CN104007617A - Positive photosensitive resin composition and pattern forming method thereof - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition and a pattern forming method thereof. This positive photosensitive resin composition includes a novolac resin (A), an esterification product of o-naphthoquinonediazide sulfonic acid (B), a hydroxy compound (C), and a solvent (D). The above-mentioned novolac resin (A) includes a hydroxyl-type novolac resin (A-1) and a xylenol-type novolac resin (A-2), wherein the hydroxyl-type novolak resin (A-1) is composed of hydroxybenzaldehyde The compound is obtained by the condensation of an aromatic hydroxy compound, and the xylenol-type novolak resin (A-2) is obtained by the polycondensation of aldehyde compounds and xylenol compounds. This positive photosensitive resin composition can form a pattern with high film thickness and good cross-sectional shape after post-baking.

Description

Positive photosensitive resin composition and pattern forming method thereof

technical field

The present invention relates to a positive-type photosensitive resin composition and a pattern forming method thereof, and in particular relates to a liquid crystal display element or a touch panel for semiconductor integrated circuit elements, thin film transistors (hereinafter referred to as TFT) During the manufacturing process, patterns with high film thickness and good cross-sectional shape can be obtained after post-baking. the

Background technique

With the miniaturization of various electronic products in life, various smart phones, thin TVs, and high-performance microprocessors have increasingly high-resolution requirements, resulting in increasingly sophisticated photolithography processes to form finer line width. the

For the above purpose, Japanese Laid-Open Patent No. 2003-98669 discloses a positive photosensitive resin composition, which comprises a novolac resin, a photoacid generator and an organic solvent. The novolac resin is prepared in organic solvents such as trimethylphenol, xylenol and o-cresol, aldehydes and other organic solvents and acid catalysts containing more than 50% by weight of m-cresol (phenols other than m-cresol). The reaction is carried out in the presence of , and a part or all of the hydroxyl groups of the novolac resin are protected by alkoxyalkyl groups, which can improve the sensitivity and resolution of the positive photosensitive resin composition. Secondly, Japanese Laid-Open Patent No. 2001-183838 discloses a positive-type photosensitive resin composition, which includes a novolac resin, a photoacid generator, and an acid-catalyzed bridging agent. In this patent, when synthesizing novolac resin, the polycondensation reaction is carried out in the presence of alkali-soluble resin, cresol compound and/or xylenol compound and acid catalyst, which can also improve the sensitivity and resolution of the positive photosensitive resin composition . the

However, in the aforementioned known technologies, the photosensitive resin composition cannot form a pattern with a high film thickness after post-baking. Secondly, the pattern thus formed has a poor cross-sectional shape, which reduces the yield rate of the subsequent process. Therefore, how to form a pattern with a high film thickness and a good cross-sectional shape after the post-baking of the positive photosensitive resin composition has become an important issue in the technical field. the

In view of this, there is an urgent need to propose a positive-type photosensitive resin composition material that forms a pattern with a high film thickness after post-baking and has a good cross-sectional shape of the pattern, so as to overcome various problems in the known technology. the

Contents of the invention

The object of the present invention is to provide a positive-type photosensitive resin composition material that basically overcomes various problems of the prior art, and can form a pattern with high film thickness and good cross-sectional shape after post-baking, and a method for forming the pattern. the

Therefore, one aspect of the present invention is to provide a positive-type photosensitive resin composition comprising a novolac resin (A), an esterified product (B) of o-naphthoquinonediazide sulfonic acids, a hydroxyl compound (C) and solvent (D). Above-mentioned novolac resin (A) comprises hydroxyl type novolak resin (A-1) and xylenol type novolak resin (A-2), wherein hydroxyl type novolac resin (A-1) is made of hydroxybenzaldehydes The compound is obtained by condensation of an aromatic hydroxyl compound, and the xylenol type novolak resin (A-2) is obtained by polycondensation of an aldehyde compound and a xylenol compound. the

Another aspect of the present invention is to provide a pattern forming method, which is to sequentially apply coating treatment, pre-baking treatment, exposure treatment, development treatment and post-baking treatment to the above-mentioned positive photosensitive resin composition, In order to form a pattern on the substrate. The above-mentioned positive photosensitive resin composition can form a pattern with high film thickness and good cross-sectional shape after post-baking. the

Another aspect of the present invention is to provide a thin-film transistor array substrate (thin-film transistor; TFT), which includes the above pattern. the

Another aspect of the present invention is to provide a liquid crystal display (liquid crystal display; LCD) element, which includes the above thin film transistor array substrate. the

The structure and pattern forming method of the positive photosensitive resin composition, the thin film transistor array substrate and the liquid crystal display element of the present invention are described as follows. the

