JP2012208323A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition with high sensitivity, capable of reducing coating irregularity and broadening a process margin.SOLUTION: The photosensitive resin composition contains an alkali-soluble novolac resin (A), an alkali-soluble phenolic resin (B), a quinonediazide sulfonic acid ester (C) and an organic solvent (D). In the composition, the ratio of the alkali-soluble novolac resin (A) to the alkali-soluble phenolic resin (B) is 95:5 to 85:15 by weight; the alkali-soluble phenolic resin (B) has a molecular weight of 1000 or less and a molecular weight distribution of 1.05 or more and 1.65 or less; and the organic solvent (D) is a compound solvent comprising propylene glycol monomethylether (D1) and a solvent (D2) having a boiling point of 150°C to 240°C at normal pressure.

Description

  The present invention relates to a photosensitive resin composition suitable for processing a large display element substrate.

  In recent years, flat display devices such as liquid crystal display devices and organic EL elements have attracted attention as electronic display devices. Since liquid crystal display devices are smaller and more compact than cathode ray tube (CRT) display devices, various devices including liquid crystal display devices have been developed. The market needs for miniaturization of various devices including consumer devices such as personal computers and video cameras are high, and miniaturized portable devices such as laptop computers and cameras with liquid crystal monitors have become widespread. In these devices, it is indispensable to have a liquid crystal display device, and in addition, there is a strong demand for higher performance and higher performance such as color display and high luminance.

  In a liquid crystal display device, an active matrix method using a thin film transistor is often adopted as a driving method. In an active matrix liquid crystal display device, since each display pixel is individually controlled by a switching element such as a thin film transistor, crosstalk is less likely to occur than in a passive matrix liquid crystal display device, and it is suitable for high definition and large size. .

  Conventionally, in the production of a display element substrate, a photosensitive resin composition is dropped on the center of the coating surface of the substrate and then spinned to form a resist layer, which is then uniformly coated on the substrate. Further, for example, when a fourth generation substrate (680 mm × 880 mm or 730 × 920 mm) or a fifth generation substrate (1000 × 1200 mm or 1300 × 1500 mm) is used, the entire coated surface of the substrate is photosensitive using a discharge nozzle. There has been proposed a method in which a photosensitive resin composition is uniformly coated on a substrate by spinning after dropping the resin composition (see, for example, Patent Document 1).

JP 2005-114920 A

  However, in recent years, the mother glass used as a substrate has further increased in size, and large-sized substrates such as an 8th generation substrate (2160 × 2460 mm), a 9th generation substrate (2400 × 2800 mm), a 10th generation substrate (2880 × 3130 mm), etc. Processing is required. When the photosensitive resin composition is applied by spinning the substrate in the manufacture of such a large display element substrate, the apparatus becomes large and a large motor is required, resulting in an increase in manufacturing cost. In view of this, there has been proposed a method (slit coating) in which a photosensitive resin composition is dropped onto a substrate and applied to the entire surface of a large substrate using a slit coater (slit coating). However, this method may cause uneven coating. It was.

  In addition, a large substrate is required to have a wide process margin. In other words, when a large substrate is used, temperature variation occurs in the substrate surface when heating such as pre-baking, or variation occurs in the contact time with the developer in the substrate surface during development. Therefore, it is necessary to suppress the influence of temperature and development time. Furthermore, it is required to increase photosensitivity in order to shorten the exposure process.

  An object of the present invention is to provide a highly sensitive photosensitive resin composition that can reduce coating unevenness and widen a process margin.

  As a result of intensive studies to achieve the above-mentioned problems, an alkali-soluble novolak resin (A) and an alkali-soluble phenol resin (B) whose molecular weight and molecular weight distribution are controlled are used in combination, and the alkali-soluble novolak resin (A) and The above-mentioned problem is that the ratio of the alkali-soluble phenol resin (B) is within a specific range, and the solvent (D) is a combination of propylene glycol monomethyl ether (D1) and a solvent (D2) having a specific boiling point. The present invention has been found to be effective in solving this problem, and the present invention has been completed based on this finding.

