CN106200267B

CN106200267B - Positive photosensitive resin composition, pattern forming method and application thereof

Info

Publication number: CN106200267B
Application number: CN201610334773.2A
Authority: CN
Inventors: 庄国平; 施俊安
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2015-05-25
Filing date: 2016-05-19
Publication date: 2020-01-03
Anticipated expiration: 2036-05-19
Also published as: CN106200267A; TW201642032A; TWI584066B

Abstract

The present invention relates to a positive photosensitive resin composition comprising a novolak resin (a), an ester (B) of an o-naphthoquinone diazide sulfonic acid, a urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule, and a solvent (D). The invention also relates to a method for forming patterns by using the positive photosensitive resin composition, and application of the positive photosensitive resin composition in a thin film transistor array substrate and a liquid crystal display element. The positive photosensitive resin composition has good pattern contrast and stripping performance.

Description

Positive photosensitive resin composition, pattern forming method and application thereof

Technical Field

The present invention relates to a positive photosensitive resin composition and a pattern forming method thereof, and more particularly, to a positive photosensitive resin composition having excellent pattern contrast and stripping property used in the manufacture of a semiconductor integrated circuit device, a liquid crystal display device of a thin film transistor (hereinafter referred to as TFT) or a touch panel, and a pattern forming method using the same.

Background

With the miniaturization of various electronic products in life, various smart phones, thin televisions and high-performance microprocessors are charged in the life, so that the photolithography process is more and more precise, and the line width formed is more and more precise.

In response to the requirements of different characteristics of the photoresist, japanese patent application laid-open No. 2010-20291 discloses a positive photosensitive resin composition comprising an alkali-soluble resin, a quinone diazide compound, a curing agent and an organic solvent. The alkali-soluble resin may include an acryl copolymer prepared by radical polymerization of monomers of an unsaturated olefin compound and an unsaturated carboxylic acid in the presence of a solvent and a polymerization initiator, and a novolac resin prepared by reacting a phenol compound with an aldehyde compound or a ketone compound in the presence of an acidic catalyst. The alkali-soluble resin can improve the heat resistance of the positive photosensitive resin composition.

Next, taiwan laid-open publication No. 201413378 discloses a positive photosensitive resin composition comprising an alkali-soluble resin, an o-naphthoquinone diazide sulfonate, a urethane (meth) acrylate compound having at least six (meth) acryloyl groups per molecule, and a solvent. Wherein the alkali-soluble resin is obtained by copolymerizing unsaturated carboxylic acid or unsaturated carboxylic acid anhydride compound, unsaturated compound containing epoxy group, and other unsaturated compounds. The protective film obtained from the positive photosensitive resin composition has a good cross-sectional shape and a low coefficient of linear expansion.

In addition, taiwan laid-open publication No. 201425476 discloses a positive photosensitive resin composition comprising a polysiloxane polymer, an o-naphthoquinone diazide sulfonate, a urethane (meth) acrylate compound having at least six (meth) acryloyl groups per molecule, and a solvent, wherein the polysiloxane polymer is obtained by hydrolysis and partial condensation of a silane monomer having a specific structure. The protective film prepared by the positive photosensitive resin composition has better sensitivity.

However, in the aforementioned prior art, the pattern contrast and the stripping property of the positive photosensitive resin composition have not yet reached the requirements of the industry.

In view of the above, there is a need to develop a positive photosensitive resin composition material with good pattern contrast and stripping property to overcome the problems of the prior art.

Disclosure of Invention

Accordingly, an aspect of the present invention is to provide a positive photosensitive resin composition having good pattern contrast and stripping property.

Another aspect of the present invention is to provide a pattern forming method for forming a pattern using the positive photosensitive resin composition.

Another aspect of the present invention is to provide a thin film transistor array substrate including a pattern formed by the method.

In another aspect, the present invention provides a liquid crystal display device including the thin film transistor array substrate.

According to the above aspect of the present invention, there is provided a positive photosensitive resin composition comprising a novolak resin (a), an esterified compound of an o-naphthoquinone diazide sulfonic acid (B), a urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule, and a solvent (D), which is analyzed as follows.

Novolac resin (A)

The novolak resin (A) of the present invention comprises a xylenol-type novolak resin (A-1) and other novolak resins (A-2).

Dimethylphenol type novolak resin (A-1)

The xylenol novolac resin (A-1) is obtained by polycondensation reaction of aldehyde compounds and aromatic hydroxyl compounds in the presence of an acid catalyst, wherein the aromatic hydroxyl compounds at least comprise xylenol compounds.

Specific examples of the aforementioned aldehyde compounds include: formaldehyde, paraformaldehyde (paraformaldehyde), trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde (acrolein), crotonaldehyde (crotonaldehyde), cyclohexanaldehyde (cyclo hexanaldehyde), furaldehyde (furfurfurfuraldehyde), furylacrolein (furylacrolein), benzaldehyde, terephthalaldehyde (terephthal aldehyde), phenylacetaldehyde, α -phenylpropionaldehyde, β -phenylpropionaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, and the like. The aldehyde compounds can be used singly or in combination. Preferably, the aldehyde compound may be formaldehyde or benzaldehyde.