Positive Photosensitive Resin Composition

The positive-type photosensitive resin composition of the present invention comprises a novolac resin (A), an esterified product (B) of o-naphthoquinone diazide sulfonic acids, a hydroxyl compound (C) and a solvent (D), in the following order elaborated. the

Novolac resin (A) 

The novolac resin (A) of the positive photosensitive resin composition of the present invention includes a hydroxyl type novolak resin (A-1) and a xylenol type novolac resin (A-2). the

The above-mentioned hydroxy-type novolac resin (A-1) is obtained by condensation reaction of hydroxybenzaldehyde compounds and aromatic hydroxy compounds in the presence of an acidic catalyst. the

Specific examples of the aforementioned hydroxybenzaldehyde compounds are: o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde and other hydroxybenzaldehyde compounds; 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde Dihydroxybenzaldehyde compounds such as hydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde; 2,3,4-trihydroxybenzaldehyde, 2 , 4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde and other trihydroxybenzaldehyde compounds; o-hydroxymethylbenzaldehyde, m-hydroxybenzaldehyde Hydroxyalkylbenzaldehyde compounds such as tolualdehyde and p-hydroxymethylbenzaldehyde. The hydroxybenzaldehyde compounds can be used alone or in combination. Wherein, the above-mentioned hydroxybenzaldehyde compounds are o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4 -Dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde and o-hydroxymethylbenzaldehyde are preferred. the

Secondly, the specific examples of the aforementioned aromatic hydroxy compounds that react with the condensation reaction of the above-mentioned hydroxybenzaldehyde compounds are: phenol (phenol); m-cresol (m-cresol), p-cresol (p-cresol), o-cresol Cresols such as phenol (o-cresol); xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, etc. Phenols (xylenol); m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butyl phenylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 6-tert-butyl-3-methylphenol Alkylphenols such as alkylphenols; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol Alkoxyphenols such as oxyphenols; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol Isopropenyl phenols such as phenylphenols; aryl phenols such as phenylphenols; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol ( polyhydroxybenzenes such as resorcinol), hydroquinone, and 1,2,3-pyrogallol, and the like. The aforementioned aromatic hydroxy compounds may be used alone or in combination. Among them, the above-mentioned aromatic hydroxyl compounds are represented by o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol Waiting is better. the

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

As for the xylenol type novolac resin (A-2), it is generally obtained by polycondensation reaction of aldehyde compounds and xylenol compounds in the presence of the aforementioned acidic catalyst. the

Specific examples of the aforementioned aldehyde compounds are: formaldehyde, paraformaldehyde (paraformaldehyde), trioxane (trioxane), acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein (acrolein), crotonaldehyde (crotonaldehyde), cyclohexanaldehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropanal, β -Phenylpropionaldehyde, o-methylbenzaldehyde, m-tolualdehyde, p-tolualdehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, etc. The aforementioned aldehydes may be used alone or in combination. Among them, the aldehyde compounds are preferably formaldehyde and benzaldehyde. the

Specific examples of the aforementioned xylenol compounds include 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol. the

The novolac resin (A) of the positive photosensitive resin composition of the present invention may further contain other novolac resins (A-3) under the premise of not affecting the overall physical properties, generally composed of aldehyde compounds and aromatic hydroxyl compounds, It is obtained by polycondensation reaction in the presence of the aforementioned acidic catalyst. The aldehyde compounds and aromatic hydroxy compounds are listed above, and will not be described in detail here, but the structures of the other novolac resins (A-3) need to be different from the above-mentioned hydroxyl-type novolac resins (A-1) and a xylenol-type novolak resin (A-2). the

The aforementioned hydroxyl type novolac resin (A-1), xylenol type novolac resin (A-2) and other novolac resins (A-3) can use a single type of novolak resin, or mix two types of novolak resin. One or two or more different types of novolac resins. Based on 100 parts by weight of novolac resin (A), the usage amount of this hydroxyl type novolac resin (A-1) is 50 parts by weight to 95 parts by weight, and the usage amount of xylenol type novolac resin (A-2) is 5 parts by weight to 50 parts by weight, and the amount of other novolac resins (A-3) is 0 parts by weight to 45 parts by weight. Since the hydroxyl type novolac resin (A-1) has better developability, while the xylenol type novolak resin (A-2) has better residual film rate, if the positive photosensitive resin composition does not use the hydroxyl type Novolac resin (A-1) or xylenol-type novolac resin (A-2), the resulting positive-type photosensitive resin composition has the problems of poor cross-sectional shape and insufficient film thickness after post-baking. Yet when using the hydroxyl type novolac resin (A-1) and the xylenol type novolak resin (A-2) of the above-mentioned range, then the obtained positive photosensitive resin composition will have a good cross-sectional shape after post-baking Advantages, it can also avoid the shortcomings of insufficient film thickness caused by the flow of graphics due to heat during post-baking. the

