TW201216003A - Positive photosensitive resin composition and method for forming pattern of the composition - Google Patents

Abstract

This invention relates to a positive photosensitive resin composition and a method for forming a pattern, and more particularly to a positive photosensitive resin composition and a method for forming a pattern of the composition with excellent dry etching resistance. The resin composition comprises novolac resin (A), ester of naphthoquinonediazido sulfonate (B), melamine based compound (C), epoxy silane compound (D) and solvent (E), wherein novolac resin (A) comprises high-ortho novolac resin (A-1), and the amount of methylene groups linked at the ortho-ortho position of high-ortho novolac resin (A-1) accounts for 18-25% of the methylene groups linked to high-ortho novolac resin (A-1).

Description

201216003 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a money-type positive-type sensor composition and a method of forming the same. The present invention provides a positive photosensitive resin composition for forming a pattern in the manufacture of a liquid crystal display element of a rotating body element and a thin film transistor (hereinafter referred to as TFT), and the resin composition is formed to have good dry residue resistance. The method of patterning. [Prior Art] On the substrate, an insulating film or a conductive metal film such as a liquid crystal display element circuit or a semiconductor integrated circuit is formed on the substrate, and the photoresist composition is uniformly applied under the mask of a specified shape. Exposure development is carried out to obtain a desired shape pattern. Then, the patterned photoresist film is removed as a mask to remove the metal film or the insulating film, and then the remaining photoresist film is removed to form a fine circuit on the substrate. According to the soluble or insoluble of the photoresist composition in the exposed portion or the photoresist film portion, it can be classified into two types: a positive type resist and a negative type resist. In a general positive resist composition, a quinone diazide-containing sensitizer such as naphthoquinonediazide or an alkali-soluble resin (for example, a novolac resin) is often used. The positive-type resist composition composed of such a composition can be used for the production of a liquid crystal display such as a semiconductor such as Ic or an LSI, or a printing original plate, etc., after being exposed to an alkali solution after exposure to obtain a high resolution. In addition, since the structure of the novolac resin contains a large amount of aromatic rings and has high heat resistance, many positive resists containing an acid-clearing varnish resin and a naphthalene-doped diaphoretic sensitizer have been developed and put into practical use. And achieved remarkable results. However, when the above-mentioned novolac resin is used as a photosensitive resin composition, when it is applied to a semiconductor integrated circuit element or a TFT liquid crystal display element, it is prone to defects such as a low residual film ratio in 201216003. Therefore, compared with the general novolak resin, Japanese Patent Laid-Open No. 2^9'22312Q discloses the use of high-viscosity lyophilized grease as a photosensitive tree, and the product can form heat resistance and residual film rate on the substrate. High pattern, however, 'this material has the problem of poor resistance to dry money. DISCLOSURE OF THE INVENTION The first object of the present invention is to provide a composition of a resin which is excellent in the side of the axis. A second object of the present invention is to provide a method for forming a pattern having a good dry etching resistance in a resin composition described above. In order to satisfy the above-mentioned purpose, the present invention is composed of a kind of positive-light-lighting composition, including an acid varnish resin (4), an o-naphthalene g-quinone-diazide acid-rich acetate (B), a melamine (10), a compound (〇, Epoxy Wei compound (9) and solvent jE) _ towel 'The secret varnish resin (4) contains high ortho-clear varnish resin (A-1) 'This, ortho-clear varnish resin (Α-υ in the ortho-ortho-bonding) The amount of the methylene group is 18 to 25% of the methylene group bonded to the high-brick lacquer lacquer, and the positive-type photosensitive resin composition is formed into a pattern excellent in dry side resistance. The method of forming a pattern by the composition is to form a photosensitive resin pattern having excellent dryness resistance on the substrate by sequentially coating, exposing, and exposing 5V and post-baking treatment as described above. A second object of the present invention is to provide a thin film transistor array substrate which comprises a substrate and a pattern as described above. A fourth object of the present invention is to provide a liquid crystal display element having a 201216003 system as described above. Thin film transistor array substrate as described below. <Detailed Photosensitive Resin Composition> [Phenic Acid Resin Resin (A)] The present invention is _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 'Optional and further step-by-step includes other varnish resins (A-2). The high-origin sclerosing varnish resin (6)) is generally based on aromatic basalized hydrazines and acids in divalent metal salts. In the presence of a catalyst, it is obtained by condensation under acidic (pH 15) and dehydration under reduced pressure. Alternatively, the catalyst may be further added to the dehydration condensation reaction of the lamp, and the unreacted monomer may be removed (refer to Japanese Patent Laid-Open Publication No. SHO-55-090523, JP-A-59-_418, and JP-A-62- Bulletin No. 230815). Among them, specific examples of the aromatic hydroxy compound are: phenol (phen〇1); m-cresol (ra-cres〇i), p-cresol (p_cres〇1), o-cresol (〇-(:^3) 〇1) etc. cresol ((:1^5〇1); 2,31-2 phenol, 2,5-2 • toluene age, 3' 5 xylene ruthenium, 3, 4 dimethyl Stupid and so on, such as dimethyl SKxyierJ); m-ethyl benzene, p-ethyl benzene, o-ethyl benzene, 2, 3, 5 - trimethyl benzoquinone 2, 3, 5-three Ethyl alum, 4_t-butyl benzene, 3 - tert-T-phenol, 2-tert-butyl phenol, 2 - tert-butyl 4-methyl phenol, 2 - f tributyl - 5 _Methylbenzene age, 6_Terti-butyl_3_methylphenanthene, etc. alkyl phenols; p-methoxy oligos, m-methoxybenzoquinones, to B Alkoxy benzoquinone (alk〇xy phen(4); o-isopropyl benzophenone, oxybenzene, m-ethoxy acetonide, p-propoxy phenyl, m-propyloxy Isopropenyl benzene, 2-methyl+isopropenylbenzene, 2_B, 201216003, 4-isopropenyl, etc. isopropenyl phenol; phenylbenzene Phenyl phen Ol) aryl phenols; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, 1,2, 3 - p〇iyhydr〇xyphenol, etc., such as pyrogallol, etc. The above compounds may be used alone or in combination, and may be used in the form of a mixture of _ _ 甲 甲 、 、 、 、 、 、 Preferably, it is a 2, 5-diphenylene, 3,5,5,3-tridecylphenol or the like. • The specific aldehydes condensed with the aromatic hydroxy compound are as follows: Formaldehyde, poly-furfural (卩8^€〇1«1 (161^(16), trioxane (1:14 (^116), ethylbenzene, propionaldehyde, butyraldehyde, tridecyl acetaldehyde, propylene Acrolein, crotonaldehyde (〇^〇1; 〇贴1(^1^(16), cyclohexanal (^7(:1〇1^乂8this&amp;1(^}^(16)) , furfural furfural, fury acrolein, benzoic acid, terephthal aldehyde, phenylacetic acid, α_benzyl-propion, 々-ben- propyl, neighbor - Benzyl ketone, m-phenyl benzoquinone, p-hydroxybenzaldehyde, o-mercaptobenzaldehyde, m-methyl benzoformaldehyde , p-methyl benzoate, o-chlorobenzoquinone, m-chlorobenzoic acid, p-benzophenone, cinnamaldehyde, etc. The above aldehydes may be used alone or in combination. Among them, formaldehyde is preferred. When the high-ortho-phenolic varnish resin (A-ι) of the present invention is prepared, the molar ratio of the aromatic hydroxy compound and the aldehyde is usually 丨: 85., preferably 1: 〇. 55~ 〇, 82, more preferably 〇: 〇6~〇. 8. Specific examples of the above-mentioned divalent metal salt catalyst are: zinc acetate, manganese acetate, cerium acetate, manganese nitrate, zinc borate, zinc hydride, zinc oxide, and the like. The above two kinds of metal catalysts may be used alone or in combination of multiple kinds. Based on the aromatic 201216003 31; !^ Γ by weight, the amount of the bisvalent metal catalyst is usually 〇. 0~!.佳为q』3 0.05~0.5 parts by weight. The specifics of the acid catalyst mentioned above are still contained in the horse. For example, sulphuric acid-correction, sulfuric acid, diethyl sulphate, citric acid-peach 4. The above acid catalyst can be used. 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 008 〜 0. 5重量份。 More than 0. 8 heavy injuries, more preferably 〇. 01~0. 5 parts by weight.

