JP2014164303A - Positive photosensitive resin composition and method for forming pattern by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition and a method for forming a pattern by using the composition.SOLUTION: The positive photosensitive resin composition comprises a novolac resin (A), an o-naphthoquinone diazide sulfonic acid ester (B), a hydroxy compound (C) and a solvent (D). The novolac resin (A) further comprises a hydroxy-type novolac resin (A-1) and a xylenol-type novolac resin (A-2). The hydroxy-type novolac resin (A-1) is synthesized by condensing a hydroxyl benzaldehyde compound with an aromatic hydroxy compound. The xylenol-type novolac resin (A-2) is synthesized by condensing an aldehyde compound with a xylenol compound. The positive photosensitive resin composition subjected to post-baking can be beneficially formed into a pattern having a large film thickness and a good cross-sectional profile.

Description

  The present invention relates to a positive photosensitive resin composition and a pattern forming method using the same. Specifically, the present invention is post-baked during the manufacture of thin-film transistor (TFT) liquid crystal displays (LCDs) or touch panels to have high film thickness and good cross-sectional profile. The present invention relates to a positive photosensitive resin composition for pattern formation.

  According to the miniaturization of various electronic products in daily life, the demand for high resolution in various high-performance smart phones, slim TVs and microprocessors will increase, so that patterns with finer line widths are formed. There is a need for a more accurate representation of the photolithography process.

  For the above purpose, Japanese Patent Application Laid-Open No. 2003-98669 discloses a positive photosensitive resin composition containing a novolac resin, a photoacid generator (PAG), and an organic solvent. ing. In the presence of an acid catalyst, the novolak resin reacts a phenol compound containing 50 wt% or more of m-cresol (in addition to m-cresol, for example, trimethylphenol, xylenol, or o-cresol) with an aldehyde. In addition, some or all of the hydroxy groups of the novolak resin are protected with alkoxyalkyl groups to improve the photosensitivity and resolution of the positive photosensitive resin composition. Japanese Patent Application Laid-Open No. 2001-183838 discloses a positive photosensitive resin composition containing a novolak resin, a photoacid generator, and a crosslinking agent catalyzed by an acid. The novolac resin can be obtained by performing a polycondensation reaction between an alkali-soluble resin and a cresol compound and / or a xylenol compound in the presence of an acid catalyst, thereby improving the photosensitivity and resolution of the positive photosensitive resin composition. It will increase.

  However, in the prior art, after the photosensitive resin composition is post-baked, there is often a problem that the post-baked photosensitive resin composition is unlikely to form a pattern having a high film thickness. It is done. Also, the yield of subsequent processes is even worse because the formed pattern has a poor cross-sectional profile. Therefore, it is important to post-bake the positive photosensitive resin composition to form a pattern having a high film thickness and a good cross-sectional profile.

Japanese Unexamined Patent Publication No. 2003-98669 Japanese Unexamined Patent Publication No. 2001-183838

  Accordingly, it is desired to provide a positive photosensitive resin composition material that forms a pattern having a high film thickness and a good cross-sectional profile after post-baking so as to overcome the above problems in the prior art. Yes.

  Therefore, in one aspect of the present invention, a positive photosensitive resin composition comprising a novolak resin (A), an o-naphthoquinonediazide sulfonic acid ester (B), a hydroxy compound (C), and a solvent (D). I will provide a. Further, the novolac resin (A) includes a hydroxy type novolac resin (A-1) and a xylenol type novolac resin (A-2). The hydroxy type novolak resin (A-1) is formed by condensing a hydroxylbenzaldehyde compound and an aromatic hydroxy compound. The xylenol type novolak resin (A-2) is formed by condensing an aldehyde compound and a xylenol compound.

  In another aspect of the present invention, there is provided a pattern forming method for forming a pattern on a substrate by passing the positive photosensitive resin composition through a coating process, a pre-bake process, an exposure process, a development process, and a post-bake process. After the post-baking, the positive photosensitive resin composition forms a pattern having a high film thickness and a good cross-sectional profile.

  In yet another aspect of the present invention, a thin film transistor (TFT) array substrate including the pattern is provided.

  In still another aspect of the present invention, a liquid crystal display (LCD) device including the TFT array substrate is provided.

  The post-baked positive photosensitive resin composition can beneficially form a pattern having a high film thickness and a good cross-sectional profile.

The following description of the accompanying drawings is intended to facilitate understanding of the characteristic structure, merits, and embodiments of the present invention.
1 is a partial cross-sectional view showing a TFT array substrate for an LCD device according to an embodiment of the present invention. Some cross-sectional views for cross-sectional profile evaluation having a protective film having a pattern as in Examples 1 to 10 and Comparative Examples 1 to 7 are shown.

  The positive photosensitive resin composition, the TFT array substrate, the structure of the LCD device, and the pattern forming method of the present invention will be described below.

[Positive photosensitive resin composition]
The positive photosensitive resin composition of the present invention contains a novolak resin (A), o-naphthoquinonediazide sulfonic acid ester (B), a hydroxy compound (C), and a solvent (D). Each of these will be described below.

[Novolac resin (A)]
The novolak resin (A) in this positive photosensitive resin composition contains a hydroxy novolak resin (A-1), and optionally further contains a xylenol novolak resin (A-2).

  The hydroxy novolak resin (A-1) is formed by condensing a hydroxylbenzaldehyde compound and an aromatic hydroxy compound in the presence of an acid catalyst.