That is, the present invention
(1) An alkali-soluble novolak resin (A), an alkali-soluble phenol resin (B), a quinonediazide sulfonate ester (C), and an organic solvent (D), the alkali-soluble novolak resin (A) and the alkali-soluble phenol resin The ratio of (B) is 95: 5 to 85:15 by weight, the molecular weight of the alkali-soluble phenol resin (B) is 1000 or less, and the molecular weight distribution is 1.05 or more and 1.65 or less, The organic solvent (D) is a photosensitive resin composition that is a composite solvent containing propylene glycol monomethyl ether (D1) and a solvent (D2) having a boiling point of 150 to 240 ° C. under normal pressure,
(2) The photosensitive resin composition according to (1), wherein the solvent (D2) has a normal pressure boiling point in the range of 150 ° C to 200 ° C.
(3) The photosensitive resin composition according to (1) or (2), wherein the solvent (D2) is diethylene glycol dialkyl ether.
(4) The photosensitive resin composition according to any one of (1) to (3), wherein the molecular weight distribution of the alkali-soluble resin composition (B) is 1.10 to 1.50.
(5) The quinonediazidesulfonic acid ester (C) is 1,2-naphthoquinonediazide-5-sulfonyl chloride and 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl]. ] The photosensitive resin composition in any one of said (1)-(4) containing the ester compound of a phenyl] ethylidene] bisphenol.

  According to the photosensitive resin composition of the present invention, it is possible to provide a highly sensitive photosensitive resin composition capable of reducing coating unevenness and widening the process margin.

  The photosensitive resin composition of the present invention contains an alkali-soluble novolak resin (A), an alkali-soluble phenol resin (B), a quinonediazide sulfonic acid ester (C), and an organic solvent (D). The ratio of the alkali-soluble novolak resin (A) and the alkali-soluble phenol resin (B) is 95: 5 to 85:15 by weight, and the molecular weight of the alkali-soluble phenol resin (B) is 1000 or less, and The molecular weight distribution is 1.05 or more and 1.65 or less, and the organic solvent (D) includes propylene glycol monomethyl ether (D1) and a solvent (D2) having a boiling point of 150 to 240 ° C. under normal pressure. It is a composite solvent.

  The alkali-soluble novolak resin (A) used in the present invention is a novolak resin soluble in a developer composed of an alkaline aqueous solution. A novolac resin is a resin obtained by dehydrating and condensing a phenol compound and an aldehyde compound using an acidic catalyst. The phenol compound used for producing the novolak resin may be a monovalent phenol compound or a divalent or higher polyhydric phenol compound such as resorcinol.

  Examples of the monovalent phenol compound include phenol; o-cresol, m-cresol, p-cresol; xylenol such as 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, and 3,5-xylenol. 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2 , 5-diethylphenol, 3,5-diethylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2-t-butyl-3-methylphenol, 2,3, Such as 5-trimethylphenol and 2,3,5-triethylphenol Killphenol; alkoxyphenol such as 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol Arylphenols such as 2-phenylphenol, 3-phenylphenol and 4-phenylphenol; 2-isopropenylphenol, 4-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenyl Alkenylphenols such as phenol; and the like. Examples of the polyhydric phenol compound include resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-methoxyresorcinol, 4-methoxyresorcinol; hydroquinone; catechol, 4-t-butylcatechol, 3-methoxy. Catechol; 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane; pyrogallol; phloroglicinol; Among these phenol compounds, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, and 2,3,5-trimethylphenol can be suitably used. A phenol compound can be used individually by 1 type, or can also be used in combination of 2 or more type.

  As the aldehyde compound to be dehydrated and condensed with the phenol compound, any of an aliphatic aldehyde, an alicyclic aldehyde, and an aromatic aldehyde can be used. Examples of the aliphatic aldehyde include formaldehyde, trioxane, paraformaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, trimethylacetaldehyde, n-hexylaldehyde, acrolein, and crotonaldehyde.

  Examples of the alicyclic aldehyde include cyclopentane aldehyde, cyclohexane aldehyde, furfural, and furyl acrolein. Examples of aromatic aldehydes include benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, p-ethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde. 3,5-dimethylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-anisaldehyde, m-anisaldehyde, p- List anisaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, cinnamaldehyde, etc. Can do. These aldehyde compounds can be used individually by 1 type, or can also be used in combination of 2 or more type.