The high ortho-clear varnish resin (A-1) of the present invention is bonded to the ortho-ortho-bonded fluorenyl group (IV), which is a silk ortho-clear blue group, usually 18, preferably 19 to 25 %, better = 〜25%. When the ratio of the methylene group bonded to the ortho-adjacent group in the subtropical varnish resin ((4), which is bonded to the ortho-clear resin (6)) is less than 18% or higher than 25% The pattern formed by the positive photosensitive resin composition has a problem that the dryness is low. The above-mentioned other novolac resin (A_2) is generally a catalyst of a known organic acid and/or inorganic acid such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or p-toluene acid, which is derived from the above-mentioned aromatic hydroxy compound and aldehyde. In the presence of a condensation reaction under ten pressures, and dehydration and removal of unreacted monomers. The other novolac resin (A-2) bonds methylene groups in the ortho-para, para-para or ortho-ortho position in a random manner. The high ortho novolak resin (A-1) is usually used in an amount of 30 to 1 part by weight, preferably 4 to 1 part by weight, based on 100 parts by weight of the acid varnish resin (A). More preferably 50 to 1 _ parts. When the amount of the high-origin varnish (A-1) is from 30 to 100 parts by weight, the pattern of 201216003 can be formed on the substrate to have a high heat resistance and a high residual film ratio. [Esteryl ester of o-naphthoquinone diazide acid (B)]