  Specific examples of the hydroxyl benzaldehyde compound include hydroxyl benzaldehyde compounds such as o-hydroxyl benzaldehyde, m-hydroxyl benzaldehyde, p-hydroxyl benzaldehyde; 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde. Dihydroxybenzaldehyde compounds such as 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde; 2,3,4-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, Trihydroxybenzaldehyde compounds such as 3,4,5-trihydroxybenzaldehyde; o-hydroxymethylbenz Including aldehyde, m- hydroxymethyl benzaldehyde, such as p- hydroxymethylbenzaldehyde hydroxyl alkyl benzaldehyde compound. The hydroxylbenzaldehyde compounds may be used alone or in combination of two or more. In these hydroxylbenzaldehyde compounds, o-hydroxylbenzaldehyde, m-hydroxylbenzaldehyde, p-hydroxylbenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,3,4-tri Hydroxybenzaldehyde and o-hydroxymethylbenzaldehyde are preferred.

  Specific examples of the aromatic hydroxy compound that can be condensed with the hydroxylbenzaldehyde compound include phenol; cresol such as m-cresol, p-cresol, and o-cresol; 2,3-xylenol, 2,5-xylenol. Xylenol such as 3,5-xylenol, 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4 Alkylphenols such as -tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-cresol, 2-tert-butyl-5-cresol, 6-tert-butyl-3-cresol; p-methoxypheno , Alkoxy phenols such as m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-iso Isopropenyl phenol such as propenylphenol and 2-ethyl-4-isopropenylphenol; arylphenol such as phenylphenol; 4,4′-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, 1,2,3-pyrogallol Contains polyhydroxyphenol. You may use the said aromatic hydroxy compound individually or in combination of 2 or more types. Among these aromatic hydroxy compounds, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol and the like are preferable.

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

  The xylenol type novolak resin (A-2) is formed by condensing an aldehyde compound and a xylenol compound in the presence of the acid catalyst.

  Specific examples of the aldehyde compounds include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α -Phenylpropylaldehyde, β-phenylpropylaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamic aldehyde and the like. The aldehyde compounds may be used alone or in combination of two or more. Among these aldehyde compounds, methanal and benzaldehyde are preferable.

  Specific examples of the xylenol compound preferably include 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol.

  Without affecting the overall characteristics, the positive photosensitive resin composition of the present invention is a novolak resin (condensed with an aldehyde compound and an aromatic hydroxy compound in the presence of the acid catalyst). A-3) may optionally be provided. Since both the aldehyde compound and the aromatic hydroxy compound are as described in the preceding sentence, they will not be described repeatedly. The novolak resin (A-3) has a different structure from the hydroxy-type novolak resin (A-1) and the xylenol-type novolak resin (A-2).

  The hydroxy type novolak resin (A-1), the xylenol type novolak resin (A-2), and another novolak resin (A-3) may be used alone or in combination of two or more. The content of the hydroxy novolak resin (A-1) is usually 50 to 95 parts by weight with respect to 100 parts by weight of the novolak resin (A), and the content of the xylenol type novolak resin (A-2) The amount is 5 to 50 parts by weight, and the content of the other novolak resin (A-3) is 0 to 45 parts by weight. The hydroxy type novolak resin (A-1) has good developability, and the xylenol type novolak resin (A-2) has a good film-remaining ratio. When the hydroxy-type novolak resin (A-1) or the xylenol-type novolak resin (A-2) is not used in the positive-type photosensitive resin composition, the obtained positive-type photosensitive resin composition includes a post-type photosensitive resin composition. Problems such as having a bad cross-sectional profile and insufficient film thickness after being baked. However, when the positive photosensitive resin composition has the hydroxy novolak resin (A-1) and the xylenol novolak resin (A-2) having the above contents, the obtained positive photosensitive resin composition is: After post-baking, it has the advantage that the cross-sectional profile is good, and this allows the resulting pattern to have defects or insufficient film thickness due to the flow of the pattern heated during the post-baking process. It can be prevented from having.

  Further, the content of the hydroxy novolac resin (A-1) is usually 50% by weight with respect to a total amount of 100% by weight of the hydroxy novolac resin (A-1) and the xylenol novolak resin (A-2). The content of the xylenol type novolak resin (A-2) is 5 to 50% by weight. When the positive photosensitive resin composition has 50 to 95 parts by weight of the hydroxy type novolak resin (A-1) and 5 to 50 parts by weight of the xylenol type novolak resin (A-2), the obtained positive type photosensitive resin. The functional resin composition has a good cross-sectional profile after post-baking.

[O-naphthoquinonediazide sulfonic acid ester (B)]
The o-naphthoquinone diazide sulfonic acid ester (B) in this positive photosensitive resin composition is not particularly limited, and may be selected from conventional o-naphthoquinone diazide sulfonic acid esters often found. In a preferred embodiment of the present invention, the o-naphthoquinone diazide sulfonic acid ester (B) comprises o-naphthoquinone diazide sulfonic acid and a hydroxy compound (for example, o-naphthoquinone diazide-4-sulfonic acid, o-naphthoquinone diazide-5-sulfone). Acid, esters such as o-naphthoquinonediazide-6-sulfonic acid), but are not limited thereto. However, the o-naphthoquinone diazide sulfonic acid and the above ester of a polyhydroxyl compound are more preferred.

  The o-naphthoquinonediazide sulfonic acid ester (B) may be completely or partially esterified. Examples of the hydroxy compound include (1) hydroxybenzophenone and / or (2) hydroxylaryl compound having chemical formula (I) and / or (3) (hydroxylphenyl) hydrocarbon having chemical formula (II). Yes, these will be explained as follows.

  (1) Specific examples of the hydroxybenzophenone include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4,4. '-Tetrahydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,3 ', 4,4', 6-pentahydroxybenzophenone, 2,2 ', 3,4,4'-pentahydroxy Benzophenone, 2,2 ′, 3,4,5′-pentahydroxybenzophenone, 2,3 ′, 4,5,5′-pentahydroxybenzophenone, or 2,3,3 ′, 4,4 ′, 5′- Contains hexahydroxybenzophenone.