  In the present invention, the condensation reaction between the phenol compound and the aldehyde compound when producing the novolak resin can be performed in the presence of an acidic catalyst. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, and the like. The condensation reaction product obtained by such a reaction can be used as it is as a novolak resin.

  In the present invention, the alkali-soluble novolac resin (A) can be used after separating and removing low molecular weight components. Examples of the method for removing low molecular weight components include a liquid-liquid fractionation method in which a resin is fractionated in two solvents having different solubilities, a method in which low molecular weight components are removed by centrifugation, and a thin film distillation method. be able to. In the case of the above-mentioned novolak resin, the obtained condensation reaction product is treated with a good solvent, for example, an alcohol solvent such as methanol or ethanol; a ketone solvent such as acetone or methyl ethyl ketone; an alkylene glycol solvent such as ethylene glycol monoethyl ether acetate; The novolak resin from which the low molecular weight component has been removed can be obtained by dissolving in an ether solvent of

  The alkali-soluble novolak resin (A) used in the present invention preferably has a weight average molecular weight of 2,000 to 20,000, more preferably 2,500 to 12,000, and 3,000 to More preferably, it is 8,000. The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method using monodispersed polystyrene as a standard sample and tetrahydrofuran (THF) as an eluent.

  The alkali-soluble phenol resin (B) used in the present invention is a phenol resin that is soluble in a developer composed of an alkaline aqueous solution. A phenol resin is obtained by dehydrating and condensing phenol and formaldehyde using an acidic catalyst. Further, the alkali-soluble phenol resin (B) used in the present invention has a weight average molecular weight (Mw) of 1000 or less and a molecular weight distribution (Mw / Mn; Mn represents a number average molecular weight) of 1.05 to 1.65. is there. If this range is not satisfied, problems such as uneven coating, large process margins, and low sensitivity arise.

  The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) can be measured using gel permeation chromatography (GPC). For example, using a solvent such as tetrahydrofuran as an eluent, obtaining a standard polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn), and using a conventional method such as calculating a dispersion ratio (Mw / Mn) Can do.

  Moreover, the ratio of alkali-soluble novolak resin (A) and alkali-soluble phenol resin (B) used in the present invention is in the range of 95: 5 to 85:15 by weight. If this range is not satisfied, problems such as uneven coating, large process margins, and low sensitivity arise.

  Examples of the quinonediazidesulfonic acid ester (C) used in the present invention include 1,2-naphthoquinonediazide-5-sulfonic acid ester (also known as: 6-diazo-5,6-dihydro-5-oxo-naphthalene-1- Sulfonic acid ester), 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide Examples include -5-sulfonic acid ester and 2,1-naphthoquinonediazide-6-sulfonic acid ester.

  The quinonediazide sulfonic acid ester is prepared by converting a quinonediazidesulfonic acid compound into a quinonediazidesulfonic acid halide according to a conventional method, and then in an organic solvent such as acetone, dioxane, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, etc. Quinonediazide in the presence of an inorganic base such as sodium or potassium hydroxide, or in the presence of an organic base such as trimethylamine, triethylamine, tripropylamine, diisopropylamine, tributylamine, pyrrolidine, piperidine, piperazine, morpholine, pyridine, dicyclohexylamine It can be obtained by a condensation reaction between a sulfonic acid halide and a compound having a hydroxy group.

  Examples of the quinonediazide sulfonic acid halide include 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (also known as 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid chloride), 1 , 2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride, 2,1-naphthoquinonediazide-4-sulfonyl chloride, 2,1-naphthoquinonediazide-5-sulfonyl chloride, Examples include 2,1-naphthoquinonediazide-6-sulfonyl chloride.

