TWI644173B - Positive photosensitive resin composition and application thereof - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition and use thereof. The positive photosensitive resin composition contains a novolak resin (A), an ester of an o-naphthoquinonediazidesulfonic acid (B), and a solvent (C). The ester of the o-naphthoquinonediazide sulfonic acid (B) comprises an ester of an o-naphthoquinonediazide sulfonic acid (B-1) and an o-naphthoquinone diazide sulfonic acid formed by different hydroxy compounds, respectively. Esterified product (B-2). The positive photosensitive resin composition prepared has a preferable resolution and residual film ratio.

Description

Positive photosensitive resin composition and application thereof

The present invention relates to a positive photosensitive resin composition and use thereof, and in particular to a positive photosensitive resin composition having a preferred resolution and residual film ratio and use thereof.

With the miniaturization of various electronic products in life, various smart phones, thin TVs, and high-performance microprocessors are flooding in today's life, and the optical lithography process is becoming more and more sophisticated, and the line width formed is also coming. The finer it is.

In view of the demand for different characteristics of the photoresist, Japanese Laid-Open Patent Publication No. 2010-20291 discloses a positive photosensitive resin composition comprising an alkali-soluble resin, a diazide compound, a curing agent, and an organic solvent. . The alkali-soluble resin may comprise an acrylonitrile-based copolymer and a novolak resin, wherein the acryl-based copolymer-based unsaturated olefin compound and the monomer of the unsaturated carboxylic acid are prepared by radical polymerization in the presence of a solvent and a polymerization initiator. And the novolac resin is prepared by the presence of a phenol compound and 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, Japanese Laid-Open Patent Publication No. 2010-39270 is a positive photosensitive resin composition comprising a high molecular polymer, a diazide compound, a crosslinking agent, and a solvent. The high molecular polymer comprises a compound represented by the following formula (V), an acrylate compound and a phenolic hydroxy compound, wherein the high molecular polymer contains 1 to 50% by weight of a compound represented by the following formula (V). When the amount of the compound represented by the formula (V) is in the range described above, the positive photosensitive resin composition obtained has good adhesion and adhesion:

In the formula (V), P ₁ represents a hydrogen atom or a methyl group; P ₂ represents a phenyl or -COO-; P ₃ and P ₄ each independently represent a phenyl group, an alkyl group having 1 to 6 carbon atoms or an alkane Alkyl; P ₅ represents an alkyl group having 1 to 6 carbon atoms; g represents an integer of 0 to 3; and f represents an integer of 1 to 10.

However, the resolution and residual film rate of the aforementioned prior art still cannot meet the requirements of the industry.

In view of the above, it is necessary in the art to develop a positive photosensitive resin composition material having a better resolution and a residual film ratio to overcome the problems of the prior art.

Therefore, one aspect of the present invention provides a positive photosensitive resin composition. The positive photosensitive resin composition contains a novolak resin (A), an ester of the o-naphthoquinonediazide sulfonic acid (B) and a solvent (C), and the positive-type photosensitive resin composition has a preferable resolution and a residual film ratio.

Another aspect of the present invention provides a pattern forming method for forming a pattern on a substrate by using the positive photosensitive resin composition described above.

Yet another aspect of the present invention is to provide a thin film transistor array substrate comprising the pattern formed by the foregoing method.

Still another aspect of the present invention provides a liquid crystal display element comprising the foregoing thin film transistor array substrate.

According to the above aspect of the invention, a positive photosensitive resin composition is proposed. The positive photosensitive resin composition contains a novolak resin (A), an ester of an o-naphthoquinonediazidesulfonic acid (B), and a solvent (C), which are described below.

Novolak resin (A)

The novolak resin (A) of the present invention may contain a bisphenol novolak resin (A-1) and/or other novolac resin (A-2).

Xylenol type novolak resin (A-1)

The bisphenol novolak resin (A-1) is formed by a polycondensation reaction of an aldehyde compound and an aromatic hydroxy compound in the presence of an acid catalyst, wherein the aromatic hydroxy compound contains at least xylenol ( Xylenol) class of compounds.

Specific examples of the aforementioned aldehyde compound are, for example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, butene aldehyde (crotonaldehyde), cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropanal, β Phenylpropanal, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, and the like. The above aldehyde compounds may be used singly or in combination of plural kinds. Preferably, the aldehyde compound can be formaldehyde or benzaldehyde.

Specific examples of the above aromatic hydroxy compound include phenol such as phenol, m-cresol, p-cresol, and o-cresol. (cresol)-like compound; xylenol compound such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol or 3,4-xylenol; Ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-third Butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 6-t-butyl-3-methylphenol Alkylphenol compounds; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxy Alkoxy phenol compound such as phenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropene Isopropenyl phenol compound such as phenol; aryl pheno of phenyl phenol l) compounds; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, etc. Polyhydroxyl A benzene (polyhydroxyphenol) compound. The aromatic hydroxy compound 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.

In the xylenol type novolac resin (A-1), the total amount used based on the aromatic hydroxy compound is 1 mol, and the xylenol compound is used in an amount of 0.05 mol to 0.2 mol, and is preferably It is from 0.1 mol to 0.2 mol.

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

The bisphenol novolak resin (A-1) may be used singly or in combination of plural kinds.

