TWI490651B - Positive photosensitive resin composition and method for forming pattern by using the smae - 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 method of forming a pattern using the composition. In particular, there is provided a positive photosensitive resin composition which is excellent in sensitivity and stability over time in the production of a liquid crystal display element of a semiconductor integrated circuit element and a thin film transistor, and a method of forming a pattern using the composition.

With the light and thin miniaturization of various electronic products in life, today's life is filled with all kinds of thin and light smart phones, thin TVs and high-performance microprocessors. In order to meet the development trend of electronic products, the photolithography process is becoming more and more precise, so that the photoresist used in the photolithography process has different characteristics.

In view of the demand for different characteristics of the photoresist, Japanese Laid-Open Patent Publication No. 2010-20291 discloses a positive photosensitive resin composition comprising an alkali-soluble resin, a diazide compound, a curing agent, and an organic solvent. . The alkali-soluble resin may comprise an acryl-based copolymer and a phenolic resin a varnish resin in which a monomer of an acrylonitrile-based copolymer-based unsaturated olefin compound and an unsaturated carboxylic acid is prepared by a radical polymerization reaction in the presence of a solvent and a polymerization initiator, and a novolak resin is a phenol compound and an aldehyde The compound or ketone compound is prepared in the presence of an acidic catalyst. The alkali-soluble resin can improve the heat resistance of the positive photosensitive resin composition.

Next, Japanese Laid-Open Patent Publication No. 2010-176012 discloses a positive photosensitive resin composition comprising an alkali-soluble novolak resin, a sensitizer, and a specific benzotriazole-based compound. The alkali-soluble novolak resin is prepared by subjecting an aromatic compound having a phenolic hydroxyl group and an aldehyde to an addition condensation reaction in the presence of an acid catalyst, and improving the heat resistance of the positive photosensitive resin composition.

However, the positive photosensitive resin composition prepared by the prior art described above has poor sensitivity and stability over time, and cannot meet the requirements of the photolithography process.

In view of the above, it is not necessary to provide a positive photosensitive resin composition and a pattern forming method thereof to improve the sensitivity of the conventional positive photosensitive resin composition and the defect of poor stability over time.

Therefore, an aspect of the present invention provides a positive photosensitive resin composition comprising a novolac resin (A) and an ester of o-naphthoquinonediazidesulfonic acid (B). , a reducing agent (C) and a solvent (D).

Another aspect of the present invention is to provide a pattern forming method, In the pattern forming method, the positive photosensitive resin composition described above is sequentially subjected to prebaking, exposure, development, and post-baking treatment to form a pattern on the substrate.

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

In still another aspect of the present invention, a liquid crystal display element comprising the above-described thin film transistor array substrate is provided.

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

Positive photosensitive resin composition Novolak resin (A)

The novolac resin (A) of the present invention is obtained by polycondensation of a cresol aromatic hydroxy compound and an aldehyde.

In a specific example of the present invention, the cresol-based aromatic hydroxy compound is cresol such as m-cresol, p-cresol, and o-cresol. a class of xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol and 3,4-xylenol. The above compounds may be used singly or in combination of plural kinds.

The novolak resin (A) of the present invention can also be obtained by polycondensation of other aromatic hydroxy compounds and aldehydes without affecting the physical properties of the positive photosensitive resin composition.

In a specific example of the present invention, the other aromatic hydroxy compound is phenol; m-ethyl phenol, p-ethyl phenol, o-ethyl phenol, 2,3,5-trimethyl phenol. , 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol and 6-t-butyl-3 - alkyl phenols such as methyl phenol; p-methoxy phenol, m-methoxy phenol, p-ethoxy phenol, m-ethoxy phenol, p-propoxy phenol and - alkoxy phenols such as propoxyphenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4- Isopropenyl phenol such as isopropenylphenol; aryl phenol of phenyl phenol; 4,4'-dihydroxybiphenyl, bisphenol A, m-benzene Polyhydroxyphenols such as resorcinol, hydroquinone, and pyrogallol.