Specific examples of the aforementioned aromatic hydroxy compound include: phenol (phenol); cresol (cresol) compounds such as m-cresol (m-cresol), p-cresol (p-cresol), o-cresol (o-cresol), and the like; xylenol (xylenol) compounds such as 2, 3-xylenol, 2, 5-xylenol, 3, 5-xylenol, and 3, 4-xylenol; alkylphenol (alkyl phenol) compounds such as m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3, 5-trimethylphenol, 2,3, 5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol and 6-tert-butyl-3-methylphenol; alkoxyphenol (alkoxy phenol) compounds such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol; isopropenylphenol (isopropenylphenol) compounds such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol; aryl phenols (aryl phenols) of phenylphenol; polyhydroxy benzenes (polyhydroxybenzenes) compounds such as 4,4' -dihydroxybiphenyl, bisphenol a, m-dihydroxybenzene (resorcinol), p-dihydroxybenzene (hydroquinone), and 1,2, 3-benzenetriol (pyromalnol). The aromatic hydroxy compounds mentioned above may be used singly or in combination of plural kinds.

Preferably, the aromatic hydroxy compound may be 3, 5-xylenol, 3, 4-xylenol, 2, 5-xylenol, o-cresol, m-cresol or p-cresol.

Specific examples of the foregoing acidic catalyst include: hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, or the like.

The above-mentioned bisphenol novolak resin (A-1) may be used singly or in combination of two or more.

The amount of the xylenol type novolak resin (a-1) used is 10 to 80 parts by weight, preferably 10 to 70 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the novolak resin (a). When the novolak resin (a) includes the xylenol novolak resin (a-1), the pattern formed by the positive photosensitive resin composition is better in stripping property.

In the xylenol type novolak resin (a-1), the amount of the xylenol compound used is 0.1 to 0.4 mol, preferably 0.1 to 0.35 mol, more preferably 0.1 to 0.3 mol, based on 1 mol of the total amount of the aromatic hydroxy compounds used. If the amount of the xylenol compound used falls within the above range, the pattern formed by the positive photosensitive resin composition has a better pattern contrast.

Other Novolac resin (A-2)

The other novolak resin (a-2) is obtained by polycondensing the aldehyde compound and the aromatic hydroxy compound in the presence of the acidic catalyst, but the aromatic hydroxy compound does not contain a xylenol (xylenol) compound.

Preferably, the aldehyde compound may be formaldehyde or benzaldehyde; preferably, the aromatic hydroxy compound may be o-cresol, m-cresol, p-cresol.

The other novolak resin (a-2) is used in an amount of 20 to 90 parts by weight, preferably 30 to 90 parts by weight, more preferably 40 to 80 parts by weight, based on 100 parts by weight of the novolak resin.

The aforementioned other novolak resins (A-2) may be used singly or in combination of plural kinds.

If the positive photosensitive resin composition of the present invention does not use the novolak resin (a), the resulting positive photosensitive resin composition has defects of poor pattern contrast and stripping property.

Ester of o-naphthoquinone diazide sulfonic acid (B)

The kind of the ortho-naphthoquinone diazide sulfonic acid ester (B) is not particularly limited, and a generally used ortho-naphthoquinone diazide sulfonic acid ester can be used. The ester (B) of the o-naphthoquinone diazide sulfonic acid may be a fully esterified (fully esterified) or partially esterified (partially esterified) ester compound (ester-based compound).

The ester (B) of an o-naphthoquinone diazide sulfonic acid is preferably prepared by reacting an o-naphthoquinone diazide sulfonic acid (o-naphthoquinone diazide sulfonic acid) or a salt thereof with a hydroxyl compound, more preferably by reacting an o-naphthoquinone diazide sulfonic acid or a salt thereof with a polyhydric hydroxyl compound.

Specific examples of the o-naphthoquinone diazide sulfonic acid include: o-naphthoquinone diazide-4-sulfonic acid, o-naphthoquinone diazide-5-sulfonic acid, o-naphthoquinone diazide-6-sulfonic acid, and the like. Specific examples of the salts of o-naphthoquinone diazide sulfonic acid include: o-naphthoquinone diazide sulfonyl halide (diazonaphthoquinone sulfonyl halide).

Specific examples of the hydroxyl compound include (1) hydroxybenzophenone compounds (hydrooxybenzophenone-based compounds); (2) hydroxyaryl-based compound (hydroxyl-based compound); (3) (hydroxyphenyl) hydrocarbon compounds (hydroxyphenyl compounds); (4) other aromatic hydroxy compounds.

The aforementioned hydroxybenzophenone compound may include, but is not limited to, 2,3, 4-trihydroxybenzophenone, 2,4,4 '-trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,3,4,4' -tetrahydroxybenzophenone, 2',4, 4' -tetrahydroxybenzophenone, 2, 3',4, 4', 6 '-pentahydroxybenzophenone, 2',3, 4,4 '-pentahydroxybenzophenone, 2',3, 4,5 '-pentahydroxybenzophenone, 2, 3',4, 5,5 '-pentahydroxybenzophenone, 2,3, 3',4, 4', 5' -hexahydroxybenzophenone, and the like.