  Examples of the compound having a hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4. , 4'-tetrahydroxybenzophenone, polyhydroxybenzophenone such as 2,2 ', 3,4,4'-pentahydroxybenzophenone; gallic esters such as methyl gallate, ethyl gallate, propyl gallate; Polyhydroxybisphenylalkanes such as bis (4-hydroxyphenyl) propane and 2,2-bis (2,4-dihydroxyphenyl) propane; tris (4-hydroxyphenyl) methane, 1,1,1-tris (4- Hydroxy-3-methylphenyl) ethane, 1,1,1-tris (4- Droxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1- (4-hydroxyphenyl) ethane, bis (4-hydroxy-3-methylphenyl) -2-hydroxy-4- Polyhydroxytrisphenylalkanes such as methoxyphenylmethane, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol; Polys such as tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,3,3-tetrakis (4-hydroxyphenyl) propane Hydroxytetrakisphenylalkane; α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -m-xylene Poly, such as α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -p-xylene, α, α, α ′, α′-tetrakis (3-methyl-4-hydroxyphenyl) -m-xylene Hydroxytetrakisphenylxylene; 2,6-bis (2,4-dihydroxybenzyl) -p-cresol, 2,6-bis (2,4-dihydroxy-3-methylbenzyl) -p-cresol, 4,6-bis (4-hydroxybenzyl) resorcin, 4,6-bis (4-hydroxy-3-methylbenzyl) resorcin, 4,6-bis (4-hydroxybenzyl) -2-methylresorcin, 4,6-bis (4- Trimer of phenolic compound such as hydroxy-3-methylbenzyl) -2-methylresorcin and formaldehyde; said phenolic compound and formaldehyde And tetramer with a nod; a novolak resin; and the like.

  The above acid halide and hydroxyl group-containing compounds can be used alone or in combination of two or more.

  Among these, from the viewpoint of increasing photosensitivity, 1,2-naphthoquinonediazido 5-sulfonyl chloride is used as an acid halide, and 2,3,4-trihydroxybenzophenone, 2,3 as a compound having a hydroxyl group. , 4,4′-tetrahydroxybenzophenone and 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol were used. It is preferable to use a quinonediazide sulfonic acid ester.

  The esterification rate of the obtained quinonediazide sulfonic acid ester is preferably 50 mol% or more, and more preferably 60 mol% or more. The esterification rate is determined by the blending ratio of the acid halide and the compound having a hydroxyl group.

  In the photosensitive resin composition of the present invention, the amount of the quinonediazide sulfonic acid ester (C) is 5 to 40 with respect to 100 parts by weight in total of the alkali-soluble novolak resin (A) and the alkali-soluble phenol resin (B). It is preferable that it is a weight part, and it is more preferable that it is 10-30 weight part. When the blending amount of the quinonediazide sulfonic acid ester (C) is 5 to 40 parts by weight with respect to a total of 100 parts by weight of the alkali-soluble novolak resin (A) and the alkali-soluble phenol resin (B), the resist pattern half It is possible to obtain a photosensitive resin composition having good tone pattern portion formability and excellent balance of resist characteristics such as effective sensitivity, residual film ratio, and resolution.

  The organic solvent (D) used in the present invention is a composite solvent containing propylene glycol monomethyl ether (D1) and a solvent (D2) having a normal pressure boiling point in the range of 150 ° C. to 240 ° C.

  The solvent (D2) having a boiling point of 150 to 240 ° C. is not particularly limited as long as it is a solvent that dissolves the alkali-soluble novolak resin (A) and the quinonediazide sulfonate ester (B). Examples thereof include a glycol solvent, an ether solvent, an ester solvent, a hydrocarbon solvent, a ketone solvent, and an amide solvent. Hereinafter, the boiling point (° C.) is shown in parentheses to illustrate the solvent (D2). The boiling point of propylene glycol monomethyl ether (D1) is 146 ° C.

  Examples of the alkylene glycol solvent include ethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether (195) and ethylene glycol monoethyl ether (202); diethylene glycol dimethyl ether (162), diethylene glycol diethyl ether (189), diethylene glycol ethyl methyl ether ( 176), diethylene glycol dialkyl ethers such as diethylene glycol butyl methyl ether (212); propylene glycol alkyl ethers such as dipropylene glycol dimethyl ether (171) and dipropylene glycol monomethyl ether (188); ethylene glycol monoethyl ether acetate (158), ethylene Glycol monobutyl ether Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate (158); acetate (188) ethylene glycol monoalkyl ether acetates such as and the like.