  (2) As a specific example of the hydroxyl aryl compound, it has a structure represented by chemical formula (I).

化学式（Ｉ）において、Ｒ_１〜Ｒ_３はそれぞれ独立的に水素原子又は低級アルキル基であり、Ｒ_４〜Ｒ_９はそれぞれ独立的に水素原子、ハロゲン原子、低級アルキル基、低級アルコキシ基、低級アルケニル基、シクロアルキルであり；Ｒ_１０及びＲ_１１はそれぞれ独立的に水素原子、ハロゲン原子、低級アルキル基であり、ｘ及びｙはそれぞれ独立的に１〜３の整数である。ｚは０〜３の整数であり、ｎは０又は１である。

In the chemical formula (I), R _{1 to} R ₃ are each independently a hydrogen atom or a lower alkyl group, and R _{4 to} R ₉ are each independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower group, R ₁₀ and R ₁₁ are each independently a hydrogen atom, a halogen atom or a lower alkyl group, and x and y are each independently an integer of 1 to 3. z is an integer of 0 to 3, and n is 0 or 1.

  In a preferred embodiment of the present invention, the hydroxylaryl compound having the structure represented by chemical formula (I) is tri (4-hydroxylphenyl) methane, bis (4-hydroxyl-3,5-dimethylphenyl) -4-hydroxylphenylmethane, Bis (4-hydroxyl-3,5-dimethylphenyl) -3-hydroxylphenylmethane, bis (4-hydroxyl-3,5-dimethylphenyl) phenylmethane, bis (4-hydroxyphenyl) phenylethane, bis (4- Hydroxy-3-t-butylphenyl) phenylethane, bis (4-hydroxyl-3,5-dimethylphenyl) -2-hydroxylphenylmethane, bis (4-hydroxyl-2,5-dimethylphenyl) -4-hydroxylphenyl Methane, bis (4-hydroxyl-2,5- Methylphenyl) -3-hydroxylphenylmethane, bis (4-hydroxyl-2,5-dimethylphenyl) -2-hydroxylphenylmethane, bis (4-hydroxyl-3,5-dimethylphenyl) -3,4-dihydroxyl Phenylmethane, bis (4-hydroxyl-2,5-dimethylphenyl) -3,4-dihydroxylphenylmethane, bis (4-hydroxyl-3,5-dimethylphenyl) -2,4-dihydroxylphenylmethane, bis (4-hydroxyl-2,5-dimethylphenyl) -2,4-dihydroxylphenylmethane, bis (4-hydroxylphenyl) -3-methoxyl-4-hydroxylphenylmethane, bis (3-cyclohexyl-4-hydroxylphenyl) ) -3-hydroxylphenylmethane, bi (3-cyclohexyl-4-hydroxylphenyl) -2-hydroxylphenylmethane, bis (3-cyclohexyl-4-hydroxylphenyl) -4-hydroxylphenylmethane, bis (3-cyclohexyl-4-hydroxyl-6-methylphenyl) 2-hydroxylphenylmethane, bis (3-cyclohexyl-4-hydroxyl-6-methylphenyl) -3-hydroxylphenylmethane, bis (3-cyclohexyl-4-hydroxyl-6-methylphenyl) -4-hydroxylphenylmethane Bis (3-cyclohexyl-4-hydroxyl-6-methylphenyl) -3,4-dihydroxylphenylmethane, bis (3-cyclohexyl-6-hydroxylphenyl) -3-hydroxylphenylmethane, bis (3-cycl Rohexyl-6-hydroxylphenyl) -4-hydroxylphenylmethane, bis (3-cyclohexyl-6-hydroxylphenyl) -2-hydroxylphenylmethane, bis (3-cyclohexyl-6-hydroxyl-4-methylphenyl) -2- Hydroxylphenylmethane, bis (3-cyclohexyl-6-hydroxyl-4-methylphenyl) -4-hydroxylphenylmethane, bis (3-cyclohexyl-6-hydroxyl-4-methylphenyl) -3,4-dihydroxylphenylmethane 1- [1- (4-hydroxylphenyl) isopropyl] -4- [1,1-bis (4-hydroxylphenyl) ethyl] benzene or 1- [1- (3-methyl-4-hydroxylphenyl) isopropyl] -4- [1,1-bis (3 Methyl-4-hydroxyphenyl) ethyl] benzene.

  (3) As a specific example of the (hydroxylphenyl) hydrocarbon, it has a structure represented by the following chemical formula (II).

化学式（ＩＩ）において、Ｒ_１２及びＲ_１３はそれぞれ独立的に水素原子又は低級アルキル基であり、ｘ’及びｙ’はそれぞれ独立的に１〜３の整数である。

In the chemical formula (II), R ₁₂ and R ₁₃ are each independently a hydrogen atom or a lower alkyl group, and x ′ and y ′ are each independently an integer of 1 to 3.

  In a preferred embodiment of the present invention, the (hydroxylphenyl) hydrocarbon having the structure represented by the chemical formula (II) is 2- (2,3,4-trihydroxylphenyl) -2- (2 ′, 3 ′, 4′- Trihydroxylphenyl) propane, 2- (2,4-dihydroxylphenyl) -2- (2 ′, 4′-dihydroxylphenyl) propane, 2- (4-hydroxylphenyl) -2- (4′-hydroxylphenyl) ) Propane, bis (2,3,4-trihydroxylphenyl) methane or bis (2,4-dihydroxylphenyl) methane.