The bisphenol novolak resin (A-1) is used in an amount of 50 parts by weight to 100 parts by weight, and preferably 70 parts by weight to 100 parts by weight based on 100 parts by weight of the novolak resin (A). Share.

When the novolac resin (A) contains a bisphenol novolak resin (A-1), the positive photosensitive resin composition obtained has a better residual film ratio.

Other novolac resin (A-2)

The above other novolac resin (A-2) is formed by a polycondensation reaction of the above-mentioned aldehyde compound and the above aromatic hydroxy compound in the presence of the above-mentioned acidic catalyst, but the aromatic hydroxy compound does not contain Xylenol compound.

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

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

Esters of o-naphthoquinonediazidesulfonic acid (B)

The ester of the o-naphthoquinonediazidesulfonic acid of the present invention (B) may comprise an ester of the o-naphthoquinonediazidesulfonic acid ester (B-1) formed from the compound represented by the following formula (I) and An ester of o-naphthoquinonediazidesulfonic acid (B-2) formed by a compound represented by the following formula (II).

Among them, the ester of the o-naphthoquinonediazidesulfonic acid of the present invention (B) may be a fully esterified or partially esterified ester-based compound. Preferably, the ester of the o-naphthoquinonediazidesulfonic acid (B) can be prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydroxy compound. More preferably, the ester of the o-naphthoquinonediazidesulfonic acid (B) can be prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a polyhydroxy compound.

Specific examples of the aforementioned o-naphthoquinonediazidesulfonic acid may include, but are not limited to, 1,2-o-naphthoquinonediazide-4-sulfonic acid, 1,2-o-naphthoquinonediazide-5-sulfonic acid or , 2-naphthoquinonediazide-6-sulfonic acid, and the like. Specific examples of the salt of the o-naphthoquinonediazidesulfonic acid may include, but are not limited to, a diazonaphthoquinone sulfonyl halide.

Esterified product of o-naphthoquinonediazidesulfonic acid (B-1)

The ester of the o-naphthoquinonediazidesulfonic acid (B-1) can be formed from a compound represented by the following formula (I):

In the formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent an alkyl group having 2 to 9 carbon atoms.

The ester of the o-naphthoquinonediazidesulfonic acid (B-1) is obtained by the above-mentioned polyphenol and the 1,2-o-naphthoquinone-2-diazidesulfonyl chloride shown in the formula (I). The reaction is carried out in the presence of an acid neutralizing agent. The ester of the o-naphthoquinonediazidesulfonic acid ester (B-1) obtained may be an ester of o-naphthoquinonediazidesulfonic acid represented by the following formula (I-1):

In the formula (I-1), Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ and Y ₈ each independently represent 1,2-o-naphthoquinone-2-diazide a mercapto group or a hydrogen atom, wherein at least two of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ and Y ₈ represent 1,2-o-naphthoquinone-2-diazidesulfonate And the rest represent a hydrogen atom; the definitions of R ₁ , R ₂ , R ₃ and R ₄ are as described above and will not be further described herein.

The aforementioned 1,2-o-naphthoquinone-2-diazidesulfonyl chloride is at least selected from the group consisting of 1,2-o-naphthoquinone-2-diazide-4-sulfonyl chloride and 1,2-naphthyl naphthalene.醌-2-diazide-5-sulfonyl chloride or 1,2-o-naphthoquinone-2-diazide-6-sulfonyl chloride constitutes a group.

Accordingly, when 1,2-o-naphthoquinone-2-diazidesulfonium chloride is reacted in the presence of an acid neutralizing agent, 1,2-naphthoquinone-2-diazidesulfonium chloride can be selected. At least one of a group consisting of alkylsulfonium chloride, arylsulfonium chloride and aralkylsulfonium chloride, and which may be added simultaneously or sequentially, to carry out the reaction.

The reaction of the polyhydric phenol as shown in the formula (I) with 1,2-o-naphthoquinone-2-diazidesulfonyl chloride is generally carried out in a solvent and in the presence of an acid neutralizing agent. The solvent may be selected from the group consisting of acetone, methyl ethyl ketone, 1,4-dioxane, tetrahydrofuran, 1,3-dioxolane, γ-butyrolactone, propylene carbonate or N-methylpyrrolidone. Forming at least one of a group. The acid neutralizing agent may preferably be an organic amine such as ethylamine, diethylamine, triethylamine, diisopropylamine, tripropylamine, triisobutylamine, triethanolamine, monomethyldicyclohexylamine, N-A. Piperidine, N-methylmorpholine, N-methylpyrrolidine, 1,4-dimethylpiperazine, pyridine, N,N-dimethylaniline, 4-dimethylaminopyridine, other suitable organic Any combination of an amine or the above organic amine.

The foregoing reaction generally involves dissolving a polyhydric phenol and 1,2-o-naphthoquinone-2-diazidesulfonium chloride in an organic solvent, and then directly adding an organic amine or an organic amine dissolved in a solvent, or firstly diversifying Phenol and organic amine dissolved in After the solvent is added, 1,2-o-naphthoquinone-2-diazidesulfonium chloride or 1,2-o-naphthoquinone-2-diazidesulfonium chloride dissolved in a solvent is directly added. Then, it is stirred for 10 minutes to 5 hours to carry out a condensation reaction. The condensation reaction is carried out at -10 ° C to 50 ° C, and preferably at 10 ° C to 40 ° C. The condensation reaction can be carried out for 10 minutes to 3 hours.