  Examples of the ester solvent include ethyl 3-ethoxypropionate (170), butyl lactate (187), methyl benzoate (200), and the like. Examples of the hydrocarbon solvent include n-nonane (150), decane (174), decalin (194), α-pinene (156), β-pinene (163), δ-pinene (161), and 1-chloro. Octane (182), 2-methylcyclohexane (racemate: 165), 3-methylcyclohexanone (racemate: 170), 4-methylcyclohexanone (171), 4-ethylcyclohexane (194), o-chlorotoluene (159) M-chlorotoluene (162), p-chlorotoluene (162), propylbenzene (159), butylbenzene (183), isobutylbenzene (173), cumene (152) and other aromatic hydrocarbons. it can. Examples of the ketone solvent include cyclohexanone (156). Examples of the amide solvent include N, N-dimethylformamide (153), N, N-dimethylacetamide (194), N-methylpyrrolidone (202), and the like. These solvents can be used alone or in combination of two or more.

  The solvent (D2) having a normal pressure boiling point in the range of 150 ° C. to 240 ° C. satisfies the normal pressure boiling point of 150 ° C. to 240 ° C. such as propylene glycol monomethyl ether (120) in addition to the above-mentioned solvents. You may mix and use the solvent which is not. In this case, the weight ratio of the solvent having a normal pressure boiling point in the range of 150 ° C. to 240 ° C. and the solvent having a normal pressure boiling point not satisfying the range of 150 ° C. to 240 ° C. 4: 1 to 1: 4 is preferable.

  The weight ratio of propylene glycol monomethyl ether (D1) to solvent (D2) having a normal pressure boiling point in the range of 150 ° C. to 240 ° C. is preferably 6: 4 to 9.5: 0.5. If this range is not satisfied, there are problems such as uneven application, large process margins, and low sensitivity.

  Moreover, it is more preferable that the solvent (D2) has a boiling point in the range of 150 ° C. to 200 ° C. from the viewpoint of suppressing uneven coating.

  Moreover, in this invention, an adhesion promoter can be mix | blended with the photosensitive resin composition. Examples of the adhesion promoter include melamine adhesion promoter and silane adhesion promoter.

  Examples of the melamine adhesion promoter include Cymel (registered trademark) 300, 303 [Nippon Cytec Industries, Ltd.], MW-30MH, MW-30, MS-11, MS-001, MX-750, MX-706. [Sanwa Chemical Co., Ltd.]. The blending amount of the melamine adhesion promoter is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the alkali-soluble novolak resin (A) and the alkali-soluble phenol resin (B). The amount is more preferably 5 to 18 parts by weight, and further preferably 1 to 15 parts by weight.

  Examples of the silane adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like. The amount of the silane adhesion promoter is preferably 0.0001 to 2 parts by weight, based on 100 parts by weight of the total of the alkali-soluble novolak resin (A) and the alkali-soluble phenol resin, and is 0.001 to 1. More preferred are parts by weight, and even more preferred is 0.005 to 0.8 parts by weight.

  In the present invention, a surfactant can be added to the photosensitive resin composition. The compounding amount of the surfactant is preferably 100 to 5,000 ppm by weight, and more preferably 200 to 2,000 ppm by weight with respect to the photosensitive resin composition. By adding a surfactant to the photosensitive resin composition, it is possible to further prevent the occurrence of coating unevenness in the coating film. Examples of the surfactant include a silicone-based surfactant, a fluorine-based surfactant, and a polyoxyalkylene-based surfactant.

  Examples of the silicone surfactant include SH28PA, SH29PA, SH30PA, polyether-modified silicone oil SF8410, SF8427, SH8400, ST80PA, ST83PA, ST86PA [Toray Dow Corning Co., Ltd.], KP321, KP323, KP324, KP340, KP341 [Shin-Etsu Silicone Co., Ltd.], TSF400, TSF401, TSF410, TSF4440, TSF4445, TSF4446 [GE Toshiba Silicone Co., Ltd.], BYK300, BYK301, BYK302, BYK306, BYK307, BYK310, BYK315, BYK333, BYK333, BYK333, BYK333, BYK333 , BYK370, BYK375, BYK377, BYK378 [Big Chemie Japan ( )] And the like.

