WO2004053595A1

WO2004053595A1 - Positive type photoresist composition for lcd production and method of forming resist pattern

Info

Publication number: WO2004053595A1
Application number: PCT/JP2003/015621
Authority: WO
Inventors: Akira Katano; Kazuhiko Nakayama; Satoshi Niikura; Kosuke Doi
Original assignee: Tokyo Ohka Kogyo Co., Ltd.
Priority date: 2002-12-06
Filing date: 2003-12-05
Publication date: 2004-06-24
Also published as: CN1720484A; JP2004191394A; KR20050085257A; CN1720484B; TWI257526B; TW200417817A; JP4071611B2

Abstract

A positive type photoresist composition for LCD production, characterized by comprising (A) an alkali-soluble resin ingredient comprising an alkali-soluble novolak resin synthesized by the condensation of one or more phenols comprising 3,4-xylenol with an aldehyde, (B) an esterified naphthoquinonediazide, (C) a compound containing a phenolic hydroxy group and having a molecular weight of 1,000 or lower, and (D) an organic solvent; and a process for producing a resist pattern. With the composition, satisfactory resolution can be attained even under low-NA conditions. The composition has excellent linearity even under low-NA conditions and is hence suitable for use in producing system LCDs.

Description

Specification

Technical Field of the Invention Positive photoresist composition for LCD production and method of forming resist pattern

The present invention relates to a positive photoresist composition for producing an LCD and a method for forming a resist pattern.

This application is based on Japanese Patent Application No. 2002-355365, the contents of which are incorporated herein. Background art

Until now, in the manufacture of liquid crystal display elements (LCDs) that form a liquid crystal display part on a glass substrate, they are relatively inexpensive and can form resist patterns with excellent sensitivity, resolution and shape. Positive photoresist materials comprising a nopolak resin-quinonediazide group-containing compound system used in the manufacture of semiconductor devices are often used.

However, for example, in the manufacture of semiconductor devices, disc-shaped silicon wafers with a maximum diameter of 8 inches (about 200 mm) to 12 inches (about 300 mm) are used, whereas in the manufacture of LCDs, a minimum is used. However, a square glass substrate of about 36 OmmX 460 mm is used.

As described above, in the field of manufacturing LCDs, the substrate on which the resist material is applied is, of course, different in terms of material and shape, but in terms of its size, the substrate used in the manufacture of semiconductor elements is used. Is very different.

For this reason, resist materials for manufacturing LCDs are required to be able to form a resist pattern having excellent characteristics such as shape and dimensional stability over a wide substrate surface.

In addition, since a large amount of resist material is consumed in the production of LCDs, resist materials for LCD production are desired to be inexpensive in addition to the above-mentioned characteristics. ing.

There have been many reports as resist materials for LCD manufacturing (for example, Patent Documents 1 to 6 below). The resist materials described in Patent Literatures 1 to 6 are inexpensive and have excellent applicability, sensitivity, resolution, shape and dimensional stability for small substrates of, for example, about 36 Omm x 46 Omm. A resist pattern can be formed. Therefore, it can be suitably used for the purpose of manufacturing a relatively small LCD.

[Patent Document 1]

JP-A-9-1160231

[Patent Document 2]

Japanese Patent Application Laid-Open No. 9-1 211855

[Patent Document 3]-JP-A-2000-112120

[Patent Document 4]

JP 2000-131835

[Patent Document 5]

JP 2000-181055 A

[Patent Document 6]

However, in recent years, with the enlargement of personal computer displays and the spread of liquid crystal televisions, the demand for larger LCDs than before has been increasing. In addition, the demand for lower prices has led to a demand for improved LCD manufacturing efficiency. Therefore, in the field of LCD manufacturing, it is desired that the exposure area be as large as possible and at least about 100 mm ² from the viewpoint of improving the throughput (the number of processes per unit time). In addition, it is extremely difficult to maintain the uniformity of the resist film over a wide exposure range on a glass substrate with large irregularities compared to a silicon wafer, so a large depth of focus (DOF) can be obtained. It is desired. For this reason, LCD manufacturing is generally described as NA (numerical aperture of lens). For example, it is preferable to use an exposure process under a low NA condition of 0.3 or less, particularly 0.2 or less.