Also based on the total usage of the hydroxy type novolac resin (A-1) and the xylenol type novolac resin (A-2) is 100% by weight, the usage amount of the hydroxy type novolac resin (A-1) 50% by weight to 95% by weight, and the amount of the xylenol-type novolak resin (A-2) is 5% by weight to 50% by weight. When the usage amount of the hydroxyl type novolac resin (A-1) is 50% by weight to 95% by weight, and the usage amount of the xylenol type novolac resin (A-2) is 5% by weight to 50% by weight , the resulting positive photosensitive resin composition has the advantage of good cross-sectional shape after post-baking. the

Esters of o-naphthoquinonediazidesulfonic acids (B)

The esterified product (B) of o-naphthoquinone diazide sulfonic acid in the present invention can be selected from known and frequently used users, and there is no special limitation. In a preferred embodiment of the present invention, the esterification (B) of the aforementioned o-naphthoquinonediazide sulfonic acids may include but not limited to o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide- 5-sulfonic acid, o-naphthoquinonediazide-6-sulfonic acid, etc., esterified products of o-naphthoquinonediazidesulfonic acid and hydroxyl compounds, or esters of the above-mentioned o-naphthoquinonediazidesulfonic acids and polyhydroxy compounds Compounds are preferred. the

The esterified product (B) of the above-mentioned o-naphthoquinone diazide sulfonic acids can be fully or partially esterified, and includes (one) hydroxybenzophenones and/or (two) hydroxyaryl compounds of formula (I) The radicals and/or (three) skeletons of (hydroxyphenyl) hydrocarbons of formula (II) are described below. the

(1) Specific examples of hydroxybenzophenones are 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone Methanone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxy Benzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2',3,4,5'-pentahydroxybenzophenone, 2,3',4, 5,5'-pentahydroxybenzophenone or 2,3,3',4,4',5'-hexahydroxybenzophenone. the

(2) A specific example of a hydroxyaryl compound has a structure shown in formula (I):

In formula (I), R ₁ to R ₃ are hydrogen atoms or lower alkyl groups (alkyl); R ₄ to R ₉ are hydrogen atoms, halogen atoms, lower alkyl groups, lower alkoxy groups (alkoxy), Lower alkenyl (alkenyl) and cycloalkyl (cycloalkyl); R ₁₀ and R ₁₁ represent a hydrogen atom, a halogen atom and a lower alkyl; x and y are integers from 1 to 3; z are integers from 0 to 3 ; and n is 0 or 1.

In a preferred embodiment of the present invention, the hydroxyaryl compound having the structure shown in formula (I) is tris(4-hydroxyphenyl)methane, bis(4-hydroxyl-3,5-dimethylphenyl )-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)benzene Methane, bis(4-hydroxyphenyl)phenylethane, bis(4-hydroxy-3-tert-butylphenyl)phenylethane, 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, 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-hydroxybenzene Methane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, 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-hydroxyphenyl Methane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-3-hydroxyphenyl Methane, bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenylmethane, 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 or 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4- hydroxyphenyl)ethyl]benzene. the

(3) A specific example of (hydroxyphenyl) hydrocarbon compound is the structure shown in the following formula (II):

In formula (II), R ₁₂ and R ₁₃ are hydrogen atoms or lower alkyl groups; and x' and _y ' are integers of 1 to 3.

In a preferred embodiment of the present invention, the (hydroxyphenyl) hydrocarbons having the structural formula shown in formula (II) are 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. the

In addition, the esterification (B) of the above-mentioned o-naphthoquinone diazide sulfonic acids may also contain (4) other aromatic hydroxyl skeletons, and its specific examples are phenol, p-methoxyphenol, dimethylphenol, p- Hydroquinone, bisphenol A, naphthol, pyrocatechol, 1,2,3-pyrogallol monomethyl ether, 1,2,3-pyrogallol-1, 3-dimethyl ether (pyrogallol-1,3-dimethyl ether), 3,4,5-trihydroxybenzoic acid (gallic acid) or partially esterified or partially etherified 3,4,5-trihydroxy benzoic acid. the