  Examples of the fluorosurfactant include Fluorinert FC-430, FC-431 [Sumitomo 3M Co., Ltd.], Surflon S-141, S-145, S-381, S-393 [Asahi Glass Co., Ltd.], F Top (registered trademark) EF301, EF303, EF351, EF352 [Gemco], MegaFuck (registered trademark) F171, F172, F173, R-30 [Dainippon Ink Chemical Co., Ltd.] . Examples of the silicone surfactant having a fluorocarbon chain may include Megafac (registered trademark) R08, F470, F471, F472SF, and F475 [Dainippon Ink Chemical Co., Ltd.].

  Examples of the polyoxyalkylene surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol And distearate.

  There is no restriction | limiting in particular in the method of apply | coating the photosensitive resin composition of this invention on a board | substrate, For example, the spray method, the roll-coating method, the spin coating method, the slit and spin method, the spinless slit method etc. can be mentioned. Among these, the spinless slit method can be preferably used. According to the spinless slit method, the positive photosensitive resin composition can be applied without moving the slit that contacts the substrate by moving the slit that supplies the positive photosensitive resin composition. For application by spinless slit method, spinless coater [Tokyo Ohka Kogyo Co., Ltd.], table coater [Nakagai Kogyo Co., Ltd.], linear coater [Dainippon Screen Mfg. Co., Ltd.], head coater [Hirata Kiko ( Co., Ltd.], slit die coater [Toray Engineering Co., Ltd.], Toray slit coater [Toray Co., Ltd.] and the like can be used.

  Drying of the coating film of the photosensitive resin composition on the substrate is performed by heating (prebaking) the coating film for the purpose of substantially eliminating the fluidity of the coating film, for example, according to a known method. Just do it. Pre-baking can be performed by heating at 60 to 120 ° C. for 10 to 600 seconds using a hot plate or an oven. It is also preferable to dry the coating film under reduced pressure according to a known method before prebaking.

  A resist film is formed on the substrate by these steps, and the thickness of the resist film is usually 0.5 to 5 μm, preferably 0.8 to 4 μm.

  Next, the resist film is exposed through a mask. In the exposure, the resist film is irradiated with actinic rays through a mask pattern to form a latent image pattern having a predetermined shape in the resist film. There is no restriction | limiting in particular in the actinic light used in the case of exposure, For example, visible light, an ultraviolet-ray, a far-ultraviolet, an X ray etc. can be mentioned. Among these, visible light and ultraviolet light can be preferably used. There is no restriction | limiting in particular in the light quantity to irradiate, According to the intended purpose of use of a resist film, the thickness of a film | membrane, it can select suitably.

  Subsequently, the latent image pattern is developed by bringing a developing solution into contact with the exposed resist film to form a resist pattern. There is no particular limitation on the developer (alkaline developer) used for developing the latent image pattern, and examples thereof include aqueous solutions of tetramethylammonium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, and the like. . The concentration of these developers is preferably 0.1 to 5% by weight.

  After developing the latent image pattern, the resist pattern on the substrate is preferably washed with pure water and air-dried with compressed air or compressed nitrogen, for example. Also, if desired, the developed pattern is heated at 100 to 250 ° C. using a heating device such as a hot plate or oven, for 2 to 60 minutes on the hot plate, and for 2 to 90 minutes in the oven (post-baking). May be.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Example 1
m-cresol and p-cresol were charged at a weight ratio of 55/45, and dehydrated with formaldehyde using oxalic acid as a catalyst to synthesize two alkali-soluble novolak resins having a weight average molecular weight of 3600 and 9500.

  In addition, phenol and formaldehyde were subjected to dehydration condensation using oxalic acid as a catalyst to obtain an alkali-soluble phenol resin having a weight average molecular weight of 620 and a molecular weight distribution of 1.21.