The amount of polyphenols used is 1 mole, and 1,2-o-naphthoquinone-2-diazidesulfonium chloride is used in an amount of from 3 moles to 8 moles, and preferably from 5 moles to 7 moles. . When 1,2-naphthoquinone-2-diazidesulfonium chloride is used in an amount of less than 3 moles, the positive photosensitive resin composition obtained has a low contrast. If 1,2-naphthoquinone-2-diazidesulfonium chloride is used in an amount greater than 8 mol, too much 1,2-o-naphthoquinone-2-diazidesulfonium chloride is liable to remain and remains. The sulfonium chloride group is easily decomposed to produce hydrogen chloride. The amount of the acid neutralizing agent is generally from 1.0 mole to 1.5 moles, and preferably from 1.05 moles, based on the amount of 1,2-naphthoquinone-2-diazidesulfonium chloride used. 1.2 Mo Er. If the acid neutralizing agent is used in an amount of less than 1.0 mol, 1,2-o-naphthoquinone-2-diazidesulfonium chloride is liable to remain. If the acid neutralizing agent is used in an amount of more than 1.5 mol, the 1,2-quinonediazide group is easily decomposed. The solvent is used in an amount of from 200 parts by weight to 1000 parts by weight, based on 100 parts by weight based on the total weight of the 1,2-o-naphthoquinone-2-diazidesulfonium chloride and the polyhydric phenol compound, and preferably 300 parts by weight to 500 parts by weight. If the amount of the solvent used is less than 200 parts by weight, the reactants are not completely dissolved, and the preservation stability of the present invention is lowered. If the amount of the solvent used is more than 1000 parts by weight, the subsequent reprecipitation step requires more water to be used, which is not economical.

The reacted mixture was poured into a poor solvent containing pure water and methanol to precipitate 1,2-naphthoquinone-2-diazidesulfonate. Filter out 1,2-naphthoquinone-2-diazidesulfonate, and washed with a mixed solution containing pure water, a thin acidic aqueous solution or methanol, and dried to obtain 1,2-naphthoquinone -2-Diazidosulfonate. However, in order to remove the hydrogen halide salt and the impurities formed by the acid neutralizing agent, the step of washing with water is repeated, and therefore, preferably, the hydrogen halide salt of the acid neutralizing agent precipitated in the reaction is filtered, and then added. Pure water. More preferably, after the reaction is carried out, an acid is added to the reaction liquid, and the hydrogen halide salt formed by the acid neutralizing agent is filtered, and then pure water is added.

The 1,2-naphthoquinone-2-diazidesulfonate in the reaction solution is filtered by reprecipitation, washed with pure water and a thin acidic aqueous solution, and dried to obtain 1,2-naphthoquinone. -2-Diazidosulfonate.

Alternatively, the reaction is carried out in an organic solvent having a phase separation property with water, and after the reaction, water washing is carried out to obtain 1,2-o-naphthoquinone-2-diazidesulfonate dissolved in an organic solvent.

An ester of o-naphthoquinonediazidesulfonic acid ester formed from a compound represented by formula (I) based on 100 parts by weight of the ester of the o-naphthoquinonediazidesulfonic acid ester-based ester (B) (B- 1) is used in an amount of from 1 part by weight to 20 parts by weight, preferably from 1.5 parts by weight to 15 parts by weight, and more preferably from 2 parts by weight to 10 parts by weight.

In the case where the ester of the o-naphthoquinonediazidesulfonic acid of the present invention (B) does not contain the ester of the o-naphthoquinonediazidesulfonic acid (B-1) formed from the compound represented by the formula (I), The positive photosensitive resin composition obtained has a defect that the residual film ratio is low.

Esterified naphthoquinone diazide sulfonic acid ester (B-2)

The ester of the o-naphthoquinonediazide sulfonic acid (B-2) can be formed from a compound represented by the following formula (II):

In the formula (II), R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, An alkoxy group or a cycloalkyl group having 1 to 6 carbon atoms; R ₁₃ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q represents a hydrogen atom and has a carbon number of 1 to An alkyl group of 6 or a cyclic structure bonded to R ₁₃ and having a carbon number of 3 to 6; a and b each independently represent an integer of 1 to 3; d represents an integer of 0 to 3; and n represents 0 to 3 Integer.

Preferably, the compound represented by the formula (II) may be a polyphenol compound represented by the following formula (II-1):

In the formula (II-1), R ₅ to R ₁₂ , a, b and d are each as defined above, and are not described herein again; and n ₁ represents an integer of 1 to 3.

The ester of the o-naphthoquinonediazidesulfonic acid ester (B-2) can be formed by esterification of a compound represented by the formula (II) and a 1,2-naphthoquinonesulfonic acid halide, and a synthesis method thereof As mentioned before, it will not be repeated here.

The ester of o-naphthoquinonediazidesulfonic acid formed from the formula (II) has an average esterification ratio of from 20% to 80%, and preferably from 40% to 60%.