The photosensitive material of the positive photosensitive resin composition of the present invention is a compound (B) which is a compound of the above-mentioned sulphuric acid, and is not particularly limited, and may be used as a regular user. Among them, an esterified product of o-naphthoquinone diazide acid and a hydroxy compound is preferred, and an esterified product of an ortho-naphthoquinone bismuth acid and a polyvalent hydroxy compound is more preferred, and the above ester compound can be completely Or partial esterification; specific examples of the o-naphthoquinonediazidesulfonic acid are: o-naphthoquinonediazide-4-supply acid, o-naphthoquinonediazide-5-supply acid, o-naphthoquinone Nitrogen_6_sulfonic acid, etc. The types of the aforementioned hydroxy compounds are listed below. (1) Hydroxybenzophenone compounds, which are specifically, for example, 2,3,4-trihydroxydibenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxyl Benzophenone, 2, 3, 4, 4'-tetrahydroxydibenzophenone, 2, 2, 4, 4, _tetrahydroxydibenzophenone, 2, 3', 4, 4', 6- Pentahydroxybenzophenone, 2, 2,, 3, 4, 4,-penta-dibenzophenone, 2, 2', 3, 4, 5'-pentahydroxydibenzophenone, 2, 3' , 4, 5, 5'-pentahydroxybenzophenone, 2, 3, 3', 4, 4', 5'-hexahydroxydibenzophenone and the like. (ii) a hydroxyaryl compound represented by the general formula (1)

In the formula (1), 'R9~R&quot; respectively represent a hydrogen atom or a lower alkyl group, and RlZ~Rn 201216003 respectively represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, and a lower level. Alkenyi or cycloalkyl, R and r respectively represent a hydrogen atom, a _ atom or a lower alkyl group X, 乂 and 2 represent an integer from 1 to 3, respectively, and k represents 〇 or 卜Specific examples of the compound represented by the general formula (1) are, for example, tris(4-hydroxyphenyl)methane, bis(4-carbazhen-3,5-dimethylphenyl)-4-pyrimidinyl, Dihydroxy-3' 5-dimethylphenyl)_3-hydroxyphenylmethane, bis(4hydroxy-3,5-dimethylphenyl)-2-silylacetone, double (4_silk_ 2,5-dimethylphenyl)-4-hydroxyphenylnonane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy- 2, 5-dimethylphenyl)_2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2, 5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, double ( 4-hydroxy-2, 5-dimethylphenyl)-2,4-dihydroxybenzene methane, bis(4-hydroxyphenyl)-3-indolyl-4-hydroxyphenylnonane, double (3 _cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-ylhydroxyphenyl)_2_ 每 每 每 、, bis(3-cyclohexyl-4- Phenyl)-4-ylphenylene, bis(3-cyclohexyl-4-yl-6-methylaryl)-2-phenylphenyl, bis(3-cyclohexyl- 4-carbyl-6-methylphenyl)-3-phenylphenylcarbamate, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-hydroxyphenylnonane, double (3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-3-hydroxyphenylcarbamate, Bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6 -hydroxy-4-methylphenyl)-2-hydroxyphenyl decane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenyl 201216003 smoldering, double (3 -cyclohexyl-6m4-decylphenyl)_3,4-dihydroxyphenyl oxime, 1-0(4-pyl)iso-yl h-q, b-bis(4-hydroxyphenyl)ethyl] Stupid, 1-[ (3 by Yue-4-yl-phenyl) isopropyl] - BU printing bis (3-4 by Yue-yl) ethyl] stupid like. (3) (hydroxyphenyl) hydrocarbon compounds represented by the general formula (2)

In the formula (2), R2° and R21 each represent a hydrogen atom or a lower alkyl group, χ, and y, and represent an integer of 1 to 3, respectively. Specific examples of the compound represented by the general formula (2) are, for example, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2) , 4-dihydroxyindolyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, bis(2, 3, 4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, and the like. (4) Other aromatic hydroxy compounds, such as phenol, p-methoxyphenol, dimethyl phenol, hydroquinone, bisphenol A, naphthol, pyrocatech 〇 l), ι, 2, 3- phenyl 盼 _ _ (pyrogall 〇 l monomethyl ether), 1, 2, 3- 三 纷 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- 1,3- , 3, 4, 5-triosyl gallie acid, partially esterified or partially purified 3, 4, 5-trihydroxybenzoic acid, and the like. The above hydroxy compound is preferably 2,3,4-trihydroxydibenzophenone or 2,3,4,4'-tetramethylene dimercapto ketone. The above hydroxy compounds may be used singly or in combination of plural kinds or more. 201216003 The photosensitive material in the resin composition of the present invention is an ophthalmic acid of o-naphthoquinonediazide acid (8), and a compound containing a bis-nitrogen group can be used, for example, o-naphthoquinonediazide-4 (or 5)- The sulfonium sulfonate salt and the hydroxy compound of the above (1) to (4) are subjected to a condensation reaction to be completely esterified or partially esterified to obtain a compound. The above condensation reaction is usually carried out in an organic solvent such as dioxane ((11), N-pyrr〇lid〇ne, acetamide, etc., while in triethanolamine ( It is advantageous to carry out an alkaline condensing agent such as triethanolamine, an alkali metal carbonate or an alkali metal hydrogencarbonate. In this case, based on the total amount of hydroxyl groups in the hydroxy compound, 100 mol%, preferably 50 mol% or more, More preferably, the hydroxyl group of 60 mol% or more is condensed with the ortho-naphthoquinone dimeric mouse-4 (or 5) acid halide salt to form an esterified product, that is, the degree of esterification is above, more preferably 60% or more. The acid varnish resin (A) is used in an amount of usually 1 to 1 part by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the acid varnish resin (A). The amount of the melamine-based compound (C) is exemplified by the following formula (3).

