TWI465851B - Positive photosensitive resin composition and method for forming patterns by using the same - Google Patents

Description

Positive type photosensitive resin composition and pattern forming method thereof

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

With the miniaturization of various electronic products in life, various smart phones, thin TVs, and high-performance microprocessors are increasingly demanding high resolution, which makes the photolithography process more and more sophisticated, so as to form finer Line width.

For the purpose described above, Japanese Laid-Open Patent Publication No. 2003-98669 discloses a positive photosensitive resin composition comprising a novolak resin, a photoacid generator, and an organic solvent. The novolak resin is an organic solvent such as a phenol containing 50% by weight or more of cresol (phenols other than m-cresol, such as trimethylphenol, xylenol, and o-cresol), and an organic solvent such as an aldehyde. The reaction is carried out in the presence of a medium, and an alkoxyalkyl group is used to protect a part or all of the hydroxyl group of the novolac resin, thereby improving the sensitivity and resolution of the positive photosensitive resin composition. Next, Japanese Laid-Open Patent Publication No. 2001-183838 discloses a positive photosensitive resin composition comprising a novolak resin, a photoacid generator, and a bridging agent catalyzed by an acid. This patent uses alkali when synthesizing novolac resin The polycondensation reaction of the soluble resin with the cresol compound and/or the xylenol compound and the acid catalyst can also enhance the sensitivity and resolution of the positive photosensitive resin composition.

However, in the above-mentioned conventional technique, the photosensitive resin composition cannot form a pattern having a high film thickness after post-baking. Secondly, the pattern formed thereby has a poor cross-sectional shape, resulting in a decrease in yield of subsequent processes. Therefore, how the positive-type photosensitive resin composition forms a pattern having a high film thickness and a good cross-sectional shape after post-baking has become an important subject in the art.

In view of the above, it is desirable to provide a positive-type photosensitive resin composition material having a high film thickness after post-baking and having a cross-sectional shape of a pattern to overcome various problems of the prior art.

Therefore, an aspect of the present invention provides a positive photosensitive resin composition comprising a novolak resin (A), an ester of an o-naphthoquinonediazidesulfonic acid (B), a hydroxy compound (C), and Solvent (D). The above novolak resin (A) comprises a hydroxy novolak resin (A-1) and a bisphenol novolak resin (A-2), wherein the hydroxy novolac resin (A-1) is a hydroxybenzaldehyde The compound is obtained by condensation of an aromatic hydroxy compound, and the bisphenol novolak resin (A-2) is obtained by polycondensation of an aldehyde compound and a xylenol compound.

Another aspect of the present invention provides a pattern forming method for sequentially applying a coating treatment, a prebaking treatment, an exposure treatment, a development treatment, and a post-baking treatment to the positive photosensitive resin composition described above. A pattern is formed on the substrate. The positive-type photosensitive resin composition can form a pattern having a high film thickness and a good cross-sectional shape after post-baking.

Yet another aspect of the present invention is to provide a thin-film transistor (TFT) array substrate comprising the above-described pattern.

Still another aspect of the present invention provides a liquid crystal display (LCD) device comprising the above-described thin film transistor array substrate.

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 below.

Positive photosensitive resin composition

The positive photosensitive resin composition of the present invention comprises a novolac resin (A), an ester of an o-naphthoquinonediazidesulfonic acid (B), a hydroxy compound (C), and a solvent (D), which are described below. It.

Novolak resin (A)

The novolac resin (A) of the positive photosensitive resin composition of the present invention comprises a hydroxy novolak resin (A-1) and a bisphenol novolak resin (A-2).

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

Specific examples of the hydroxybenzaldehyde compound are: hydroxybenzaldehyde compounds such as o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, etc.; 2,3-dihydroxybenzaldehyde, 2,4-di Dihydroxybenzaldehyde compound of hydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, etc.; 2,3,4-trihydroxybenzaldehyde, 2 ,4,5-trihydroxybenzaldehyde, 2,4,6- a trihydroxybenzaldehyde compound such as trihydroxybenzaldehyde or 3,4,5-trihydroxybenzaldehyde; a hydroxyalkane such as o-hydroxymethylbenzaldehyde, m-hydroxymethylbenzaldehyde or p-hydroxymethylbenzaldehyde; Benzoaldehyde compound. The hydroxybenzaldehyde compound may be used alone or in combination of plural kinds. Wherein, the above hydroxybenzaldehyde compound is o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4 - Dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, o-hydroxymethylbenzaldehyde is preferred.