Specific examples of the compound represented by the above formula (II) may include, but are not limited to, 1,4-bis[1-(3,5-dimethyl-4-hydroxyphenyl)isopropyl]benzene, 2, 4 -bis(3,5-dimethyl-4-hydroxyphenylmethyl)-6-methylphenol, 2,6-bis[1-(2,4-dihydroxyphenyl)isopropyl]-4 -methylphenol, 4,6-bis[1-(4-hydroxyphenyl)isopropyl]resorcinol, 4,6-bis(3,5-dimethoxy-4-hydroxyphenyl) Pyrogallol, 4,6-bis(3,5-dimethyl-4-hydroxyphenylmethyl)benzenediol, 2,6-bis(3-methyl-4,6-dihydroxyl Phenylmethyl)-4-methylphenol, 2,6-bis(2,3,4-trihydroxyphenylmethyl)-4-methylphenol, 1,1-bis(4-hydroxyphenyl) Cyclohexane, bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, 2,6-bis[2,5-dimethyl -3-(2-hydroxy-5-methylbenzyl)-4-hydroxybenzyl]-4-methylphenol, bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4 -Hydroxyphenyl]methane, other suitable compounds or any mixture of the above.

An ester of o-naphthoquinonediazidesulfonic acid ester formed from a compound represented by formula (II) based on 100 parts by weight of the ester of the o-naphthoquinonediazidesulfonic acid ester-based ester (B) (B- 2) is used in an amount of 5 parts by weight to 50 parts by weight, preferably 7 parts by weight to 45 parts by weight, and more preferably 10 parts by weight to 40 parts by weight.

In the case where the ester of the o-naphthoquinonediazidesulfonic acid of the present invention (B) does not contain the ester of the o-naphthoquinonediazidesulfonic acid (B-2) formed from the compound represented by the formula (II), The positive photosensitive resin composition obtained has a defect of poor resolution.

Other esters of o-naphthoquinonediazide sulfonic acid (B-3)

An o-naphthoquinonediazide sulfonate (B-1) formed by the compound represented by the formula (I) and an o-naphthoquinonediazide sulfonate formed from the compound represented by the formula (II) In addition to the acid ester (B-2), the positive photosensitive resin composition of the present invention may optionally contain other esters of an ortho-naphthoquinonediazidesulfonic acid (B-3). The ester of the other o-naphthoquinonediazide sulfonic acid (B-3) may include, but is not limited to, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone , 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxydiphenyl Methyl ketone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2',3,4,5'-pentahydroxybenzophenone, 2,3',4,5, O-naphthoquinonediazidesulfonic acid formed by a hydroxybenzophenone compound such as 5'-pentahydroxybenzophenone, 2,3,3',4,4',5'-hexahydroxybenzophenone Esterified; tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethyl Phenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl) )-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, double (4- Yl-3,5-dimethylphenyl) -2,4-dihydroxyphenyl methane, bis (4- Hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(3-ring Hexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl) 4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylbenzene 3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methyl Phenyl)-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-hydroxy-4-methylphenyl)-2-hydroxyl Phenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-3 Hydroxyaryl compound such as 4-dihydroxyphenylmethane or 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene Formed An ester of o-naphthoquinonediazidesulfonic acid; phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, catechol, benzenetriol monomethyl ether, benzene O-naphthoquinonediazide sulfonate formed from other aromatic hydroxy compounds such as phenol-1,3-dimethyl ether, gallic acid, partially esterified or partially etherified trihydroxybenzoic acid An ester of an acid.

The total amount of the o-naphthoquinonediazidesulfonic acid ester ester (B) is from 6 parts by weight to 70 parts by weight, preferably 9 parts by weight, based on 100 parts by weight of the total amount of the novolac resin (A). 60 parts by weight, and more preferably 12 parts by weight to 50 parts by weight.

Solvent (C)

The solvent (C) used in the positive photosensitive resin composition of the present invention means an organic solvent which is more easily dissolved with other organic components but does not react with the above components.

Specific examples of the solvent (C) of the present invention are as follows: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene 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, (poly)alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate (poly)alkylene glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, ring Ketones such as ketone, 2-heptanone, 3-heptanone, 4-hydroxy-4-methyl-2-pentanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate (also known as lactic acid) Ethyl lactate such as ethyl ester; methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, Isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, Other esters such as ethyl acetate, ethyl acetate, ethyl 2-oxybutyrate, etc.; aromatic hydrocarbons such as toluene and xylene a carboxylic acid amine such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide. The solvent (C) may be used singly or in combination of plural kinds. Preferably, the solvent (C) may be propylene glycol monoethyl ether, propylene glycol methyl ether acetate or ethyl lactate.

The solvent (C) is used in an amount of usually 200 to 2000 parts by weight, preferably 250 to 1800 parts by weight, and more preferably 300 to 1500 parts by weight, based on 100 parts by weight of the novolak resin (A).

Sensitizer (D)

The sensitizer (D) of the present invention may optionally further comprise a compound represented by the following formula (III) and/or formula (IV):

In the formula (III), D ₁ , D ₂ , D ₃ , D ₄ , D ₅ , D ₆ , D ₇ , D ₈ and D ₉ each independently represent an alkyl group, a hydrogen atom, a halogen atom or an —OH group. And at least one of D ₁ , D ₂ , D ₃ , D ₄ , D ₅ , D ₆ , D ₇ , D ₈ and D ₉ represents an -OH group; X ₁ , X ₂ , X ₃ , X ₄ , X ₅ And X ₆ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aromatic group.

Preferably, the compound of formula (III) may include, but is not limited to, 4-[3-hydroxy-spiro(5,6,7,8,10a,8a-hexahydroxyoxazepine-9,1'- Cyclohexane)-10a-yl]benzene-1,3-diol, 4-[2,3-dihydroxy-spiro (5,6,7,8,10a,8a-hexahydrooxaindole-9,1'-cyclohexane)-10a-yl]benzene-1,2,3-triol, other suitable compounds Any mix.