However, when using an exposure process under low NA conditions, conventional resist materials for LCD manufacturing can form resist patterns with excellent shapes at high resolution under low NA conditions of, for example, 0.3 or less. It was difficult.

That is, in general, the resolution (resolution limit) is expressed by the following formula of the following equation:

[Where R is the resolution limit, is the proportionality constant determined by the resist, process, and image formation method, λ is the wavelength of light used in the exposure process, and ΝΑ is the numerical aperture of the lens]

It is represented by Therefore, the resolution can be increased by using a light source having a short wavelength λ or by using a high-speed exposure process. For example, instead of the g-line (436 nm) exposure used in conventional LCD manufacturing, photolithography technology using shorter-wavelength i-line (365 nm) exposure is used to increase resolution. Can be raised.

However, in the manufacture of LCD, as described above, it is not preferable to increase the NA, which results in a smaller exposure area and a smaller depth of focus, and it has been desired to use an exposure process under low NA conditions. Therefore, it was difficult to obtain high resolution.

In addition, even if a high-resolution resist pattern, that is, a fine resist pattern, is obtained, the finer the pattern dimension, the more the focus depth width characteristic tends to be significantly deteriorated. It was difficult to form with good width characteristics.

Furthermore, as a next-generation LCD, integrated circuits such as drivers, DACs (digital-to-analog converters), image processors, video controllers, and RAMs are mounted on a single glass substrate at the same time as the display. Technology is being actively developed for the high-performance LCDs that are formed, so-called “system LCDs” (Semiconductor FPD World 2001. 9, pp. 50-67).

In this case, the integrated circuit part is formed on the substrate in addition to the display part. Therefore, the substrate tends to be larger. Therefore, it is desirable to perform exposure under a lower NA condition than in normal LCD manufacturing.

Further, in such a system LCD, for example, the pattern size of the display portion is about 2 to 10 m, whereas the integrated circuit portion is formed with a fine size of about 0.5 to 2.0 m. . Therefore, it is preferable to simultaneously form the display portion and the integrated circuit portion having different pattern dimensions under the same exposure condition, and to set the linearity [the same exposure condition (different mask size on the reticle but the same exposure light amount)]. A resist material that excels in the characteristics of accurately reproducing a resist pattern corresponding to different mask dimensions on a reticle when exposed at a higher resolution than conventional resist materials for LCD manufacturing is desired.

However, as described above, conventional resist materials for LCD manufacturing are difficult to form at high resolution under low NA conditions, and thus are difficult to use for manufacturing system LCDs. For example, under a low NA condition of 0.3 or less, it is difficult to form a fine resist pattern excellent in shape, for example, 2.0 m or less, and the obtained resist pattern tends to have a tapered shape instead of a rectangular shape. And the depth of focus characteristics were also inferior.

Specifically, for example, Patent Literature 6 (Japanese Patent Application Laid-Open No. 2001-75272) describes a liquid crystal resist containing a soluble resin and a photosensitive component, but not containing a sensitizer.

However, this liquid crystal resist had problems such as being unsuitable for i-line exposure, difficulty in forming a resist pattern of 2.0 or less required for manufacturing system LCDs, and lacking linearity.

Therefore, there has been a demand for a resist material that has good linearity and that can form a fine resist pattern having an excellent shape even under a low NA condition of 0.3 or less, for example, in a system LCD manufacturing process. Disclosure of the invention

That is, the present invention has excellent linearity under low NA For the manufacture of LCDs, in which the integrated circuit and the liquid crystal display part are formed on one substrate, the display part and the finer resist pattern of the integrated circuit part can be simultaneously obtained in a good pattern shape. It is an object of the present invention to provide a resist material and a method for forming a resist pattern which are suitable as the above.

In order to solve the above-mentioned problems, a positive photoresist composition for an LCD according to the present invention comprises (A) an alkali-soluble nopolak which can be synthesized by a condensation reaction of a phenol containing 3,4-xylenol with an aldehyde. (C) a phenolic hydroxyl group-containing conjugate having a molecular weight of 1000 or less,

(D) an organic solvent,

It is characterized by including.