The aforementioned hydroxyaryl compound may comprise a hydroxyaryl compound represented by the formula (I):

in the formula (I), R¹And R²Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; r³、R⁴And R⁷Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; r⁵、R⁶、R⁸、R⁹、R¹⁰And R¹¹Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a cycloalkyl group (cycloakyl); a. c and d each independently represent an integer of 1 to 3; b represents 0 or 1.

Specific examples of the hydroxyaryl compound represented by the formula (I) are as follows: tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -3-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -3, 4-dihydroxyphenylmethane, bis (4-hydroxy-2, 5-dimethylphenyl) -3, 4-dihydroxyphenylmethane, bis (4-hydroxy-3, 5-dimethylphenyl) -2, 4-dihydroxyphenylmethane, bis (4-hydroxy-2, 5-dimethylphenyl) -2, 4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2, 4-dihydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (4-hydroxyphenyl-4-hydroxyphenyl), Bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -3, 4-dihydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl), Bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -3, 4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (3-methyl-4-hydroxyphenyl) ethyl ] benzene, and the like.

The (hydroxyphenyl) hydrocarbyl compound has a structure as shown in formula (II):

in the formula (II), R¹²And R¹³Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; e and f each independently represent an integer of 1 to 3.

Specific examples of the (hydroxyphenyl) hydrocarbon-based compound having the formula (II) are as follows: 2- (2,3, 4-trihydroxyphenyl) -2- (2',3',4 '-trihydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) -2- (2',4 '-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4' -hydroxyphenyl) propane, bis (2,3, 4-trihydroxyphenyl) methane or bis (2, 4-dihydroxyphenyl) methane, and the like.

Specific examples of the aforementioned other aromatic hydroxy compounds include: phenol (phenol), p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol a, naphthol, catechol, 1,2, 3-benzenetriol methyl ether, 1,2, 3-benzenetriol-1, 3-dimethyl ether, 3,4, 5-trihydroxybenzoic acid, partially esterified or partially etherified (etherified) 3,4, 5-trihydroxybenzoic acid, and the like.

The above-mentioned hydroxyl compounds may be used singly or in admixture of plural kinds. Preferably, the hydroxy compound may be 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene, 2,3, 4-trihydroxybenzophenone, 2,3,4,4' -tetrahydroxybenzophenone.

The reaction of the o-naphthoquinone diazide sulfonic acid or its salt with the hydroxyl compound is usually carried out in an organic solvent such as dioxane (dioxane), N-pyrrolidone (N-pyrrolidone), or acetamide (acetamide). Preferably, the reaction is carried out in a basic condensing agent (condensing agent) such as triethanolamine, alkali metal carbonate or alkali metal bicarbonate.

The degree of esterification (degree of esterification) of the ester (B) of an o-naphthoquinonediazide sulfonic acid is preferably 50% or more, that is, 50 mol% or more of the hydroxyl groups in the hydroxyl compound are esterified with the o-naphthoquinonediazide sulfonic acid or a salt thereof based on 100 mol% of the total amount of the hydroxyl groups in the hydroxyl compound. More preferably, the degree of esterification of the ortho-naphthoquinone diazide sulfonic acid ester (B) is 60% or more.

The amount of the esterified product of o-naphthoquinone diazide sulfonic acid (B) is 5 to 50 parts by weight, preferably 10 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the novolak resin (a).

Urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule

The urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule of the present case can be obtained by a known method. Specific preparation methods may be, for example but not limited to: the urethane (meth) acrylate compound (C) is prepared by reacting a polyisocyanate with a polyol, and then reacting with a hydroxyl group-containing (meth) acrylate; or the urethane (meth) acrylate compound (C) can be obtained by reacting a polyisocyanate with a hydroxyl group-containing (meth) acrylate and then reacting with a polyol. Preferably, the urethane (meth) acrylate compound (C) is obtained by reacting a bifunctional polyisocyanate with a bifunctional polyol, and then reacting with pentaerythritol tri (meth) acrylate. More preferably, the preparation method further comprises using a reaction catalyst, which can be, for example, but not limited to, known urethanization catalysts such as dibutyltin dilaurate.

Hydroxyl-containing (meth) acrylates may be exemplified by, but not limited to: 2-hydroxyethyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl di (meth) acrylate, triglycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, epoxy acrylate, and the like, and may be used alone or in combination of 2 or more. Preferably, the hydroxyl group-containing (meth) acrylate is pentaerythritol tri (meth) acrylate.

Preferably, the polyisocyanate is a polyisocyanate having 2 or more isocyanate groups in the molecule, such as but not limited to: aromatic system such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate (hexamethylene diisocyanate), isophorone diisocyanate (isophorone diisocyanate), xylylene diisocyanate (xylylene diisocyanate), hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, and the like; the above-mentioned polyisocyanates may be used singly or in admixture of 2 or more.

Preferably, the polyol may be, for example but not limited to: poly (propylene oxide) diol, poly (propylene oxide) triol, copoly (ethylene oxide-propylene oxide) diol, poly (tetrahydrofuran) diol, ethoxylated bisphenol a, ethoxylated bisphenol S, spiroglycol, caprolactone-modified diol, carbonate diol, trimethylolpropane, pentaerythritol, and the like; the above polyols may be used singly or in admixture of 2 or more.

