive photosensitive resin composition of the present invention can form a coating film having a high storage stability, a sufficiently high sensitivity, a very small reduction in film thickness at the time of development, and a fine pattern by the positive photosensitive resin composition of the present invention.

In addition, the cured film obtained from this coating film has a feature that there are few pattern residues. Therefore, various films such as an interlayer insulating film, a protective film, an insulating film, and the like in a liquid crystal display or an organic EL display can be suitably used in applications such as an array planarizing film of a TFT type liquid crystal element.

Example

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

[Abbreviations used in the examples]

The meanings of the weak symbols 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?,?,? '- tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride A compound synthesized by a condensation reaction

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

GT-401: Butane tetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) -substituted ε-caprolactone

MPTS:? -Methacryloxypropyltrimethoxysilane

R30: DIC ImegaPac R-30 (trade name)

[Measurement 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 product obtained according to the following Synthesis Examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L, manufactured by Nippon Bunko K.K.) Hydrofluorene was measured under the condition that it was eluted by flowing in a column (column temperature: 40 캜) at a flow rate of 1 ml / min. On the other hand, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed as polystyrene conversion values.

&Lt; Synthesis Example 1 &

12.0 g of MAA, 21.0 g of CHMI and 27.0 g of MMA were used as monomer components constituting the specific copolymer and 3.8 g of AIBN was used as a radical polymerization initiator, and these were dissolved in 95.8 g of solvent PGMEA at a temperature of 60 ° C to 100 ° C (Specific copolymer concentration: 40.0 mass%) of an alkali-soluble acrylic polymer component (specific copolymer) having Mn of 4,500 and a Mw of 7,800 was obtained. (P1)

&Lt; Synthesis Example 2 &

4.2 g of MAA, 21.0 g of CHMI, 27.6 g of HEMA and 7.2 g of MMA were used as the monomer components constituting the specific copolymer and 3.8 g of AIBN was used as the radical polymerization initiator, and these were dissolved in 95.8 g of solvent PGME at a temperature of 60 (Specific copolymer concentration: 40.0% by mass) of an alkali-soluble acrylic polymer component (specific copolymer) having Mn of 4,200 and Mw of 7,500 was obtained by carrying out a polymerization reaction at a temperature of 0 to 100 ° C. (P2)

&Lt; Synthesis Example 3 &

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

&Lt; Synthesis Example 4 &

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 as monomer components constituting the specific copolymer, and 3.8 g of AIBN as a radical polymerization initiator was used, (Specific copolymer concentration: 40.0 mass%) of an alkali-soluble acrylic polymer component (specific copolymer) having Mn of 4,100 and Mw of 7,600 was obtained by polymerization reaction at a temperature of 60 to 100 ° C. (P4)

&Lt; Example 1 >

(Hereinafter referred to as a photosensitive agent), a crosslinking compound, a surfactant, an adhesion promoter and a solvent were added to the specific copolymer solution (P4) obtained in Synthesis Example 4 as an alkali-soluble resin solution, And the mixture was stirred for a time to prepare a positive photosensitive composition having the composition shown in Table 1.

&Lt; Comparative Examples 1 to 3 >

A sensitizer, a crosslinking compound, a surfactant, an adhesion promoter and a solvent were added to the specific copolymer solutions (P1 to P3) obtained in Synthesis Examples 1 to 3 as an alkali-soluble resin solution, and then stirred at room temperature for 8 hours, A positive photosensitive composition having the composition shown in Table 1 was prepared.

Each of the obtained positive photosensitive resin compositions of Example 1 and Comparative Examples 1 to 3 was evaluated for sensitivity, adhesion at the time of development, and residue in a pattern at the time of thermal curing by the methods described below.

[Evaluation of Sensitivity]

The positive-type photosensitive resin composition was coated on a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 110 캜 for 120 seconds to form a coating film having a film thickness of 4.0 탆. The film thickness was measured using a FILMETICS F20 . This coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time by an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Inc. Thereafter, development was carried out by immersing in an aqueous solution of 0.4 mass% of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 90 seconds, followed by water washing with ultra pure water for 20 seconds. The lowest exposure dose (mJ / cm ² ) at which the dissolved residue disappears in the exposed area was taken as the sensitivity.

[Evaluation of adhesion]

The positive photosensitive resin composition was coated on a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 110 캜 for 120 seconds to form a coating film. This coating film was irradiated with ultraviolet rays having a light intensity of 5.5 mW / cm ² at 365 nm through a mask for a predetermined period of time, and a pattern in which 10 μm × 10 μm contact holes were arranged at intervals of 130 μm was produced. Thereafter, development was carried out by immersing in an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) of 0.4 mass% for 90 seconds, followed by washing with ultrapure water for 90 seconds. Thereafter, post-baking was performed at 230 DEG C for 30 minutes using CLEANOVENPVHC-210 manufactured by Espec Co., Ltd. to form a cured film having a film thickness of about 4.0 mu m. Thereafter, the adhesion of the 10 탆 x 10 탆 formed pattern was evaluated using a Hitachi field emission scanning electron microscope S-4100. It was judged that the end of the void pattern was not open but closely adhered (?), And that the end was floating was bad (X).

[Evaluation of residue in pattern]

The residue in the void pattern of 10 mu m x 10 mu m prepared in the above evaluation of the adhesion was confirmed by a Hitachi field emission scanning electron microscope S-4100. At this time, it was judged that the residue remained in the void pattern was good (O) and the remaining remnant was bad (X).

[Results of evaluation]

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

As can be seen from the results shown in Table 2, all of the positive photosensitive resin compositions of Example 1 had high sensitivity and had sufficient adhesion at the time of development. Furthermore, there was no residue in the pattern after pattern formation.

The positive photosensitive resin composition according to the present invention is suitable as a material for forming a cured film such as a protective film, a planarizing film and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, But also as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an array planarizing film, a concave-convex film on the lower side of a reflective film of a reflective display, an insulating film of an organic EL element, It is also a good material.

Claims (11)

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