TW594391B - Chemical amplified type positive resist composition for liquid crystal element - Google Patents

Abstract

A chemical amplified type positive resist composition for liquid crystal element prepared by dissolving the following components (A) to (C) in an organic solvent: (A) an alkali soluble resin comprising a novolac resin having a solubility of 37.5 to 100 nm/sec. in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, (B) a compound which generates an acid upon irradiation, and (C) a crosslinkable polyvinyl ether compound; and a resist pattern for a liquid crystal element obtainable by the steps of providing a coating on a glass substrate using the chemical amplified type positive resist composition for liquid crystal element, drying the coating, thereafter irradiating the coating through a mask pattern, followed by heat treatment, and then alkali developing.

Description

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 594391 A7 B7 V. INTRODUCTION (彳) TECHNICAL FIELD The present invention relates to thin film transistor (THIN FILM TRANSISTOR) with excellent characteristics such as excellent resolution, excellent sensitivity, and small film loss. ) And other liquid crystal elements made of liquid crystal elements, and a chemically enhanced positive type photoresist composition and a photoresist pattern using the same. Prior art In recent years, the use of liquid crystal displays has been rapidly spreading to various electronic devices. The reason for this is the lower price of liquid crystal displays. of course. With the reduction in price, the cost of various materials such as photoresistors used in manufacturing is also expected to be reduced. With such a background, today's cost-effectiveness of photoresistors for the manufacture of liquid crystal elements is of paramount importance. In addition, as a substrate photoresist, a low-temperature polysilicon film or a continuous intergranular crystal film is provided. In recent years, high resolution has been strongly demanded. In addition, the thickness of the photoresist film after development is smaller than the thickness of the photoresist film before development, that is, the so-called film loss is large, and the contrast between the dry etching in the subsequent steps and the selection of the underlying substrate is small, causing an unsuitable situation. The liquid crystal element Manufacturing photoresist is also required to reduce film damage. Furthermore, the photoresist used in the manufacture of liquid crystal elements cannot be compared with silicon wafers. It can be applied to the latest substrates such as 680 mm X 880 mm, 600 mm X 7 2 0 mm, 5 50 mm X 6 7 0 mm, old For generations of very large glass substrates of 360 mm x 460 mm, the exposure must be increased, and high sensitivity must be achieved in order to achieve high output. In addition, in order to be applied to an ultra-large glass substrate, the photoresist for semiconductor elements is completely different, and the following requirements have to be satisfied. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm), 0G7S32 -4- (Please read the precautions on the back before filling this page)

594391 A7 B7 V. Description of the invention (5) Condensation of aromatic hydroxy compounds such as cresol, xylenol, tricresol, and aldehydes such as formaldehyde in the presence of a catalyst. Specific examples include m-cresol formaldehyde novolac lacquer type resin obtained by condensing m-cresol 100% with an average molecular weight of 5000 to 14000 under an acid catalyst, and m-cresol 30 to 80 mol. %, Ideally 30 to 50 mol% and p-cresol 70 to 20 mol%, ideally 70 to 50 mol% of mixed cresol, the weight average molecular weight obtained by the condensation of formaldehyde in the presence of a catalyst 2500 ~ 10000 cresol formaldehyde novolac lacquer type resin. Examples of the catalyst include oxalic acid, P-toluenesulfonic acid, and acetic acid. The use of oxalic acid is preferable because it is inexpensive and readily available. The formaldehydes include, for example, formaldehyde, or formalin or trioxane dissolved in water. Formalin is usually used. About (B) component: (A) component and (C) component are cross-linked by heating during pre-baking to form an alkali-insoluble photoresist layer on the substrate, and (B) component has acid in the exposed part due to exposure, It is only necessary for the acid to decompose the cross-linking, and the insolubilized photoresist layer may be changed to an alkali-soluble function. A compound having such an acid function by irradiating radiation can be used as an acid initiator for enhancing chemical photoresist. Many compounds have been proposed, and any of them can be selected arbitrarily. As a photoresist for liquid crystal production, any of ultraviolet rays including g-line, h-line, and i-line can be used. Among them, compounds that generate an acid when irradiated with these ultraviolet rays, and particularly compounds having a high acid growth rate are preferred. Examples of such compounds include the following compounds. (Please read the notes on the back before filling in this page) -5-tv Γ · This paper is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs sew # National Standard (〇 阳) 8 4 Specifications (210 Father 297 mm) -8 594391

i. Description of the invention (6)