  The o-naphthoquinonediazide sulfonic acid ester (B) may optionally contain (4) another aromatic hydroxy compound. Specific examples of other aromatic hydroxy compounds include phenol, p-methoxyphenol, xylenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, 1,2,3-pyrogallol monomethyl ether, 1,2,3-pyrogallol-1 , 3-dimethyl ether, gallic acid (3,4,5-trihydroxybenzoic acid) or partially esterified or etherified gallic acid (3,4,5-trihydroxybenzoic acid).

  In those examples, the o-naphthoquinone diazide sulfonate ester (B) preferably comprises the hydroxyl aryl compound and the (hydroxylphenyl) hydrocarbon. Specific examples of the hydroxylaryl compound and the (hydroxylphenyl) hydrocarbon include 1- [1- (4-hydroxylphenyl) isopropyl] -4- [1,1-bis (4-hydroxylphenyl) ethyl]. Esters of benzene and naphthoquinone-1,2-diazide-5-sulfonate, esters of 4,4′-ethylene-bis (2-methylphenol) and naphthoquinone-1,2-diazide-5-sulfonate And esters of 2,3,4,4′-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonate. The o-naphthoquinonediazide sulfonic acid ester (B) may be used alone or in combination of two or more.

  The compound containing quinonediazide can be used as the o-naphthoquinonediazide sulfonic acid ester (B) in the positive photosensitive resin composition of the present invention. For example, the compound is o-naphthoquinonediazide-4 (or 5) Fully or partially esterified by a condensation reaction of -sulfonyl halogenide and the above (1) to (4) hydroxy compound. The condensation reaction is performed in an organic solvent (for example, dioxane, N-pyrrolidone, etc.), and more preferably in the presence of an alkaline condensing agent (for example, triethanolamine, alkali carbonate, or alkaline bicarbonate). .

  In a preferred embodiment of the present invention, the hydroxy compound and o-naphthoquinonediazide, preferably exceeding 50 mol%, more preferably exceeding 60 mol%, relative to 100 mol% of the total content of hydroxy groups in the hydroxy compound -4 (or 5) -sulfonyl halogenide is condensed to an ester, and the degree of esterification of the condensation reaction exceeds 50%, and preferably exceeds 60%.

  In a specific example of the present invention, the content of the o-naphthoquinonediazide sulfonic acid ester (B) in the present invention is 5 to 50 parts by weight, preferably 10 parts per 100 parts by weight of the novolak resin (A). It is -45 weight part, More preferably, it is 15-40 weight part. When the o-naphthoquinonediazide sulfonic acid ester (B) contains the hydroxylaryl compound or the (hydroxylphenyl) hydrocarbon, the obtained positive photosensitive resin composition has a good cross-sectional profile after being post-baked. Have

[Hydroxy Compound (C)]
This hydroxy compound (C) may contain the said hydroxy compounds (1)-(4) used for the said o-naphthoquinone diazide sulfonic acid ester (B), and hydroxy compounds (1)-(3) are preferable.

  In these hydroxy compounds, it is preferable to use the hydroxy compound (2) as the hydroxy compound (C). Specific examples of the hydroxy compound (2) include tri (4-hydroxylphenyl) methane, 1- [1- (4-hydroxylphenyl) isopropyl] -4- [1,1-bis (4-hydroxylphenyl) Ethyl] benzene, bis (4-hydroxyl-3,5-dimethylphenyl) phenylmethane, 2,4,6-trihydroxybenzophenone, 1,2,3-pyrogallol monomethyl ether, and the like. The hydroxy compound (C) may be used alone or in combination of two or more.

  The content of the hydroxy compound (C) is 1 to 30 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight with respect to 100 parts by weight of the novolak resin (A). It is. When the hydroxy compound (C) is not used in the positive photosensitive resin composition, the obtained positive photosensitive resin composition has a problem that the cross-sectional profile is poor after post-baking. When the positive photosensitive resin composition has the above-mentioned content of the hydroxy compound (C), the obtained positive photosensitive resin composition has a merit that the cross-sectional profile is good after post-baking.

[Solvent (D)]
The solvent (D) of the positive photosensitive resin composition of the present invention is an organic solvent that can dissolve other organic components but does not react with other organic components.

  In a specific embodiment of the present invention, the solvent (D) is, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mononormal propyl ether, diethylene glycol mononormal 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 mononormal propyl ether, dipropylene glycol mononormal butyl ether, tripropylene glycol Monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether; (poly) alkylenes such as ethylene glycol monomethyl ether acetate ether, ethylene glycol monoethyl ether acetate ether, propylene glycol monomethyl ether acetate ether, propylene glycol acetate ether Glycol monoalkyl acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate (lactic acid Also called methyl), ethyl 2-hydroxypropanoate (milk) Lactic acid alkyl esters such as ethyl); methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, ethoxyethyl acetate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-methylbutyl propionate, ethyl acetate , Normal propyl acetate, isopropyl acetate, normal butyl acetate, isobutyl acetate, normal amyl acetate, isoamyl acetate, normal butyl propionate, ethyl butyrate, normal propyl butyrate, isopropyl butyrate, normal butyl butyrate, methyl pyruvate, Other esters such as ethyl pyruvate, normal propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as methylbenzene and dimethylbenzene; N-methylpyrrolidone, N, N -Carboxylic acid amides such as dimethylformamide and N, N-dimethylacetamide. The solvent (D) may be used alone or in combination of two or more. The solvent (D) is preferably propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate ether, or ethyl lactate.

  In a specific embodiment of the present invention, the content of the solvent (D) is 100 to 500 parts by weight, preferably 100 to 450 parts by weight with respect to 100 parts by weight of the novolak resin (A). More preferably, it is 100-400 weight part.