R\ /R2 N

I N /, N - general (3)

R4 R6 wherein 'R1 to R6' respectively represent a hydrogen atom, CH2〇H, CH2〇CH3, CMC2H5, 201216003 CH2OC3H7 or CH2OC4H9' may be the same or different. The melamine-based compound (c) of the present invention may further comprise a compound represented by the general formula (3) modified with a compound such as urea, dicyandiamine, benzoguanamine or acetoguanamine. a compound of a compound. Specific examples of the melamine-based compound (C) of the present invention are: hexamethoxymercapto melamine, hexaethoxymercapto melamine, hexapropoxydecyl melamine, hexabutoxybutyl melamine, and Cymel_3()(), Cymel_

303CCYTEC system, MW-30MH, MW-30, MS-11, MS-001, MX-750, MX-706 (Sanhe Chemical) and other commercial products. The melamine-based compound (C) of the present invention is used in an amount of usually 1 to 2 parts by weight, preferably 3 to 18 parts by weight, more preferably 5 to 15 parts by weight based on 100 parts by weight of the Ik·varnish resin (A). Parts by weight. [Epoxydecane compound (D)] The epoxydecane compound (D) of the present invention contains the compound represented by the general formula (4) below. CH2—CH—CH20(CH2)mSi(0R7)nR9, V General formula (4) where R and R^7 represent independent alkyl groups, and m represents an integer of 1 to 20' η represents an integer of 1 to 3 . Specific examples of the epoxy decane compound (D) of the present invention include 3-glycidoxypropyl trimethoxy decane, 3-glycidoxypropyl triethoxy oxane, etc. 3-trialkoxyoxydecanes; 3-glycidoxypropyldimethoxy: 3,weipropoxypropyl, di-weiweiwei, etc.; 3-glycidoxypropyl ethoxylate L suspected of 3_glycidoxypropyl alkoxy 12 201216003 A 垸 基梦 burning class. The phenol_slight grease (4) is a loo ^ component, and the __ __saki (four) 〜5 嶋 ^ is = 4 weight I, more preferably 0.1 to 3 parts by weight. In the present invention, when the melamine-based compound (c) and the epoxidized compound are used, the positive-type sensation of the sensitizing tree can form a pattern excellent in dry smoke resistance. [Solvent (8)]