This positive photoresist composition for LCD is preferable as a positive photoresist composition for LCD for an i-ray exposure process.

Further, it is suitable as a positive photoresist composition for an LCD having an NA of 0.3 or less for an exposure process.

Further, it is suitable as a positive photoresist composition for LCD for producing LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate.

In the description of the present invention, the system LCD refers to “LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate”. Further, the method for forming a resist pattern of the present invention comprises:

(1) a step of applying the positive photoresist composition of the present invention on a substrate to form a coating film;

(2) heat-treating (pre-baking) the substrate on which the coating film is formed to form a resist coating on the substrate;

(3) Selective exposure is performed on the above resist film using a mask on which both a mask pattern for forming a resist pattern of 2.0 or less and a mask pattern for forming a resist pattern of more than 2.0 m are drawn. Process, (4) subjecting the resist film after the selective exposure to a heat treatment (post-exposure bake);

(5) The resist film after the heat treatment is subjected to a development treatment using an alkaline aqueous solution, and a resist pattern for an integrated circuit having a pattern size of 2.0 m or less is formed on the substrate. Simultaneously forming a resist pattern for the liquid crystal display part of

(6) a rinsing step of washing away the developer remaining on the surface of the resist pattern. '' Brief description of the drawings

Fig. 1 shows a positive photoresist composition applied to a glass substrate, baked, dried, and exposed to a pattern for evaluation of linearity under low NA conditions. FIG. 5 is an explanatory view showing that liquid is pooled from a substrate end portion X to a substrate end portion Z. BEST MODE FOR CARRYING OUT THE INVENTION

[Positive photoresist composition for LCD]

<(A) component>

The component (A) is an alkali-soluble resin component containing an alkali-soluble nopolak resin which can be synthesized by a condensation reaction between a phenol containing 3,4-xylenol and an aldehyde.

By using 3,4-xylenol in the phenols, it is possible to obtain a nopolak resin which is excellent in resolution under low NA conditions and is suitable for preparing a resist material for LCD production. .

In addition, a nopolak resin having excellent linearity and suitable as a resist material for a system LCD can be obtained.

In addition, the heat resistance is good. If the heat resistance of the positive photoresist composition is good, the dimensions of the resist pattern after the heat treatment step Suitable for LCD because of low change rate, and suitable for system LCD because the rectangular shape of the resist pattern is good for forming integrated circuits.

Further, an effect that scum after the formation of the resist pattern is small is also obtained. The lower limit of the proportion of 3,4-xylenol in the phenols is at least 5 mol%, preferably at least 7 mol%, and the upper limit is at most 40 mol%, preferably at most 30 mol%, more preferably 20 mol% or less. By setting the lower limit or more, a good effect can be obtained. The content of 3,4-xylenol in the phenols may be 100 mol%, but if the amount of 3,4-xylenol is too large, the sensitivity may decrease. It is preferable that it is not more than the upper limit.

In the above-mentioned phenols, one or more arbitrarily selected from those generally used as a nopolak resin material for a positive photoresist composition may be used in addition to 3,4-xylenol. be able to. Examples thereof include phenols such as m-cresol, ρ-cresol, xylenol other than 3,4-xylenol, and trimethylphenol, and among them, m-cresol is preferable in terms of improving sensitivity.

In the case of a positive photoresist composition for LCD, a high sensitivity of, for example, about 5 OmJ is considered preferable from the viewpoints of improvement in production efficiency, throughput, and the like. Satisfying things are easily obtained.

When 3,4-xylenol is combined with phenols other than 3,4-xylenol, the content of 3,4-xylenol is 5 to 30 mol%, preferably 7 to 20 mol%. It is preferable because the effect of phenols other than 3,4-xylenol can be exerted while maintaining the effect of 3,4-xylenol.

Setting the lower limit or more is effective in terms of resolution and linearity under low NA conditions. Further, heat resistance is also improved, which is preferable in terms of suppressing scum. It is preferable from the viewpoint of sensitivity that the content is not more than the upper limit.