In the formula (IV), D ₁₀ and D ₁₁ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 4 to 6 carbon atoms, and at least one of D ₁₀ and D ₁₁ Represents a cycloalkyl group having a carbon number of 4 to 6; and m each independently represents an integer of 1 to 3.

The compound represented by the formula (IV) may include, but is not limited to, 1,1-bis(4-hydroxy-5-cyclohexylphenyl)-1-(2-hydroxyphenyl)methane, 1,1-di (4) -hydroxy-2-cyclohexylphenyl)-1-(2-hydroxyphenyl)methane, 1,1-bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)-1-(2- Hydroxyphenyl)methane, 1,1-bis(3-methyl-4-hydroxy-5-cyclohexylphenyl)-1-(2-hydroxyphenyl)methane, 1,1-di(2-ethyl 4-hydroxy-5-cyclohexylphenyl)-1-(2-hydroxyphenyl)methane, 1,1-bis(2-n-propyl-4-hydroxy-5-cyclohexylphenyl)-1 -(2-hydroxyphenyl)methane, 1,1-bis(2-isopropyl-4-hydroxy-5-cyclohexylphenyl)-1-(2-hydroxyphenyl)methane, other suitable compounds or Any combination of the above compounds.

The total amount of the novolac resin (A) used is 100 parts by weight, and the sensitizer (D) is used in an amount of 1 part by weight to 15 parts by weight, preferably 1.5 parts by weight to 13 parts by weight, and more preferably 2 parts by weight. Parts by weight to 10 parts by weight.

When the positive photosensitive resin composition of the present invention contains the sensitizer (D), the positive photosensitive resin composition obtained has a better resolution.

Additive (E)

The positive photosensitive resin composition of the present invention may optionally contain the additive (E). The additive (E) may include, but is not limited to, an adhesion aid, a surface leveling agent, a diluent, and the like.

The adhesion aid may include, but is not limited to, a melamine compound and a silane compound to increase the adhesion between the positive photosensitive resin composition and the attached substrate. Specific examples of the aforementioned melamine, such as: CYTEC company, model of Cymel-300 or Cymel-303; Sanhe chemical manufacturing, model MW-30MH, MW-30, MS-11, MS-001, MX-750 Or MX-706 goods. Specific examples of the aforementioned silane-based compound are, for example, vinyltrimethoxydecane, vinyltriethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-propenyloxypropane Trimethoxy decane, vinyl tris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2 -Aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropane Propyl dimethyl methoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxy Basear, 3-mercaptopropyltrimethoxydecane, bis-1,2-(trimethoxyindenyl)ethane.

In a specific example of the present invention, the amount of the melamine compound-based adhesion aid is generally from 0 part by weight to 20 parts by weight, preferably 0.5 part by weight, based on 100 parts by weight of the novolak resin (A). To 18 parts by weight, more preferably 1.0 part by weight to 15 parts by weight; the amount of the adhesion aid of the aforementioned decane-based compound is generally from 0 part by weight to 2 parts by weight, preferably from 0.001 part by weight to 1 part by weight, more preferably It is preferably from 0.005 parts by weight to 0.8 parts by weight.

The above surface smoothing agent may include, but is not limited to, a fluorine-based surfactant or a lanthanoid surfactant. Specific examples of the fluorine-based surfactant are, for example, those manufactured by 3M Company, manufactured by Fluorad FC-430 or FC-431, or manufactured by Tochem Product Co., Ltd., and models of F top EF122A, 122B, 122C, 126 or BL20. Specific examples of the aforementioned lanthanide surfactants are, for example, manufactured by Dow Corning Toray Silicone, model SF8427 or SH29PA.

In a specific example of the present invention, the amount of the surfactant used is generally from 0 part by weight to 1.2 parts by weight, preferably from 0.025 part by weight to 1.0 part by weight, based on 100 parts by weight of the novolak resin (A). More preferably, it is 0.050 parts by weight to 0.8 parts by weight.

Specific examples of the above diluents are, for example, manufactured by Imperial Ink, model RE801 or RE802.

The aforementioned additives (E) may be used singly or in combination of plural kinds.

In addition, the present invention may optionally further add other additives such as a plasticizer or a stabilizer.

Method for preparing positive photosensitive resin composition

The preparation of the positive photosensitive resin composition of the present invention is generally carried out by adding the above-mentioned novolak resin (A), an ester of an o-naphthoquinonediazide sulfonic acid (B) and a solvent (C) to a conventional stirring. The mixture is stirred, uniformly mixed to a solution state, and a sensitizing agent (D) and various additives (E) may be added as needed to obtain a positive photosensitive resin composition.

Pattern forming method

The positive photosensitive composition obtained above can be sequentially applied to a coating step, a prebake step, an exposure step, a development step, and a postbake treatment step to form a pattern on the substrate.

In a method of forming a pattern using the positive photosensitive resin composition described above, the positive photosensitive resin composition described above can be applied by a coating method such as spin coating, cast coating or roll coating. Coated on the substrate. After coating, the solvent is removed by pre-baking to form a pre-baked film. Among them, the pre-baking step is usually carried out at 70 ° C to 110 ° C for 1 minute to 15 minutes depending on the type of each component and the blending ratio.