R 4 R 5 R5 / 〇I li C = N — 0 — S_ II 〇 R3, (Π) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) u II -S — R3 II 〇 (ΠΙ) (In the formula, m is 0 or 1, x is 1 or 2, 1 is phenyl, 1 or more is substituted by C! ~ Cu alkyl group, 1 or more The phenyl group substituted by the alkoxy group of Cl ~ Cu and the phenyl group substituted by the halogen atom are C 2-(: 12 alkylene group, phenyl group, naphthyl group, and the square 2 is 0 1 ^ group, & amp 3 and 1 are independent Cl ~ C " alkyl groups, or Cl ~ Cl8 alkyl groups replaced by halogen atoms, and r4 and R5 are independent iA gas atoms, halogen atoms, Cl ~ C6 courtyards, or Cl ~ A compound represented by C6 oxygen, A is sulfur or oxygen) (U.S. Patent No. 6004724). Specific examples are X ^ CC = N-0 · R2

The mineralization of the white sulfur compound base is deficient. Or National Paper Standard (CNS) A4 (210X297 mm)

1T -9-594391 A7 B7 V. Description of the invention (7 R6〇—⑶ 二 ⑶ R? 〇Ν Ν = ^ CC13 αν) CC13 (wherein R6 and R7 are each an alkyl group having 1 to 3 carbon atoms ) Bis (chloromethyl) triamidine compound, or the compound (IV) and N-if NN = < ^ CC13 (V) (Please read the precautions on the back before filling this page) CCls (in the formula , Z is a composition of a bis (trichlorofluorenyl) triazine compound represented by alkoxyphenyl, etc. (Japanese Patent Application Laid-Open No. 6-2896 14 and Japanese Patent Application Laid-Open No. 7-1 344 1 2 ). Specific examples include 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-methoxy4-ethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3- Methoxy4-propoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-ethoxy4-methyl Oxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-diethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-ethoxy4-propoxyphenyl) vinyl] -4,6-bis (Trichloromethyl) -1,3,5-triazine, 2- [2- (3-propoxy4-methoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-propoxy4-ethoxyphenyl) vinyl > 4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- [2- (3,4-dipropoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, and the like. This 丨 National Standard ([?) 8 4 specifications (210 father 297 mm) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 10 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (8) etc. The xylazine compounds can be used alone or in combination of two or more. ~ Aspect The above-mentioned triazine compound (IV) is used in combination with the above-mentioned compound (V) as desired, for example 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -triazine, -(4-ethoxyphenyl) -4,6-bis (trichlorofluorenyl) -1,3,5-triazine 'h (4-propoxyphenyl) -4,6-bis (tri Chloromethyl) -1,3,5-triazine, 2- (4-butoxyphenyl) _4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Methoxynaphthyl) bis (trichloromethyl) -1,3,5-triazine '2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4-propoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxynaphthyl) ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-6-carboxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (bromomethoxy-6-hydroxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triamidine '2- [2 -(2-furyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl-2-furyl) vinyl ] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-ethyl-2-furanyl) vinyl] -4,6-bis (tri Chloromethyl) -1, 3,5-triazine, 2- [2- (5-propyl-2-furanyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5 · triazine, 2- [2- (3,5-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triamidine, 2- [2- (3-methoxy Methyl-5-ethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-methoxy-5-propane Oxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-ethoxy-5-methoxyphenyl) Vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-diethoxyphenyl) vinyl] -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-ethoxy-5-propoxyphenyl) vinyl] -4,6-bis (trichloromethyl) Group) -1,3,5-triazine, 2- [2- (3-propoxy-5-methoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- [2- (3-propoxy-5-ethoxyphenyl) vinyl paper? ^^^ Pine National Standard (〇 奶) 8 Specification (210 > < 297) Li) (Please read the notes on the back before filling this page)