Next, specific examples of the aromatic hydroxy compound which is condensed with the above hydroxybenzaldehyde compound are: phenol, m-cresol, p-cresol, ortho-A. Cresols such as phenol (o-cresol); dimethyl phthalate, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, etc. Phenol (xylenol); m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-third Butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 6-third An alkylphenol such as butyl-3-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxy Alkoxy phenols such as phenol and m-propoxy phenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-B Isopropenyl phenol such as 4-isopropenylphenol; aryl phenol of phenyl phenol (a Ryl phenol); 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, etc. Polyhydroxyphenols and the like. The above aromatic hydroxy compounds may be used singly or in combination of plural kinds. Wherein, the above aromatic hydroxy compound is o-cresol, m-cresol, p-cresol, 2,5- Preferably, xylenol, 3,5-xylenol, 2,3,5-trimethylphenol or the like is preferred.

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

The bisphenol novolak resin (A-2) is generally obtained by polycondensation of an aldehyde compound and a xylenol compound, and is obtained by a condensation reaction in the presence of the above-mentioned acidic catalyst.

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

Specific examples of the aforementioned bisphenol compound are: 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol.

The novolak resin (A) of the positive photosensitive resin composition of the present invention may further contain other novolac resin (A-3) before being affected by the overall physical properties, and is generally composed of an aldehyde compound and an aromatic hydroxy compound. The condensation is obtained by a condensation reaction in the presence of the above-mentioned acidic catalyst, and the aldehyde compound and the aromatic hydroxy compound are as described above, and are not described herein again, but the other novolac resin (A-3) The structure is different from the above-mentioned hydroxy novolac resin (A-1) and bisphenol novolak resin (A-2).

The above-mentioned hydroxy novolac resin (A-1), xylenol type novolac For the lacquer resin (A-2) and other novolac resin (A-3), a single type of novolak resin may be used, or two or more types of different types of novolak resins may be mixed. The hydroxy novolak resin (A-1) is used in an amount of 50 parts by weight to 95 parts by weight based on 100 parts by weight of the novolac resin (A), and the xylenol type novolac resin (A-2) is used in an amount of 50 parts by weight to 95 parts by weight. The other novolac resin (A-3) is used in an amount of from 0 part by weight to 50 parts by weight, based on 5 parts by weight to 50 parts by weight. Since the hydroxy novolak resin (A-1) has better developability, the bisphenol novolak resin (A-2) has a preferable residual film ratio, and if the positive photosensitive resin composition does not use a hydroxyl group When the novolak resin (A-1) or the bisphenol novolak resin (A-2) is obtained, the obtained positive photosensitive resin composition may have a poor cross-sectional shape and insufficient film thickness after baking. . However, when the hydroxy novolak resin (A-1) and the bisphenol novolak resin (A-2) in the above range are used, the obtained positive photosensitive resin composition has a good cross-sectional shape after baking. The advantage is also that it avoids the disadvantage that the pattern is insufficient due to the heat flowing during the post-baking.

Further, the total amount of the hydroxy novolak resin (A-1) and the bisphenol novolak resin (A-2) is 100% by weight, and the amount of the hydroxy novolac resin (A-1) is used. It is 50% by weight to 95% by weight, and the xylenol type novolak resin (A-2) is used in an amount of 5 to 50% by weight. When the hydroxy novolak resin (A-1) is used in an amount of 50% by weight to 95% by weight, and the bisphenol novolak resin (A-2) is used in an amount of 5 to 50% by weight Then, the obtained positive photosensitive resin composition has an advantage of a good cross-sectional shape after baking.

Esters of o-naphthoquinonediazidesulfonic acid (B)

The ester of the o-naphthoquinonediazidesulfonic acid of the present invention (B) can be selected from conventional users and is not particularly limited. In a preferred embodiment of the present invention, the ester of the o-naphthoquinonediazidesulfonic acid (B) may include, but is not limited to, o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5. An esterified product of o-naphthoquinonediazidesulfonic acid and a hydroxy compound, such as a sulfonic acid or an o-naphthoquinone diazide-6-sulfonic acid, and an esterified product of the above o-naphthoquinonediazidesulfonic acid with a polyvalent hydroxy compound It is better.