After the pre-baking step, the coating film is exposed to a designated mask, and then immersed in a developing solution at 21 ° C to 25 ° C for 15 seconds to 5 minutes, thereby removing unnecessary portions to form a specific picture of. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet irradiation device may be a (ultra) high-pressure mercury lamp and a metal halide lamp.

Specific examples of the developer used in the present invention may be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate or cesium. Sodium, sodium methyl citrate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diaza A basic compound of bicyclo-[5,4,0]-7-undecene.

Preferably, the concentration of the developer may be from 0.001% by weight to 10% by weight, more preferably from 0.005% by weight to 5% by weight, still more preferably from 0.01% by weight to 1% by weight.

When the developing solution is constituted by using the above-mentioned basic compound, it is usually washed with water after development, and the above-mentioned coating film is air-dried with compressed air or compressed nitrogen. 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 from 100 ° C to 250 ° C, wherein the heating time using the hot plate is from 1 minute to 60 minutes, and the heating time using the oven is from 5 minutes 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 present invention is obtained by the aforementioned method. In short, the positive photosensitive resin composition of the present invention can be applied to a material containing aluminum, chromium, tantalum nitride or non-crystalline by a coating method such as spin coating, cast coating or roll coating. A positive photoresist layer is formed on a glass substrate or a plastic substrate of a film such as ruthenium. Next, the prebaking, exposure, development, and post-baking treatment are sequentially performed to form a photosensitive resin pattern. Then, etching and photoresist peeling are performed. The thin film transistor array substrate having a plurality of thin film transistors or electrodes can be obtained by repeating the above steps.

Please refer to FIG. 1 , which is a partial cross-sectional view showing a thin film transistor array substrate for a liquid crystal display (LCD) device according to an embodiment of the invention. First, a gate electrode 102a and a 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 covering (SiO _x) 103 or a silicon nitride film (SiN _x) 104 and the like on the gate insulating film 102a is formed, and this film is formed as an insulating layer, amorphous silicon semiconductor active layer (a -Si) 105. Next, in order to reduce the junction resistance, an amorphous germanium layer 106 doped with nitrogen impurities may be disposed on the amorphous germanium layer 105. Then, using a metal such as aluminum, the drain 107a and the source 107b are formed, wherein the drain 107a is connected to the data signal line (not shown), and the source 107b is connected to the pixel electrode (or the sub-pixel electrode). 109 on. Thereafter, in order to protect the amorphous germanium layer 105, the drain electrode 107a, the source electrode 107b, and the like as the semiconductor active layer, a tantalum nitride film or the like is provided as the protective film 108.

Liquid crystal display element

The liquid crystal display device of the present invention comprises at least the aforementioned thin film transistor array substrate, and may include other components as needed.

A specific example of the basic configuration of the liquid crystal display device is (1) the thin film transistor array substrate (drive substrate) of the present invention formed by arranging a driving element such as a thin film transistor and a pixel electrode (conductive layer). The spacer is interposed between the color filter substrate composed of the color filter and the counter electrode (conductive layer) and disposed opposite to each other, and finally the liquid crystal material is sealed in the gap portion. (2) a color filter-integrated thin film transistor array substrate in which a color filter is directly formed on the above-mentioned thin film transistor array substrate, and a spacer is interposed between the opposite substrate on which the counter electrode (conductive layer) is disposed and In the opposite direction, the liquid crystal material is sealed in the gap portion, and the liquid crystal used in the foregoing The material may be any liquid crystal compound or liquid crystal composition, and is not particularly limited herein.

Specific examples of the conductive layer may be an indium tin oxide film; a metal film of aluminum, zinc, copper, iron, nickel, chromium, molybdenum or the like; a metal oxide film of cerium oxide or the like. Preferably, the conductive layer is a film layer having transparency. The conductive layer is more preferably an indium tin oxide film.

Specific examples of 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 conventional glass base such as soda lime glass, low expansion glass, alkali-free glass, or quartz glass. material. Further, as the substrate, a substrate made of a plastic film or the like can be used.

The following embodiments are used to illustrate the application of the present invention, and are not intended to limit the present invention. Those skilled in the art can make various changes without departing from the spirit and scope of the present invention. Retouching.

101‧‧‧ glass substrate

102a‧‧‧ gate

102b‧‧‧ Storage Capacitor Cs Electrode

103‧‧‧Oxide film

104‧‧‧ nitride film

105‧‧‧Amorphous layer

106‧‧‧Amorphous layer

107a‧‧‧Bungee

107b‧‧‧ source

108‧‧‧Protective film

109‧‧‧ pixel electrodes

For a more complete understanding of the embodiments of the invention and the advantages thereof, reference should be made to the above description and the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustrative purposes only. The relevant schema description is as follows:

FIG. 1 is a partial cross-sectional view showing a thin film transistor array substrate for a liquid crystal display device according to an embodiment of the present invention.

Preparation of novolac resin (A)

The novolac resin (A) of Preparation Examples A-1-1 to A-2-3 was synthesized according to Table 1 below.

