TWI304918B - Positive photoresist composition for manufacturing lcd and method for forming resist pattern - Google Patents

Description

1304918 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a method of forming a positive-type photoresist composition for a LCD and a photoresist pattern. [Prior Art] Up to now, when a liquid crystal display (LCD) in which a liquid crystal display portion is formed on a glass substrate is manufactured, it is relatively inexpensive, or has excellent sensitivity, resolution, and shape, and is often used as a semiconductor device. A positive resistive composition of a series of phenolphthalein-containing lacquer-containing compounds containing a phenylhydrazine diazide group. However, for example, in the manufacture of semiconductor components, a disk-type germanium wafer having a diameter of 8 Å (about 200 mm) to 12 Å (about 300 mm) is used, but in comparison, in the manufacture of the LCD, the minimum is There are also square glass substrates of 3 60mm x 460mm. Thus, in the field of LCD manufacturing, the substrate on which the photoresist is applied is of course different in material or shape, but in terms of its size, it is quite different from that used in the manufacture of semiconductor elements. Therefore, the photoresist material for LCD manufacturing requires a photoresist pattern having excellent characteristics such as shape and dimensional stability for a wide substrate surface. Further, in the manufacture of an LCD, since a large amount of photoresist material is consumed, a photoresist material for LCD manufacturing requires a low cost consideration in addition to the above characteristics. To date, there have been many reports on photoresist materials for LCD manufacturing (Example (2) 1304918, for example, Patent Documents 1 to 6 below). The photoresist materials described in Patent Documents 1 to 6 are inexpensive, and are excellent in coating properties such as sensitivity, resolution, shape, and dimensional stability, for example, on a small substrate of about 6,000 mm x 460 mm. Photoresist pattern. Therefore, it is suitable for use in the purpose of manufacturing a relatively small LCD. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9- 1 0 0 2 3 1 [Patent Document 2] Japanese Patent Laid-Open No. Hei 9-2 1 1 8 5 5 [Patent Document 3] Japanese Patent Laid-Open No. 2 0 0 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-131835 (Patent Document 5) Japanese Patent Laid-Open No. 2000-180 6] 曰 专利 2 2 2 2 2 2 2 发明 发明 发明 发明 发明 发明 发明 [ 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人 个人Etc., the demand for large LCDs has increased. Moreover, there is a need to improve the manufacturing efficiency of LCDs due to the low price of LCDs. Therefore, in the field of manufacturing of LCDs, a photoresist material having a sensitivity of about 3 〇 to 5 OmJ is required from the viewpoint of improvement in yield ((3) 1304918 throughput per unit time) and process control. Further, from the viewpoint of an increase in the yield (the amount of treatment per unit time), it is necessary to maximize the exposure area to at least 100 mm 2 . In general, in the manufacture of LCDs, it is considered preferable to use ΝΑ (the number of openings of the lens), for example, at 0.3 or less, particularly at a low ΝΑ condition of 〇·2 or less. However, in the case of an exposure process with a low-lying condition, in the conventional photoresist material for LCD manufacturing, for example, under a low-lying condition of 〇·3 or less, a photoresist pattern having excellent shape is formed with high resolution. The difficulty exists, that is, in general, the resolution (resolution boundary) can be expressed as the following formula: R = k, x λ / ΝΑ [where R is the resolution boundary 'h is due to photoresist or process 'The proportional constant determined by the formation method is the wavelength of the light used in the exposure process, and NA indicates the number of apertures of the lens.' indicates that 'the resolution can be improved by using a light source with a short wavelength λ or a high-temperature exposure process. . For example, the resolution can be improved without using a g-line (4 3 6 n m ) ' used for L C D fabrication and photolithography using a shorter wavelength i-line (365 nm) exposure. However, in the manufacture of an LCD, as described above, a high NA of an exposure area which is narrowed is not suitable, and it is desirable to use an exposure process under a low NA condition. Therefore, it is difficult to obtain high resolution. Furthermore, as a new generation of LCDs, it is now prevalent in a glass-based (4) 1304918 board to form a driver at the same time as the display part, DAC (Digital-Analog Converter, digital analog converter, image processor 'video controller' RAM (Random Access Memory) is a so-called "system LCD" technology development for high-performance LCDs (Semiconductor Flat Panel Display (FPD) World, September 2001, pp. 50-67). At this time, on the substrate In addition to the display portion, the integrated circuit portion is formed, and the substrate tends to be larger. Therefore, exposure under a lower NA condition than that in the conventional LCD manufacturing is required. In the system LCD, for example, the display portion has a pattern size of 2 to 10 μηα, and the integrated circuit portion is formed with a fine size of about 0.5 to 2.0 μm. Therefore, it is preferable to form 0.5. A photoresist pattern of up to 2.0 μm, which requires a high-resolution photoresist material for LCD manufacturing materials. However, due to the photoresist materials used in LCD manufacturing, It is difficult to use it as a system LCD in low NA conditions, and it is difficult to use it as a system LCD. For example, under a low NA condition of 0.3 or less, it is difficult to form a fine photoresist having an excellent shape, for example, 2.0 μm or less. In the case of the pattern, the resulting resist pattern is non-rectangular and has a tendency to be tapered. Specifically, for example, Japanese Patent Laid-Open Publication No. Hei. No. 2-75 2 72 discloses the inclusion of an alkali-soluble resin and sensitization. Sexual component' does not contain a photoresist for liquid crystals of Sensitizer. However, the photoresist for liquid crystals is not suitable for ig exposure, and it is difficult to form a photoresist pattern of 2.0 μm or less which is required for system LCD manufacturing. Problem (5) 1304918 Thus, as a manufacturing process of the system LCD, it is desirable to have a photoresist material suitable for i-line exposure, for example, a fine photoresist pattern excellent in shape even under a low NA condition of 0.3 or less. That is, the present invention provides sensitivity with a degree of 3 〇 to 50 mJT, and excellent resolution under low NA conditions. It is suitable for LCD manufacturing in which an integrated circuit and a liquid crystal display portion are formed on one substrate. The method of forming a positive-type photoresist composition and a photoresist pattern of a photoresist material is a problem. [Means for Solving the Problem] In order to solve the above problems, the positive-type photoresist composition for LCD of the present invention It is characterized by: (A) alkali-soluble resin, (2) average esterification ratio of low molecular weight phenolic enamel resin and naphthoquinonediazidesulfonic acid compound with a mass average molecular weight of 300 to 130 00. In the case of 30 to 90% of the esterification reaction product, (C) a compound having a phenolic hydroxyl group having a molecular weight of 1 000 or less, an organic solvent is used. The positive resistive composition for the LCD is suitable for use as a positive resistive composition for LCDs for i-line exposure processes. In addition, it is suitable for a positive-type photoresist group for LCDs with an exposure process of NA of 0.3 or less. Further, it is suitable as a positive resistive composition for LCD for LCD manufacturing in which an integrated circuit and a liquid crystal display portion are formed on one substrate. 