The ester of the above o-naphthoquinonediazide sulfonic acid (B) may be completely esterified or partially esterified, and comprises (i) hydroxybenzophenones and/or (ii) hydroxyaryl groups of formula (I) The skeleton of the (hydroxyphenyl) hydrocarbons of the formula and/or (iii) formula (II) is described below.

(A) Specific examples of hydroxybenzophenones are 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxydiphenyl Methyl ketone, 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.

(2) A specific example of the hydroxyaryl compound is a structure represented by the formula (I): In the formula (I), R ₁ to R ₃ are a hydrogen atom or a lower alkyl group; R ₄ to R ₉ are a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, Lower alkenyl and cycloalkyl; R ₁₀ and R ₁₁ represent a hydrogen atom, a halogen atom and a lower alkyl group; x and y are integers from 1 to 3; z is an integer from 0 to 3. ; and n is 0 or 1.

In a preferred embodiment of the present invention, the hydroxyaryl compound having the structure represented by the formula (I) is tris(4-hydroxyphenyl)methane or bis(4-hydroxy-3,5-dimethylphenyl). )-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)benzene Methane, 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, double (4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxybenzene Methane, bis(4-hydroxy-3,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4 -dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, Bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4 -hydroxyl -6-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4 -hydroxy-6-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis (3 -cyclohexyl-6-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxybenzene 2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methyl Phenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyl Phenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene or 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]- 4-[1,1-bis(3-methyl-4-hydroxyl) Phenyl)ethyl]benzene.

(III) A specific example of the (hydroxyphenyl) hydrocarbon compound is a structure represented by the following formula (II): In the formula (II), R ₁₂ and R ₁₃ are a hydrogen atom or a lower alkyl group; and x' and y' are an integer of 1 to 3.

In a preferred embodiment of the present invention, the (hydroxyphenyl) hydrocarbon having the formula of the formula (II) is 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.

Further, the above ester of the o-naphthoquinonediazidesulfonic acid (B) may further comprise (iv) a skeleton of another aromatic hydroxyl group, and specific examples thereof are phenol, p-methoxyphenol, dimethylphenol, and benzene. Diphenol, bisphenol A, naphthol, pyrochatechol, pyrogallol monomethyl ether, 1,2,3-benzenetriol-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-trihydroxyl benzoic acid.

The ester of the above o-naphthoquinonediazide sulfonic acid (B) is preferably a skeleton comprising a hydroxyaryl group or a hydroxyphenyl hydrocarbon, and a specific example thereof is 1-[1-(4-hydroxyphenyl)isopropyl group. Esterified ester of 4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene with 1,2-naphthoquinonediazide-5-sulfonic acid, 4,4'-ethylene double Esterified product of (2-methylphenol) with 1,2-naphthoquinonediazide-5-sulfonic acid, 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone An ester of nitrogen-5-sulfonic acid. The esters (B) of the above o-naphthoquinonediazidesulfonic acid may be used singly or in combination of several kinds.

According to the ester of the o-naphthoquinonediazidesulfonic acid ester (B) in the positive photosensitive resin composition of the present invention, a compound containing a quinonediazide group such as o-naphthoquinonediazide-4 can be used. Or a compound obtained by subjecting a sulfonic acid halide salt to a hydroxy compound of the above (1) to (4) by condensation reaction, which may be completely esterified or partially esterified. The condensation reaction is usually carried out in an organic solvent such as dioxane, N-pyrrolidone or acetamide, preferably triethanolamine or alkali metal carbonate. It is carried out in the presence of an alkaline condensing agent such as an alkali metal hydrogencarbonate.

In a preferred embodiment of the present invention, the total amount of hydroxyl groups in the hydroxy compound is 100 mol%; more preferably 50 mol% or more; more preferably 60 mol% or more of hydroxyl group and o-naphthoquinone diazide- The 4 (or 5) sulfonic acid halide salt is condensed to form an esterified product, that is, the degree of esterification is 50% or more; more preferably 60% or more.