594391 A7 B7 V. Description of the invention (9) (Please read the notes on the back before filling this page) Base] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [ 2- (3,5-dipropoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 · [2- (3,4-methyl Dioxophenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine and the like. These triamidine compounds can be used alone or in combination of two or more. Relevant component (C): The crosslinkable polyvinyl ether compound of component (C) and component (A) are crosslinked by heating during pre-fire, and an alkali-insoluble photoresist layer is formed on the substrate. The acid produced by the ingredients will be cross-linked and decomposed by the acid, and the exposed part will become alkali soluble, and the unexposed part will remain alkali insoluble. Therefore, there is no particular limitation on the component (C) that has the function of crosslinking with the magic component by heating during pre-baking to form an alkali-insoluble photoresist layer on the substrate in its entirety. Japanese Patent Laid-Open No. 6-148889, Japanese Patent Kaiping No. 6-230574 enumerates a number of such polyvinyl ether compounds, which can be used arbitrarily, especially considering the shape of the light-blocking surface of thermal crosslinkability and acid decomposability, and the comparison of exposed portions and unexposed portions. It is desirable that some or all of the alcoholic radicals of the alcohols shown in the following general formula are vinyl etherified compounds. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, R Π-(OH) η ( I) (In the formula, R n is a group in which n hydrogen atoms are removed from a hydrocarbon containing a linear group, a branched group, or a cyclic group, where n is an integer of 2, 3, or 4.) Specific examples thereof include Ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, trimethylolpropane divinyl ether, trimethylol Ethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethyl Alcohol Divinyl Ether, Pentaerythrylene Glycol This paper is dimensioned to the Chinese National Standard (CNS) A4 (210X297 mm) 0G7S00 -12- 594391 A7 B7 V. Description of the invention (1) Divinyl ether, cyclohexanedimethanol Divinyl ether, etc. Among them, a crosslinkable divinyl ether compound is preferred, and cyclohexanedimethanol divinyl ether is most preferred. The blending amount of component (B) and component (C) is 100 parts by mass. 1 to 30 parts by mass of the component (B), particularly preferably 1 to 20 parts by mass, and the component (C) is preferably 0.1 to 25 parts by mass, and particularly preferably 1 to 15 parts by mass. Related (D) ingredients: To prevent From the viewpoint of the diffusion of the excess acid in the exposed part and the stability of the photoresist pattern over time, the liquid crystal element of the present invention is preferably a chemically-enhanced positive photoresist composition that is preferably compounded with amines. As amines, for example, During pre-baking heating, the second- or third-stage alkanolamine, such as diethanolamine, triethanolamine, tributanolamine, and triisopropanolamine, or diethylamine and Secondary or tertiary alkyl, such as ethylamine, dibutylamine, tributylamine, etc. The blending amount of the amines is preferably 100 parts by mass (A) and 0.01 to 5 parts by mass, and more preferably 0.1 to 1 part by mass. The organic solvent used in the present invention, such as acetone, Ketones such as methyl ethyl ketone, cyclohexanone, isobutyl methyl ketone, isopentyl fluorenyl ketone, m-trimethylacetone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate Or polyvalent alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether, butyl ether, or monophenyl ether of diethylene glycol monoacetate and derivatives thereof; such as Dicyclic cyclic ethers; and methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl propionate, ethyl propionate, and ethyl 3-ethoxypropionate And other esters. These can be used alone or in combination of two or more of the national standard (CNS) A4 size of this paper (210x297 mm) (Please read the precautions on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 合作 3- 594391 A7 B7 V. Description of the invention (11) (Please read the precautions on the back before filling in this page) The chemically-enhanced positive-type photoresist composition for liquid crystal elements of the present invention, as long as it does not interfere with the purpose of the present invention, it can be used as necessary Contains compatible additives, such as additional resins to improve the performance of the photoresist film, plasticizers, surfactants, colorants that make the image more visible after development, sensitizers or halos to improve the sensitization effect Preventive use of conventional additives such as dyes and adhesion promoters. The chemically-enhanced positive type photoresist composition for a liquid crystal element of the present invention can be prepared by dissolving (A) component '(B) component, (C) component, and other components as necessary in an organic solvent. The photoresist pattern for a liquid crystal element of the present invention uses an associated chemically-enhanced positive photoresist composition for a liquid crystal element. A coating film is coated on a substrate, and after drying, it is exposed through an exposure pattern. After exposure, it is heat-treated. , Followed by a developing step. That is, a glass substrate is coated with the above-mentioned reinforced chemical positive type photoresist composition for a liquid crystal element, and is coated as a coating film. This is prebaked using a hot plate or the like, and then exposed through a photoresist pattern. After the heat treatment (PEB), it is coated with an alkali developer such as TMAH in a curtain flow method, or it is impregnated with an alkali developer and applied with alkali development, and then washed and dried to form a photoresist pattern. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The present invention will be described in detail with reference to the following examples. The present invention is not limited to the following examples. Example 1 Relevant (A) ingredients are 100 mol% m-cresol added with oxalic acid and formalin Chinese National Standard (CNS) A4 specifications (210X297 mm) 14 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 594391 Α7 B7 V. Description of the invention (12): The m-cresol formaldehyde acetaldehyde lacquer type resin having a weight average molecular weight of 1 000 is obtained through a condensation reaction. The alkali-solubility of a 2.38% by mass TMAH aqueous solution of this resin was 75 nm / second. (B) Use of C3H7 ^ / 0