For example, as described above, when combining 3,4-xylenol, m-cresol, and other phenols as necessary as described below, By adjusting the content to the above ratio, it is possible to provide a material having high resolution, high heat resistance, high sensitivity, and the ability to suppress generation of scum under low NA conditions. In addition, a product excellent in linearity can be provided.

At this time, the proportion of m-cresol in the phenols is preferably 95 to 40 mol%, and more preferably 93 to 60 mol%, from the viewpoint of sensitivity. Sensitivity is improved by setting the content to 40 mol% or more, and the content of 3,4-xylenol can be ensured by setting the content to 95 mol% or less, which is preferable in terms of resolution, linearity, and the like.

Further, as described above, other phenols other than 3,4-xylenol and m-cresol can be used as necessary, but other phenols are, in particular, 3,4-xylenol. When used together with m-cresol, it may be 0 to 30 mol% in the phenols (that is, whether or not other phenols are used is optional), and preferably 5 to 20 mol%. It is preferable in terms of resolution, linearity characteristics, and sensitivity.

As the aldehyde, one or more arbitrarily selected ones can be used without particular limitation as long as they are generally used for synthesizing a nopolak resin for a positive photoresist composition. For example, there are acetoaldehyde, propionaldehyde, salicylaldehyde, formaldehyde, formaldehyde precursor, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, and the like. And formaldehyde are preferred, and those in which both are combined are particularly preferred. In the case of using propionaldehyde, it is preferable to use 5% by mole or more, preferably 15% by mole or more of aldehydes, since resolution is good and a rectangular resist pattern tends to be obtained.

When formaldehyde is used, it is preferable to use 50 mol% or more, preferably 60 mol% or more of aldehydes from the viewpoint of sensitivity. The molar ratio of ropionaldehyde: formaldehyde is 10:90 to 30:70, Preferably it is 25:75. Within this range, the effects of high sensitivity, high resolution, and high heat resistance can be obtained.

Here, a particularly preferred embodiment of the soluble nopolak resin essential in the present invention is summarized as follows.

That is, it is preferable to include an alkali-soluble nopolak resin that can be synthesized using a phenol containing 3,4-xylenol and m-cresol.

A phenol containing 3,4_xylenol 5 to 30 mol%, m-cresol 95 to 40 mol%, and other phenols 0 to 30 mol% (other phenols are optional). It is preferable to include a soluble nopolak resin which can be synthesized by using a compound.

It is preferable that the aldehydes include an alcohol-soluble novolak resin that can be synthesized using an aldehyde containing one or both (preferably both) of propionaldehyde and formaldehyde.

Therefore, most preferred are alkali-soluble nopolak resins that can be synthesized using phenols containing 3,4-xylenol and m-cresol, and aldehydes containing propionaldehyde and formaldehyde. At this time, it is more preferable to satisfy the conditions of 5 to 30 mol% of 3,4-xylenol, 95 to 40 mol% of m-cresol, and 0 to 30 mol% of other phenols in the phenol.

The alkali-soluble nopolak resin can be synthesized according to a conventional method, for example, by subjecting a phenol and an aldehyde to a condensation reaction in the presence of an acid catalyst.

The molar ratio of the phenols to the aldehydes is, for example, 1: 0.5 to 1: 0.95, preferably 1: 0.6 to 1: 0.9.

The mass-average molecular weight (Mw) of the alkali-soluble nopolak resin is 3000 to 30,000, preferably 4000 to 20000 in terms of polystyrene by GPC (gel permeation chromatography) from the viewpoint of coating properties and heat resistance. The alkali-soluble nopolak resin may be used alone or in combination of two or more. Can be used.

In the present invention, the component (A) may contain, in addition to the essential alkali-soluble nopolak resin, other alcohol-soluble resins.

The compounding amount of the other alkali-soluble resin in the component (A) is, for example, 50% by mass or less, preferably 30% by mass or less (the lower limit is not particularly limited, but may be 0% by mass). . Within this range, the effect of the essential alkali-soluble nopolak resin is not likely to be impaired, which is preferable.