In a specific example of the present invention, the ortho-naphthoquinone diazide sulfonic acid ester ester (B) of the present invention is usually used in an amount of from 5 parts by weight to 50 parts by weight based on 100 parts by weight of the novolak resin (A). The parts by weight are preferably from 10 parts by weight to 45 parts by weight, more preferably from 15 parts by weight to 40 parts by weight. When the ester of the o-naphthoquinonediazidesulfonic acid (B) comprises the skeleton of the above-mentioned hydroxyaryl or hydroxyphenyl hydrocarbon, the resulting positive photosensitive resin composition has a cross section after post-baking The advantage of good shape.

Hydroxy compound (C)

The hydroxy compound (C) of the present invention can be used in the same kind as the hydroxy compound of (a) to (iv) used in the esterified product of the above o-naphthoquinonediazide sulfonic acid (B), and is (a) to (three) The hydroxy compound is preferred.

The hydroxy compound (C) is more preferably a hydroxyaryl compound of (b), and specific examples thereof are tris(4-hydroxyphenyl)methane and 1-[1-(4-hydroxyphenyl). Isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, bis(4-hydroxy-3,5-dimethylphenyl)phenylmethane, 2,4,6 - Trihydroxybenzophenone, pyrogallol monomethyl ether, and the like. The above hydroxy compound (C) may be used singly or in combination of several kinds.

The hydroxy compound (C) is used in an amount of from 1 part by weight to 30 parts by weight, based on 100 parts by weight of the novolac resin (A), preferably from 5 to 30 parts by weight, more preferably from 10 to 25 parts by weight. Better. When the hydroxy compound (C) is not used in the positive photosensitive resin composition, the resulting positive photosensitive resin composition has a problem of poor cross-sectional shape after baking. When the hydroxy compound (C) is used in the above range, the obtained positive photosensitive resin composition has an advantage that the cross-sectional shape is good after baking.

Solvent (D)

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

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, 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; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, a ketone such as cyclohexanone, 2-heptanone or 3-heptanone; 2- An alkyl lactate such as methyl hydroxypropionate or ethyl 2-hydroxypropionate (ethyl lactate); methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate Ester, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, N-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyric acid Other esters of propyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxybutyrate, etc. An aromatic hydrocarbon such as toluene or xylene; a carboxylic acid amine such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide. The above solvent (D) may be used singly or in combination of plural kinds. Preferably, the solvent (D) is propylene glycol monoethyl ether, propylene glycol methyl ether acetate or ethyl lactate.

In a specific example of the present invention, the amount of the solvent (D) used is usually 100 to 500 parts by weight, preferably 100 to 450 parts by weight, based on 100 parts by weight of the novolac resin (A); more preferably It is 100 to 400 parts by weight.

Additive (E)

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

The adhesion aid may include, but is not limited to, a melamine compound and a silane compound to increase the adhesion between the positive photosensitive resin composition and the attached substrate. Specific examples of the aforementioned melamine: city Commercially available as Cymel-300, Cymel-303 (manufactured by CYTEC), MW-30MH, MW-30, MS-11, MS-001, MX-750 or MX-706 (manufactured by Sanwa Chemical Co., Ltd.). Specific examples of the aforementioned silane compound are, for example, vinyltrimethoxydecane, vinyltriethoxydecane, 3-(meth)acryloxypropyltrimethoxydecane, vinyltris(2-methyl) Oxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Trimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane or Bis-1,2-(trimethoxyindenyl)ethane.

In a specific example of the present invention, the use amount of the melamine resin (A) is 100 parts by weight, and the amount of the adhesion aid of the melamine compound is generally from 0 part by weight to 20 parts by weight, and then 0.5 part by weight to 18 parts by weight is more preferably 1.0 part by weight to 15 parts by weight; the amount of the adhesion aid of the above decane-based compound is generally from 0 part by weight to 2 parts by weight, and then from 0.001 part by weight to 1 part by weight. The portion is preferably further preferably 0.005 parts by weight to 0.8 parts by weight.

The above surface smoothing agent may include, but is not limited to, a fluorine-based surfactant or a lanthanoid surfactant. Specific examples of the fluorine-based surfactant include commercially available Flourate FC-430, FC-431 (manufactured by 3M), or F top EF122A, 122B, 122C, 126, and BL20 (manufactured by Tochem Product). Specific examples of the aforementioned lanthanoid surfactants include commercially available SF8427 or SH29PA (manufactured by Toray Dow Corning Silicone Co., Ltd.).