The esterified product (B) of the aforementioned o-naphthoquinone diazide sulfonic acids is preferably a skeleton comprising hydroxyaryls or hydroxyphenyl hydrocarbons, and its specific example is 1-[1-(4-hydroxyphenyl)iso Propyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene and 1,2-naphthoquinonediazide-5-sulfonic acid, 4,4'-ethylene Esterification of bis(2-methylphenol) and 1,2-naphthoquinonediazide-5-sulfonic acid, 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone Ester of azide-5-sulfonic acid. The esterified products (B) of the above-mentioned o-naphthoquinonediazidesulfonic acids may be used alone or in combination. the

According to the esterified product (B) of o-naphthoquinonediazidesulfonic acids in the positive photosensitive resin composition of the present invention, a compound containing a quinonediazide group can be used, for example: o-naphthoquinonediazide-4 (or 5) - A compound obtained by condensation reaction between sulfonic acid halide salt and the hydroxyl compound in (1) to (4) above, which can be completely or partially esterified. The aforementioned condensation reaction is usually carried out in organic solvents such as dioxane (dioxane), N-pyrrolidone (N-pyrrolidone), acetamide (acetamide), preferably in triethanolamine (triethanolamine), alkali metal carbonate or in the presence of a basic condensing agent such as an alkali metal bicarbonate. the

In a preferred embodiment of the present invention, based on 100 mole % of the total amount of hydroxyl groups in the hydroxyl compound; more preferably more than 50 mole %; especially preferably more than 60 mole % of hydroxyl and o-naphthoquinonediazide-4 (or 5) The sulfonic acid halide salt is condensed to form an esterified product, that is, the degree of esterification is above 50%; more preferably above 60%. the

In a specific example of the present invention, based on the usage amount of novolac resin (A) being 100 parts by weight, the usage amount of the esterified product (B) of o-naphthoquinone diazide sulfonic acids of the present invention is usually 5 parts by weight to 50 parts by weight, preferably 10 to 45 parts by weight, more preferably 15 to 40 parts by weight. When the esterification (B) of o-naphthoquinone diazide sulfonic acids contains the skeleton of the above-mentioned hydroxyaryl or hydroxyphenyl hydrocarbons, the resulting positive-type photosensitive resin composition will have a fractured surface after post-baking. Advantages of good shape. the

Hydroxy compound (C)

The hydroxy compound (C) of the present invention can use the same species as the hydroxy compound (one) to (four) used in the esterification product (B) of the aforementioned o-naphthoquinone diazide sulfonic acids, and the hydroxy compound in (one) to ( 3) The hydroxyl compound is preferred. the

The aforementioned hydroxy compound (C) is more preferably the hydroxyaryl compound of (two), and its specific examples are three (4-hydroxyphenyl) methane, 1-[1-(4-hydroxyphenyl) isopropyl] -4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, bis(4-hydroxy-3,5-dimethylphenyl)phenylmethane, 2,4,6-trihydroxydi Benzophenone, 1,2,3-pyrogallol monomethyl ether, etc. The said hydroxy compound (C) can be used individually by 1 type or in mixture of multiple types. the

Based on 100 parts by weight of the novolak resin (A), the amount of the aforementioned hydroxyl compound (C) is 1 to 30 parts by weight, preferably 5 to 30 parts by weight, and 10 to 25 parts by weight. better. When the positive photosensitive resin composition does not use the hydroxyl compound (C), the obtained positive photosensitive resin composition will have a problem of poor cross-sectional shape after post-baking. When the hydroxy compound (C) is used in the above range, the obtained positive photosensitive resin composition has the advantage of good cross-sectional shape after post-baking. the

Solvent (D)

The solvent (D) used in the positive photosensitive resin composition of the present invention refers to an organic solvent that is easily soluble with other organic components but does not interact with the above components. the

In a specific example of the present invention, the solvent (D) is 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 and tripropylene glycol monoethyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate (poly)alkylene glycol monoalkyl ether acetates such as esters; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; methyl ethyl ketone, Ketones such as cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate (ethyl lactate); 2-hydroxy-2- Methyl Methylpropionate, Ethyl 2-Hydroxy-2-Methylpropionate, Methyl 3-Methoxypropionate, Ethyl 3-Methoxypropionate, Methyl 3-Ethoxypropionate, Ethyl 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, Other esters such as ethyl acetoacetate and ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N- Carboxylic acid amines such as dimethylacetamide. The above-mentioned solvents (D) may be used alone or in combination. Preferably, the solvent (D) is propylene glycol monoethyl ether, propylene glycol methyl ether acetate or ethyl lactate. the

In a specific example of the present invention, based on 100 parts by weight of the novolak resin (A), the usage amount of the above-mentioned solvent (D) is generally 100 to 500 parts by weight; preferably 100 to 450 parts by weight; more preferably 100 to 400 parts by weight. the

Additive (E)