9-(6) 1304918 In the description of the present invention The system LCD is intended to mean "an LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate". Further, the method for forming a photoresist pattern of the present invention is characterized in that: (1) a process of applying the above-described positive-type photoresist composition of the present invention to a substrate to form a coating film, (2) forming the above-mentioned The substrate of the coating film is subjected to heat treatment (Prebake 'prebake') to form a photoresist film on the substrate, and (3) the photoresist film is selected by using a mask patterned with a mask pattern. (4) a process of performing post-exposure bake (post-exposure bake) on the photoresist film after the selective exposure, and (5) using the resist film after the heat treatment The development process of the aqueous alkali solution to form a photoresist pattern on the substrate (6) is a rinse process in which the developer remaining on the surface of the resist pattern is washed away. Further, in the process of performing the above (3) selective exposure, a mask pattern for forming a photoresist pattern of 2.0 μm or less and a photoresist pattern of 2.0 μm or more are used as the mask ′. In the process of forming the (5) photoresist pattern at the same time, the photoresist pattern for the integrated circuit of the pattern size 2. 〇μηη can be simultaneously formed on the substrate. Types of photoresist patterns used in the '' and liquid crystal display parts below 2.0 μηη. (7) 1304918 [Effect of the Invention] When the positive resist composition for a liquid crystal of the present invention and the method for producing a resist pattern are used, a good resolution can be obtained even under a low NA condition, and it can be used as a system. LCD manufacturing is very suitable. [Embodiment] [Embodiment of the Invention] [Positive photoresist composition for LCD] φ < (A) component > (A) component 'is not particularly limited, but may be from a positive photoresist composition In general, one or two or more kinds of the film-forming materials can be used. For example, phenols (phenol, m-cresol, p-cresol, xylene oxime, trimethylphenol, etc.), aldehydes (formaldehyde, formaldehyde precursor, 2-hydroxy-benzaldehyde, 3-hydroxybenzoic acid) Wake up '4-hydroxybenzaldehyde, etc.) and/or ketones (methyl ethyl ketone, acetone, etc.) to obtain a phenolic enamel resin obtained by condensation in the presence of an acidic catalyst; Or a copolymer of hydroxystyrene with other styrenic monomers, a hydroxystyrene resin such as a copolymer of hydroxystyrene with acrylic acid or methyl propyl succinic acid or a derivative thereof; itself is acrylic acid or methacrylic acid A copolymer of a derivative such as a propionic acid or a methacrylic resin. In particular, a novolac resin obtained by condensation reaction of a phenol containing m-cresol and p-cresol with an aldehyde containing formaldehyde is suitable for adjusting a photoresist having high sensitivity and excellent resolution. -11 - (8) 1304918 (A), which can be manufactured according to the usual method. (A) The polystyrene-converted mass average molecular weight of the component by gel permeation chromatography varies depending on the type, but it is from 2,000 to 100,000, preferably from 3,000 to 20,000 in terms of sensitivity or pattern formation. . <(B) component> (B) The average of the low molecular weight phenolphthalein lacquer resin and the naphthoquinonediazidesulfonic acid compound having a mass average molecular weight (hereinafter, abbreviated as Mw) of 300 to 1 300 in terms of polystyrene The esterification reaction product is an esterification reaction product of 30 to 90%, and may be used alone or in combination of two or more of the esterification reaction products. Here, the polystyrene-converted mass average molecular weight is measured by, for example, GP C (gel permeation chromatography). In the low-molecular-weight phenolic enamel paint, for example, those having an adjusted average molecular weight in the alkali-soluble novolac lacquer resin similar to those used in the above (A) component can be used. The Mw of the low molecular weight phenolic enamel resin is from 300 to 1 300, the lower limit is preferably more than 350, and the upper limit is preferably more than 700. If the mass average molecular weight is adjusted to this range, it is possible to provide a photoresist material which is highly sensitive and excellent in resolution and suitable for i-line exposure processes under low NA conditions. When the mass average molecular weight is adjusted to the above range, the following three methods can be exemplified. (i) a phenolic enamel resin having a Mw of from about 2,000 to 30,000, obtained by a condensation reaction between a desired phenol and an aldehyde and/or a ketone, using a fraction of -12-(9) 1304918 to select a low molecular weight region and a high A well-known sorting operation of the molecular weight region can be obtained by taking out a portion of the low molecular weight region. In addition, in the synthesis of the alkali-soluble novolac resin of the component (A), the general technical knowledge is to use a sorting operation to selectively take out a high molecular weight field, and to prepare such a low molecular weight phenolic enamel resin. The sorting operation is different only in the case where the object to be selectively taken out is a low molecular weight, and the rest can be applied to the same operation. (ϋ) In the condensation reaction between the desired phenols and aldehydes and/or ketones, the Mw of the condensate in the reaction solution is successively measured during the reaction, for example, Mw reaches 300 to 1300. When the reaction is terminated in the range, it can be obtained. In addition, if the various raw materials used for the synthesis, the type of the catalyst, or the amount and ratio thereof, and the reaction conditions (solution concentration, reaction temperature, mixing means of various raw materials, etc.) are the same, such as measuring the Mw in the reaction, the next synthesis In the case of the same low molecular weight phenolic resin, it is only necessary to control the reaction time to obtain the desired Mw. (iii) condensing a desired phenol with an aldehyde and/or a ketone in the presence of an acidic catalyst or a basic catalyst to synthesize a low molecular phenolic compound of 2 to 4 nucleus or a dihydroxyl group of the compound A methyl group (abbreviated as "phenol A") can be obtained by reacting a hydroxymethyl group-containing phenol or a hydroxymethyl group-free phenol (referred to as "phenol B"). The reaction between benzoquinone A and benzoquinone B is controlled so that the Mw can be in the range of 3 Torr to 1 30,000. For example, the reaction time can be controlled. Here, the above-mentioned control can be easily carried out by adding a solution containing a low concentration of phenol B in a small amount of a solution containing a high concentration of phenol A per non-13-(10) 1304918. Further, the ratio of the phenol to the aldehyde and/or the ketone may be appropriately adjusted depending on the intended compound and the synthesis means, but may be, for example, 1 : 1 to 2 : 1 (mole ratio). The (B) component is particularly suitable for the following two types ((i) and (ii), and it is suitable from the viewpoint of effect. (i) As a phenol, only a bifunctional phenol compound is used. An aldehyde and/or a ketone (preferably formaldehyde only) is used as a condensing agent to synthesize it. (Π) As a phenol, only a bifunctional phenol compound and a monofunctional phenol compound are used, and an aldehyde is used as a condensing agent. And/or ketones (preferably formaldehyde only) are synthesized. The above "functional group" refers to the presence of sites (2, 4, 6) where phenols react with aldehydes and/or ketones. The number of hydrogen atoms (that is, the reaction with the aldehydes and/or the ketones) means the above-mentioned bifunctional phenol compound, which can be represented by the following general formula (I).