In a specific example of the present invention, the aldehyde condensed with the cresol aromatic hydroxy compound is formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethyl Acetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, Phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-Methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde and cinnamaldehyde. The above aldehydes may be used singly or in combination of plural kinds. Among them, the aldehyde is preferably formaldehyde. More preferably, the novolak resin (A) is subjected to shrinkage under normal pressure in the presence of a conventional organic acid and/or a mineral acid catalyst such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or p-toluenesulfonic acid. The reaction is carried out, and is obtained by dehydrating and removing unreacted monomers.

Esters of o-naphthoquinonediazidesulfonic acid (B)

The ester of the o-naphthoquinonediazidesulfonic acid (B) according to the present invention can be selected from conventional users and is not particularly limited. In a preferred embodiment of the present invention, the ester of the o-naphthoquinonediazide sulfonic acid (B) is an esterified product of an o-naphthoquinonediazidesulfonic acid compound and a hydroxy compound, more preferably the above o-naphthoquinone An esterified compound of azide sulfonic acid compound with a polyvalent hydroxy compound which is fully esterified or partially esterified.

The above o-naphthoquinonediazidesulfonic acid compound may, for example, be an ortho-naphthoquinonediazidesulfonic acid or an o-naphthoquinonediazidesulfonic acid halide salt, and the ortho-naphthoquinonediazidesulfonic acid specific example is: o-naphthoquinone di Azide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid or o-naphthoquinonediazide-6-sulfonic acid. Specific examples of the ortho-naphthoquinonediazide halide salt are: o-naphthoquinonediazide-4-sulfonyl chloride, o-naphthoquinonediazide-5-sulfonyl chloride or o-naphthoquinonediazide-6-sulfonic acid. Acid chloride. The above o-naphthoquinonediazidesulfonic acid compound is preferably o-naphthoquinonediazide-4-sulfonyl chloride, o-naphthoquinonediazide-5-sulfonyl chloride or o-naphthoquinonediazide-6-sulfonic acid. Acid chloride. The above o-naphthoquinonediazidesulfonic acid compounds may be used singly or in combination of several kinds.

The type of the hydroxy compound may, for example, be a hydroxybenzophenone, a hydroxyaryl compound represented by the following formula (I), a (hydroxyphenyl) hydrocarbon compound represented by the following formula (II), and other aromatic hydroxy groups. The compound is described below.

Specific examples of the above hydroxybenzophenones are 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, and 2,4,6-trihydroxybenzophenone. Ketone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 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.

A specific example of the above hydroxyaryl compound is a structural formula represented by the formula (I):

In the formula (I), R ₁ to R ₃ represent a hydrogen atom or a lower alkyl group; R ₄ to R ₉ represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, and a lower order. Alkenyl or cycloalkyl; R ₁₀ and R ₁₁ represent a hydrogen atom, a halogen atom or a lower alkyl group; x, y and z represent an integer from 1 to 3; and n represents 0 or 1 .

In a preferred embodiment of the present invention, the hydroxyaryl compound represented by the above 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)-2 -hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyl Phenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-di Hydroxyphenylmethane, 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-hydroxyl Phenyl)-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-hydroxy-6-methylaryl)-2 -hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl) 4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl) 3-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenylmethane, Bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenyl Methane, 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.

A specific example of the above (hydroxyphenyl) hydrocarbon compound is a structural formula represented by the following formula (II):

In the formula (II), R ₁₂ and R ₁₃ represent a hydrogen atom or a lower alkyl group; and a and b represent an integer of 1 to 3.

In a preferred embodiment of the present invention, the (hydroxyphenyl) hydrocarbon having the structural formula represented by the above 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-hydroxybenzene 2-(4'-hydroxyphenyl)propane, bis(2,3,4-trihydroxyl) Phenyl)methane or bis(2,4-dihydroxyphenyl)methane.

Specific examples of the other aromatic hydroxy compound described above are phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, 1, Pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, 3,4,5- Galic acid, or partially esterified or partially etherified 3,4,5-trihydroxybenzoic acid.

The aforementioned hydroxy compound is preferably 2,3,4-trihydroxybenzophenone, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl). Ethyl]benzene or 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane. The above hydroxy compounds may be used singly or in combination of several kinds.