The positive photosensitive resin composition of the present invention may optionally contain additives (E), which may include but not limited to: adhesion aids, surface leveling agents, diluents, and sensitizers. the

The above adhesion aids may include but not limited to melamine compounds and silane compounds to increase the adhesion between the positive photosensitive resin composition and the attached substrate. Specific examples of the aforementioned melamine: commercially available Cymel-300, Cymel-303 (manufactured by CYTEC), MW-30MH, MW-30, MS-11, MS-001, MX-750, or MX-706 (manufactured by Sanwa Chemical Industry) commercially available. Specific examples of the aforementioned silane-based compounds: vinyltrimethoxysilane, vinyltriethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, vinyltris(2-methoxysilane) Oxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyl Trimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxydimethylmethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane or bis- 1,2-(Trimethoxysilyl)ethane. the

In a specific example of the present invention, based on 100 parts by weight of the novolak resin (A), the amount of the adhesion aid of the aforementioned melamine compound is generally 0 parts by weight to 20 parts by weight, but 0.5 parts by weight to 18 parts by weight. Parts by weight are preferred, and 1.0 parts by weight to 15 parts by weight are more preferred; the amount of adhesion aids for the aforementioned silane compounds is generally 0 parts by weight to 2 parts by weight, but 0.001 parts by weight to 1 part by weight. Preferably, it is more preferably 0.005 to 0.8 parts by weight. the

The above-mentioned surface leveling agent may include, but not limited to, a fluorine-based surfactant or a silicon-based surfactant. Specific examples of the aforementioned fluorine-based surfactants include commercially available Flourate FC-430 and FC-431 (manufactured by 3M) or Ftop EF122A, 122B, 122C, 126, and BL20 (manufactured by Tochem Products). Specific examples of the aforementioned silicon-based surfactants include commercially available SF8427 or SH29PA (manufactured by Toray Dow Corning Silicone). the

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

Specific examples of the above diluent include commercially available RE801 and RE802 (manufactured by Imperial Ink). the

Specific examples of the above-mentioned sensitizers: TPPA-1000P, TPPA-100-2C, TPPA-1100-3C, TPPA-1100-4C, TPPA-1200-24X, TPPA-1200-26X, TPPA-1300-235T, TPPA- 1600-3M6C or TPPA-MF are commercially available (manufactured by Honshu Chemical Industries, Japan), among which TPPA-600-3M6C or TPPA-MF is preferred. The aforementioned sensitizers may be used alone or in combination. the

The above-mentioned additives (E) may be used alone or in combination. In a specific example of the present invention, based on 100 parts by weight of the novolac resin (A), the usage amount of the aforementioned sensitizer is usually 0 parts by weight to 20 parts by weight, but 0.5 parts by weight to 18 parts by weight. Preferably, it is more preferably 1.0 to 15 parts by weight. In addition, the present invention can also add other additives as required, such as: plasticizer, stabilizer and so on. the

Preparation method of positive photosensitive resin composition

The preparation of the positive-type photosensitive resin composition of the present invention generally comprises the above-mentioned novolac resin (A), the esterification product (B) of o-naphthoquinone diazide sulfonic acids, the hydroxyl compound (C) and the solvent (D) , stirring in a known stirrer to make it uniformly mixed into a solution state, and various additives (E) may be added as required to obtain a positive-type photosensitive resin composition. the

pattern forming method

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

In other words, the method for forming a pattern using the positive photosensitive resin composition of the present invention is to apply the positive photosensitive resin composition It is coated on the substrate, and after coating, the solvent is removed by pre-baking to form a pre-baked coating film. Wherein, the pre-baking conditions vary according to the types and compounding ratios of the components, and are generally at a temperature of 70 to 110° C. for 1 to 15 minutes. the

After pre-baking, expose the coating film under a designated mask, and then immerse it in a developer solution at a temperature of 23±2°C for 15 seconds to 5 minutes, thereby removing unnecessary parts to form a specific pattern. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet irradiation device can be (ultra) high pressure mercury lamp and metal halide lamp. the

Specific examples of the developer used in the present invention are sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia water, ethylamine, diethylamine , dimethylethanolamine, tetramethylamine hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene basic compound. the

Preferably, the concentration of the developer is 0.001% by weight to 10% by weight; more preferably 0.005% by weight to 5% by weight; most preferably 0.01% by weight to 1% by weight. the

When using the developer composed of the above-mentioned basic compound, it is usually washed with water after developing, and then the above-mentioned coating film is air-dried with compressed air or compressed nitrogen. Next, post-baking is performed on the coating film using a heating device such as a hot plate or an oven. The post-baking temperature is generally 100 to 250° C., 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, patterns can be formed on the substrate. the