  90 parts by weight of alkali-soluble novolak resin, 10 parts by weight of alkali-soluble phenol resin, quinonediazide sulfonic acid ester, PAC320 (6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid and 2,3,4 -Ester with trihydroxybenzophenone) and 15 parts by weight of PAC430 (6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid with 2,3,4,4'-tetrahydroxybenzophenone) 10 parts by weight was dissolved in 708 parts by weight of solvent. Here, in Example 1, a solvent composed of 90 wt% of propylene glycol monomethyl ether (PGMEA) and 10 wt% of diethylene glycol ethyl methyl ether (EDM) was used.

  Further, by using BYK302 (polyether-modified dimethylpolysiloxane) as an activator, the concentration was adjusted to 400 ppm.

  Further, the alkali-soluble novolak resin has a weight average molecular weight of 3600 in such a ratio that the residual film ratio (ratio of the film thickness after development with respect to 1.5 μm which is the film thickness after coating) calculated at the time of sensitivity evaluation is 95%. The resin (F) and a resin having a weight average molecular weight of 9500 (S) were mixed. The ratio of F and S was 60:40.

(Example 2)
The photosensitive resin composition was prepared in the same manner as in Example 1 except that the ratio of F and S was 53:47, the alkali-soluble novolak resin dissolved in the organic solvent was 85 parts by weight, and the alkali-soluble phenol resin was 15 parts by weight. Prepared.

(Example 3)
The photosensitive resin composition was prepared in the same manner as in Example 1 except that the ratio of F and S was 66:34, 95 parts by weight of the alkali-soluble novolak resin dissolved in the organic solvent and 5 parts by weight of the alkali-soluble phenol resin were used. Prepared.

Example 4
Preparation of photosensitive resin composition in the same manner as in Example 1 except that the ratio of F and S was 58:42, and a solvent composed of PGMEA 90 wt% and diethylene glycol butyl methyl ether (BDM) 10 wt% was used as the organic solvent. Went.

(Example 5)
The photosensitive resin composition was the same as in Example 1 except that the ratio of F and S was 58:42 and the organic solvent was a solvent composed of PGMEA 70 wt%, propylene glycol monomethyl ether (PGME) 20 wt% and BDM 10 wt%. The product was prepared.

(Example 6)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that an alkali-soluble phenol resin having a weight average molecular weight (Mw) of 721 and a molecular weight distribution (Mw / Mn) of 1.54 was used. went.

(Comparative Example 1)
The photosensitive resin composition was prepared in the same manner as in Example 1 except that the ratio of F and S was 72:28, 100 parts by weight of the alkali-soluble novolak resin was dissolved in the organic solvent, and the alkali-soluble phenol resin was not dissolved. Prepared.

(Comparative Example 2)
The photosensitive resin composition was prepared in the same manner as in Example 1, except that the ratio of F and S was 48:52, the alkali-soluble novolak resin dissolved in the organic solvent was 80 parts by weight, and the alkali-soluble phenol resin was 20 parts by weight. Prepared.

(Comparative Example 3)
Example 1 except that the ratio of F and S was 63:37, and an alkali-soluble phenol resin having a weight average molecular weight (Mw) of 1600 and a molecular weight distribution (Mw / Mn) of 1.72 was used. In the same manner, a photosensitive resin composition was prepared.

(Comparative Example 4)
Example 1 except that the ratio of F and S was 62:38, and an alkali-soluble phenol resin having a weight average molecular weight (Mw) of 620 and a molecular weight distribution (Mw / Mn) of 3.22 was used. In the same manner, a photosensitive resin composition was prepared.

(Comparative Example 5)
A photosensitive resin composition was prepared in the same manner as in Example 1 except that a solvent composed of 100 wt% PGMEA was used as the organic solvent.

(Comparative Example 6)
Photosensitive resin composition as in Example 1 except that the ratio of F and S was 58:42 and a low molecular phenol compound (Mw = 424, Mw / Mn≈1) was used instead of the alkali-soluble phenol resin. The product was prepared.

(Evaluation method)
The photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were evaluated by the following methods.