[Auxiliary agent (E)]
The positive photosensitive resin composition of the present invention may selectively include an auxiliary agent (E). The auxiliary agent (E) includes, but is not limited to, a viscosity improver, a surface conditioner, a diluent, a photosensitizer and the like.

  In order to improve the adhesiveness of the positive photosensitive resin composition to the substrate, the viscosity improver may include a melamine compound and a silane compound, but is not limited thereto. Specific examples of the melamine include, for example, commercially available Cymel-300, Cymel-303 (manufactured by CYTEC); MW-30MH, MW-30, MS-11, MS-001, MX-750 or MX-706 (three Available from Sanwa Chemical Co., Ltd. Specific examples of the silane compound include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 3- (methyl) acryloxypropyltrimethoxysilane, vinyltri (2-methoxyethoxy) silane, and N- (2-aminoethyl). -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyldimethylmethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane or bis-1,2- (to It is methoxy silane) ethane.

  In a specific embodiment of the present invention, the content of the viscosity improver in the melamine compound is 0 to 20 parts by weight, preferably 0.5 parts by weight with respect to 100 parts by weight of the novolak resin (A). Part to 18 parts by weight, and more preferably 1.0 part to 15 parts by weight. The content of the viscosity improver in the silane compound is 0 to 2 parts by weight, preferably 0.001 to 1 part by weight, and more preferably 0.005 to 0.8 part by weight. Parts by weight.

  The surface conditioner may include, but is not limited to, a fluorine-based interface activator or a silane surfactant. Specific examples of the fluorine-based interface activator include, for example, commercially available Flourate FC-430, FC-431 (manufactured by 3M), or F top EF122A, 122B, 122C, 126, BL20 (manufactured by Tochem product). Specific examples of the silane surfactant include commercially available SF8427 or SH29PA (manufactured by Toray Dow Corning Silicone).

  In a specific embodiment of the present invention, the content of the surface conditioner is 0 to 1.2 parts by weight, preferably 0.025 parts by weight with respect to 100 parts by weight of the novolak resin (A). It is -1.0 weight part, More preferably, it is 0.050 weight part -0.8 weight part.

  Specific examples of the diluent include, for example, a commercially available product (for example) RE801 or RE802 (manufactured by Teikoku Printing Inks Mfg. Co., Ltd.).

  Specific examples of the photosensitizer include, for example, commercially available products (for example) 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 (manufactured by Honshu Chemical Industry Co., Ltd.), and preferably TPPA-1600-3M6C or TPPA-MF. You may use the said photosensitive agent individually or in combination of 2 or more types.

  You may use the said adjuvant (E) individually or in combination of 2 or more types. In a specific embodiment of the present invention, with respect to 100 parts by weight of the novolak resin (A), the content of the photosensitive agent is 0 to 20 parts by weight, preferably 0.5 to 18 parts by weight. Parts, and more preferably 1.0 to 5 parts by weight. The present invention may also use other auxiliaries such as plasticizers and stabilizers as needed.

[Method for Preparing Positive Photosensitive Resin Composition]
Usually, the positive photosensitive resin composition of the present invention is prepared by the following steps. Mix the above novolak resin (A), o-naphthoquinonediazide sulfonic acid ester (B), hydroxy compound (C) and solvent (D) uniformly with a conventional mixer until all the components are in solution. Accordingly, various auxiliary agents are selectively added to the above mixture to obtain a positive photosensitive resin composition.

[Pattern formation method]
The obtained positive photosensitive resin composition is processed in the order of a pre-bake process, an exposure process, a development process, and a post-bake process to form a pattern on the substrate.

  Particularly, in the pattern forming method using the positive photosensitive resin composition of the present invention, the positive photosensitive resin composition is applied to a substrate by spin coating, curtain coating, roll coating or the like, and the solvent is removed. After pre-baking and painting, it is removed to form a pre-baked coating film. The prebaking state can be changed according to the types and mixing ratios of various components, and the prebaking is performed at a temperature of 70 to 110 ° C. for 1 to 15 minutes.

  After pre-baking, after exposing the coating film with a desired exposure mask, the coating film is immersed in a developer at a temperature of 23 ± 2 ° C. for 15 seconds to 5 minutes to remove unnecessary regions, Also, a specified pattern is formed. The exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet rays may be generated by an ultraviolet illumination facility (for example, (ultra) high-pressure mercury lamp and metal halide lamp).

  Specific examples of the developer used in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia solution, ethylamine, diethylamine, Alkaline compounds such as dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5,4,0] -7-undecene.

  The concentration of the developer is preferably 0.001 wt% to 10 wt%, more preferably 0.005 wt% to 5 wt%, and even more preferably 0.01 wt% to 1 wt%.

  When using the developing solution containing the said alkaline compound, after developing, after washing a coating film with water, the said coating film is dried with compressed air or compressed nitrogen gas. Thereafter, the coating film is post-baked by a heating device (for example, a heating plate or an oven). The post-baking step may be performed at a temperature of 100 ° C. to 250 ° C. for 1 to 60 minutes with the heating plate or for 5 to 90 minutes with the oven. After the above process, a pattern can be formed on the substrate.

  The thickness of the obtained pattern is 5 μm to 25 μm, preferably 8 μm to 25 μm, and more preferably 10 μm to 25 μm. When the thickness of the obtained pattern is 5 μm to 25 μm, the pattern contributes to fine arrangement of the conductive layer, the insulating layer, or the protective film.