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

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

Specific examples of the above sensitizers are: 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 commercial product (manufactured by Honshu Chemical Co., Ltd.), preferably TPPA-1600-3M6C or TPPA-MF. The aforementioned sensitizers may be used singly or in combination of plural kinds.

The above additives (E) may be used singly or in combination of plural kinds. In a specific example of the present invention, the amount of the sensitizing agent used is usually from 0 part by weight to 20 parts by weight, based on 100 parts by weight of the novolak resin (A), and is usually from 0.5 part by weight to 18 parts by weight. Preferably, it is more preferably from 1.0 part by weight to 15 parts by weight. In addition, the present invention may also add other additives as needed, such as a plasticizer, a stabilizer, and the like.

Method for preparing positive photosensitive resin composition

The preparation of the positive photosensitive resin composition of the present invention is generally the above-mentioned novolac resin (A), an ester of an o-naphthoquinonediazidesulfonic acid (B), a hydroxy compound (C), and a solvent (D). The positive photosensitive resin composition can be obtained by stirring in a conventional agitator, uniformly mixing it into a solution state, and adding various additives (E) as needed.

Pattern forming method

The positive photosensitive composition obtained above can be pre-baked by sequential application After the (prebake) step, the exposure step, the development step, and the postbake processing step, a pattern is formed on the substrate.

In the present invention, the method of forming a pattern using the positive photosensitive resin composition is a positive photosensitive resin composition by a coating method such as spin coating, cast coating or roll coating. It is coated on the substrate, and after coating, the solvent is removed by pre-baking to form a pre-baked coating film. The pre-baking conditions vary depending on the type and blending ratio of each component, and are usually carried out at a temperature of 70 to 110 ° C for 1 to 15 minutes.

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

Specific examples of the developer used in the present invention are sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine. , dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene Basic compound.

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

When the developer composed of the above basic compound is used, it is usually washed with water after development, and then the coating film is air-dried with compressed air or compressed nitrogen. Next, the coating film is post-baked using a heating device such as a hot plate or an oven. The post-baking temperature is usually from 100 to 250 ° C, wherein the heating time using the hot plate is from 1 to 60 minutes, and the heating time using the oven is from 5 to 90 minutes. through After the above processing steps, a pattern can be formed on the substrate.

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, the insulating layer or the protective film.

Thin film transistor array substrate

The thin film transistor array substrate of the present invention is obtained by the aforementioned method. In short, the positive photosensitive resin composition of the present invention can be applied to a material containing aluminum, chromium, tantalum nitride or non-crystalline by a coating method such as spin coating, cast coating or roll coating. A positive photoresist layer is formed on a glass substrate or a plastic substrate of a film such as ruthenium. Next, after prebaking, exposure, development, and post-baking treatment to form a photosensitive resin pattern, etching and photoresist peeling are performed. After repeating the above steps, a thin film transistor array substrate comprising a plurality of thin film transistors or electrodes can be obtained.

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

Liquid crystal display element

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

Specific examples of the basic configuration of the liquid crystal display device include (1) the above-described TFT array substrate (drive substrate) of the present invention formed by arranging a driving element such as a TFT and a pixel electrode (conductive layer), and color filter The color filter substrate composed of the light sheet and the counter electrode (conductive layer) is interposed between the spacers and disposed opposite to each other, and finally the liquid crystal material is sealed in the gap portion. Alternatively, (2) a color filter-integrated TFT array substrate in which a color filter is directly formed on the TFT array substrate of the present invention, and an inter-substrate interposed between the counter electrode (conductive layer) The spacer is disposed in the opposite direction, and finally the liquid crystal material is sealed in the gap portion, and the liquid crystal material used may be any liquid crystal compound or liquid crystal composition, and is not particularly limited herein.

Specific examples of the conductive layer include an ITO film; a metal film of aluminum, zinc, copper, iron, nickel, chromium, molybdenum or the like; or a metal oxide film of cerium oxide or the like. Preferably, it is a film layer having transparency; more preferably, it is an ITO film.