CHs I CN 100 parts by mass of component (A), 6 parts by mass of component (B), 8 parts by mass of hexanedimethanol ether as component (C), 0.2 parts by mass of isopropanolamine as component (D), and 0.0 4 parts by mass of a nonionic fluorine-lauric surfactant (trade name: MEGAFACK R-〇8 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) was dissolved in 395 parts by mass of propylene glycol monomethyl ether acetate to prepare a reinforcement for a liquid crystal element. Chemical positive photoresist composition. Second, on the glass substrate with a chromium film, the enhanced chemical positive photoresist composition for the liquid crystal element to be modulated can be coated with a spinner to form a 1.5 // m film. The thick coating film was dried (prebaked) on a hot plate at 13 (rc temperature) for 90 seconds to obtain a coating film. Next, a test pattern cover film was used to reflect the projection linear aligner MPA-600FA (manufactured by CANON, Japan). ) Exposure. Then, post-exposure heat treatment (PEB) was performed on a hot plate at 120. (Continued, immersion in 23.2.0% by mass of TMAH aqueous solution for 60 seconds, and rinsing with pure water for 30 seconds. After that, it is dried to remove the exposed part, and a photoresist pattern is formed on the substrate. (CNS) A4 size (210X297 mm) '~' (Please read the notes and then fill in the back of this page)

-15- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 594391 A7 _____—_ B7 V. Description of the Invention (13) The photoresist pattern obtained in this way was observed with a scanning electron microscope. The limit resolution and the exposure amount at this time are shown in Table 1 as sensitivity. In addition, in the above pattern forming process, the change in film thickness from before exposure to after exposure at the unexposed portion when the development time is 20 seconds is not as good as that in Table 1. Moreover, in the above-mentioned pattern formation process, the size of the photoresist pattern obtained from each temperature on a hot plate with only 1CTC temperature change, and the amount of dimensional change of the photoresist pattern per unit temperature are taken as the prebaking limit. The results are shown in Table 1. In the above pattern forming process, only the development process was changed from immersion to curtain flow, and the difference between the size of the photoresist pattern at the start of development and the size of the photoresist pattern at the end was determined as the development limit. The results are shown in Table 1. As shown. In addition, after the above-mentioned pattern forming process, baking was performed at 20 ° C. to form a deteriorated film, and the deteriorated film was ST-106 (trade name of a representative peeling solution). The time required for the peeling was measured as an evaluation of the peelability. The results are shown in Table 1. Example 2 The composition of the positive chemically-enhanced photoresist composition for a liquid crystal element of Example 1 was changed as follows except for the following examples. 1. The characteristics were evaluated in the same way. Regarding the component (A), 35 mol% m-cresol and 65 mol% p-cresol were added to oxalic acid and formalin, and a cresol formaldehyde novolac with a weight average molecular weight of 4000 was obtained through a condensation reaction. Lacquer-type resin. The solubility of the 2.38% by mass TMA Η solution in water is 50 nm / sec. (B), (C), and (D) are the same as in Example 1. (Please read the note on the back first (Fill in this page again)