OH

R3 (wherein R1 to R5 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms' and 2 of R1, R3, m and R5 are a hydrogen atom, and 1 is a carbon atom number 1 The alkyl group of 5 to 5). In the bifunctional phenol compound, the alkyl group having 1 to 5 carbon atoms (preferably 1 to 14 to 1304918 3 and preferably a methyl group) may be linear or branched. Chained. Further, in the case of R1, R3 and R5, the position at which the alkyl group is bonded is not preferable. The bifunctional phenol compound is preferably inexpensive, and has excellent properties, and is preferably o-cresol, p-cresol, 2'. 5-xylenol, 3,4-xylene oxime, 2,3,5-trimethylphenol. The above-mentioned monofunctional phenol compound can be represented by the following general formula (Π)

(wherein R11 to R15 are each independently a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and one of Rn, R13, and R15 is a hydrogen atom, and 2 are 1 to 5 carbon atoms; In the monofunctional phenol compound, the alkyl group having 1 to 5 (preferably 1 to 3, more preferably methyl) carbon atoms may be linear or branched. Further, in R11 'RJ3 and Ri5, the position at which the alkyl group will be bonded is not good or bad. The monofunctional phenol compound is preferably 2,4-xylenol or 2,6-xylenol because it is inexpensive and excellent in properties. Further, in the above (i), since the characteristics are excellent, the bifunctional phenol compound: aldehyde and/or ketone (preferably formaldehyde) is used in an amount of from 1:1 to 2:1 (mole ratio). -15- (12) 1304918 In the above (ii), the bifunctional phenol compound: 1-functional phenol compound is based on 1 〇: 1 to 1: 1 〇', preferably 5: 1 to 1: 5 (Morbi) is used. The total of phenols is excellent in the characteristics: aldehydes and/or ketones (preferably formaldehyde) are used in a ratio of 1:1 to 2:1 (mole ratio). The method for synthesizing the low molecular weight phenolic enamel resin of the above (ii) includes a solution of a dihydroxymethyl group of a bifunctional phenol compound obtained by a usual method, and a solution of a monofunctional phenol compound in an acid catalyst. a method of performing a condensation reaction in the presence of a two-functional phenol compound, a condensation reaction product with an aldehyde and/or a ketone, a solution of a monofunctional phenol compound, and a condensation reaction in the presence of an acid catalyst, Wait. The above 1 is suitable for the synthesis of a low molecular weight phenol resin containing three or less benzene rings, and the above 2 is suitable for the synthesis of a low molecular weight phenol resin containing four or more benzene rings. Next, an esterification reaction of such a low molecular weight phenolic enamel resin with a naphthoquinonediazidesulfonic acid compound can be carried out to obtain an esterification reaction product having an average esterification ratio of 30 to 90% [(B) ingredient]. The naphthoquinonediazidesulfonic acid compound can be used in one or two or more kinds from the general use of the positive-type resist composition. The method of the esterification reaction is not particularly limited, and a known reaction can be used. For example, naphthoquinonediazidesulfonium chloride is condensed with a low molecular weight phenolic enamel resin. Specifically, naphthoquinone-1,2-diazide-4 (or 5)-opening chlorine is condensed and reacted with a low molecular weight ruthenium resin. Specifically, 将 'Jing Cai Shipu 1 ' 2 — _ _ nitrogen - 4 (or 5) - expanded chlorine, and low score -16 - (13) 1304918 phenolic resin is quantitatively dissolved in dioxane, orthodontic In an organic solvent such as pyrrolidone, dimethylacetamide or tetrahydrofuran, an alkaline catalyst such as triethylamine, triethanolamine, pyridine, alkali carbonate or hydrogencarbonate is added to cause a reaction to "wash the resulting product with water". ' Dry can be obtained. The average esterification ratio of the esterification reaction product obtained in this manner is from 30 to 90%, preferably from about 40 to 70%. If it is made at 30% or more, a contrast pattern excellent in contrast can be formed. On the other hand, if it is made 90% or less, the decrease in sensitivity can be prevented. If it exceeds 90%, it may cause significant sensitivity degradation, which may not be suitable for positive resistive compositions for LCDs, even for system L C D. The esterification ratio can be adjusted by changing the ratio of the ratio of the low molecular weight novolac resin to the naphthoquinonediazidesulfonic acid compound or the reaction time of the esterification reaction. Here, the ratio of the low molecular weight phenolic enamel resin and the naphthoquinonediazide sulfonic acid compound is determined to be naphthoquinone in the low molecular weight phenolic enamel resin by adjusting the esterification rate. The diazide sulfonic acid compound is from 0.3 to 0.9 mol, preferably from 0.4 to 0.7 mol. Here, the component (B) is a so-called photosensitive component. In the positive resist composition of the present invention, in addition to the component (B), other naphthoquinonediazide compounds generally used in the positive resist composition can be used. For example, an esterification reaction product of a phenol compound such as polycarbonyl benzophenone or an alkyl carbamate with a naphthoquinonediazidesulfonic acid compound can also be used. However, in order to prevent the effects of the present invention from being affected, the amount of use is -17·(14) 1304918, and the total photosensitive component containing the component (B) is '50% by mass or less', preferably 20% by mass. the following. In the positive resist composition, the total amount of the photosensitive component containing the component (B) is preferably 10 to 70 by mass in the total amount of the alkali-soluble resin of the component (A) and the component (C) below. It is preferably selected in the range of 20 to 60% by mass. Further, the amount of the component (B) in the photosensitive component is set to be 50% by mass or more and preferably 80 to 100% by mass. If the amount of the component (B) is set to a lower limit or more, the image drawn to the vacuum of the pattern can be obtained, and the transcription can be improved. When the blending amount of the component (B) is made the upper limit or more, the deterioration of the sensitivity can be prevented, and the homogeneity of the resist film formed from the positive resist composition can be improved to improve the resolution. <(C) Component> The component (C) is preferably a non-benzophenone-based phenolic hydroxyl group-containing compound. By using such a component (C), the sensitivity improvement effect is excellent, and even in the i-line exposure process under low NA conditions, the sensitivity is high sensitivity and high resolution, and is suitable for the material of the system L C D . The molecular weight of the component (C) is preferably 1,000 or less in view of the above effects, and is preferably 700 or less, and is substantially 200 or more, preferably 300 or more. The component (C) is generally a compound containing a phenolic hydroxyl group as a photoresist composition, preferably a condition which satisfies the above molecular weight, and is not particularly limited, and may be optionally selected or Two or more types are used. Moreover, -18-(15) 1304918, wherein the following general formula (IV) is preferred