(sensitivity)
After dropping the preparation solution onto a silicon wafer substrate and spinning it, vacuum drying was performed with a slow vacuum time of 20 seconds and a main pressure of 35 Pa, and then heat drying at 110 ° C./180 s to obtain a film thickness of 1.5 μm. A film was formed. Then, it exposed with the ultrahigh pressure mercury lamp through a 3 micrometer line and space mask. Next, a development step of immersing in an aqueous tetramethylammonium hydroxide solution adjusted to 2.5% for 70 seconds was performed to pattern the film.

  The line width of the formed pattern was observed, and the exposure amount having a length of 3 μm, similar to the mask design, was used as the sensitivity. A smaller value indicates that the time required for the exposure process is shortened. Therefore, the smaller the value, the better the energy saving.

(Bake temperature margin)
A film was formed by the same method as the sensitivity evaluation except that the heating and drying conditions were 90 ° C./180 s, 100 ° C./180 s, 110 ° C./180 s, and 120 ° C./180 s. The film thickness after the development process was observed, and the remaining ratio of the film thickness after the development process was observed as the remaining film ratio (film thickness after development / film thickness before development). The difference between the maximum value and the minimum value of the remaining film rate under various heating conditions was defined as the baking temperature margin. A smaller value indicates that the film thickness does not change even if the conditions change. Therefore, the smaller the value, the more uniform the pattern can be formed on the large substrate.

(Development time margin)
After film formation by the same method as the sensitivity evaluation, development was performed under three conditions of 70 s, 90 s, and 110 s. The residual film ratio under various conditions was observed, and the difference between the maximum value and the minimum value of the residual film ratio was defined as the development time margin. A smaller value indicates that the film thickness does not change even if the conditions change. Therefore, the smaller the value, the more uniform the pattern can be formed on the large substrate.

(Coating unevenness)
A pedestal having a length of 3 mm, a width of 3 mm, and a height of 5 μm was placed under the substrate, and was applied onto a 730 mm × 920 mm (thickness 0.7 mm) glass substrate using a slit coater. Thereafter, the change in film thickness at the pedestal portion was observed, and the difference between the maximum film thickness value and the minimum film thickness value was calculated. A smaller value indicates that coating unevenness is less likely to occur. Therefore, the smaller the value is, the more preferable it is as a resist when coating with a large substrate.

The results of Examples 1 to 6 and Comparative Examples 1 to 6 are shown in Table 1.

  As seen in Table 1, the alkali-soluble novolak resin (A) and the alkali-soluble phenol resin (B) whose molecular weight and molecular weight distribution are controlled are used in combination, and the alkali-soluble novolak resin (A) and the alkali-soluble phenol are used. When the ratio of the resin (B) is set to a specific range, and PGMEA (D1) and the solvent (D2) having a specific boiling point are used in combination as the organic solvent (D), the sensitivity is high, and It was found that the process margin (baking temperature margin and development time margin) is large and coating unevenness can be suppressed.

  On the other hand, as seen in Comparative Examples 1 to 6, it was found that when these conditions were not satisfied, the coating unevenness was increased, the process margin was decreased, and the sensitivity was decreased.

Claims (5)

Having an alkali-soluble novolak resin (A), an alkali-soluble phenol resin (B), a quinonediazide sulfonic acid ester (C) and an organic solvent (D),
The weight ratio of the alkali-soluble novolac resin (A) and the alkali-soluble phenol resin (B) is 95: 5 to 85:15,
The molecular weight of the alkali-soluble phenol resin (B) is 1000 or less, and the molecular weight distribution is 1.05 or more and 1.65 or less,
The organic solvent (D) is a photosensitive resin composition which is a composite solvent containing propylene glycol monomethyl ether (D1) and a solvent (D2) having a boiling point of 150 to 240 ° C. under normal pressure.   The photosensitive resin composition according to claim 1, wherein the solvent (D2) has a boiling point of 150 ° C. to 200 ° C. under normal pressure.   The photosensitive resin composition according to claim 1, wherein the solvent (D2) is diethylene glycol dialkyl ether.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin composition (B) has a molecular weight of 1.10 or more and 1.50 or less.   The quinonediazide sulfonate ester (C) is 1,2-naphthoquinonediazide-5-sulfonyl chloride and 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl]. The photosensitive resin composition as described in any one of Claims 1-4 containing the ester compound of an ethylidene] bisphenol.