The above condensation reaction is usually carried out in the presence of a basic compound such as an aliphatic amine compound and a cyclic amine compound. The aliphatic amine compound may comprise ethylamine, ethanolamine, diethylamine, diethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine or trioctylamine. The cyclic amine compound may comprise pyridine, quinoline, 2,6-lutidine, pyrimidine, N,N-dimethylaniline or N,N-diethylaniline. Further, an inorganic basic compound such as sodium carbonate or sodium hydrogencarbonate may be added as needed. The above basic compounds may be used singly or in combination of plural kinds. The molar ratio of the basic compound to the o-naphthoquinonediazidesulfonic acid compound is usually from 1.05 to 4.5, preferably from 1.05 to 4.2, more preferably from 1.1 to 4.0.

The above condensation reaction is usually carried out in a reaction solvent. Suitable reaction solvents are, for example, solvents such as ethers, esters, aliphatic ketones and guanamines. Among them, preferred is 1,3-dioxolane, 1,4-dioxane Dioxane, tetrahydrofuran, γ-butyrolactone, acetone, 2-heptanone, N-pyrrolidone or acetamide, more preferably 1,4-dioxane Dioxane or acetone. The above-mentioned reaction solvents may be used singly or in combination of plural kinds. The weight of the reaction solvent is usually from 2 to 6 times, preferably from 3 to 5 times, more preferably from 4 to 5 times, based on the weight of the o-naphthoquinonediazidesulfonic acid compound and the hydroxy compound. The above esterification reaction is preferably carried out under normal temperature and normal pressure. Usually, the reaction temperature is from 20 ° C to 30 ° C, and the reaction time is from 2 hours to 10 hours.

After the reaction is completed, glacial acetic acid may be added to neutralize the basic compound, and further, an aqueous acetic acid solution may be added, for example, a 0.1% by weight (wt%) to 2% by weight aqueous acetic acid solution to neutralize the basic compound and precipitate a solid precipitate. The solid precipitate is an ester of the o-naphthoquinonediazide sulfonic acid (B). The solid precipitate of the ester of the o-naphthoquinonediazide sulfonic acid (B) can be obtained by filtration, washing and drying.

The residual amount of the amine compound in the positive photosensitive resin composition can adjust the residual amount of the amine compound by changing the amount of the amine compound added during the esterification reaction. Alternatively, the amount of acetic acid added for neutralization may be adjusted after completion of the esterification reaction, or may be washed only with water but not with an acidic solution, thereby adjusting the residual amount of the amine compound in the positive photosensitive resin composition. The above method of adjusting the residual amount of the amine compound may be selected singly or in combination of plural kinds.

In a preferred embodiment of the present invention, the total amount of hydroxyl groups in the hydroxy compound is 100% by mole, preferably 50% by mole or more, more preferably 60% by mole or more of the hydroxyl group and the o-naphthoquinonediazide. Sulfonic acid compound condensation The degree of esterification is preferably 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 5 to 50 parts by weight based on 100 parts by weight of the novolak resin (A). It is preferably from 8 to 45 parts by weight, more preferably from 10 to 40 parts by weight.

Reduction inhibitor (C)

The reduction inhibitor (C) may be an anthraquinone compound or a benzenediol compound.

The above lanthanide compound may be benzoquinone or naphthoquinone.

The above benzoquinone may be 1,2-benzoquinone or 1,4-benzoquinone or the like.

The above naphthoquinone may be 1,2-naphthoquinone, 1,4-naphthoquinone or 2,6-naphthoquinone.

The above benzenediol compound may be 2-tert-Butyl-1,4-hydoquinone or 4-tert-butyl catechol (4-tert) -Butylpyrocatechol) and so on.

Among them, preferred are 1,2-benzoquinone, 1,4-benzoquinone, 1,2-naphthoquinone or 2,6-naphthoquinone.