The solvent (8) to be used in the present invention requires an organic solvent which is relatively easy to dissolve with other organic components. Specific examples of the solvent (E) used in the present invention are: ethylene glycol monothiol test, ethylene glycol monoethyl (tetra), diethylene glycol monoethyl (tetra), diethylene glycol mono-n-propyl ether, diethyl Glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropanol monomethyl ether, dipropylene glycol single B (poly)alkylene glycol monoalkyl ethers such as monoether, dipropylene glycol mono-n-propyl ether, mono-propanol mono-n-butyl mystery, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates such as diol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate 'One ethylene glycol dioxime test, diethylene glycol methyl ethyl shunt, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl g, cyclohexanone, 2 - heptanone, 3- Ketones such as heptanone; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; decyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-mercaptopropyl Ethyl acetate, 3- Ethyl oxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 13 201216003 ethyl hydroxyacetate , 2-hydroxy-3-indolyl decanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-decyloxybutyl propionate, ethyl acetate, acetic acid N-propyl ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate Other esters such as ester, n-butyl butyrate, decyl pyruvate, ethyl pyruvate, n-propyl pyruvate, decyl acetate, ethyl acetate, ethyl 2-oxybutyrate; An aromatic hydrocarbon such as hydrazine or diphenylbenzene; a carboxylic acid amine such as N-mercaptopyrrolidone, N,N-dimercaptomethylamine or N,N-dimercaptoacetamide. The foregoing solvents may be used singly or in combination of plural kinds. Among them, propylene glycol monodecyl ether acetate and ethyl lactate are preferred. The solvent (E) of the photosensitive resin composition of the present invention is usually used in an amount of from 5 〇〇 to 2,000 parts by weight, preferably from 600 to 1,800 parts by weight based on 1 part by weight of the novolak resin (A). More preferably, it is from 7 to 1,500 parts by weight. [Additive (F)] The positive photosensitive resin composition of the present invention may further contain an aromatic transbasic compound as a sensitizer to adjust the sensitivity or viscosity of the composition. Specific examples of aromatic hydroxy compounds suitable for the present invention are, for example: TPPA-1000P, TPPA-100-2C, TPPA-1100-3C, TPPA-1100-4C 'TPPA-1200-24X 'TPPA-1200-26X 'TPPA-1300 -235T ' TPPA-l 600-3M6C, TPPA-MF and other commercial products (manufactured by Benben Chemical Industry Co., Ltd.) - TPPA-600-3M6C, TPPA-MF is preferred, which can be used alone or in combination use'. The amount of the aromatic hydroxy compound is usually from 0 to 2 parts by weight, preferably from 0.5 to 18 parts by weight, more preferably from 15 to 15 parts by weight, based on 100 parts by weight of the novolac resin (A). The positive photosensitive resin composition of the present invention may further contain a surface 201216003 flattening agent, a diluent, and a dye having good compatibility. The surface flat agent of the present invention contains a fluorine-based surfactant, a lanthanoid surfactant, and the like. Specific examples of the fluorine-based surfactant include commercially available products such as Flourate FC-430, FC-431 (manufactured by 3M), F topEF122A, 122B, 122C, 126, and BL20 (manufactured by Tochem Product). Specific examples of the lanthanoid surfactants include commercially available products such as SF8427 and SH29PA (manufactured by T〇ray Dow Corning Silicon). The surfactant is usually used in an amount of 〇~丨.2 parts by weight, preferably 〇〇25~1. 〇 by weight, more preferably 〇. 〇50, based on the weight of the novolac resin (A). 〜0. 8 parts by weight. Commercially available products such as RE8〇1, RE8〇2 (manufactured by Imperial Ink) are suitable as the diluent of the present invention. Specific examples of dyes suitable for the compatibility of the present invention include curcumin, coumarin, azo dyes, and the like. Further, other additives may be added to the present invention as needed. For example: plasticizers, stabilizers, etc. &lt;Preparation of Positive Photosensitive Resin Composition> The preparation of the positive-type sensation tree of the present invention is an esterified resin (A), an ester of an o-naphthoquinonediazidesulfonic acid (B), The melamine-based compound (C), the epoxidized compound (8) and the solvent (8) are stirred in a mixer to uniformly mix them into a solution state, and a surface flattening agent, a diluent, a dye having good compatibility, and the like may be added as needed. Additives such as plasticizers and stabilizers (F). '&lt;Method of Forming Pattern of Positive Photosensitive Resin Composition> The method of forming a pattern using the positive photosensitive resin composition of the present invention is a method of spin coating, cast coating or roll coating (four) cloth , 201216003 The photosensitive tree test composition is coated on a substrate, and after coating, the solvent is removed by prebake to form a prebaked coating film. Here, the pre-baked condition ' varies depending on the type and blending ratio of each component, and is usually carried out at a temperature of 70 to 110 ° C for 1 to 15 minutes. After pre-baking, the exposure is carried out under the specified fresh condition, and then immersed in the developing solution at a temperature of 23 ± 2 C for 15 seconds to 5 minutes, thereby removing the unnecessary portion (four) into a specific ugly. The light used for exposure is preferably ultraviolet rays such as g lines, lines, and i lines, and the ultraviolet irradiation device may be (ultra) high pressure mercury lamps and metal nucleus lamps. 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 methacrylate, ammonia, ethylamine, diethyl Amine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and biliary test "% ratio, mouth bite and I 8 diazabicyclo-[5, 4, 0]-7- Preferably, the concentration of the developer is between 〇1% by weight and 1% by weight, more preferably between 5% and 5% by weight, and further More preferably, it is between 1% by weight and 1% by weight. When the developer composed of the above basic compound is used, it is usually washed with water after development, and then air-dried with compressed air or compressed nitrogen. The film is then post-baked using a heating device such as a hot plate or an oven. The post-baking temperature is usually 100 to 25 (rc, wherein the heating time using the hot plate is 1 minute to 60 minutes, The heating time of the oven is 5 minutes to 90 minutes. After the above processing steps, the substrate can be patterned. &lt;Thin-film transistor array substrate&gt; The 201216003 and the manufacturing method of the thin film transistor array substrate (abbreviated as TFT array substrate) of the present invention are configured according to the above-described method of forming the film. The resin composition is applied by a coating method such as spin coating, cast coating, or the like to a glass filament "plastic & plate ± film containing a film of sho, chrome, nitrite or non-diamond. A positive light: the agent layer, followed by the formation, exposure, development and post-baking treatment to form a photosensitive resin pattern after the 'side and photoresist stripping; repeat the above steps can be obtained - containing a majority of _ transistor or electrode thief Here, a pair of LCD TFT array substrates will be described with reference to the drawings. Fig. 1 is a cross-sectional view showing a τρΤ array substrate for LCD. (1) First, an aluminum thin film on the glass substrate 101, etc. The gate 1〇2a and the storage capacitor Cs electrode l〇2b are disposed at the place; (2) Next, the gate electrode 102a is covered with an oxidized oxide film (SiOx) l〇3 or a tantalum nitride film (SiNx) l〇4, etc. Forming an insulating film on the insulating layer; (3) forming a non-crystalline layer of a semiconductor active layer (a-Si) l〇5; (4) Next, in order to reduce the junction resistance, a non-crystalline layer 106 of nitrogen-doped impurities is provided; (5) then, using a metal such as Forming the collector and the source 嶋', the collector 〇7a is connected to the data signal line (not shown), and the source 〇7b is connected to the morpheano electrode (or sub-pixel electrode) 109 (6) Finally, in order to protect the amorphous fracture layer (a-Si) 10, the electrode i 7a or the source 1 〇 7 b 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 comprises the above-described TFT array substrate of the present invention, which is constructed according to the pattern forming method of the present invention. In addition, other parts may be included as needed. Specifically, the basic configuration of the liquid crystal display device is, for example, (1) the TFU train substrate (drive substrate) of the present invention in which the 201216003 TFT-specific drive element and the halogen electrode (conductive layer) are arranged, and The color filter and the color filter substrate formed of the counter electrode (conductive layer) are interposed between the spacers and the opposite arrangement of the liquid crystal material in the gap portion. Alternatively, (2) a color filter-integrated TFT array substrate in which a color light-receiving sheet is directly formed on the TFT array substrate of the present invention, and a spacer interposed between the opposite substrate on which the counter electrode (conductive layer) is disposed, and In the arrangement, the liquid crystal material is sealed in the gap portion to form and the like. Lu The specific V electric layer is, for example, ιτο film; metal film of slag, zinc, copper, iron, chrome, molybdenum, etc.; metal oxide film such as cerium oxide. Among them, it is better to use a transparent film layer, and the IT0 film is the best. Specific examples of the substrate used for the TFT array substrate, the color filter substrate, and the counter substrate of the present invention include, for example, soda lime glass, low expansion glass, alkali-free glass, quartz glass, and the like. A substrate made of a plastic film or the like can also be used. [Embodiment] The present invention will be further described with respect to the following examples, but it should be understood that these implementations are the basis of the wording, and the invention is limited to the implementation. Χ &lt;Synthesis Example of Novolak Resin&gt; [Synthesis Example 1] A nitrogen inlet, a trap, a heater, a condenser, and a thermometer were placed on a four-necked flask having a volume of 1000 ml, and nitrogen was introduced to introduce a mixture. Enzyme 64.89g (〇.6 moles), p-nonylphenol 43 26g (〇4 moles), manganese acetate 〇·5g (0. 