The film thickness of the above pattern is 5 μm to 25 μm, preferably 8 μm to 25 μm, more preferably 10 μm to 25 μm, when the film thickness of the pattern is 5 μm to 25 μm, the pattern can facilitate the fine laying of the conductive layer, insulating layer or protective film . the

Thin film transistor array substrate

The thin film transistor array substrate of the present invention is manufactured by the aforementioned method. In short, the positive-type photosensitive resin composition of the present invention can be coated on a surface containing aluminum, chromium, silicon nitride or amorphous A positive photoresist layer is formed on a glass substrate or a plastic substrate of a thin film such as silicon. Next, after pre-baking, exposure, development and post-baking to form a photosensitive resin pattern, etching and photoresist stripping are performed. After repeating the above steps, a thin film transistor array substrate containing multiple thin film transistors or electrodes can be produced. the

Please refer to FIG. 1 , which is a schematic partial cross-sectional view of a TFT array substrate for liquid crystal display (LCD) elements according to an embodiment of the present invention. Firstly, the gate electrode 102a and the storage capacitor Cs electrode 102b are disposed on the aluminum film etc. on the glass substrate 101 . Next, an insulating film is formed to cover the gate electrode 102a with a silicon oxide film (SiO _x ) 103 or a silicon nitride film (SiN _x ) 104, etc., and an amorphous silicon layer (a -Si) 105. Next, in order to reduce the junction resistance, an amorphous silicon layer 106 doped with nitrogen impurities can be disposed on the amorphous silicon layer 105 . After that, metal such as aluminum is used to form the drain electrode 107a and the source electrode 107b, wherein the drain electrode 107a is connected to the data signal line (not shown in the figure), and the source electrode 107b is connected to the pixel electrode (or sub-pixel electrode) 109 . Then, a silicon nitride film or the like is provided as a protective film 108 in order to protect the amorphous silicon layer 105 as a semiconductor active layer, the drain electrode 107a, the source electrode 107b, and the like.

Liquid crystal display element

The liquid crystal display device of the present invention at least includes the above-mentioned TFT array substrate, and may include other components as required. the

The specific example of the basic configuration form of the above-mentioned liquid crystal display element is (1) the above-mentioned TFT array substrate (drive substrate) of the present invention formed by arranging drive elements such as TFTs and pixel electrodes (conductive layers), and a color filter composed of The spacer is interposed between the color filter substrates and the counter electrode (conductive layer) is arranged facing each other, and finally the liquid crystal material is sealed in the gap part. In another way, (2) a color filter-integrated TFT array substrate in which a color filter is directly formed on the above-mentioned TFT array substrate of the present invention, and an opposite substrate on which an opposite electrode (conductive layer) is arranged Spacers are interposed and arranged facing each other, and finally a liquid crystal material is sealed in the gap to form a structure. The liquid crystal material used above can be any liquid crystal compound or liquid crystal composition, which is not particularly limited here. the

Specific examples of the conductive layer are an ITO film; a metal film such as aluminum, zinc, copper, iron, nickel, chromium, molybdenum, or the like; or a metal oxide film such as silicon dioxide. Preferably, it is a transparent film layer; more preferably, it is an ITO film. the

The substrates used in the TFT array substrate, color filter substrate, and counter substrate of the present invention are specifically exemplified by known glass such as soda-lime glass, low-expansion glass, alkali-free glass, or quartz glass. A substrate composed of a plastic film or the like is used. the

The advantage of the present invention is that the pattern prepared by the positive photosensitive resin composition of the present invention has the advantages of high film thickness and good cross-sectional shape after post-baking. the

Several embodiments are used below to illustrate the application of the present invention, but it is not intended to limit the present invention. Those with ordinary knowledge in the technical field of the present invention can make various changes without departing from the spirit and scope of the present invention. Move and retouch. the

Description of drawings

In order to make the above-mentioned and other purposes, features, advantages and embodiments of the present invention more obvious and understandable, the accompanying drawings are described as follows:

FIG. 1 is a partial cross-sectional schematic diagram illustrating a TFT array substrate for a liquid crystal display element according to an embodiment of the present invention;

Figure 2 is a schematic diagram showing the cross-sectional shape of the protective film with patterns obtained in the evaluation examples 1 to 10 and comparative examples 1 to 7 of the present invention;

Among them, the symbol description:

101: glass substrate liquid crystal display element 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 08: Protective film

109: Pixel electrode 01: Vertical section

203: Conical section 205: Reverse conical section

207: oblate section. the

Detailed ways

Preparation of Novolak Resin (A)

The hydroxy-type novolac resins (A-1) of Synthesis Examples A-1-1 to A-3-3 were prepared according to Table 1 as follows. Synthesis Example A-1-1