R R ‘ 39 (HO)

(〇H)b (IV) [wherein R31 to R3 8 represent independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or carbon a cycloalkyl group having 3 to 6 atoms; R 4 G and R 41 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and when R 3 9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, (^ Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a residue represented by the following chemical formula (V)

(V) (wherein R42 and R43 represent independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbon number of 3 to 6; a cycloalkyl group; c represents an integer of 1 to 3) or alternatively, the q system is bonded to the terminal of the r39 and together with the carbon atom between R39 and Q and r39 to form a cycloalkyl group having a carbon chain of 3 to 6; An integer representing from 1 to 3; d represents an integer from 〇 to 3; η represents an integer from 〇 to 3] Here, as with a carbon atom between Q and R39, a carbon chain is formed 3 to 6 -19- (16) In the case of a cycloalkyl group of 1,304,918, Q and R39 are bonded to each other to form an alkylene group having 2 to 5 carbon atoms. The phenol compound corresponding to the above general formula (IV) is exemplified by: (4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis ( 4-hydroxy- 2,3,5-trimethylphenyl)- 2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-tetrahydroxyphenylmethane, bis ( 4-hydroxy- 3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, double (4 Hydroxy- 2,5-dimethylphenyl)-tetrahydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxyl- 2,5-Dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)- 3,4-dihydroxyphenylmethane, bis(4-hydroxyl) a 2,5-dimethylphenyl)- 3,4-dihydroxymethylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, double (4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, double (4 Hydroxyphenyl) 4-tetrahydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, Bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-12 a phenolic compound such as hydroxyphenylmethane; 2,4-bis(3,5-dimethyl-4-tetrahydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-dimethyl a linear 3-nuclear phenol compound such as 4-tetrahydroxybenzyl)-tetramethyl phenol; 1,1 pair of [3 -( 2 -hydroxy-5-methyl-20-(17) 1304918-benzyl)- 4 Hydroxy-5-cyclohexylphenyl]isopropane, bis[2,5-dimethyl-3-(4-mono-amino-5-methyl-carbyl)- 4-phenyl-phenyl], double [2, 5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy--5- Methylphenyl]methane, bis[3-(3,5-dimethyl-1,4-hydroxybenzyl)-4 5-O-ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3—(3 , 5-diethyl-1,4-hydroxybenzyl)- 4-hydroxy-5-ethylphenyl]methane, bis[2-amino- 3-(3,5-monomethyl-4)-based hydrazine (5)-methylphenyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methyl-based] (2 - thiol 5-methylbenzyl) 5-methylphenyl]methane, bis[2,5-dimethyl-3-2-2-hydroxy-5-methylbenzyl)-4-hydroxybenzene Linear 4-nuclear phenolic compound such as methane; 2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexanol, 2,4 pair [4-hydroxy 3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexanol, 2,6-bis[2,5-dimethyl-3-(2-hydroxyl) Linear polyphenolic compound of linear 5-nuclear phenolic compound such as 5-methylbenzyl)-4-tetrahydroxybenzyl]-4-methylphenol; double (2,3,4 Trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl- 4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyl Phenyl)-2-(2',3,4'-trishydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl) Propane '2-(3-fluoro-1,4-hydroxyphenyl)-2-(3'-fluoro- 4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2 -21 - (18) 1304918 (4'-hydroxyphenyl)methane, 2-(2,3,4-trihydroxyphenyl)-2(4'-hydroxyphenyl)propane, 2-(2,3 , bisphenolic compound such as 4,3-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane; 1-[1 -(4-hydroxyphenyl)iso Propyl]- 4-u, 丄-bis(4-monophenyl)ethyl]benzene, 1-[1 -(3-methyl-4-tetraphenyl)isopropyl]- 4-[1, 1-mono(3-methyl-4-hydroxyphenyl)ethyl]benzene, a multinuclear branched compound; 1,1 bis(4-hydroxyphenyl) And condensed type compounds such as hexane. These may be used alone or in combination of two or more. Among them, preferred is 1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene. The blending amount of the component (C) is, in terms of effect, in the range of 10 to 70% by mass, preferably 15 to 60% by mass in the component (a). <Component (D)> (D) is not particularly limited as long as it is used in the general composition of the photoresist composition, and may be selected from one or two or more types, and is excellent in coating properties in large glass. In view of excellent film thickness uniformity of the photoresist film on the substrate, propylene glycol monoalkyl ether acetate and/or alkyl lactate are preferred. Propylene glycol monoalkyl ether acetate, for example, a linear or branched chain alkyl group having 1 to 3 carbon atoms, wherein the film thickness uniformity of the photoresist film on a large glass substrate is excellent For this reason, propylene glycol monomethyl ether acetate (hereinafter, abbreviated as PGMEA) is particularly preferred. The alkyl lactate