In addition to the essential alcohol-soluble novolak resin, any other alcohol-soluble resin that can be blended can be used without particular limitation as long as it is generally used in a positive photoresist composition. For example, hydroxystyrene such as a homopolymer of hydroxystyrene, a copolymer of hydroxystyrene and another styrene monomer, and a copolymer of hydroxystyrene and acrylic acid or methacrylic acid or a derivative thereof. Acrylic acid or methacrylic acid resin which is a copolymer of acrylic acid or methacrylic acid and a derivative thereof.

<(B) component>

The component (B) is a naphthoquinonediazide esterified product.

The component (B) is not particularly limited as long as it is generally used as a photosensitive component in a positive photoresist composition, and one or more components can be arbitrarily selected and used.

Among them, the following general formula (I)

Wherein RR ⁸ independently represents 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 cycloalkyl group having 3 to 6 carbon atoms. R ^1Q and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; when R ⁹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q ¹ represents a hydrogen atom or a carbon atom; An alkyl group of the formulas 1 to 6 or a residue represented by the following chemical formula (II)

(Wherein R ¹² and R ¹³ are each 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 cycloalkyl group having 3 to 6 carbon atoms. the expressed; c a is an integer of 1 to 3), if Q ¹ is bonded with the end end of R ⁹ is, Q ¹ is R ⁹ and, together with the carbon atoms between Q ^1, R ^9, A, b represents an integer of 1 to 3; d represents an integer of 0 to 3; n represents an integer of 0 to 3]

The esterified product of a phenolic compound and a naphthoquinonediazidosulfonic acid compound represented by the formula is suitable for photolithography using i-line and forms a fine resist pattern of 2.0 m or less under low NA conditions with good shape It is suitable for trying. That is, it is preferable in terms of high resolution and also in terms of linearity. When Q ¹ and R ⁹ and the carbon atom between Q ¹ and R ⁹ form a cycloalkyl group having a carbon chain of 3 to 6, Q ¹ and R ⁹ combine to form a carbon atom It forms 2 to 5 alkylene groups.

The phenolic compounds corresponding to the general formula include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, and bis (4-hydroxy-2,3,5-trimethylphenyl). — 2-Hydroxyphenylmethane, bis (4-hydroxy-1,3,5-dimethylphenyl) 1,4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -1,3-hydroxyphenylmethane, bis ( 4-Hydroxy-1,3,5-dimethylphenyl-1-hydroxyphenylmethane, bis (4-hydroxy 2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5) 1-hydroxyphenylmethane, bis (4-hydroxy-1,2,5-dimethylphenyl) 1,2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) 1,3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis ( 4-Hydroxy-2,5-dimethylphenyl) _2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -1,3-methoxy-1-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-1 2-Methylphenyl) 1-4-Hydroxyphenylmethane, Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) 1-3-Hydroxyphenylmethane, Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) Trisphenol-type compounds such as i-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane;

2; · 4-bis (3,5-dimethyl-4-hydroxybenzyl) _5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) linear trinuclear such as 1,4-methylphenol Body phenolic compounds;

1,1-bis [3- (2-hydroxy-1-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-1-31 (4-hydroxy-5-methylbenzyl) ) 1-4-Hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) 1-4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4- Hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-14-hydroxybenzyl) -1-hydroxy-5-ethylphenyl] methane, Bis [3- (3,5-Jetyl-1-hydroxybenzyl) 1-4-Hydroxy-5-methylphenyl] methane, Bis [3- (3,5-Getyl-4-hydroxybenzyl) 1-4-Hydroxy-5-ethylphenyl] Methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -15-methylphenyl] methane, bis [2-hydroxy-13- (2-hydroxy-15-methylbenzyl) 1-Methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) —5-methylphenyl] methane, bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) Linear 4-nucleated phenolic compounds such as [1-4-hydroxyphenyl] methane;

2,4-bis [2-hydroxy-1- (4-hydroxybenzyl) -1-methylbenzyl] -16-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) 1,5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) 1-4-hydroxybenzyl] -4-methylphenol Linear polyphenol compounds such as linear pentanuclear phenol compounds;