Preparation A-1-1

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 1000 ml volume. After introducing nitrogen, 0.4 mol of cresol was added, and 0.5 mol of p-cresol, 0.1 mol was added. 3,4-xylenol, 0.65 moles of formaldehyde and 0.2 moles of oxalic acid. The reaction solution was warmed to 100 ° C with gentle stirring, and polycondensed at this temperature for 6 hours. Then, the reaction solution was heated to 180 ° C, and dried under reduced pressure at a pressure of 10 mmHg, and the solvent was devolatilized to obtain a bisphenol novolak resin (A-1-1 of Preparation Example A-1-1). ).

Preparation Examples A-1-2 to A-1-4

Preparation Examples A-1-2 to A-1-4 were prepared in the same manner as in the synthesis method of the bisphenol novolak resin of Preparation Example A-1-1, except that Preparation Example A-1-2 The type and amount of the raw materials in the novolak resin are changed to A-1-4, and the formulations are as shown in Table 1, and are not described here.

Preparation Example A-2-1

Nitrogen inlet, stirrer, heater, condenser and thermometer were placed on a four-necked flask with a volume of 1000 ml. After introducing nitrogen, add 0.7 mol of cresol, 0.3 mol of p-cresol, 0.7 mol. Formaldehyde in the ear and 0.015 mol of oxalic acid. The reaction solution was warmed to 100 ° C with gentle stirring, and polycondensed at this temperature for 6 hours. Then, the reaction solution was heated to 180 ° C, Further, it was dried under reduced pressure at a pressure of 10 mmHg, and the other novolak resin (A-2-1) of Preparation Example A-2-1 was obtained by devolatilizing the solvent.

Preparation Examples A-2-2 and A-2-3

Preparation Examples A-2-2 and A-2-3 were prepared in the same manner as in the synthesis of the hydroxy novolak resin of Preparation Example A-2-1 except that Preparation Examples A-2-2 and A were used. The -2-3 system changes the type and amount of the raw materials in the novolak resin and the reaction temperature. The formulation and preparation conditions are as shown in Table 1, and are not described here.

Preparation of positive photosensitive resin composition

The positive photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared according to Table 2 below.

Example 1

100 parts by weight of the xylenol novolak resin of the above Preparation Example A-1-1, and 1 part by weight of an ester of o-naphthoquinonediazidesulfonic acid represented by the formula (I) (B-1- 1; wherein R ₁ to R ₄ each represent a C ₂ H ₅ group), 20 parts by weight of bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4- Esterified ester formed from hydroxyphenyl]methane (B-2-1), 1 part by weight of 4-[3-hydroxy-spiro(5,6,7,8,10a,8a-hexahydroxazepine-9 , 1'-cyclohexane)-10a-yl]benzene-1,3-diol (D-1) and 1 part by weight of a surfactant (E-1; manufactured by Dow Corning Toray Silicone, and its model number SF8427) is added to 200 parts by weight of a solvent (C-1) of propylene glycol monomethyl ether acetate (PGMEA), and the mixture is dissolved in a solvent by stirring with a stirring stirrer. The positive photosensitive resin composition of the present invention. The positive photosensitive resin composition obtained was evaluated by the following evaluation methods, and the results are as described in Table 2, and the methods for detecting the resolution and the residual film ratio will be described later.

Examples 2 to 9 and Comparative Examples 1 to 3

In Examples 2 to 9 and Comparative Examples 1 to 3, the same production method as that of the positive photosensitive resin composition of Example 1 was used, except that Examples 2 to 9 and Comparative Examples 1 to 3 were changed. The type and amount of the raw material in the positive photosensitive resin composition are shown in Table 2, respectively, and are not described here.

Evaluation method

Resolution

The positive photosensitive resin compositions prepared in the above Examples 1 to 9 and Comparative Examples 1 to 3 were each applied to a glass substrate by spin coating. Then, prebaking at 100 ° C for 2 minutes gave a prebaked coating film having a thickness of about 1 μm. Next, the prebaked coating film was placed under a line and space mask (manufactured by Filcon, Japan), and ultraviolet light having an energy of 50 mJ/cm ² was used (exposure model AG500-4N; M&R Nano Technology) Irradiation. After the irradiation, development was carried out at 23 ° C for 1 minute in a TMAH aqueous solution having a concentration of 2.38%, and the coating film on the exposed portion of the substrate was removed. After washing with pure water, the minimum value of the line width formed on the glass substrate was measured and evaluated according to the following criteria:

◎: The minimum value of the line width is <1.5 μm.

○: The minimum value of the line width of 1.5 μm is <2 μm.

△: The minimum value of the line width of 2 μm is <3 μm.

╳: The minimum value of the line width of 3μm.

2. Residual film rate

The positive photosensitive resin compositions prepared in the above Examples 1 to 9 and Comparative Examples 1 to 3 were each applied to a glass substrate by spin coating. Then, prebaking at 100 ° C for 2 minutes gives a prebaked coating film. A measurement point was taken on the pre-baked film, and the film thickness (δ _i ) was measured by a Tencor α-step stylus meter. Next, the coating film was immersed in a developing solution (concentration of 2.38% tetramethylammonium hydroxide) at 23 °C. After 1 minute, the film thickness (δ _f ) at the same measurement point was measured. The residual film ratio of the coating film was calculated by the following formula (VI) and evaluated according to the following criteria: residual film ratio (%) = [(δ _f ) / (δ _i )] × 100% (VI)

◎: 95% <residual film ratio.

○: 90% <residual film ratio ≦ 95%.

△: 80% < residual film ratio ≦ 90%.

╳: The residual film rate is ≦80%.