Preferably, the weight average molecular weight of the urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule is in the range of 1,000 to 200,000, preferably 1,200 to 100,000, more preferably 1,500 to 50,000.

Preferably, the urethane (meth) acrylate compound (C) is a urethane (meth) acrylate compound having at least seven (meth) acryloyl groups per molecule.

More preferably, the urethane (meth) acrylate compound (C) is a urethane (meth) acrylate compound having at least eight (meth) acryloyl groups per molecule.

Commercially available products of the urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule can be exemplified by, but are not limited to:

(1) a urethane (meth) acrylate compound having six (meth) acryloyl groups per molecule: violet UV-7600B and violet UV-7605B manufactured by japan synthetic chemistry (stock); art Resin UN-3320HA, Art Resin UN-3320HC, manufactured industrially (on-the-counter) from root; NK Oligo U-6HA and NK Oligo U-6LPA manufactured by the New Zhongcun chemical industry (Strand); EBECRYL 5129, EBECRYL 220, EBECRYL 8301, KRM8200AE, manufactured by DAICEL-CYTEC corporation; beam Set575, Beam Set 577 and the like manufactured by the seikagawa chemical industry (stock);

(2) a urethane (meth) acrylate compound having seven (meth) acryloyl groups per molecule: such as violet UV-6300B manufactured by Japanese synthetic chemistry (Strand);

(3) a urethane (meth) acrylate compound having at least eight (meth) acryloyl groups per molecule: violet UV-7610B, violet UV-7620EA, and violet UV-1700B manufactured by Nippon synthetic chemistry (Strand Co., Ltd.); art Resin UN-901T, Art Resin UN-3320HS manufactured by Okinawa industries (Strand); NK Oligo UA-33H, NK Oligo UA-53H manufactured by New Zhongcun chemical industry (Strand); KRM 8452 manufactured by DAICEL-CYTEC, Inc.

The commercially available products can be used singly or in combination of 2 or more. Among them, the preferable one is: violet UV-1700B, violet UV-6300B and violet UV-7605B manufactured by Nippon synthetic chemistry, NK Oligo U-6HA manufactured by New Zhongcun chemical industry, and Art Resin UN-3320HC, Art Resin UN-3320HS and Art Resin UN-901T manufactured by Nakamura industry.

The urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule is used in an amount ranging from 0.5 parts by weight to 10 parts by weight, based on 100 parts by weight of the novolac resin (a). Preferably, the urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule is used in an amount ranging from 0.5 parts by weight to 8 parts by weight. More preferably, the urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule is used in an amount ranging from 1 part by weight to 8 parts by weight.

When the positive photosensitive resin composition does not contain the urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule, the pattern contrast and the strippability are not good. When the positive photosensitive resin composition contains the urethane (meth) acrylate compound (C) having at least seven (meth) acryloyl groups per molecule, the formed pattern has better pattern contrast. When the positive photosensitive resin composition contains the urethane (meth) acrylate compound (C) having at least eight (meth) acryloyl groups per molecule, the formed pattern has better pattern contrast.

Solvent (D)

The solvent (D) used in the positive photosensitive resin composition of the present invention is an organic solvent which is relatively soluble in other organic components but does not react with the above components.

Specific examples of the solvent (D) of the present invention include: (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, and propylene glycol ethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and 4-hydroxy-4-methyl-2-pentanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate (also called ethyl lactate); methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, methyl propionate, ethyl butyrate, ethyl propionate, n-propyl pyruvate, methyl acetoacetate, methyl propionate, ethyl, Other esters such as ethyl acetoacetate and ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; and carboxylic acid amines such as N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide. The above-mentioned solvent (D) may be used singly or in combination of plural kinds. Preferably, the solvent (D) may be propylene glycol monoethyl ether, propylene glycol methyl ether acetate or ethyl lactate.

The amount of the solvent (D) is usually 100 to 800 parts by weight, preferably 100 to 700 parts by weight, more preferably 100 to 600 parts by weight, based on 100 parts by weight of the novolak resin (a).

Additive (E)

The positive photosensitive resin composition of the present invention may optionally contain an additive (E). Additives (E) may include, but are not limited to, adhesion promoters, surface flatteners, diluents, sensitizers, and the like.

The adhesion promoter may include, but is not limited to, a melamine (melamine) compound and a silane (silane) compound to increase adhesion between the positive photosensitive resin composition and the attachment substrate. Specific examples of the melamine include: a commodity manufactured by CYTEC corporation, and having a model number of Cymel-300 or Cymel-303; and a commodity of chemical make, type MW-30MH, MW-30, MS-11, MS-001, MX-750 or MX-706. Specific examples of the aforementioned silane (silane) -based compound include: vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methoxysilane, 3-hydroxyethoxypropyltrimethoxysilane, 3-glycidyloxypropyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl, Bis-1, 2- (trimethoxysilyl) ethane.

In specific embodiments of the present invention, the adhesion promoter of the above melamine compound is used in an amount of generally 0 to 20 parts by weight, preferably 0.5 to 18 parts by weight, more preferably 1.0 to 15 parts by weight, based on 100 parts by weight of the novolak resin (a); the adhesion promoter of the silane compound is used in an amount of usually 0 to 2 parts by weight, preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.8 part by weight.