This paper ^^^^^ 1 standard (〇 奶) 8 4 specifications (210/297 mm)-* 16 _ 594391 A7 B7 V. Description of the invention (15) Positive type of enhanced chemical resistance for liquid crystal elements of Example 1 The composition of the photoresist composition was changed as described below, and each characteristic was evaluated in the same manner as in Example 1. 100 mol% m-cresol was added with oxalic acid and formalin, and an m-cresol formaldehyde novolac lacquer resin having a weight average molecular weight of 10 was obtained through a condensation reaction. The alkali solubility of this resin to a 2.38% by mass TMAH aqueous solution was 75 nm / second. The acid initiator component was the same as in Example 1. Dissolution inhibitor component 1 is for use

(Please read the notes on the back before filling out this page.) Some or all of the hydrogen atoms of hydroxyl groups printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are substituted by tert-butoxycarbonylmethyl. The dissolution inhibitor component 2 is a compound in which a part or all of the carboxyl group and hydroxyl group hydrogen atom of deoxycholic acid are substituted with 1-methoxy-1-ethyl group. The amine component is the same as in Example 1. 100 parts by mass of alkali-soluble component, 5 parts by mass of acid initiator component, 18 parts by mass of dissolution inhibitor component 1, 28 parts by mass of dissolution inhibitor component 2, 0.1 part by mass of triisopropanolamine, and 0.04 part by mass of nonionic fluorine -Silicon-based surfactant (trade name: MEGAFACK R-08 (manufactured by Daiichi Ink Chemical Industry Co., Ltd.)) is dissolved in 395 parts by mass of propylene glycol monomethyl ether acetate to prepare a positive chemically-enhanced photoresist for liquid crystal elements.组合 物。 Composition. The results are shown in Table 1. Binding Paper 00¾ National Standard (CNS) A4 Specification (210X297 mm) -18- 594391 A7 B7 ............ .. · __- '" 1 ..................................................... ) (3) The pre-baking limit is increased: the change in the size of the photoresist pattern is less than one third of @ 来. The temperature change of the photoresist to the photoresist pattern has always been 0.41 // m / ° C. In this regard, Examples 1 and 2 can reach 0.08 to 0.12 // m / t: ○ (4) Increase in the development limit: the difference in the size of the photoresist pattern can be greatly reduced. The conventional photoresist pattern size difference is 0.75 // m. In contrast, Examples 1 and 2 can be suppressed to 0.03 to 0.04 // m. (5) Improved releasability: it can greatly suppress the deterioration of the light pattern. The conventional photoresist pattern is baked at 160 ° C. It takes 10 minutes to peel the modified film at a peeling liquid temperature of 60 ° C. The composition of the present invention is baked at 200 ° C and peeled at 23 ° C. Liquid temperature peeling takes less than 2 minutes. (6) Cost reduction: Photoresistors for liquid crystal elements have been strongly requested to be cost-effective due to the impact of the price reduction of electronic devices equipped with liquid crystals such as personal computers. The reinforced chemical positive type photoresist composition for liquid crystal elements of the present invention has the above-mentioned characteristics (1) to (5), and can correspond to low cost. The photoresist composition for reinforced chemical liquid crystal elements is easily commercialized. (Please read the precautions on the back before filling out this page) Order Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Printed by the Consumer Cooperatives of the Ministry of Economic Affairs (CNS) A4 Specification (210X297 mm) -20- 594391 A7 B7