may, for example, be methyl lactate or ethyl lactate (hereinafter referred to as '-22-(19) 1304918 for short). Among them, ethyl lactate is preferred, and when a large glass substrate of 500 mm χ 600 mm or more is used, coating streaks tend to occur. Therefore, it is preferably used in a mixture with other solvents which can suppress such disadvantages. From the above effects, the amount of the propylene glycol monoalkyl ether acetate is preferably from 2 to 1% by mass in the component (D). From the above effects, the amount of the alkyl lactate to be added is preferably from 20 to 100% by mass in the component (D). In addition, when the component (D) containing both propylene glycol monoalkyl ether acetate and alkyl lactate is used, it is possible to obtain a photoresist pattern having excellent film uniformity of the photoresist film and excellent shape, and heat resistance. It is also better to suppress and suppress the occurrence of scum. In the case of a mixture of propylene glycol monoalkyl ether acetate and alkyl lactate, the propylene glycol monoalkyl ether acetate is used in an amount of from 0.1 to 10 times, preferably from 1 to 5 times by mass. Amount of lactate. Further, 2-heptanone (hereinafter abbreviated as HE) is also a suitable organic solvent. Although it is not particularly limited, as described above, it is a solvent which is suitable when combined with a non-benzophenone-based photosensitive component. 2-Heptone is a solvent which is excellent in heat resistance compared to PGMEA and has a characteristic of a photoresist composition which reduces scum generation. 2 - heptanone, from the above effects, it is preferably 20 to 100% by mass in the component (D). Further, the "specifically" other organic solvents which can be blended can be exemplified as follows. -23- (20) 1304918, ie, butyrolactone; propylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone; ethylene glycol, Propylene glycol 'diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or one of these methyl ether, diethyl ether, monopropyl ether, monobutyl ether or Polyols such as monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and methyl acetate, ethyl acetate, butyl acetate, methyl acetate, ethyl pyruvate, methoxy An ester of methyl propyl propionate, ethyl ethoxy propionate or the like. # When using such a solvent, the component (D) is preferably 50% by mass or less. The positive-type resist composition of the present invention may contain an additive which is compatible as needed, for example, an additive resin for improving the performance of the photoresist film, etc., within a range not impairing the object of the present invention. A plasticizer, a storage stabilizer, a surfactant, a coloring material for making the image of the developed image more visible, a sensitizer or a halation for enhancing the sensitization effect, preventing the dye, and bonding Additives such as sex improvers and the like. ® For the light-preventing dye, a UV absorber can be used (for example, 2,2',4,4'-tetrahydroxybenzophenone, 4-dimethylamino- 2', 4'-dihydroxyl Benzophenone, 5-amino-3-methyl-1 1-phenyl-4-(4-hydroxyphenylazo)pyrazole, 4-dimethylamino- 4, monohydroxy azo Alkylbenzene, 4-diethylamino- 4'-ethoxy azobenzene, 4-diethylamino azobenzene, curcumin, etc.). The surfactant may be, for example, a stripe prevention or the like, and for example, Fluorat FC - 4 3 0, FC - 4 3 1 (Commodity-24-(21) 1304918, Sumitomo 3M may be used. (Fly) system, Effort EF 122A, EF 122B, EF 122C, EF 126 (trade name, manufactured by Toki Chemical Co., Ltd.), etc., fluorine-based surfactant, R - 〇8 (trade name, large Japanese ink chemical industry (shares) system, etc. The positive resist composition of the present invention is preferably prepared by dissolving (A) component, (B) component, (C) component, and other components as needed in (D) an organic solvent. Here, the amount of the component (D) is preferably such that the components (A) to (C) and other components used as needed are dissolved, and can be appropriately adjusted in such a manner that a uniform positive resist composition can be obtained. . It is preferably used in such a manner that the total solid component concentration can be from 1 to 40% by mass, more preferably from 20 to 30% by mass. [Method of Forming Photoresist Pattern] The following 'an example of a formation pattern which is a suitable pattern of the photoresist pattern in the manufacture of an LCD is shown. First, the positive resist composition of the present invention described above is applied onto a substrate by using a centrifugal spinner or the like to form a coating film. The substrate is preferably a glass substrate. As the glass substrate, amorphous amorphous silica is usually used, but in the field of system LCD, it is considered that low temperature polycondensation is preferable. In such a substrate, since the positive resist composition of the present invention is excellent in resolution under low NA conditions, a large substrate of 500 mm x 600 mm or more, particularly 550 mm x 65 mm or more can be used.