The surface planarization agent may include, but is not limited to, a fluorine-based surfactant or a silicon-based surfactant. Specific examples of the fluorine-based surfactant include: manufactured by 3M company under model number Fluorad FC-430 or FC-431 or manufactured by Tochemprodute under model number F top EF122A, 122B, 122C, 126 or BL 20. Specific examples of the aforementioned silicon-based surfactant include: commercially available products are available from Dow Corning Toray Silicone as model Nos. SF8427 or SH29 PA.

In specific embodiments of the present invention, the surfactant is used in an amount of generally 0 to 1.2 parts by weight, preferably 0.025 to 1.0 part by weight, more preferably 0.050 to 0.8 parts by weight, based on 100 parts by weight of the novolak resin (a).

Specific examples of the above diluent include: products manufactured by empire INK, model RE801 or RE 802.

Specific examples of the sensitizer include: the commercial products manufactured by the chemical industry of Benzhou, Japan, and having the models TPPA-1000P, TPPA-100-2C, TPPA-1100-3C, TPPA-1100-4C, TPPA-1200-24X, TPPA-1200-26X, TPPA-1300 and 235T, TPPA-1600-3M6C or TPPA-MF, and the commercial products having the models TPPA-1600-3M6C or TPPA-MF are preferred.

The aforementioned additives (E) may be used singly or in admixture of a plurality.

In the specific embodiment of the present invention, the aforementioned sensitizer is used in an amount of usually 0 to 20 parts by weight, preferably 0.5 to 18 parts by weight, more preferably 1.0 to 15 parts by weight, based on 100 parts by weight of the novolak resin (a). In addition, other additives can be optionally added according to the requirement, such as: plasticizers, stabilizers, and the like.

Method for producing positive photosensitive resin composition

The positive photosensitive resin composition of the present invention is generally prepared by adding the above novolak resin (a), the ester compound (B) of an o-naphthoquinone diazide sulfonic acid group, the urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule, and the solvent (D) to a known stirrer and stirring them to uniformly mix them in a solution state, and adding various additives (E) according to need.

Pattern forming method

The positive photosensitive composition obtained above may be subjected to a coating step, a prebake (prebake) step, an exposure step, a development step, and a postbake (postbake) treatment step in this order, to form a pattern on a substrate.

In the method of forming a pattern using the positive photosensitive resin composition, the positive photosensitive resin composition can be applied to a substrate by an application method such as spin coating, cast coating, or roll coating. After coating, the solvent is removed by pre-baking to form a pre-baked coating. Wherein the pre-baking step is generally performed at 70 to 110 ℃ for 1 to 15 minutes, depending on the kind and compounding ratio of each component.

After the pre-baking step, the coating film is exposed to light under a prescribed mask and then immersed in a developing solution at 21 to 25 ℃ for 15 seconds to 5 minutes, thereby removing the exposed portion to form a specific pattern. The light used for the exposure is preferably ultraviolet rays such as g-rays, h-rays, i-rays, etc., and the ultraviolet irradiation apparatus may be an (ultra) high pressure mercury lamp or a metal halide lamp.

Specific examples of the developing solution used in the present invention may be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methylsilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylamine hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or an alkaline compound of 1, 8-diazabicyclo- [5,4,0] -7-undecene.

Preferably, the concentration of the developer solution can be 0.001 wt% to 10 wt%, more preferably 0.005 wt% to 5 wt%, and even more preferably 0.01 wt% to 1 wt%.

When the developer is formed using the above-mentioned alkali compound, the coating film is usually air-dried by washing with water after development and by using compressed air or compressed nitrogen gas. Next, the coating film is subjected to a post-baking step using a heating device such as a hot plate or an oven. The post-baking temperature is usually 100 to 250 ℃, wherein the heating time using a hot plate is 1 to 60 minutes, and the heating time using an oven is 5 to 90 minutes. After the above processing steps, a pattern can be formed on the substrate.

Thin film transistor array substrate

The thin film transistor array substrate of the invention is prepared by the method. In brief, the positive photosensitive resin composition of the present invention can be applied to a glass substrate or a plastic substrate containing a thin film of aluminum, chromium, silicon nitride, amorphous silicon, or the like by a coating method such as spin coating, cast coating, roll coating, or the like, to form a positive photoresist layer. Then, a photosensitive resin pattern is formed by sequentially carrying out pre-baking, exposure, development and post-baking treatments. Then, etching and photoresist stripping are performed. Repeating the above steps to obtain the thin film transistor array substrate with a plurality of thin film transistors or electrodes.

Fig. 1 is a schematic partial cross-sectional view illustrating a thin film transistor array substrate for a Liquid Crystal Display (LCD) device according to an embodiment of the present invention. First, the gate electrode 102a and the storage capacitor Cs electrode 102b are provided on an aluminum thin film or the like on the glass substrate 101. Next, a silicon oxide film (SiO) is formed on the gate 102a_x)103 or silicon nitride film (SiN)_x)104, and an amorphous silicon layer (a-Si)105 as a semiconductor active layer is formed on the insulating film. Next, in order to reduce the junction resistance, an amorphous silicon layer 106 doped with nitrogen impurity may be disposed on the amorphous silicon layer 105. Then, a drain 107a and a source 107b are formed using a metal such as aluminum, wherein the drain 107a is connected to a data signal line (not shown), and the source 107b is connected to a pixel electrode (or sub-pixel electrode) 109. Thereafter, a silicon nitride film or the like is provided as a protective film 108 for protecting the amorphous silicon layer 105, the drain 107a, the source 107b, or the like, which is a semiconductor active layer.