In the specific example of the present invention, the reducing agent (C) of the present invention is used in an amount of usually 0.1 parts by weight to 5 parts by weight, preferably 0.2% by weight based on 100 parts by weight of the novolak resin (A). Parts to 4 parts by weight, more preferably 0.3 parts by weight to 3 parts by weight

The component of the positive photosensitive resin composition tends to aggregate due to the prolonged storage time to form a dimer, which in turn affects the stability of the positive photosensitive resin composition over time. Condensation can be avoided by adding a reduction preventing agent (C) to a positive photosensitive resin composition It can improve the stability of the positive photosensitive resin composition over time. Therefore, if the reduction preventing agent (C) is not used, the positive photosensitive resin composition may have a disadvantage that the stability over time is not good.

Solvent (D)

The solvent (D) referred to in the present invention means an organic solvent which is easily dissolved with other organic components but does not react with the above organic 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 or tripropylene glycol monoethyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate or 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 or other ethers such as tetrahydrofuran; methyl ethyl ketone, a ketone such as cyclohexanone, 2-heptanone or 3-heptanone; an alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate (ethyl lactate); 2-hydroxy-2- Methyl methacrylate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane Ethyl ester, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, butyl Acid ethyl ester, butyric acid Ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate or ethyl 2-oxybutyrate Other esters; aromatic hydrocarbons such as toluene or xylene; carboxylic acid amines such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide . The above solvent (D) may be used alone 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 300 parts by weight to 3,000 parts by weight, preferably 400 to 2800 parts by weight, based on 100 parts by weight of the novolac resin (A). More preferably, it is 500 to 2500 parts by weight.

Additive (E)

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

Specific examples of the adhesion aid are a melamine compound and a silane compound. The adhesion promoter acts to increase the adhesion between the positive photosensitive resin composition and the attached substrate, and a specific example of the melamine is a product manufactured by CYTEC Co., Ltd. under the trade name Cymel-300 or Cymel-303, or three. It is a product of MW-30MH, MW-30, MS-11, MS-001, MX-750 or MX-706. Specific examples of the silane compound are vinyltrimethoxydecane, vinyltriethoxydecane, 3-(meth)acryloxypropyltrimethoxydecane, vinyltris(2-methoxygen). Ethyl ethoxy) decane, N-(2-amino B 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 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 novolak resin (A) is 100 parts by weight, and the amount of the adhesion aid of the melamine compound is from 0 part by weight to 20 parts by weight, preferably from 0.5 part by weight to 18 parts by weight. The parts by weight are more preferably from 1.0 part by weight to 15 parts by weight; the amount of the adhesion aid of the decane-based compound is from 0 part by weight to 2 parts by weight, preferably from 0.001 part by weight to 1 part by weight, more preferably 0.005 part by weight. Parts to 0.8 parts by weight.

Specific examples of the surface flattening agent are fluorine-based surfactants or lanthanoid surfactants. Specific examples of the fluorine-based surfactant are commercially available from 3M Company under the trade name of Flourate FC-430 or FC-431 or manufactured by Tochem Product Co., Ltd. under the trade name of F top EF122A, 122B, 122C, 126 or BL20. A specific example of the lanthanide surfactant is manufactured by Toray Dow Corning Silicone, Inc. under the trade name of SF8427 or SH29PA.

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

A specific example of the diluent is manufactured by Imperial Ink Manufacturing Co., Ltd. Products made under the trade name RE801 or RE802.

A specific example of the sensitizer is manufactured by Honda Prefecture Chemical Co., Ltd., Japan, and trade names are TPPA-1000P, TPPA-100-2C, TPPA-1100-3C, TPPA-1100-4C, TPPA-1200-24X, TPPA-1200. Commercial products of -26X, TPPA-1300-235T, TPPA-1600-3M6C or TPPA-MF, of which TPPA-600-3M6C or TPPA-MF is preferred. The above sensitizers 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 0 to 20 parts by weight, preferably 0.5 to 18 parts by weight, more preferably 1.0, based on 100 parts by weight of the novolak resin (A). Up to 15 parts by weight.

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

Preparation of photoresist

The novolac resin (A), the o-naphthoquinone diazide sulfonic acid ester ester (B), the reduction inhibitor (C), the solvent (D) and other optional substances in the positive photosensitive resin composition of the present invention The added additive (E) is dissolved in an organic solvent to prepare a positive photosensitive resist liquid.