0028 moles) and 37% by weight of enamel disk aqueous solution 48·70g (〇6 Mo 201216003 ears) 'Slowly mix and polymerize for 3 hours. Then, add salicylic acid i. 38g (〇莫耳) to adjust the pH to 3_ 5 ' and then dry under reduced pressure at a pressure of 300mmHg for 30 minutes 'final' slowly warm the reaction solution to the column of seven, remove the solvent After the wave, the adjacent acid varnish resin (A-1-1) can be passed. The high-ortho phthalic acid varnish resin (A+1) measured the number of bonds of the sub-f group by nuclear magnetic resonance (13 〇臓), and calculated the ortho-ortho-bonding bond by the calculation method described in the test item. The ratio of methyl groups is shown in Table 1. [ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 64-89g (0.6m), 曱-曱37. 86g (0. 35m), manganese acetate 〇. 5g (〇.〇〇28mol) and 37% by weight of formaldehyde solution 52. 75 g (〇. 65 mol) 'slow stirring and polymerization for 3 hours. Then, add salicylic acid 1. l〇g (〇. 008 Moer) to adjust the value of Qi to 4_ 〇, then dry under reduced pressure of 300 mmHg for 3 〇 minutes, and finally, slowly raise the reaction solution to 150 C After the solvent is devolatilized, the high-end sclerosing varnish 3 (A+2) can be obtained. The high-neighboring varnish resin (A-1-2) measured the number of bonds of the fluorene group by nuclear magnetic resonance (13C-NMR), and calculated the ortho-ortho bond on the calculation method described in the test item. The results of the ratio of methylene groups are shown in Table 。. [Synthesis Example 3] A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked flask having a volume of 1000 ml, and after introducing nitrogen gas, cresol was added, 64' (0.6 m), and _A test 43 26 willow 4 Moule), acetic acid mammoth. 5g (Q. GG28 Moer) and 37% by weight of 曱 Jun aqueous solution 56. 82g (〇. 7 moles), slowly lining and polymerization for 3 hours. Then, adding benzoic acid Q·37g (〇〇〇3 201216003 Moer) to adjust the pH to 4.8 ′ and then drying under reduced pressure for 300 minutes under vacuum of 300 coffee, adding dimethyl sulfate 〇 〇3g (〇. 〇〇〇2mol), and the reaction solution was slowly heated to 150 ° C, and the solvent was devolatilized to obtain a high ortho-novolac resin (A-1-3). The high-ortho- novolak resin is measured by the nuclear magnetic resonance (CHVMR) to determine the number of methylene bonds, and the ratio of the ortho-ortho-bonded methylene groups is calculated by the calculation method described in the test item. The results are shown in the table. [Synthesis Example 4] • A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked flask having a volume of 1000 ml, and after introducing nitrogen, m-cresol was added to 64-89 g (0.6 m), and The phenol was 43.26 g (0.4 mol), oxalic acid i. 80 g (0.02 mol), and 37 wt% aqueous formaldehyde solution 48.7 g (〇. 6 mol), slowly stirred and polymerized for 3 hours. Then, the reaction solution was heated to 15 Torr, and the solvent was devolatilized to obtain a novolak resin (Α_2_υ. The novolac resin (Α-2-1) was measured by nuclear magnetic resonance (13c-MR) to obtain a methylene bond. The number of knots is calculated by the calculation method described in the test item, and the ratio of the methylene groups in the ortho-ortho position is calculated as shown in Table 1. [Synthesis Example 5] Four neck cones in a volume of 1000 ml A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer are arranged on the bottle, and after introducing nitrogen, m-cresol 64·89 g (0.6 mol) and p-cresol π. 45 g (〇. 3 mol) are added. 2,5, dimethyl phenol, 12.22g (0'·1 mole), oxalate oxalate. 9〇g (〇· 〇1 mole) and 37% by weight of formaldehyde aqueous solution 44. 64g (0. 55 Mo The ear was slowly stirred and polymerized for 3 hours. Then, the reaction solution was heated to 15 Torr, and the solvent was devolatilized to obtain a novolac resin (A-2-2). The novolac resin (A_2-2) was subjected to nuclear magnetic Resonance (13C_NMR) 20 201216003 The number of bonds of the fluorenylene group was measured and the ratio of the ortho-nezed bonded fluorenylene groups was calculated by the calculation method described in the test item. The results are shown in Table 1. Example and Comparative Example of Resin Composition&gt; [Example 1] 100 parts by weight of a high ortho novolak resin (A-1-1), 20 parts by weight of 2' 3' 4-trihydroxydiphenyl Esters of ketone and anthracene, 2-naphthoquinonediazide-5-sulfonic acid (average degree of esterification is 85%, hereinafter referred to as B-1), 2, 3, 4, 4,-tetrahydroxydiphenyl An ester of a ketone with 1,2-naphthoquinonediazide-5-sulfonic acid (average ester degree: 85%, hereinafter referred to as core 2), 10 parts by weight of a melamine-based compound (Cymel-303, manufactured by CYTEC, Hereinafter, (M), ! parts by weight of 3_glycidoxypropyltrimethoxydecane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as D-1), and 1 part by weight of propylene glycol monomethyl ether In the solvent of the acetate (hereinafter referred to as E-1), the positive photosensitive resin composition of the present invention can be obtained by stirring uniformly with a shaking stirrer. The following test results are as follows: [Tables 2 to 7] [Examples 2 to 7] The same as the operation method of Example 1, the difference is that the meaning of the raw materials and the amount thereof are changed, and the Wei Fang and the evaluation results are shown in Table 2. &lt; Comparative example 1 to 4&gt; The same as the operation method of Example 1, the difference is that the type of raw materials and the amount of use thereof are changed, and the formulation and evaluation results are shown in Table 2. [Test items] &lt;Miscellaneous varnish touches , the position of the bond _ _ _ knot ratio &gt; using nuclear magnetic resonance (13C-_) (model is Qing 〇; order system) to measure the number of methylene bonds of the secret varnish resin, and calculate the secret according to the following formula 201216003 In the lacquer resin, the ratio of 'near position _ neighboring 结 卩 卩 赖 。 。 。. The ortho-position bonding ratio (8) = {(ortho-_orting key) / [(ortho-neighboring key) + (adjacency 'paragraph key) + (alignment-paragraph key)]} χ 100 Ortho-o-position bond: the methylene group is in the ortho-ortho-position bond: the methylene group is in the ortho-positional position = the para-positional bond · The sub-yin is based on the para-positional Number of Bonds <Resistance Resistantness> The positive-type photosensitive resin composition of the present invention is coated on a spin-on wafer at a time of 6 o'clock, and then pre-baked at a temperature of 11 Torr. " ο sec -1 · lin coat film. Then, immersed in 23t developer solution (2.38% tetramethylammonium hydroxide) for 6 sec seconds, washed with pure water and then at a temperature of 14 ° C After baking for 3 minutes, the final ashing test condition of the Weibian side machine (model AS 2002, manufactured by Huisheng Technology) is as follows: Power: 1000 W Flow: 100 seem Pressure: 100 mtorr Time: 5 min Finally, the film thickness (de) is measured by optical film thickness, and the dryness resistance can be obtained by the following formula: Resistance to dryness (%) = [( 6e) / l. 2] X 1〇〇〇: dry etching resistance ^80% ' △ : 80%> dry etching resistance gt 60% X: dry etching resistance S 60% &lt;heat resistance&gt; 22 201216003, the test item &lt;wei side property> obtained by Lin Wei, under the specified mask, with ultraviolet light (exposure machine model AG500 -4N; manufactured by Nano Technology) After irradiation with a light amount of 6 mj/cm2, the coating film was then immersed in a developing solution of 23.C (2.38% tetramethylammonium hydroxide) for 6 seconds, and the exposed portion of the substrate was exposed. The film was removed, and then washed with pure water, and then baked at a temperature of 160 ° C for 5 minutes, and then observed by a scanning electron microscope. The pattern was not collapsed, and its appearance was: /-\ △' The pattern has begun to collapse. The appearance is: • X: The pattern is heavily collapsed, and its appearance is: _^ &lt; residual film rate&gt; on the pre-baked film obtained from the test item &lt;dry etching resistance&gt; - measured at the measurement point - film thickness Udl). Then the film was immersed in 23t, and the liquid (2.38% tetramethylammonium hydroxide) was used for 60 seconds, and another film thickness was measured at the same measurement point (&lt;;5α). Finally, the residual film rate can be obtained by the following formula: Residual film rate (%) = [(") / (")] X 1 〇〇〇: residual film rate 290% • △: 90% &gt; Residual film rate &gt ; 8〇% X : Residual film rate S80% However, the above description is only a preferred embodiment of the present invention, and the scope of the present invention cannot be limited thereto, that is, the patent application scope and invention specification according to the present invention. The simple equivalent changes and modifications made to the content are still within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a TFT array substrate for LCD. 23 201216003 [Description of main components] 101 Glass substrate 102a Gate 102b Cs electrode 103 Cerium oxide film (SiOx) 104 Tantalum nitride film (SiNx) 105 Amorphous germanium layer (a-Si) 106 Impurity of nitrogen-doped impurity矽 layer 107a collector 107b source 108 protective film 109 pixel electrode