[TFT array substrate]
The TFT array substrate of the present invention is manufactured by the above method. In short, for example, by using a coating method such as spin coating, curtain coating, or roll coating, the positive photosensitive resin composition of the present invention is coated on a glass substrate or a plastic substrate, and a positive photoresist layer is formed. Form. Thereafter, the positive photoresist layer is processed by a pre-bake, an exposure process, a development process, and a post-bake process, and then the obtained photosensitive resin pattern is etched and released. After repeating the above steps, a TFT array substrate including a plurality of TFTs or electrodes is obtained.

  Please refer to FIG. 1, which is a partial cross-sectional view showing a TFT array substrate for an LCD device according to an embodiment of the present invention. First, the gate electrode 102 a and the storage capacitor Cs electrode 102 b are disposed on the aluminum thin film of the glass substrate 101. Further, a silicon oxide (SiOx) thin film 103 or a silicon nitride (SiNx) thin film 104 is coated on the gate electrode 102a to form an insulating film, and then amorphous silicon (a-Si) as a semiconductor active layer is formed on the insulating film. Layer 105 is formed. In order to reduce the interface impedance, the amorphous silicon layer 105 may be provided with an amorphous silicon layer 106 doped with nitrogen impurities. After that, a drain electrode 107 a connected to a data signal line (not shown) and a source electrode 107 b connected to an image electrode (or a sub-image electrode) 109 are formed using a metal such as aluminum. Thereafter, a silicon nitride thin film is provided as the protective film 108 and used to protect the lower semiconductor active layer (for example, the amorphous silicon layer 105, the drain electrode 107a, the source electrode 107b, etc.).

[LCD device]
The LCD device of the present invention includes at least the TFT array substrate, and may include other members as necessary.

  Specific examples of the basic structure of the LCD device will be described below. (1) The TFT array substrate (driving substrate) is provided by a driving device (for example, the TFT and the image electrode). The color filter substrate includes a filter and a counter electrode (also referred to as a conductive layer). The TFT array substrate (drive substrate) and the color filter substrate are provided to face each other, and a spacer is inserted between them. The space between the two substrates is filled with a liquid crystal material and then sealed to form the LCD device. Alternatively, (2) an integrated TFT array substrate including a filter directly formed on the TFT array substrate of the present invention is provided. The integrated TFT array substrate and a counter substrate having a counter electrode (conductive layer) are provided to face each other, and a spacer is inserted between them. The space between the two substrates is filled with a liquid crystal material and then sealed to form the LCD device. The liquid crystal material may be any conventional LC compound or composition, and there is no limitation.

  Specific examples of the conductive layer include an indium tin oxide (ITO) thin film, a metal thin film (eg, aluminum, zinc, copper, iron, nickel, chromium, molybdenum, etc.); or a metal oxide thin film ( For example, silicon dioxide). Preferably, the conductive layer is a transparent film layer, specifically an ITO thin film.

  Specific examples of the TFT array substrate, color filter substrate, and counter substrate used in the present invention include, for example, conventional glass such as Na—Ca glass, low expansion glass, alkali-free glass, or quartz glass. Moreover, you may use the board | substrate comprised from the plastic thin film.

  Hereinafter, various applications of the present invention will be described in more detail with reference to various exemplary embodiments described below. However, these exemplary embodiments do not limit the application of the present invention. Accordingly, those skilled in the art can easily understand the basic features of the present invention, and various modifications can be made to the present invention so as to suit various uses and conditions without departing from the spirit and scope of the present invention. Changes and corrections can be made.

  The present embodiment and its examples relating to details of the invention are shown in the accompanying drawings. Wherever possible, the same reference numbers are used for the same parts used in the drawings and the description.

[Preparation of novolak resin (A)]
Based on Table 1, novolak resin (A) was prepared through Synthesis Examples A-1-1 to A-3-3.

［合成例Ａ−１−１］
窒素ガスによって、窒素ガス入口、攪拌器、加熱器、冷却器、温度計付きの１０００ｍＬの四口フラスコを洗浄して、下記成分を前記フラスコに入れた。上記成分として、０．７０モルのｍ−クレゾール、０．３０モルのｐ−クレゾール、０．５モルの３，４−ジヒドロキシベンズアルデヒド、０．０２０モルのシュウ酸という成分を、ゆっくり攪拌して１００℃まで加熱して、重縮合反応を６時間行わせた。次に、反応物を再び１８０℃に加熱して、１０ｍｍＨｇの低下する圧力で乾燥させて、前記溶剤を蒸発させて、ヒドロキシ型ノボラック樹脂（Ａ−１−１）を得た。

[Synthesis Example A-1-1]
A 1000 mL four-necked flask equipped with a nitrogen gas inlet, a stirrer, a heater, a cooler, and a thermometer was washed with nitrogen gas, and the following components were put into the flask. As the above components, 0.70 mol of m-cresol, 0.30 mol of p-cresol, 0.5 mol of 3,4-dihydroxybenzaldehyde and 0.020 mol of oxalic acid were slowly stirred and mixed with 100 components. The polycondensation reaction was performed for 6 hours by heating to 0 ° C. Next, the reaction product was again heated to 180 ° C. and dried at a pressure of 10 mmHg, and the solvent was evaporated to obtain a hydroxy type novolak resin (A-1-1).

[Synthesis Examples A-1-2 to A-3-3]
As Synthesis Examples A-1-2 to A-3-3, the same method as Synthesis Example A-1-1 was used, using components that differ in type and amount from the hydroxy type novolak resin (A-1-1). Achieved by. The compositions of Synthesis Examples A-1-2 to A-3-3 were also exemplified in Table 1, but were not mentioned in detail.

[Preparation of positive photosensitive resin composition]
In the following examples, the positive photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were prepared according to Tables 2 and 3.