Liquid crystal display element

The liquid crystal display element at least comprises the thin film transistor array substrate and can comprise other components according to requirements.

A specific example of the basic configuration of the liquid crystal display device is (1) a thin film transistor array substrate (drive substrate) of the present invention in which drive elements such as thin film transistors and pixel electrodes (conductive layers) are arranged, and a color filter substrate composed of a color filter and a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and finally a liquid crystal material is sealed in the gap portion. (2) The color filter integrated thin film transistor array substrate in which the color filter is directly formed on the thin film transistor array substrate is configured by interposing a spacer between the color filter integrated thin film transistor array substrate and the counter substrate provided with the counter electrode (conductive layer) and disposing the counter substrate in an opposite manner, and finally sealing a liquid crystal material in a gap portion.

Specific examples of the conductive layer include an indium tin oxide film; metal films of aluminum, zinc, copper, iron, nickel, chromium, molybdenum, and the like; a metal oxide film of silicon dioxide or the like. Preferably, the conductive layer is a transparent film. The conductive layer is preferably an indium tin oxide film.

The substrate used for the thin film transistor array substrate, the color filter substrate, the counter substrate, and the like of the present invention may be a known glass substrate such as soda lime glass, low-expansion glass, alkali-free glass, or quartz glass. In addition, as the substrate, a substrate made of a plastic film or the like may be used.

Compared with the prior art, the positive photosensitive resin composition has good pattern contrast and stripping performance.

The present invention is described in detail below with reference to the embodiments, but the present invention is not limited thereto, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention.

Drawings

In order to make the aforementioned and other objects, features, advantages and embodiments of the invention more comprehensible, the following description is given:

FIG. 1 is a schematic partial cross-sectional view of a TFT array substrate for an LCD device according to an embodiment of the present invention;

FIG. 2 is a schematic view showing a pattern section formed on a substrate by a positive photosensitive composition according to an embodiment of the present invention;

wherein, the notation:

101 glass substrate 102a grid

102b storage capacitor Cs electrode 103 silicon oxide film

104 silicon nitride film 105 amorphous silicon layer

106 amorphous silicon layer 107a drain

107b Source 108 protective film

109 pixel electrode 201 reverse taper pattern section

203 oval pattern section.

Detailed Description

Preparation of Novolac resin (A)

The novolak resins (A) of Synthesis examples A-1-1 to A-2-3 were prepared according to Table 1.

Synthesis example A-1

A four-necked flask having a volume of 1000 ml was equipped with a nitrogen inlet, a stirrer, a heater, a condenser and a thermometer, and 0.4 mol of m-cresol, 0.5 mol of p-cresol, 0.1 mol of 3, 4-xylenol, 0.65 mol of formaldehyde and 0.2 mol of oxalic acid were added thereto after introducing nitrogen gas. The reaction solution was warmed to 100 ℃ with slow stirring and polymerized for 6 hours at this temperature. Then, the reaction solution was heated to 180 ℃ and dried under reduced pressure of 10mmHg, and the solvent was devolatilized to obtain a xylenol novolak resin (A-1-1).

Synthesis examples A-1-2 to A-1-6

Synthesis examples A-1-2 to A-1-6 used the same procedures as the synthesis of the xylenol-type novolak resin of Synthesis example A-1-1, except that the kinds and amounts of the raw materials used in the novolak resin were changed in the synthesis examples A-1-2 to A-1-6, and the respective formulations are shown in Table 1, and thus, they are not described again.

Synthesis example A-2-1

A four-necked flask having a volume of 1000 ml was equipped with a nitrogen inlet, a stirrer, a heater, a condenser and a thermometer, and 0.7 mol of m-cresol, 0.3 mol of p-cresol, 0.7 mol of formaldehyde and 0.015 mol of oxalic acid were added thereto after introducing nitrogen gas. The reaction solution was warmed to 100 ℃ with slow stirring and polymerized for 6 hours at this temperature. Then, the reaction solution was heated to 180 ℃ and dried under reduced pressure of 10mmHg, and the solvent was devolatilized to obtain a hydroxyl type novolak resin (A-2-1).

Synthesis examples A-2-2 and A-2-3

Synthesis examples A-2-2 and A-2-3 used the same procedures as the synthesis of the hydroxyl novolak resin of Synthesis example A-2-1, except that the types and amounts of the raw materials used and the reaction temperature in the novolak resin were changed in Synthesis examples A-2-2 and A-2-3, and the formulations and preparation conditions thereof are shown in Table 1, respectively, and thus, they are not described again.