As is apparent from the results of the second table, when the ester of the o-naphthoquinonediazidesulfonic acid of the present invention (B) does not contain the ester of o-naphthoquinonediazidesulfonic acid formed from the compound represented by the formula (I) In the case of the compound (B-1), the positive photosensitive resin composition obtained has a defect that the residual film ratio is low.

Next, if the ester of the o-naphthoquinonediazidesulfonic acid of the present invention (B) does not contain the o-naphthoquinonediazide formed from the compound represented by the formula (II) In the case of the sulfonic acid ester ester (B-2), the positive photosensitive resin composition obtained has a defect of poor resolution.

Further, when the novolac resin (A) of the present invention contains a xylenol novolak resin (A-1) and the amount of the bisphenol novolak resin (A-1) used is in the above range, The positive photosensitive resin composition obtained has a better residual film ratio.

When the positive photosensitive resin composition of the present invention contains the sensitizer (D), the positive photosensitive resin composition obtained has a better resolution.

It should be noted that, although the present invention is exemplified by specific compounds, compositions, reaction conditions, processes, analytical methods, or specific instruments, the positive photosensitive resin composition of the present invention and its application are described, but in the technical field to which the present invention pertains It is to be understood by those skilled in the art that the present invention is not limited thereto, and other compounds, compositions, reaction conditions, and the like may be used for the positive photosensitive resin composition of the present invention and its application without departing from the spirit and scope of the present invention. Process, analytical method or instrumentation.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

Claims (10)

A positive photosensitive resin composition comprising: a novolak resin (A); an ester of an o-naphthoquinonediazide sulfonic acid (B); and a solvent (C), wherein the o-naphthoquinone diazide sulfonic acid The esterified product (B) comprises an ester of an o-naphthoquinonediazidesulfonic acid ester (B-1) formed from a compound represented by the following formula (I) and a compound represented by the following formula (II). An ester of o-naphthoquinonediazidesulfonic acid (B-2): In the formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent an alkyl group having 2 to 9 carbon atoms; In the formula (II), R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, An alkoxy group or a cycloalkyl group having 1 to 6 carbon atoms; R ₁₃ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q represents a hydrogen atom and has a carbon number of 1 to An alkyl group of 6 or a cyclic structure bonded to R ₁₃ and having a carbon number of 3 to 6; a and b each independently represent an integer of 1 to 3; d represents an integer of 0 to 3; and n represents 0 to 3 Integer. The positive photosensitive resin composition according to claim 1, wherein the novolac resin (A) comprises a bisphenol novolak resin (A-1), and the bisphenol novolak resin ( A-1) is formed by polycondensation of an aldehyde compound and an aromatic hydroxy compound, and the aromatic hydroxy compound contains at least a xylenol compound. The positive photosensitive resin composition according to claim 1, wherein the ortho-naphthoquinone diazide sulfonic acid ester ester (B) is used based on 100 parts by weight of the novolak resin (A). The amount of the o-naphthoquinonediazidesulfonic acid ester ester (B-1) formed by the compound represented by the formula (I) is from 1 part by weight to 20 parts by weight, based on 6 parts by weight to 70 parts by weight. The ester of the o-naphthoquinonediazidesulfonic acid ester (B-2) formed by the compound represented by the formula (II) is used in an amount of 5 parts by weight to 50 parts by weight, and the solvent (C) is used. The amount is from 200 parts by weight to 2000 parts by weight. The positive photosensitive resin composition according to claim 2, wherein the aromatic hydroxy compound is used in an amount of 1 mol, and the xylenol compound is used in an amount of 0.05 mol to 0.2 mol. . The positive photosensitive resin composition according to the second aspect of the invention, wherein the use amount of the novolac resin (A) is 100 parts by weight, and the xylenol novolak resin (A-1) is used. The amount is from 50 parts by weight to 100 parts by weight. The positive photosensitive resin composition according to claim 1, further comprising: a sensitizer (D), and the sensitizer (D) comprises the formula (III) and/or the formula (IV) Compounds shown: In the formula (III), D ₁ , D ₂ , D ₃ , D ₄ , D ₅ , D ₆ , D ₇ , D ₈ and D ₉ each independently represent an alkyl group, a hydrogen atom, a halogen atom or an —OH group. And at least one of D ₁ , D ₂ , D ₃ , D ₄ , D ₅ , D ₆ , D ₇ , D ₈ and D ₉ represents an -OH group; X ₁ , X ₂ , X ₃ , X ₄ , X ₅ And X ₆ independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aromatic group; In the formula (IV), D ₁₀ and D ₁₁ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 4 to 6 carbon atoms, and at least one of D ₁₀ and D ₁₁ Represents a cycloalkyl group having a carbon number of 4 to 6; and m each independently represents an integer of 1 to 3. The positive photosensitive resin composition according to claim 6, wherein the sensitizing agent (D) is used in an amount of 1 part by weight based on 100 parts by weight of the novolak resin (A). 15 parts by weight. A pattern forming method for sequentially applying a positive photosensitive resin composition according to any one of claims 1 to 7 to a coating treatment, a prebaking treatment, an exposure treatment, and the like. The development process and the post-baking process are performed to form a pattern on a substrate. A thin film transistor array substrate comprising a pattern formed by the method of claim 8 of the patent application. A liquid crystal display element comprising a thin film transistor array substrate according to claim 9 of the patent application.