Next, the substrate on which such a coating film is formed is subjected to heat treatment (prebake) at, for example, 1 0 0 to 140 ° C -25 - (22) 1304918 to remove the residual solvent and form a photoresist film. Preferably, the prebaking method is carried out by buffing (p r ο X i m i t y b a k i n g) between the heating plate and the substrate via a gap. Further, selective exposure is performed on the photoresist film using a mask having a mask pattern. For the light source, in order to form a fine pattern, it is preferable to use an i-line (3 65 nm). Further, the exposure process employed in the exposure is preferably an exposure process in which N A is 0.3 or less, preferably 0.2 or less, and more preferably 0.15 or less. Next, the photoresist film after selective exposure is subjected to heat treatment (baked after exposure: PEB). In the PEB method, it is preferred to carry out the proximity baking between the heating plate and the substrate at intervals. For example, after the development of a developing solution using a developing solution such as a 1 to 1 〇% by mass aqueous solution of tetramethylammonium hydroxide, the exposed portion will be dissolved and removed, and the substrate will be removed. The upper layer simultaneously forms a photoresist pattern for the collective circuit and a photoresist pattern for the liquid crystal display portion. Further, the developing solution remaining on the surface of the resist pattern is washed away with a rinsing liquid such as pure water to form a photoresist pattern. In the method of forming the photoresist pattern, when the system LCD is manufactured, in the process of performing the selective exposure described above, it is preferable to use a photoresist pattern having a thickness of 2.0 μm or less as the photomask. The mask pattern and the photoresist pattern of 2.0 μm or more form a mask for both of the mask patterns. Therefore, since the positive-type photoresist composition of the LCD of the present invention is excellent in resolution, a photoresist pattern -26-(23) 1304918 having a fine pattern of a vacuum-reproducing photoresist pattern can be obtained. Therefore, in the process of simultaneously forming the above-mentioned photoresist pattern, a photoresist pattern for an integrated circuit having a pattern size of 2.0 μπ or less and a photoresist for a liquid crystal display portion of 2.0 μm or more can be simultaneously formed on the substrate. Graphic type. As described above, the positive resist composition of the present invention is suitable for an exposure process under low enthalpy conditions. Also, it is suitable for the exposure process. Therefore, at least at the time of manufacture of the LCD, a photoresist pattern of at least a portion of the display can be produced with high resolution. Further, since the positive resist composition of the present invention is excellent in resolution even under low NA conditions, a rough pattern and a fine pattern can be formed on one substrate under the same exposure conditions. Therefore, even in the case of low NA, the display portion of the system LCD can be simultaneously produced with high resolution, and the photoresist pattern of the integrated integrated circuit portion can be used as a system LCD. The positive-type photoresist composition for LCD is generally considered to be highly sensitized in terms of improvement in manufacturing efficiency and improvement in productivity, and can be made practical in this respect. Moreover, it also has the effect of producing less scum. Further, if the method for forming a photoresist pattern of the present invention using the positive resist composition having excellent resolution under low NA conditions is employed, the yield in LCD manufacturing can be improved. Further, according to the method for forming a photoresist pattern of the present invention, a high resolution photoresist pattern can be formed during exposure to a low N A condition suitable for LCD manufacturing. In particular, since a photoresist for an integrated circuit having a pattern size of 2.0 μm or less can be simultaneously formed on a substrate, and a photoresist pattern for a liquid crystal display portion of, for example, 2.0 μηι -27-(24) 1304918 or more can be formed at the same time. It is very suitable for the manufacture of system LCD. [Examples] The present invention will now be described in more detail, but the invention is not limited by the following examples. [Evaluation Method of Positive Photoresist Composition] The evaluation methods of the following physical properties (1) to (3) are described below for the positive resist composition of the following examples or comparative examples. (1) Sensitivity evaluation: A photoresist coating device (device name: TR 3 6 0 0 0 'Tokyo Chemical Industry Co., Ltd.) was used to coat a positive resist composition with a large square substrate. After the glass substrate of the Cr film (550×1000 mm), the temperature of the hot plate was set to 130° C., and the first drying was performed for 60 seconds by the proximity baking at intervals of about 1 mm, and then The temperature of the hot plate was set to 120 ° C, and drying was performed for the second time of 60 seconds by the proximity baking of 0.5 mm intervals to form a photoresist film having a film thickness of 1.5 μm. Next, a test chart mask (reticule) is formed by simultaneously drawing a mask pattern for reproducing a photoresist pattern of 0.3 μπι line and space (L&S) and 1.5 μηι L&S. The reticle is used, and the i-line exposure device (device name: FX-702J, manufactured by Nikon Corporation; ΝΑ = 0·14) is used, and the exposure amount (Εορ exposure amount) of 3_0μηι L&S can be reproduced realistically. 28- (25) 1304918 Selective exposure. Then, using a developing device having a long coater nozzle (device name: TD-3 900 demonstration machine, manufactured by Tokyo Ohka Kogyo Co., Ltd.), 2.38% by mass of TMA Η (tetramethylammonium hydroxide) The aqueous solution, from the substrate 纟 and the portion X through the Υ Υ ζ 耗 耗 耗 耗 耗 耗 耗 耗 耗 耗 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺 铺), a photoresist pattern of 3·0μηι L&S and a photoresist pattern of 1.5μηι L&S are simultaneously formed on the substrate. The above-mentioned Ε ο p exposure amount is expressed as sensitivity in mj units. (2) Resolving property evaluation: The boundary resolution at the above Εορ exposure amount is obtained. (3) Dross evaluation: The surface of the substrate on which 1·5 μηι L&S was drawn was observed using an SEM (scanning electron microscope) under the above Εορ exposure amount to check for the presence or absence of scum. The 记 mark indicates the result of its evaluation. 〇 : 殆 No confirmation of the presence of scum. Δ : It was confirmed that there was a slight scum present. χ : A large amount of scum is confirmed. (Preparation Example 1) As the components (A) to (D), the following were prepared. -29- (26) 1304918 (A ) Alkali-soluble phenolic enamel resin 1 〇〇 parts by mass A 1 : For m-cresol/p-cresol (mole ratio 7 / 3) mixed phenol 1 mol, use formaldehyde 0.8 The physicochemical resin obtained by Mol = 6000, Mw / Mn = 4.0 was synthesized by the conventional method. (B) Esterification reaction product (PAC 1/PAC3 = 2/1 (mass ratio)) 30 parts by mass of PAC1: Mw 1 3 00 gallicol produced as a polycondensate of pyrogallol and acetone An esterification reaction product of an acetone resin and an esterification rate of 1,2-naphthoquinonediazide-5-sulfonyl chloride (5-NQD) of 78%. PAC3: bis(2,3,5-trimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane produced as a condensate of 2,3,6-trimethylphenol and 2-hydroxybenzaldehyde (M (molecular weight) = 3 76 ) 1 Molar, an esterification reaction product with an esterification rate of 5 - NQD 2.02 mole of 67.3%. (C) Compound containing a phenolic hydroxyl group 20 parts by mass of 1-[1 -(4-hydroxyphenyl)isopropyl]-4-iso[1,1-bis(4-hydroxyphenyl)ethyl]benzene (D) ) Organic solvents