Set up a nitrogen inlet, a stirrer, a heater, a condenser and a thermometer on a four-necked conical flask with a volume of 1000 ml. After introducing nitrogen, add 0.70 moles of m-cresol, 0.30 moles of p-cresol, 3,4-dihydroxy 0.5 moles of benzaldehyde and 0.020 moles of oxalic acid. Stir slowly to raise the temperature of the reaction solution to 100°C, and polycondense at this temperature for 6 hours. Then, the temperature of the reaction solution was raised to 180° C., and the pressure of 10 mmHg was used for drying under reduced pressure. After the solvent was devolatilized, the hydroxyl-type novolac resin (A-1-1) was obtained. the

Synthesis Examples A-1-2 to A-3-3

With the synthetic method of the hydroxyl type novolac resin of synthesis example A-1-1, difference is that synthesis example A-1-2 to A-3-3 is to change the reactant in the hydroxyl type novolac resin (A-1) Type and dosage, its formula is as shown in Table 1, does not go into details here. the

Preparation of positive photosensitive resin composition

The positive photosensitive compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were prepared according to Table 2 and Table 3 as follows. the

Example 1

With 70 weight parts by the hydroxyl type novolak resin (A-1-1) of synthesis example A-1-1 gained, 30 weight parts by the hydroxyl type novolac resin (A-2-1) of synthesis example A-2-1 gained 1), 30 parts by weight of 1-[1-(4-hydroxyphenyl) isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene and 1,2-naphthoquinone Ester (B-1) of diazide-5-sulfonic acid (average degree of esterification 85%), 10 parts by weight of tris (4-hydroxyphenyl) methane (C-1), add 300 parts by weight of propylene glycol In the solvent (D-1) of methyl ether acetate (propylene glycol monomethyl ether acetate; PGMEA), stir with a shaking type agitator to dissolve the above-mentioned mixture in the solvent, and the positive photosensitive resin composition of the present invention can be obtained. . The obtained positive photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 2, wherein the detection methods of decolorization after etching, resolution and residual film rate will be described later. the

Examples 2 to 10

The same as the preparation method of the positive-type photosensitive resin composition in Example 1, the difference is that the types and usage amounts of the raw materials in the positive-type photosensitive resin composition are changed in Examples 2 to 10, and its formula and test results are shown in Table 2. , which will not be repeated here. the

Comparative Examples 1 to 7

The same as the preparation method of the positive-type photosensitive resin composition in Example 1, the difference is that Comparative Examples 1 to 7 are to change the types and usage amounts of raw materials in the positive-type photosensitive resin composition, and its formula and test results are also shown in Table 3 shown. the

evaluation method

1. Measure the thickness of the baked pattern film

The positive-type photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were coated on a plain glass substrate by spin coating, and pre-baked at 100°C for 120 seconds to obtain a pre-cured photosensitive resin composition of about 10 μm. Baked coating. Under the mask (manufactured by Filcon, Japan), the pre-baked coating film is irradiated with 200mJ/cm ² of ultraviolet light (exposure machine model AG500-4N; manufactured by M&R Nano Technology) After that, develop with 2.38% TMAH aqueous solution at 23°C for 3 minutes to remove the coating film on the exposed part of the substrate, and then wash it with pure water to obtain a pattern. After post-baking at 120°C for 2 minutes, a protective film with a pattern on the plain glass substrate can be obtained, and the film thickness is measured by an optical film thickness meter (Hongming Technology, MFS-630-F).

2. Cross-sectional shape of baked pattern after evaluation

The protective films with patterns obtained in the above-mentioned Examples 1 to 10 and Comparative Examples 1 to 7 were photographed by SEM, and the cross-sectional shape of the subsequent baked pattern was observed. The criteria for judging are as follows and shown in the cross-sectional shape of Figure 2:

◎: vertical section 201

○: Conical section 203

╳: reverse conical section 205, oblate section 207

Table 2 and Table 3 show the evaluation results of the film thickness of the post-baking pattern and the cross-sectional shape of the post-baking pattern of the positive photosensitive resin composition obtained in the above-mentioned examples and comparative examples. the

From the results of Table 2 and Table 3, it can be seen that when the positive photosensitive resin composition uses the above-mentioned ratio of hydroxyl type novolac resin (A-1) and xylenol type novolak resin (A-2), the prepared The pattern will have the advantages of high film thickness and good cross-sectional shape after post-baking. Secondly, when the positive-type photosensitive resin composition uses the esterification product (B) of o-naphthoquinone diazide sulfonic acid containing the skeleton of hydroxyaryl or hydroxyphenyl hydrocarbons, and then uses the hydroxyaryl compound as the hydroxyl When the compound (C) is used, the pattern thus obtained will have the advantage of a better cross-sectional shape, so the object of the present invention can indeed be achieved. the