24 201216003 Table 1 Synthesis Example Methylene ortho-ortho linkage ratio A-1-1 18% A-1-2 20% A-1-3 25% A-2-1 16% A-2-2 14%

25 201216003 Bl B-2 2,3,4&gt;-θϊ1®ΗEPMSV ph 豳 -5-5-is隳N-憩{cv ridge C-lagn nyll_303; cytecm C-2asnptfiMX-706 :1113⁄4^熝Dl D,2 - is E-lalN 职 -3 ⁄ PG PG PG (PGMEA, propylene glycol monometl ether acetate) E-2^^z^Qrethyllactate) Fl soil to sweet F#M:Mgn^SH29PA ; Toray Dow Coming Silicone^ F-2 疏颜凛:MlsnptfiTPPA-MF ;0 oblique 3 cold #11撇鲣Test item additive (F) (parts by weight) Solvent (E) (parts by weight) Epoxy decane compound (D) (parts by weight) ) melamine-based compound (c) I (parts by weight) ester of o-naphthoquinonediazidesulfonic acid _(Β)_ furfural varnish resin (A) (parts by weight) residual film rate heat resistance dry etching) 1 Ψ m σ tsJ σ 〇1 tsJ) Ο 1 dd 1 dd 1 H-* A-2-2 A-2-1 A-1-3 Al-2 &gt; 1 Η-» 1 ►—* 〇〇〇 〇〇ο 1—* h—* 〇Example 〇〇〇NJ 〇g ο ο L/l 〇NJ 〇〇〇oo ο 5; H-* t—» Ο LO 〇〇〇g ο 1—* 谷〇 〇〇1000 &gt;—* Ο 1~1 1~~* 〇 〇〇g ο *—* ίο Ι_Λ g 〇\ 〇〇〇〇LO g ο CO 〇〇XXX oo ο Η—* »—* ο h—* 〇»—» Comparative Example 1 XXX g ο ►—* ο Ln T—» 〇ts-3 〇〇X g ο o UJ 〇〇X oo ο μ—* t-Ti H-* o β 26