Synthesis comparative example A-3-1

In a three-neck flask having a capacity of 500 ml, 0.30 mol of methyltrimethoxysilane, 0.65 mol of phenyltrimethoxysilane, 0.05 mol of 3- (triethoxysilyl) propylsuccinic anhydride and 200 g of propylene glycol monoethyl ether were charged, and an aqueous oxalic acid solution (0.40 g of oxalic acid/75 g of water) was added over 30 minutes at room temperature with stirring. Next, the flask was immersed in an oil bath at 30 ℃ and stirred for 30 minutes, the oil bath was then heated to 120 ℃ within 30 minutes, and when the internal temperature of the solution reached 105 ℃, the solution was continuously heated and stirred for polycondensation for 6 hours, and the solvent was removed by distillation to obtain polysiloxane polymer (A-3-1).

Synthesis comparative example A-4-1

A four-neck flask having a capacity of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser and a thermometer, and nitrogen gas was introduced. 10 parts by weight of methacrylic acid, 65 parts by weight of glycidyl methacrylate, 15 parts by weight of dicyclopentadienyl methacrylate, 10 parts by weight of styrene, and 240 parts by weight of diethylene glycol dimethyl ether as a solvent were added to the above four-necked flask in one portion. After the inside of the flask was filled with nitrogen gas, the contents of the four-necked flask were stirred and the oil bath was heated to 85 ℃, 3.0 parts by weight of the catalyst 2, 2' -azobis (2, 4-dimethylvaleronitrile) was dissolved in 20 parts by weight of diethylene glycol dimethyl ether, and the solution was added to the four-necked flask in five equal parts at intervals over one hour. The reaction temperature in the polymerization process was maintained at 70 ℃ and the polymerization time was 5 hours, and after completion of the polymerization, the polymerization product was taken out from the four-necked flask, and the solvent was devolatilized to obtain an alkali-soluble resin (A-4-1).

Preparation of Positive photosensitive resin composition

The following are positive photosensitive resin compositions of examples 1 to 8 and comparative examples 1 to 4 prepared according to table 2.

Example 1

The positive photosensitive resin composition of the present invention was prepared by adding 100 parts by weight of the hydroxy novolak resin of Synthesis example A-2-1, 5 parts by weight of the esterified product B-1 of 2,3, 4-trihydroxybenzophenone and 1, 2-naphthoquinone diazide-5-sulfonic acid, and 0.5 part by weight of Beam Set575 (manufactured by Mikawa chemical industries, Ltd.; C-1) to 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA; D-1), and stirring with a shaker mixer to dissolve the mixture in a solvent. The obtained positive photosensitive resin composition was evaluated in the following evaluation methods, and the results thereof are shown in table 2, in which the detection methods of pattern contrast and peelability will be described later.

Examples 2 to 14 and comparative examples 1 to 2

Examples 2 to 14 and comparative examples 1 to 2 were prepared by the same method as that for the positive photosensitive resin composition of example 1, except that the types and amounts of the raw materials used in the positive photosensitive resin compositions were changed in examples 2 to 14 and comparative examples 1 to 2, and the formulations and evaluation results thereof are shown in table 2, respectively, and are not repeated herein.

Comparative example 3

The positive photosensitive resin composition of comparative example 3 was prepared by adding 100 parts by weight of the polysiloxane polymer of comparative example A-3-1, 3 parts by weight of 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene and o-naphthoquinone diazide-5-sulfonic acid (trade name "DPAP 200", manufactured by DKC, average degree of esterification 67%), and 10 parts by weight of Beam Set575 (manufactured by Mikawa chemical industries), to 500 parts by weight of propylene glycol methyl ether acetate, and stirring the mixture uniformly with a shaking stirrer, and the pattern contrast and the peelability were X as evaluated by the following test items.

Comparative example 4

100 parts by weight of the alkali-soluble resin of comparative example A-4-1, 30 parts by weight of an o-naphthoquinone diazide sulfonate ester (product name: DPAP200, manufactured by DKC, average degree of esterification 67%) formed by 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1, 1-bis (4-hydroxyphenyl) ethyl ] benzene and o-naphthoquinone diazide-5-sulfonic acid), 10 parts by weight of Beam Set575 (manufactured by Mikawa chemical industries), 5 parts by weight of UV-7605B (manufactured by Japan synthetic chemical Co., Ltd.), and 400 parts by weight of PGMEA were put into a three-necked flask having a volume of 500 ml, and stirred uniformly by a shaker to obtain the positive photosensitive resin composition of comparative example 4. The pattern contrast and the strippability were both X as evaluated by the following test items.

Evaluation method

1. Contrast of pattern

A positive photosensitive resin composition was applied by spin coating on a mother glass substrate (100X100X0.7mm) and prebaked at 110 ℃ for 120 seconds to obtain a prebaked film having a thickness of about 7 μm. A pre-baked coating film was formed on a line-to-space (line and space) mask (made by Filcon, Japan) at 800mJ/cm²Ultraviolet light (Exposure machine model AG 500-4N; M)&R Nano Technology), then, the substrate was developed with 0.13N KOH aqueous solution at 23 ℃ for 135 seconds to remove the coating film on the exposed portion of the substrate, then, the substrate was cleaned with pure water, the cut surface of the pattern was photographed by SEM, and the lengths of the upper and lower bottoms of the cut surface of the pattern were calculated by the following formula (III):

the criteria for determining the contrast of the pattern are as follows:

ratio of upper sole to lower sole (upper sole/lower sole type (III)