The amount of the organic solvent used can be appropriately adjusted so that the novolac resin (A), the ester of the o-naphthoquinonediazidesulfonic acid (B), the reduction inhibitor (C), the solvent (D), and the additive (E) are dissolved. To obtain a positive photosensitive resin composition of a uniform phase. Preferably, the novolak resin (A), the ester of the o-naphthoquinonediazidesulfonic acid (B), the anti-reduction agent (C), and the anti-reduction agent (C) in the positive photosensitive resin composition The total solid content of the solvent (D) and the additive (E) is from 10% by weight to 50% by weight, more preferably from 20% by weight to 35% by weight.

After the arrangement of the positive photosensitive resist liquid is completed, the amine compound in the positive photosensitive resist liquid is measured by a gas chromatograph to obtain the residual amount of the amine compound. The residual amount of the amine compound in the positive photosensitive resin composition is usually from 1 ppm to 50 ppm, preferably from 3 ppm to 40 ppm, more preferably from 5 ppm to 30 ppm. When the residual amount of the amine compound in the positive photosensitive resin composition is less than 1 ppm, the sensitivity of the positive photosensitive resin composition is not good. When the residual amount of the amine compound is more than 50 ppm, the stability of the positive photosensitive resin composition is not good.

Production of photoresist film pattern

The method for forming a pattern by using the positive photosensitive resin composition described above in the present invention is to apply the above-mentioned positive photosensitive resist liquid by a coating method such as spin coating, cast coating or roll coating. 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 proportion of each component, and the temperature is usually between 70 ° C and 110 ° C and is carried out for 1 minute 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 21 ° C to 25 ° 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, hydrogen and oxygen. Potassium, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, hydrogen hydroxide A basic compound such as ethylammonium, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene.

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, most 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 ° C to 250 ° C, wherein the heating time using the hot plate is from 1 minute to 60 minutes, and the heating time using the oven is from 5 minutes to 90 minutes. After the above processing steps, a pattern can be formed on the substrate.

Thin film transistor array substrate

The present invention further provides a thin film transistor array substrate comprising a pattern obtained by the above-described formation method.

In a specific example of the present invention, the positive photosensitive resin composition of the present invention is applied to a coating containing aluminum, chromium, and nitride by spin coating, cast coating, or roll coating. A positive photoresist layer is formed on a glass substrate or a plastic substrate of a film of ruthenium or amorphous ruthenium. Next, steps such as prebaking, exposure, development, and post-baking are performed to form a photosensitive resin pattern. Then, the steps of etching and photoresist stripping are performed. Repeating the above steps to obtain a thin film transistor array base containing a plurality of thin film transistors or electrodes board.

Referring to FIG. 1 , a partial cross-sectional view of a thin film transistor array substrate for a liquid crystal display device according to an embodiment of the present invention is shown. First, a gate electrode 121 and a storage capacitor electrode 123 are provided on an aluminum film or the like on a glass substrate. Next, an oxide film is formed on the gate electrode 121 by covering a yttrium oxide film (SiO _x ) 130 or a tantalum nitride film (SiN _x ) 140 or the like, and an amorphous germanium layer as a semiconductor active layer is formed on the insulating film (a) -Si) 150. Next, in order to reduce the junction resistance, an amorphous germanium layer 160 doped with nitrogen impurities may be disposed on the amorphous germanium layer 150. Thereafter, a metal such as aluminum is used to form a drain 171 and a source 173, wherein the drain 171 is connected to the data signal line (not shown), and the source 173 is connected to the pixel electrode (or the sub-pixel electrode). 190. Then, in order to protect the amorphous germanium layer 150, the drain 171 or the source 173, which are semiconductor active layers, a tantalum nitride film or the like is provided as the protective film 180.

Liquid crystal display element

The present invention further provides a liquid crystal display element comprising the aforementioned thin film transistor array substrate.

According to the liquid crystal display device of the present invention, it is preferable to include other members as needed.

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

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

Specific examples of the substrate used in the above-described thin film transistor array substrate, color filter substrate, and counter substrate of the present invention are conventional materials of soda lime glass, low expansion glass, alkali-free glass or quartz glass, and A substrate made of a plastic film or the like can also be used.