Dl: PGMEA (propylene glycol monomethyl ether acetate) The above-mentioned (A) to (C) components, and the total mass of the components (A) to (C) are equivalent to 3 5 Oppm of the surfactant (product name "R-08": manufactured by Dainippon Ink Co., Ltd.), dissolved in pGMEA which is itself a component (D), and can be 25 in terms of solid content [total of components (A) to (C)] Adjust to a mass of 28, and filter with a membrane filter of -30-(27) 1304918 μιη to prepare a positive photoresist composition. (Examples 2 to 9) and (Comparative Examples 1 to 4) In the same manner as in Example 1, except that the components (() and (C) were changed to those described in Table 1 below, the positive type was prepared in the same manner as in Example 1. Photoresist composition [Table 1]

(Β) (D) (mass ratio) 1 PAC1/PAC3(2/1) PGMEA 2 PAC2/P AC3 (2/1) PGMEA Real 3 PAC2/PAC3(l/2) PGMEA Shi 4 PAC1/PAC3(2/ 1) EL Example 5 PAC1/PAC3(2/1) EL/PGMEA(7/3) 6 PAC1/PAC3(2/1) HE 7 PAC8/P AC3 (2/ 1 ) PGMEA 8 PAC9/PAC3 (2/1 PGMEA 9 PAC10/PAC3(2/1) PGMEA vs. 1 PAC4 PGMEA 2 PAC5 PGMEA Example 3 PAC6 PGMEA 4 PAC7 PGMEA Here, in Table 1, the EL component of (D) is EL/PGMEA ( 7/3 ), ( 28) 1304918 means the mixing of EL (ethyl lactate) / PGMEA by mass ratio: 7/3. Further, PAC 2 to 10 are as follows. PAC2: bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)-3 produced as a condensate of 3-methyl-6-cyclohexanol with 3,4-dihydroxybenzaldehyde. 4-dihydroxyphenylmethane (M=500) 1 Molar, esterification reaction product with 5-NQD 2.1 1 molar esterification rate of 52.75%. PAC3: bis(2,3,5-trimethyl-4-hydroxyphenyl)-2-hydroxyphenyl group produced as a condensate of 2,3,6-trimethylphenol and 2-hydroxybenzaldehyde Methane (M = 376) 1 molar, esterification reaction product with a 5-NQD 2.02 molar esterification rate of 6 7 _ 3 %. PAC4: Mw 1500 phenolic enamel resin manufactured as a polycondensate of m-cresol/p-cresol/2,3,5-trimethylphenol=35:40:25 (mole ratio), with formaldehyde, Esterification reaction product with 5% esterification rate of 5-NQD 〇PAC5: bis(2,4-dihydroxyphenyl)methane (M = 23 2 ) 1 mol, with 5-NQD 3.76 mol ester 94% esterification reaction product 〇PAC6: ginseng (4-hydroxyphenyl)methane (M = 292) 1 mol, esterification reaction product with esterification rate of 5-NQD 2 molar 66.7% . PAC7: methyl ester of gallic acid 1 mol, an esterification reaction product with an esterification rate of 5-NQD 3 molar of 100%. PAC8: 2,5-xylenol/p-cresol (mole ratio 2/1)' with formaldehyde as the raw material M = 376 of 2' 6-bis (2,5-dimethyl-32- ( 29) 1304918-monohydroxybenzyl)-4-methylphenylhydrazine 1 mole, esterification reaction product with 6-NQD 2 molar esterification rate of 6 6 %. PAC9: 2,6-xylenol/p-cresol (European t, Wu Erbi 2 /1), and formaldehyde as raw material, M = 3 76 2, 6__隹隹广一又 C 3 , 5 - dimethyl ~ 4 - hydroxybenzyl) - 4 - methyl phenol 1 Mo 77 1 big ear ' and 5-NQD 2 molar esterification rate of 60% esterification reaction product. PAC10: 2 - cyclohexanol / p-type ( 卞 旲, 旲 ear ratio 1 / 1), and formaldehyde m ketone (Merbi as a raw material synthesized M = 6 3 2 double [3 - (hydroxyl-5 -methylbenzyl)hydroxy-5-cyclohexylphenyl]isopropyl k 1 molar, with 5-NQD 2 molar, esterification reaction product with an esterification rate of 5 %.