Very good: 1 ≧ the ratio of the upper bottom to the lower bottom is > 0.9

O: 0.9 ≧ 0.8

And (delta): 0.8 ≧ 0.6

X: 0.6 ≧ ratio of upper base to lower base, or pattern section having reverse taper 201 or ellipse 203 as shown in FIG. 2

2. Stripping property

A positive photosensitive resin composition was applied by spin coating on a mother glass substrate (100X100X0.7mm), and prebaked at 110 ℃ for 120 minutes to give a prebaked film of about 7 μm. A pre-baked coating film was irradiated with ultraviolet light (model AG500-4N of exposure machine; manufactured by M & R Nano Technology) at 800mJ/cm2 using a mask (manufactured by Nippon corporation) with a line and space (line and space) therebetween, and then developed with a 0.13N KOH aqueous solution at 23 ℃ for 135 seconds to remove the coating film on the exposed portion of the substrate, followed by washing with pure water.

Next, the patterned mother glass substrate was immersed in a stripping solution (model ST897, manufactured by Chimei industries), and the number of seconds required for stripping the pattern was observed.

Very good: stripping seconds < 60 seconds

O: 60 seconds ≦ stripping seconds < 120 seconds

X: 120 seconds ≦ stripping seconds

The evaluation results of the pattern contrast and the strippability of the positive photosensitive resin compositions prepared in the examples and comparative examples are shown in table 2.

As is clear from the results in table 2, when the novolac resin (a) and the urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule are used for the positive photosensitive resin composition, the obtained positive photosensitive resin composition has good pattern contrast and stripping property.

Next, when the novolak resin (a) in the positive photosensitive resin composition contains the xylenol novolak resin (a-1), a positive photosensitive resin composition having a better stripping property can be obtained. Further, if the urethane (meth) acrylate compound (C) having at least seven (meth) acryloyl groups per molecule is used, the pattern contrast is better.

On the other hand, according to comparative examples 1 and 2 of table 2, if the urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule is not used, or if the urethane (meth) acrylate compound having less than six (meth) acryloyl groups per molecule is used, the obtained positive photosensitive resin composition is poor in both pattern contrast and strippability. In addition, the positive photosensitive resin composition obtained by the method of comparative example 3 or comparative example 4 does not use the novolak resin (a) of the present invention, and thus the pattern contrast and the stripping property of the composition are also poor.

It should be noted that, although the positive photosensitive resin composition and the pattern forming method thereof according to the present invention are exemplified by specific compounds, compositions, reaction conditions, processes, analysis methods, or specific devices, it is clear to those skilled in the art that the present invention is not limited thereto, and the positive photosensitive resin composition and the pattern forming method thereof according to the present invention may be carried out using other compounds, compositions, reaction conditions, processes, analysis methods, or devices without departing from the spirit and scope of the present invention.

Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.

TABLE 1

O-cresol

M-cresol

P-cresol

2, 5-xylenol

3, 5-xylenol

3, 4-xylenol

Formaldehyde formaldehydes

Benzaldehyde

3, 4-dihydroxybenzaldehyde 3, 4-dihydrobenzodiazepinehydrate

2,3, 4-trihydroxybenzaldehyde

O-hydroxymethylbenzaldehyde

Oxalic acid

Claims

1. A positive photosensitive resin composition, characterized by comprising:

a novolak resin (a) comprising a bisphenol novolak resin (a-1), wherein the bisphenol novolak resin (a-1) is formed by condensing an aldehyde compound with an aromatic hydroxy compound, the aromatic hydroxy compound contains at least a bisphenol compound, and the amount of the bisphenol compound used is 0.2 to 0.4 mol based on 1 mol of the aromatic hydroxy compound condensing the bisphenol novolak resin (a-1);

an ester (B) of an o-naphthoquinone diazide sulfonic acid;

a urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule; and

a solvent (D).

2. The positive photosensitive resin composition according to claim 1, wherein the urethane (meth) acrylate compound (C) is a urethane (meth) acrylate compound having at least seven (meth) acryloyl groups per molecule.

3. The positive photosensitive resin composition according to claim 1, wherein the urethane (meth) acrylate compound (C) is a urethane (meth) acrylate compound having at least eight (meth) acryloyl groups per molecule.

4. The positive photosensitive resin composition according to claim 1, wherein the amount of the ortho-naphthoquinone diazide sulfonic acid ester (B) is 5 to 50 parts by weight, the amount of the urethane (meth) acrylate compound (C) having at least six (meth) acryloyl groups per molecule is 0.5 to 10 parts by weight, and the amount of the solvent (D) is 100 to 800 parts by weight, based on 100 parts by weight of the novolak resin (a).

5. The positive photosensitive resin composition according to claim 1, wherein the amount of the xylenol novolak resin (a-1) is 10 to 80 parts by weight based on 100 parts by weight of the novolak resin (a).

6. A pattern forming method comprising subjecting the positive photosensitive resin composition according to any one of claims 1 to 5 to a coating step, a prebaking step, an exposure step, a development step, and a post-baking step in this order to form a pattern on a substrate.

7. A thin film transistor array substrate comprising the pattern formed by the method of claim 6.

8. A liquid crystal display device comprising the thin film transistor array substrate according to claim 7.