Ml: Supplement V. Description of the invention (2) (Improve the pre-baking limit) (Please read the precautions on the back before filling out this page) Regarding the photoresist for the manufacture of liquid crystal elements, it is necessary to obtain a uniform size photoresist for the entire large substrate pattern. In recent years, in order to reduce the cost, it is necessary to obtain a large number of liquid crystal display devices from one substrate. Therefore, glass substrates are rapidly increasing in size, and the size of photoresists is required to be uniform. However, the conventional photoresist is easily affected by the pre-baking temperature, and the pattern size of the obtained photoresist is different. (Enhancement of development limit) As the substrate becomes larger, a curtain-type development method is adopted. The development method is to drip the developer solution through a slit from one end to the other end of the substrate. This development method occurs from the beginning to the end of the development. Time difference in seconds. Due to this time difference, the size of the photoresist pattern at the start of development differs from the size of the photopattern at the end of development. Therefore, the influence of the time difference is reduced as much as possible, and the size of the photoresist pattern is required to be uniform. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (improvement of peelability) The manufacturing steps of the liquid crystal element are formed with a photoresist pattern, and the photoresist pattern is used as a cover film, which is applied according to different manufacturing procedures of each user according to different conditions. Various processes such as wet etching, dry etching, and ion coating. When various treatments are applied as described above, the photoresist pattern is deteriorated, and the photoresist peeling solution is not easily peeled. Therefore, it is necessary to improve the releasability even if it is changed to be difficult to peel. However, the conventional naphthoquinonediazide-based non-reinforced positive photoresist is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) on this paper scale. -5- 391391 — A7 B7 5. Description of the invention (3 ) When the sensitivity is increased, the trade-off relationship between the film loss also increases, and it is difficult to satisfy the two. In addition, as mentioned above, the problem of substrate enlargement has been recognized, but the means for solving it have not been discovered. In addition, conventional photoresists for liquid crystal manufacturing, as g-line or i-line positive photoresistors for semiconductor device manufacturing, have long-term practical high reliability and low cost, and can use naphthoquinonediazide-based non- Enhance chemical photoresist. On the one hand, photoresistors for semiconductor device manufacturing have accepted the requirements of ultra-fine and high-sensitivity semiconductor devices in recent years. Part of the process below 0.35 / m uses enhanced chemical photoresistance, which will make finer processes in the future. Will gradually strengthen the chemical photoresist as the mainstream. In accordance with the current trend of photoresists for semiconductor device manufacturing, related photoresists for semiconductor device manufacturing have to consider the use of enhanced chemical photoresists. However, although high resolution and high sensitivity can be achieved, it cannot be said that it is sufficient as a photoresist for the manufacture of liquid crystal devices. The conventional enhancement of chemical photoresist has a very decisive problem and is not fully reviewed. Although the present invention is conventionally applicable to the enhancement of a chemical photoresist for a photoresist used in the manufacture of liquid crystal elements, the above-mentioned problem that has not been achieved is to provide a liquid crystal with excellent characteristics such as low price, excellent resolution and sensitivity, and low film loss. The purpose is to provide a photoresist composition for device manufacturing and a photoresist pattern of the photoresist composition. DISCLOSURE OF THE INVENTION In order to achieve the above-mentioned object, the present inventors and others have conducted intensive research and found that a phenolic lacquer-type resin having a specific alkali solubility, a compound that generates an acid by radiation irradiation, and a crosslinkable polyvinyl ester compound are organic solvents. The paper size of the dissolution institute is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)-(Please read the precautions on the back before filling this page) Order f Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs-6- 594391 γ Α7 _Β7_ .. V. Description of the invention (4) The enhanced chemical photoresist composition for liquid crystal elements has excellent characteristics such as low price, excellent resolution, excellent sensitivity, and low film loss, and completed the present invention. (Please read the notes on the back before filling this page) That is, the present invention provides a phenolic lacquer type with (A) alkali solubility range of 2.38% by mass of tetramethylammonium hydroxide aqueous solution from 37.5 to 100 nm / sec. Alkali-soluble resin made of resin, (B) Compounds that generate acid by radiation and (0 cross-linkable polyvinyl ester compounds, (A) to (C) components are dissolved in organic solvents to enhance the chemical properties of liquid crystal