Specific examples of the substrate used for the TFT array substrate, the color filter substrate, and the counter substrate of the present invention are conventional glasses of soda lime glass, low expansion glass, alkali-free glass or quartz glass, and may also be used. A substrate made of a plastic film or the like is used.

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

Preparation of novolac resin (A)

The hydroxy novolak resin (A-1) of Synthesis Examples A-1-1 to A-3-3 was prepared according to Table 1 below.

Synthesis Example A-1-1

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 1000 ml volume. After introducing nitrogen, m-cresol 0.70 mol, p-cresol 0.30 mol, 3,4- was added. Dihydroxybenzaldehyde 0.5 moles and oxalic acid 0.020 moles. The reaction solution was warmed to 100 ° C with gentle stirring, and polycondensed at this temperature for 6 hours. Then, the reaction solution was heated to 180 ° C, dried under reduced pressure at a pressure of 10 mmHg, and the solvent was devolatilized to obtain a hydroxy novolak resin (A-1-1).

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

The method for synthesizing the hydroxy novolak resin of the synthesis example A-1-1 is different in that the synthesis examples A-1-2 to A-3-3 change the reactants in the hydroxy novolak resin (A-1). The type and amount of use are as shown in Table 1, and are not described here.

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 Tables 2 and 3 below.

Example 1

70 parts by weight of the hydroxy novolak resin (A-1-1) obtained in Synthesis Example A-1-1, and 30 parts by weight of the hydroxy novolac obtained in Synthesis Example A-2-1 Varnish resin (A-2-1), 30 parts by weight of 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene Esterified with 1,2-naphthoquinonediazide-5-sulfonic acid (B-1) (average degree of esterification 85%), 10 parts by weight of tris(4-hydroxyphenyl)methane (C-1) The invention is prepared by adding 300 parts by weight of a solvent (D-1) of propylene glycol monomethyl ether acetate (PGMEA) and stirring the mixture in a solvent by stirring with a stirring stirrer. A positive photosensitive resin composition. The positive photosensitive resin composition obtained was evaluated by the following evaluation methods, and the results are as described in Table 2, wherein the film thickness of the post-baking pattern and the method for detecting the cross-sectional shape thereof will be described later.

Examples 2 to 10

The method for preparing the positive photosensitive resin composition of the first embodiment differs in that the examples 2 to 10 change the kind and amount of the raw material in the positive photosensitive resin composition, and the formulation and the detection result are as shown in the second table. As shown, it will not be repeated here.

Comparative Examples 1 to 7

The method for preparing the positive photosensitive resin composition of the first embodiment differs in that the comparative examples 1 to 7 change the kind and amount of the raw material in the positive photosensitive resin composition, and the formulation and the detection result are also the third. The table shows.

Evaluation method

1. After measuring the film thickness of the baked pattern

The positive photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were applied by spin coating on a plain glass substrate, and prebaked at 100 ° C for 120 seconds to obtain a pre-boiler of about 10 μm. Baking the film. The prebaked coating film was placed under a line and space mask (manufactured by Filcon, Japan), and irradiated with ultraviolet light of 200 mJ/cm ² (exposure model AG500-4N; manufactured by M&R Nano Technology). Further, it was developed with a 2.38% TMAH aqueous solution at 23 ° C for 3 minutes to remove the exposed coating film on the substrate, and then washed with pure water to obtain a pattern. After baking at a temperature of 120 ° C for 2 minutes, a protective film having a pattern on a glass substrate was obtained, and the film thickness was measured by an optical film thickness meter (Hongming Technology, MFS-630-F).

2. Evaluation of the cross-sectional shape of the baked pattern

The protective films having the patterns obtained in the above Examples 1 to 10 and Comparative Examples 1 to 7 were photographed by SEM, and the cross-sectional shape of the post-baking pattern was observed, and the judgment criteria were as follows and the cross-sectional shape of FIG. 2 was matched. Shown as follows:

◎: vertical section 201

○: cis taper section 203

×: reverse tapered section 205, oblate section 207

The evaluation results of the post-bake pattern film thickness and the cross-sectional shape of the post-baking pattern of the positive-type photosensitive resin composition obtained in the above Examples and Comparative Examples are shown in Tables 2 and 3.