Claims (1)

201216003 VII. Patent application scope: 1. A positive photosensitive resin composition comprising: novolac resin (A); an ester of o-naphthoquinonediazidesulfonic acid (B); a melamine compound (C); Oxygen oxalate compound (D); and solvent (E); wherein the novolac resin (A) comprises a high ortho novolac resin _ (A-1), the high ortho novolac resin (a_d in the ortho position) - the number of ortho-bonded methylene groups is 18 to 25% of the methylene group bonded to the high-position varnish resin (A-1). 2. The positive type as described in claim 1 The photosensitive resin composition, wherein the high ortho novolac resin (A-1) is used in an amount of 30 to 1 part by weight based on 100 parts by weight of the novolac resin (A). The positive photosensitive resin composition according to the above item 1, wherein the high-ortho phenolic aldehyde varnish resin (A-1) is used in an amount of 40% by weight based on 100 parts by weight of the novolak resin (A). 1% by weight. 4. The positive photosensitive resin composition as described in claim 1, wherein 'based on novolac resin (A) 100 parts by weight, the high-ortho phenol varnish resin (A-1) is used in an amount of 50 to 100% by weight, wherein the positive-type photosensitive resin composition according to claim 1, wherein The dimeric amidine compound 'C (C) contains the compound represented by the following general formula (3); 27 201216003 General formula (3) wherein R1 to R6 represent a hydrogen atom, CH2〇H, CH2〇CH3, CH2OC2H5, respectively. , CH2OC3H7 or CHUg. 6. The composition of Zhengheguang Na Na as described in the first application of the patent, wherein the epoxy-based compound (d) contains a compound represented by the following general formula (4); CH2—CH-CH20(CH2)mSi (0R7)nR8(3n) General formula (4) wherein R7 and R8 represent independently Cl to C3 alkyl groups, m represents an integer of 1 to 20, and η represents an integer of 1 to 3 The melamine resin (C) is used in an amount of from 1 to 2% by weight based on 100 parts by weight of the novolak resin (Α). Share. 8. If the application is as follows, the composition of the ruthenium resin according to the first item, wherein the epoxy decane compound (D) is used in an amount of 〇. 〇 based on 100 parts by weight of the novolak resin (VIII). 1 to 5 parts by weight. 9. A pattern forming method, which comprises applying a positive photosensitive resin composition according to any one of claims to claim 8, wherein the composition is applied to an exposure, development, and post-baking treatment. A pattern is formed according to the substrate. 28 201216003 10. A thin film transistor array substrate comprising a pattern formed by the method of claim 9 of the patent application. A liquid crystal display element comprising the thin film transistor array substrate as described in claim 10 of the patent application. 29