elements. A positive photoresist composition. The present invention also provides a liquid crystal element with a chemically enhanced positive photoresist composition, such as a liquid crystal element, which is coated with a film, and after drying, it is exposed through a patterned mask and exposed. The photoresist pattern for the liquid crystal element obtained after the heat treatment followed by the alkali development step. About (A) component: (A) component printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs must be used at 23 ° C. Alkali-soluble resin made of phenol-formaldehyde lacquer-type resin with a mass-soluble tetramethylammonium hydroxide (TMAΗ) aqueous solution in an alkali solubility range of 37.5 to 100 nm / sec. Its ideal range is 50 to 75 mm / Seconds. Above 100 nm, After that, the film loss of the unexposed part is large. When it is less than 37.5, scum is likely to be generated and the image formation is difficult. Moreover, this number is based on the solubility test tree of a predetermined thickness on the substrate, which is 2.38. The time required for the mass% TMAH solution to be impregnated and the film to be zero divided by the initial thickness of the above-mentioned alkali-soluble resin is used to test the alkali-solubility of the soluble resin per unit time. Alkali-soluble resins are not particularly soluble if they have the aforementioned definition Made by jp. For example, conventional film-forming materials commonly used in positive-type light compositions, such as the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -7- 594391 A7 B7 V. Description of the invention (14) (Please read the precautions on the back before filling this page) 100 parts by mass (A) ingredients, 3 parts by mass (B) ingredients, 4 parts by mass (C) ingredients, 0.1 parts by mass (D) ingredients, and 0.04 parts by mass non-ionic Fluoro-silicone surfactant (trade name MEGAFACK R-08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.)) is dissolved in 395 parts by mass of propylene glycol monomethyl ether acetate, and is prepared to enhance chemical properties for liquid crystal elements. The photoresist composition is shown in Table 1. Comparative Example 1 (naphthoquinonediazide-based photoresist) The composition of the positive-type photoresist composition for enhancing the chemical properties of the liquid crystal element of Example 1 was changed as follows, Each characteristic was evaluated in the same manner as in Example 1. 35 mole% m-cresol and 65 mole% P-cresol were added to oxalic acid and formalin, and a cresol formaldehyde novolac lacquer resin having a weight average molecular weight of 4000 was obtained through a condensation reaction. As an alkali-soluble resin component, the alkali solubility of the 2.38% by mass TMAH aqueous solution of this resin is 50 nm / sec. With 1 mole 2,3,4,4'-tetrahydroxybenzophenone and 2.4 mole The esterified product of naphthalene 1,2-quinone azide-5-sulfonic acid chloride is used as a photosensitive component. 100 parts by mass of the resin, 25 parts by mass of the photosensitive component, and 10 parts by mass of the (4-hydroxy-2,3,5-trimethyl) Phenyl) -2-hydroxyphenylmethane, 0.04 parts by mass of a non-ionic fluorine-silicone surfactant (trade name MEGAFACK R-〇8 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.)) The ether ether acetate is dissolved to prepare a positive chemical-resistance-enhancing composition for a liquid crystal element. The results are shown in Table 1. Comparative Example 2 (Three-component positive photoresist with enhanced chemical resistance) The paper size applies the Chinese National Standard (CNS) A4 specification (210'〆297 mm) -17- 594391 A7 __ B7 V. Description of the invention (16) « [Table 1] Limit resolution (" m) Sensitivity (mJ / cm2) Film loss (βτη) Photoresist film pattern size (βΙΤλ) Prebaking limit (/ ζιή / ° 〇 Development limit (" m / 20 seconds) Peelability (minutes) Example 1 1.3 10 0.064 2Ό 0.12 0.04 2 Example 2 1.3 30 0.060 2.0 0.08 0.03 2 Comparative Example 1 1.5 18 0,162 3.0 0.41 0.75 10 Comparative Example 2 2.5 12 0.07 3.5 1.14 0.70 2 (Please read the back first Please note this page and fill in this page) i # From Table 1, you can see that any of the items, Examples 丨 and 2 are better than Comparative Examples 1 and 2. In the field of commercial use, the enhanced chemical resistance of the liquid crystal element of the present invention is positive. The photoresist pattern for liquid crystal elements of the photoresist composition has the following effects: (1) Three characteristics of high resolution, high sensitivity, and reduced film loss. The conventional naphthoquinonediazide-based non-enhanced chemical positive type Photoresistance, which has an abnormal relationship that the film loss becomes larger when the sensitivity is high. There are difficulties for both. According to the present invention, both can be satisfied. Moreover, according to the composition of the present invention, a high limit resolution can be achieved. Both Examples 1 and 2 have a limit resolution of 1 · 3 // m. Moreover, the conventional naphthoquinone The high-resolution resolution of the azide-based non-enhanced chemical positive photoresist is 1.4 // m. Moreover, the high-resolution resolution of the three-component system-enhanced chemical positive photoresist is 2.5 // m 〇 (2) Improve the light The rectangularity of the resistance pattern. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm),? 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Claims (1)