From the results of the second and third tables, when the positive photosensitive resin composition is used in the above ratio of the hydroxy novolak resin (A-1) and the bisphenol novolak resin (A-2), The resulting pattern has the advantages of high film thickness and good cross-sectional shape after being baked. Next, when the positive photosensitive resin composition is simultaneously used, an ester of an o-naphthoquinonediazidesulfonic acid ester (B) containing a skeleton of a hydroxyaryl group or a hydroxyphenyl hydrocarbon, and a hydroxyaryl compound as a hydroxy compound is used in combination. In the case of (C), the pattern thus obtained has an advantage that the cross-sectional shape is preferable, and the object of the present invention can be attained.

It should be noted that the present invention is illustrated by the specific compounds, compositions, reaction conditions, processes, analytical methods, or specific instruments. The present invention is not limited thereto, and the present invention is not limited to the spirit and scope of the present invention, and the present invention is not limited to the spirit and scope of the present invention. The photosensitive resin composition and the pattern forming method thereof can also be carried out using other compounds, compositions, reaction conditions, processes, analytical methods, or instruments.

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

101‧‧‧ glass substrate liquid crystal display elements

102a‧‧‧ gate

102b‧‧‧ Storage Capacitor Cs Electrode

103‧‧‧Oxide film

104‧‧‧ nitride film

105‧‧‧Amorphous layer

106‧‧‧Amorphous layer

107a‧‧‧Bungee

107b‧‧‧ source

108‧‧‧Protective film

109‧‧‧ pixel electrodes

201‧‧‧Vertical section

203‧‧‧Scissive section

205‧‧‧ inverse cone section

207‧‧‧ oblate section

The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Partial cross-sectional view.

Fig. 2 is a schematic cross-sectional view showing the protective film of the pattern obtained in the evaluation of Examples 1 to 10 and Comparative Examples 1 to 7 of the present invention.

Claims (8)

A positive photosensitive resin composition comprising: a novolac resin (A), wherein the novolac resin (A) comprises a hydroxy novolak resin (A-1) and a bisphenol novolak resin (A-2) The hydroxy novolac resin (A-1) is obtained by condensing a hydroxybenzaldehyde compound with an aromatic hydroxy compound, and the bisphenol novolak resin (A-2) is derived from an aldehyde compound and xylenol. a compound obtained by polycondensation, based on the total amount of the hydroxy novolak resin (A-1) and the bisphenol novolak resin (A-2) being 100% by weight, the hydroxy novolac resin (A) -1) is used in an amount of 50% by weight to 95% by weight, and the xylenol type novolac resin (A-2) is used in an amount of 5 to 50% by weight; o-naphthoquinonediazidesulfonic acid Ester compound (B); hydroxy compound (C); and solvent (D). The positive photosensitive resin composition according to claim 1, wherein the ortho-naphthoquinone diazide sulfonic acid ester (B) comprises a hydroxybenzophenone and/or a hydroxyaryl group and/or Or a skeleton of a hydroxyphenyl hydrocarbon. The positive photosensitive resin composition according to claim 1, wherein the hydroxy compound (C) comprises a hydroxybenzophenone compound and/or a hydroxyaryl compound and/or a hydroxyphenyl hydrocarbon compound. The positive photosensitive resin composition according to claim 1, wherein the hydroxy novolak resin (A-1) is used in an amount of 50 parts by weight based on 100 parts by weight of the novolak resin (A). The bisphenol novolak resin (A-2) is used in an amount of 5 parts by weight to 50 parts by weight, and the ortho-naphthoquinone diazide sulfonic acid ester (B) is used in an amount of 5 parts by weight to 5 parts by weight. The hydroxy compound (C) is used in an amount of from 1 part by weight to 30 parts by weight per part by weight to 50 parts by weight, and the solvent (D) is used in an amount of from 100 parts by weight to 500 parts by weight. A pattern forming method for sequentially applying a coating treatment, a pre-baking treatment, and an exposure treatment to a positive photosensitive resin composition according to any one of claims 1 to 4 And a development process and a post-baking process to form a pattern on a substrate. The pattern forming method of claim 5, wherein the patterned film has a film thickness of from 5 μm to 25 μm . A thin film transistor array substrate comprising the pattern as described in claim 6 of the patent application. A liquid crystal display element comprising the thin film transistor array substrate according to claim 7 of the patent application.