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

110‧‧‧ glass substrate

121‧‧‧ gate

123‧‧‧铯 electrode

130‧‧‧Oxide film

140‧‧‧ nitride film

150‧‧‧Amorphous layer

160‧‧‧Amorphous layer

171‧‧‧汲polar

173‧‧‧ source

180‧‧‧Protective film

190‧‧‧ pixel electrodes

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

Preparation of novolac resin (A)

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

Preparation Example A-1

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-neck reaction flask having a volume of 1000 ml. After introducing nitrogen, 0.7 mol of cresol was added, and 0.3 mol of p-cresol, 0.65 was added. Moxaldehyde and 0.02 mol of oxalic acid were added to the reaction flask. 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 novolak resin (A-1).

Preparation Examples A-2 and A-3

The preparation method of the novolak resin (A) of the preparation example A-1 is different in that the preparation examples A-2 and A-3 are used to change the kind and amount of the raw materials and the reaction temperature in the novolac resin, as shown in Table 1. Show.

Preparation of esters of o-naphthoquinone diazide sulfonic acid (B)

The esterified product (B) of o-naphthoquinonediazidesulfonic acid of Preparation Examples B-1 to B-8 was prepared according to Table 2 below.

Preparation B-1

A thermometer, a stirrer, a reactant inlet and a dry nitrogen inlet were placed in a four-neck reaction flask, and 0.2 liter of 1,4-dioxane, 0.1 m was added after passing dry nitrogen. O-naphthoquinone diazide-4-sulfonate Acid acid chloride (hereinafter referred to as NQD-4S) and 0.05 mol of 2,3,4-trihydroxybenzophenone (hereinafter referred to as 3HBP) were added to the reaction flask. Then, 0.3 mol of diethanolamine (hereinafter referred to as DEOA) was dropped into the reaction flask, and the temperature of the reaction flask was maintained at 20 °C. After stirring for 4 hours, 0.06 mol of glacial acetic acid was added to carry out the first neutralization reaction. Next, the neutralized solution was filtered, and 1.5 liter of a 0.1% by weight aqueous acetic acid solution was added to carry out the second neutralization reaction. Then, the precipitated solid precipitate was collected, washed with ion-exchanged water, and vacuum-dried at room temperature to obtain an ester of the o-naphthoquinonediazidesulfonic acid ester (B-1).

Preparation Examples B-2 to B-8

The preparation method of the esterified product (B) of o-naphthoquinonediazidesulfonic acid of Preparation Example B-1, except that the preparation examples B-2 to B-8 are modified to change the ester of o-naphthoquinonediazidesulfonic acid. The type and amount of the composition in (B) and the reaction conditions are shown in Table 2.

Preparation of positive photosensitive resin composition

The positive photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 6 were prepared according to Table 3 below.

Example 1

100 parts by weight of Preparation Example A-1, 20 parts by weight of Preparation Example B-1, and 0.1 part by weight of 1,2-benzoquinone (hereinafter referred to as C-1) were dissolved in 1000 parts by weight. Propylene Glycol Monomethyl Ether Acetate (PGMEA; hereinafter referred to as D-1). Then, the above-mentioned solution was filtered using a filter made of a fluororesin to obtain a positive photosensitive resin composition in which the pore diameter of the filter was 0.2 μm . The positive photosensitive resin composition obtained was evaluated by the following evaluation methods, and the results are shown in Table 3, and the method for detecting the content, sensitivity, and stability over time of the amine compound will be described later.

Examples 2 to 8 and Comparative Examples 1 to 6

In Examples 2 to 8 and Comparative Examples 1 to 6, the same production method as that of the positive photosensitive resin composition of Example 1 was used, except that Examples 2 to 8 and Comparative Examples 1 to 6 were changed. The type and amount of the raw material in the photosensitive resin composition, the formulation thereof and the following evaluation results are shown in Table 3.

Evaluation method

1. Amine compound content

The content of the amine compound in the positive photosensitive resin composition was measured using a gas chromatograph (manufactured by Agilent Technologies, Model No. 7890A).