-33- (30) 1304918 [Table 2] Sensitivity Evaluation (mJ) Resolution Evaluation (μηι) Dross Evaluation 1 30 1.3 〇 2 30 1.3 〇 3 42.5 1.2 4 4 35.0 1.3 5 Example 5 32.5 1.3 〇 6 37.5 1.3 〇7 37.5 1.1 〇8 40.0 1.1 〇9 47.5 1.3 Δ ratio 1 30 1.6 X 2 27.5 1.5 X Example 3 3 0 1 .5 X 4 25 1 .6 〇

A positive photoresist composition for LCDs needs to have high resolution under low enthalpy conditions. As is apparent from the results shown in Table 2, the compositions of the examples were all excellent in resolution. Moreover, the degree of sensitivity is also practical, and there is no generation of scum, which is good in these respects. On the other hand, since the molecular weight of the composition of Comparative Example 1 was too high, the resolution of -34-(31) 1304918 was poor. And there is scum. Since the esterification ratio of the composition of Comparative Example 2 exceeded 90%, the resolution was poor. Also, the dross is slightly bad. Since the molecular weight of the composition of Comparative Example 3 was low, the resolution was poor. Also, there is scumming. Since the composition of Comparative Example 4 does not have a skeleton of a low molecular weight phenolic enamel resin, the sensitivity is too fast and the resolution is also inferior. [Effects of the Invention] Since the positive-type photoresist composition for a LCD of the present invention and the method for producing a photoresist pattern can impart good resolution even under low NA conditions, it is suitable for use as a system LCD. The industry is extremely useful. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view in which a positive resist composition is applied onto a glass substrate, baked to be dried and patterned, and then a developing device having a slit coater is used. An illustration of the meaning of the substrate end portion X to Z being filled with liquid. -35-

Claims (1)

1304918 'May Days Correction Pickup, Patent Application No. 93 1 0 1 8 8 5 Patent Application Revision Chinese Patent Application Revision Amendment September 1, 1997. 1. A positive photoresist composition for LCD manufacturing And (A) an alkali-soluble resin, wherein the total amount of the component (A) and the component (C) is from 1% to 70% by mass based on the total amount of the photosensitive agent component, and the following component (B) exceeds 50% by mass, wherein the average esterification ratio of the low molecular weight novolac resin and the naphthoquinonediazidesulfonic acid compound having a mass average molecular weight of 300 to 1 300 in the above (B) is 40 to 70%. The esterification reaction product is a compound having a phenolic hydroxyl group having a molecular weight of 1000 or less relative to the (A) component, and a total solid concentration of 1 to 40% by mass (D). An organic solvent which is a mixture containing an alkyl lactate, 2-heptanone or propylene glycol monoalkyl acetate acetate and an alkyl lactate. 2. The method of claim 1, wherein the low molecular weight novolak resin comprises the following general formula (I) OH 1304918 (wherein R1 to R5 are independently independent) a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and 2 of which are a hydrogen atom 'and 1 is an alkyl group having 1 to 5 carbon atoms and an aldehyde A low molecular weight novolac resin synthesized by a condensation reaction of a class and/or a ketone. 3. The positive resist composition of claim 1, wherein the low molecular weight novolak resin comprises the following general formula (〇 (wherein R1 to R5 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms' and 2 of R, R3 and R5 are hydrogen atoms, and 1 is a carbon number of 1 to 5 a bifunctional phenol compound represented by an alkyl group, and the following general formula (II) (wherein R11 to R15 are each independently a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and one of R11, Ri3, and R!5 is a hydrogen atom, and 2 are a carbon atom number 1 A low molecular weight 酣-2-1304918 aldehyde varnish resin synthesized by a condensation reaction of a monofunctional phenol compound represented by an alkyl group of 5 with a Xue and/or a ketone. 4. The positive-type photoresist composition as claimed in claim 1, wherein the low-molecular-weight novolac resin contains the general formula (I) (wherein R1 to R5 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and 2 of RhR3 and R5 are a hydrogen atom, and 1 is an alkyl group having 1 to 5 carbon atoms. a condensate synthesized by a condensation reaction of a bifunctional phenol compound represented by an aldehyde and/or a ketone, and the following general formula (Π) (wherein R11 to R15 are each independently a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and one of RU'R13, and R15 is a hydrogen atom, and 2 are a carbon number of 1 to 5 A low molecular weight awake varnish resin synthesized by reacting a monofunctional phenol compound represented by an alkyl group. 5. The positive resist composition according to any one of claims 1 to 4, wherein the component (D) contains propylene glycol monoalkyl ether acetate. 6. For the positive resist composition of claim 1 of the patent scope, -3- 1304918 is the user of the i-line exposure step. 7. A positive-type photoresist composition as claimed in claim 1, wherein the NA is an exposure step user of 0.3 or less. 8. The positive-type resist composition according to claim 1, wherein the LCD manufacturer is formed by forming an integrated circuit and a liquid crystal display portion on one substrate. A method for forming a photoresist pattern, comprising: (1) coating a substrate with a positive photoresist composition as claimed in claim 1 to form a coating film, (2) a step of performing heat treatment (prebaking) on the substrate on which the coating film is formed to form a photoresist film on the substrate, and (3) using a mask pattern for forming a photoresist pattern of 2.0 μm or less, and exceeding 2.0 μηι forms a photoresist pattern with a mask of both mask patterns, a step of selectively exposing the photoresist film, and (4) performing heat treatment on the photoresist film after selective exposure ( (5) The step of calcination after exposure, (5) performing a development process using an alkali aqueous solution on the photoresist film after the heat treatment to simultaneously form a photoresist pattern for an integrated circuit having a pattern size of 2·0 μηι or less And a step of using a photoresist pattern for the liquid crystal display portion of 2 _ 0 μιη or more on the substrate, and (6) a rinsing step of rinsing the liquid remaining on the surface of the photoresist pattern. A method of forming a photoresist pattern according to claim 9 wherein the step of performing the selective exposure is carried out by using an exposure step in which the i-line is a -4- 1304918 light source. A method of forming a photoresist pattern according to claim 9 wherein the step of performing the selective exposure is carried out by an exposure step under a low NA condition in which the NA is 0.3 or less.