Ｂ−１
１−［１−（４−ヒドロキシルフェニル）イソプロピル］−４−［１，１−ビス（４−ヒドロキシルフェニル）エチル］ベンゼンとナフトキノン−１，２−ジアジド−５−スルホン酸塩とのエステル
Ｂ−２
４，４’−エチレン−ビス（２−メチルフェノール）とナフトキノン−１，２−ジアジド−５−スルホン酸塩とのエステル
Ｂ−３
２，３，４，４’−テトラヒドロキシベンゾフェノンとナフトキノン−１，２−ジアジド−５−スルホン酸塩とのエステル
Ｃ−１
トリ（４−ヒドロキシルフェニル）メタン
Ｃ−２
１−［１−（４−ヒドロキシルフェニル）イソプロピル］−４−［１，１−ビス（４−ヒドロキシルフェニル）エチル］ベンゼン
Ｃ−３
ビス（４−ヒドロキシル−３，５−ジメチルフェニル）フェニルメタン
Ｃ−４
２，４，６−トリヒドロキシベンゾフェノン
Ｃ−５
１，２，３−ピロガロールモノメチルエーテル
Ｄ−１
プロピレングリコールモノメチルエーテル酢酸エーテル（ＰＧＭＥＡ）
Ｄ−２
乳酸エチル（ＥＬ）
Ｄ−３
プロピレングリコールモノエチルエーテル（ＰＧＥＥ）
Ｅ−１
表面活性剤；商品名ＳＦ８４２７（東レダウコーニング株式会社製）
Ｅ−２
粘性改良剤；商品名Ｃｙｍｅｌ−３０３（ＣＹＴＥＣ社製）
（実施例１）
合成例Ａ−１−１の７０重量部のヒドロキシ型ノボラック樹脂（Ａ−１−１）、３０重量部の合成例Ａ−２−１のヒドロキシ型ノボラック樹脂（Ａ−２−１）、３０重量部の１−［１−（４−ヒドロキシルフェニル）イソプロピル］−４−［１，１−ビス（４−ヒドロキシルフェニル）エチル］ベンゼン、ナフトキノン−１，２−ジアジド−５−スルホン酸エステルのエステル（Ｂ−１）（平均エステル化度８５％）、及び１０重量部のトリ（４−ヒドロキシルフェニル）メタン（Ｃ−１）を、３００重量部のプロピレングリコールモノメチルエーテル酢酸エーテル（ｐｒｏｐｙｌｅｎｅ ｇｌｙｃｏｌ ｍｏｎｏｍｅｔｈｙｌ ｅｔｈｅｒ ａｃｅｔａｔｅ；ＰＧＭＥＡ）溶剤（Ｄ−１）に添加して、シェーキングミキサーによって上記混合物を攪拌し前記溶剤に溶解させて、本発明の実施例１におけるポジ型感光性樹脂組成物を形成した。次に、以下の評価方法によって、前記ポジ型感光性樹脂組成物の性質を確定し、結果を表２に記録した。ポストベークされたパターンの膜厚及び断面プロフィールの検査方法については、下記のように説明した。

B-1
Esters of 1- [1- (4-hydroxylphenyl) isopropyl] -4- [1,1-bis (4-hydroxylphenyl) ethyl] benzene and naphthoquinone-1,2-diazide-5-sulfonate B- 2
Esters of 4,4′-ethylene-bis (2-methylphenol) and naphthoquinone-1,2-diazide-5-sulfonate B-3
Ester of 2,3,4,4′-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonate C-1
Tri (4-hydroxylphenyl) methane C-2
1- [1- (4-hydroxylphenyl) isopropyl] -4- [1,1-bis (4-hydroxylphenyl) ethyl] benzene C-3
Bis (4-hydroxyl-3,5-dimethylphenyl) phenylmethane C-4
2,4,6-trihydroxybenzophenone C-5
1,2,3-pyrogallol monomethyl ether D-1
Propylene glycol monomethyl ether acetate ether (PGMEA)
D-2
Ethyl lactate (EL)
D-3
Propylene glycol monoethyl ether (PGEE)
E-1
Surfactant; trade name SF8427 (manufactured by Toray Dow Corning Co., Ltd.)
E-2
Viscosity improver; trade name Cymel-303 (manufactured by CYTEC)
Example 1
70 parts by weight of the hydroxy type novolak resin (A-1-1) of Synthesis Example A-1-1, 30 parts by weight of the hydroxy type novolak resin (A-2-1) of Synthesis Example A-2-1, 30% by weight Parts of 1- [1- (4-hydroxylphenyl) isopropyl] -4- [1,1-bis (4-hydroxylphenyl) ethyl] benzene, naphthoquinone-1,2-diazide-5-sulfonic acid ester ( B-1) (average degree of esterification 85%), and 10 parts by weight of tri (4-hydroxylphenyl) methane (C-1), 300 parts by weight of propylene glycol monomethyl ether acetate; PGMEA) is added to the solvent (D-1), and the mixture is mixed with a shaking mixer. The mixture was stirred and dissolved in the solvent to form a positive photosensitive resin composition in Example 1 of the present invention. Next, the properties of the positive photosensitive resin composition were determined by the following evaluation method, and the results were recorded in Table 2. The method for inspecting the film thickness and cross-sectional profile of the post-baked pattern was explained as follows.

(Examples 2 to 10)
Examples 2 to 10 were achieved in the same manner as in Example 1 using components that differ in type and amount from the positive photosensitive resin composition of Example 1. The compositions of Examples 2-10 were also exemplified in Table 2, but were not mentioned in detail.

(Comparative Examples 1-7)
Comparative Examples 1 to 7 were achieved by the same method as in Example 1, using ingredients different in type and dose from those in Example 1. The composition and evaluation results are exemplified in Table 3.