It should be added that although the present invention uses specific compounds, compositions, reaction conditions, manufacturing processes, analysis methods or specific instruments as examples to illustrate the positive-type photosensitive resin composition of the present invention and its method for forming patterns, the present invention belongs to the technology Anyone with ordinary knowledge in the field can know that the present invention is not limited thereto. Without departing from the spirit and scope of the present invention, the positive photosensitive resin composition and pattern forming method thereof of the present invention can also use other compounds and components , reaction conditions, process, analytical methods or instruments. the

Although the present invention has been disclosed above in terms of implementation, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various changes without departing from the spirit and scope of the present invention. Changes and modifications, so the scope of protection of the present invention should be as defined by the appended claims. the

table 3

B-1 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene and 1,2-naphthoquinonediazide- Ester of 5-sulfonic acid

B-2 Esterification of 4,4'-ethylenebis(2-methylphenol) and 1,2-naphthoquinonediazide-5-sulfonic acid

B-3 Esterification of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid

c-1 Tris(4-hydroxyphenyl)methane

C-2 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene

C-3 Bis(4-hydroxy-3,5-dimethylphenyl)-4-phenylmethane

C-4 2,4,6-trihydroxybenzophenone

c-5 1,2,3-pyrogallol monomethyl ether

D-1 Propylene glycol monomethyl ether acetate (PGMEA, propylene glycol monomethyl ether acetate)

D-2 Ethyl lactate (EL, ethyl lactate)

D-3 Propylene glycol monoethyl ether (PGEE, propylene glycol monoethyl ether)

E-1 surfactant: trade name SF8427; manufactured by Toray Dow Corning Silicone

E-2 adhesion aid: trade name Cyme1-303; manufactured by CYTEC. the

Claims (9)

1. a positive type photosensitive organic compound, comprises:

Novolac resin (A), wherein said novolac resin (A) comprises oh type novolac resin (A-1) and xylenol type novolac resin (A-2), described oh type novolac resin (A-1) is by hydroxy benzaldehyde compound and aromatic hydroxy compound condensation and obtain, and described xylenol type novolac resin (A-2) is by aldehyde compound and xylenol compounds polycondensation and obtain;

The carboxylate (B) of adjacent naphthoquinones two nitrine sulphonic acids;

Hydroxyl compound (C); And

Solvent (D).

2. positive type photosensitive organic compound as claimed in claim 1, the skeleton that the carboxylate (B) of wherein said adjacent naphthoquinones two nitrine sulphonic acids comprises hydroxy benzophenone ketone and/or hydroxyaryl class and/or hydroxy phenyl hydro carbons.

3. positive type photosensitive organic compound as claimed in claim 1, wherein said hydroxyl compound (C) comprises hydroxy benzophenone ketone compounds and/or hydroxy aryl compound and/or hydroxy phenyl hydrocarbon compound.

4. positive type photosensitive organic compound as claimed in claim 1, be wherein 100 weight portions based on described novolac resin (A), the use amount of described oh type novolac resin (A-1) is 50 weight portion to 95 weight portions, the use amount of described xylenol type novolac resin (A-2) is 5 weight portion to 50 weight portions, the use amount of the carboxylate (B) of described adjacent naphthoquinones two nitrine sulphonic acids is 5 weight portion to 50 weight portions, the use amount of described hydroxyl compound (C) is 1 weight portion to 30 weight portion, and the use amount of described solvent (D) is 100 weight portion to 500 weight portions.

5. positive type photosensitive organic compound as claimed in claim 4, be wherein 100 percentage by weights based on described oh type novolac resin (A-1) with the total use amount of described xylenol type novolac resin (A-2), the use amount of described oh type novolac resin (A-1) is 50 percentage by weight to 95 percentage by weights, and the use amount of described xylenol type novolac resin (A-2) is 5 percentage by weight to 50 percentage by weights.

6. a pattern formation method, it is by the positive type photosensitive organic compound as described in claim 1 to 5 any one sequentially being bestowed to a coating processing, a pre-baked processing, an exposure-processed, a development treatment and a rear roasting processing, being used and form a pattern on a substrate.

7. pattern formation method as claimed in claim 6, the thickness of the pattern that wherein formed is between 5 μ m to 25 μ m.

8. a thin-film transistor array base-plate, it comprises pattern as claimed in claim 7.

9. a liquid crystal display cells, it comprises thin-film transistor array base-plate as claimed in claim 8.