2. Sensitivity

The positive photosensitive resin composition was applied by spin coating on a plain glass substrate (having a size of 100 mm × 100 mm × 0.7 mm), and prebaked at 110 ° C for 120 seconds to obtain a pre-baked thickness of about 1.5 μm. Coating film. Then, the prebaked coating film was placed under the designated mask containing the pattern, and irradiated with ultraviolet light of 7.5 mJ/cm ² (manufactured by M&R Nano Technology Co., Ltd., model: AG500-4N). Then, it was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C for 1 minute to remove the coating film on the exposed portion of the substrate, and the film thickness of the pattern was measured. (III) Calculate the residual film rate and evaluate according to the following criteria:

○: 90% <residual film ratio.

△: 80% < residual film ratio ≦ 90%.

╳: Residual film rate (%) ≦ 80%.

3. Stability over time

The various positive photosensitive resin compositions prepared were placed in an oven at 45 ° C for 1 month. Next, the above various positive photosensitive resin compositions were applied by spin coating on a glass substrate (having a size of 100 mm × 100 mm × 0.7 mm), and prebaked at 110 ° C for 120 seconds to obtain a thickness of about Pre-baked film of 1.5 μm. Then, the prebaked coating film was placed under a designated mask containing a pattern of a line width of 10 μm and irradiated with ultraviolet light (manufactured by M&R Nano Technology Co., Ltd., model AG500-4N). Subsequently, it was developed with a 2.38% aqueous TMAH solution at 23 ° C for 1 minute, and evaluated according to the exposure energy when the coating film could form a pattern of 10 μm line width and the following criteria:

○: Exposure energy <8.0 mJ/cm ² .

╳: 8.0 mJ/cm ² ≦ exposure energy.

The positive photosensitive resin composition obtained by the foregoing examples, the amines thereof The results of the evaluation of the content, sensitivity and stability of the compound are shown in Table 3.

As is apparent from the results of the third table, when the reduction preventing agent (C) is used, the positive photosensitive resin composition obtained has good stability over time. Further, when the residual amount of the amine compound of the positive photosensitive resin composition is from 1 ppm to 50 ppm, the positive photosensitive resin composition obtained has better sensitivity and stability over time. In Comparative Examples 1 to 3 and 6, the residual amount of the amine compound of the positive photosensitive resin composition was less than 1 ppm, and the sensitivity of the positive photosensitive resin composition obtained was not good. In Comparative Example 4, the content of the amine compound of the positive photosensitive resin composition was more than 50 ppm, and the composition of the positive photosensitive resin composition synthesized had poor stability with time, so that the object of the present invention can be attained.

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

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

Claims (8)

A positive photosensitive resin composition comprising: a novolac resin (A); an ester of an o-naphthoquinonediazidesulfonic acid (B); a reduction inhibitor (C); and a solvent (D); The ester of the o-naphthoquinonediazide sulfonic acid (B) is obtained by dissolving an o-naphthoquinonediazidesulfonic acid compound and a hydroxy compound in another solvent, and using an amine compound as a condensing agent, by condensation reaction. In the positive photosensitive resin composition, the residual amount of the amine compound is from 1 ppm to 50 ppm, and the o-naphthoquinone diazide sulfonic acid is used based on 100 parts by weight of the novolak resin (A). The esterified product (B) is used in an amount of 5 parts by weight to 50 parts by weight, the reducing agent (C) is used in an amount of 0.1 part by weight to 5 parts by weight, and the solvent (D) is used in an amount of 300 parts by weight to 3000 parts by weight. The positive photosensitive resin composition according to claim 1, wherein the residual amount of the amine compound is from 3 ppm to 40 ppm. The positive photosensitive resin composition according to claim 1, wherein the residual amount of the amine compound is from 5 ppm to 30 ppm. The positive photosensitive resin composition according to claim 1, wherein the amine compound comprises an aliphatic amine and/or a cyclic amine compound. The positive photosensitive resin composition according to claim 1, wherein the reduction preventing agent (C) comprises a lanthanoid compound. A pattern forming method for sequentially applying a pre-bake, an exposure, a development, and a post-baking treatment to a positive photosensitive resin composition according to any one of claims 1 to 5. The pattern is formed on a substrate. A thin film transistor array substrate comprising the pattern formed by the method of 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.