594391 8 8 8 8 ABCD 6. Scope of Patent Application 1 Annex 4: Patent Application No. 9 1 1 1 6898 Chinese Application for Patent Scope Amendment August 15th, 1992 Amendment 1. A type of positive chemically enhanced liquid crystal element The photoresist composition is characterized by dissolving the following components (A) to (C) in an organic solvent: (A) The alkali solubility range for a 2.38 mass% tetramethylammonium hydroxide aqueous solution is 37.5 to Alkali-soluble resin made of 100 nm / sec phenol-formaldehyde lacquer-type resin, with respect to (A) component. 100 parts by mass of 1 to 30 parts by mass (B) Compounds that generate acid by irradiation with radiation, and (A) component 100 parts by mass is 0.25 to 25 parts by mass of (C) a crosslinkable polyvinyl ester compound. 2. The enhanced chemical positive photoresist composition for a liquid crystal device as described in the first item of the patent application, wherein the solubility range of the component (A) to a 2.38% by mass tetramethyl hydroxide aqueous solution is 50 to 75. nm / sec. formazan | ridge lacquer type resin. 3. For example, the enhanced chemical positive photoresist composition for liquid crystal elements in the first patent application scope, wherein (B) component is irradiated g-line (436 nm), h, line (405 nm) and i-line ( 3 6 5 nm) produces an acidic compound. 4. The enhanced chemical positive photoresist composition for a liquid crystal element according to item 1 of the patent application scope, in which the component (C) is a part or all of the hydroxyl groups shared by the general formula (I) shown below. Vinyl etherified compound: R η-(OH) η (I) (In the formula, R n is a group in which η hydrogen atoms are removed from a hydrocarbon containing a linear group, a branched group, or a ring · group, η Is an integer of 2, 3 or 4). This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -1-(Please read the precautions on the back before filling out this page) • 1Τ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative 594391 ABCD ^, application Scope of patent 2 5. If the scope of patent application is Type 1 photoresist composition, which further contains 0.0 1 to 5 parts by mass of amines as the scope of patent application. pattern. The enhancement chemical property of the liquid crystal element of the item is that the (D) component is blended with 100 parts by mass of the (A) component. Any of the ~ 5 items of the liquid crystal element is used for manufacturing the liquid crystal element light ---------- ^ ------ II ------ ^ (Please read the back first Please pay attention to this page, please fill out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with China National Standard (CNS) A4 (210X297 mm) -2-