[Evaluation method]
1. Film thickness of post-baked pattern The positive photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were spin-coated on a glass substrate, and then pre-baked at 100 ° C. for 120 seconds. A 10 μm pre-baked and painted thin film was obtained. Next, the pre-baked and painted thin film was placed on a specified mask (manufactured by Nippon Filcon) and irradiated with 200 mJ / cm ² ultraviolet light (standard AG500-4N exposure machine, manufactured by M & R Nano Technology). . Then, the thin film was developed for 3 minutes in a 2.38% TMAH solution at 23 ° C. to remove the exposed portion of the thin film on the substrate. The pattern remaining in the thin film was obtained by washing with pure water. The thin film was post-baked at 120 ° C. for 2 minutes to obtain a glass substrate including a pattern as a protective film. The thickness of the protective film was measured with an optical reflection spectral film thickness meter (standard MFS-630-F, manufactured by Hong-Ming Technology).

2. Cross-sectional profile of post-baked pattern A cross-sectional profile of the protective film having the patterns of Examples 1 to 10 and Comparative Examples 1 to 7 was photographed with a scanning electron microscope (SEM). The cross-sectional profile was evaluated by a few cross-sectional views.

A: Vertical cross section of vertical side wall 201 B: Vertical cross section of cone portion 203 ×: Vertical cross section of inverted cone portion 205 and elliptical shape 207 of the positive photosensitive resin composition obtained by the above examples and comparative examples Table 2 and Table 3 show the evaluation results of the film thickness and cross-sectional profile of the post-baked pattern.

  As shown in the results in Table 2 and Table 3, it is obtained when the positive photosensitive resin composition comprises a specific ratio of hydroxy-type novolak resin (A-1) and xylenol-type novolak resin (A-2). The pattern has the advantage of having a high film thickness and a good cross-sectional profile after post-baking. Moreover, when o-naphthoquinone diazide sulfonic acid ester (B) which has a hydroxylaryl compound or (hydroxylphenyl) hydrocarbon is used for the said positive photosensitive resin composition, such positive photosensitive resin composition is obtained. Since the hydroxyl aryl compound is further provided as the hydroxy compound (C), a good cross-sectional profile of the obtained pattern can be well achieved, and the object of the present invention can be practically achieved.

  It should be noted that as an example of the present invention, a specific compound, component, reaction condition, process, evaluation method and specific equipment will be described, and the positive photosensitive resin composition of the present invention and pattern formation using the same. Although the method has been described, those skilled in the art are not limited to the above examples, and the positive photosensitive resin composition of the present invention and the same are used without departing from the spirit and scope of the present invention. It should be understood that the patterning method can also be produced by other compounds, components, reaction conditions, processes, evaluation methods and specific equipment.

  Although the present invention has been disclosed with reference to the above examples, these examples are not intended to limit the present invention. In view of the above circumstances, the present invention includes various modifications and similar methods included in the spirit and scope of the appended claims. Accordingly, the scope of the invention should be accorded the broadest interpretation and include any modifications and similar structures.

101: Glass substrate 102a: Gate electrode 102b: Storage capacitor Cs electrode 103: Silicon oxide (SiOx) thin film 104: Silicon nitride (SiNx) thin film 105: Amorphous silicon (a-Si) layer 106: Amorphous silicon layer 107a: Drain electrode 107b : Source electrode 108: Protective film 109: Image electrode 201: Vertical side wall 203: Conical part 205: Overturned conical part 207: Ellipse shape

Claims (9)

A hydroxy novolak resin (A-1) formed by condensing a hydroxylbenzaldehyde compound and an aromatic hydroxy compound, and a xylenol type novolak resin (A-2) formed by condensing an aldehyde compound and a xylenol compound. Novolac resin (A),
o-naphthoquinonediazide sulfonic acid ester (B);
A hydroxy compound (C);
A positive photosensitive resin composition comprising a solvent (D). The positive photosensitive resin composition according to claim 1, wherein the o-naphthoquinonediazide sulfonic acid ester (B) includes hydroxybenzophenone and / or a hydroxylaryl compound and / or (hydroxylphenyl) hydrocarbon. The positive photosensitive resin composition according to claim 1, wherein the hydroxy compound (C) includes hydroxybenzophenone and / or a hydroxylaryl compound and / or (hydroxylphenyl) hydrocarbon. For 100 parts by weight of novolac resin (A),
The content of the hydroxy type novolac resin (A-1) is 50 to 95 parts by weight,
The content of the xylenol type novolak resin (A-2) is 5 to 50 parts by weight,
The content of the o-naphthoquinonediazide sulfonic acid ester (B) is 5 to 50 parts by weight,
The content of the hydroxy compound (C) is 1 to 30 parts by weight,
The positive photosensitive resin composition according to claim 1, wherein the content of the solvent (D) is 100 to 500 parts by weight. For a total content of 100% by weight of the hydroxy type novolak resin (A-1) and the xylenol type novolak resin (A-2),
The content of the hydroxy type novolac resin (A-1) is 50 to 95% by weight,
The positive photosensitive resin composition according to claim 4, wherein the content of the xylenol type novolak resin (A-2) is 5 to 50% by weight. A pattern forming method of forming a pattern on a substrate by treating the positive photosensitive resin composition according to any one of claims 1 to 5 in the order of a pre-bake step, an exposure step, a development step, and a post-bake step. The pattern formation method according to claim 6, wherein a film thickness of the pattern is 5 μm to 25 μm. A thin film transistor array substrate comprising the pattern according to claim 7. A liquid crystal display comprising the thin film transistor array substrate according to claim 8.

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