Bis (2,3,4-trihydroxyphenyl) methane, Bis (2,4-dihydroxyphenyl) methane, 2,3,4-Trihydroxyphenyl 4'-hydroxyphenylmethane, 2- (2, 3, 4-trihydroxyphenyl) 1- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) 1-2- (2 ', 4' dihydroxyphenyl) Enyl) propane, 2- (4-hydroxyphenyl) -1- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) 1-2- (3'-fluoro-4'-hydroxyphenyl Nil) propane, 2- (2,4-dihydroxyphenyl) 1 2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) —2— (4'— Hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) - 2 - (4,-hydroxy one 3 ', 5' over-dimethyl-phenylalanine) bisphenol type compounds such as propane;

1- [1— (4-Hydroxyphenyl) isopropyl] —4-1- [1,1-bis (4-Hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] —4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene Polynuclear branched compounds such as and

Examples include condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane.

These can be used alone or in combination of two or more.

Among them, bis (5-cyclohexyl-1-hydroxy-2-methylphenyl) —3,4-dihydroxyphenylmethane [hereinafter abbreviated as (B 1 ′)]. ], Bis (2,4-dihydroxyphenyl) methane [hereinafter abbreviated as (B2 ')]. ], Bis (4-hydroxy-2,3,5-trimethylphenyl) -12-hydroxyphenylmethane [hereinafter abbreviated as (B3 ')]. Among these three types, a photoresist composition containing one or more (preferably these three types) naphthoquinonediazide ester of a phenol compound is a resist having high sensitivity, high resolution, and good shape. This is preferable in that a pattern can be formed.

Hereinafter, the naphthoquinonediazide esterified compounds of (B1 ′), (B2 ′) and (B3 ′) are abbreviated as (Bl), (B2) and (B3).

When (B1), (B2) or (B3) is used, the amount of the component (B) is preferably at least 10% by mass, more preferably at least 15% by mass.

When all of (Bl), (B2) and (B3) are used, from the viewpoint of the effect, the compounding amount of (B1) is 50 to 90% by mass, preferably 60 to 80% by mass. The amount of (B2) is 5 to 20% by mass, preferably 10 to 15% by mass, and the amount of (B3) is 5 to 20% by mass, preferably 10 to 15% by mass.

All or part of the phenolic hydroxyl group of the compound represented by the above general formula (I)

The tellurization can be carried out by a conventional method.

For example, it can be obtained by condensing naphthoquinonediazidosulfonyl chloride with the compound represented by the above general formula (I).

Specifically, for example, a compound represented by the above general formula (I) and naphthoquinone-1-1, A predetermined amount of 2-diazido 4 (or 5) -sulfonyl chloride is dissolved in an organic solvent such as dioxane, n-methylpyrrolidone, dimethylacetamide, and tetrahydrofuran, and tritylamine, triethanolamine, pyridine, and carbonic acid are dissolved therein. One or more basic catalysts such as alkali and alkali bicarbonate can be added and reacted, and the resulting product can be prepared by washing with water and drying.

As the component (B), as described above, other naphthoquinone diazide esterified compounds may be used in addition to the preferred exemplified naphthoquinone diazide esterified compounds. For example, an esterification reaction product of a phenolic compound such as polyhydroxybenzophenone-alkyl gallate and a naphthoquinonediazidosulfonic acid compound may be used.

The use amount of these other naphthoquinonediazide esterified compounds is preferably 80% by mass or less, particularly 50% by mass or less in the component (B), from the viewpoint of improving the effects of the present invention.

The amount of the component (B) in the photoresist composition is 20 to 70% by mass, preferably 25 to 60% by mass, based on the total amount of the component (A) and the following component (C). .

By setting the amount of the component (B) to be not less than the above lower limit, an image faithful to the pattern can be obtained, and transferability is improved. When the content is not more than the above upper limit, the sensitivity can be prevented from deteriorating, the uniformity of the formed resist film can be improved, and the resolution can be improved.

<(C) component>

The component (C) is a phenolic hydroxyl group-containing compound. By using this component (C), a material that is excellent in sensitivity improvement effect, has high sensitivity and high resolution even in the i-line exposure process under low NA conditions, and is suitable for LCD manufacturing, more preferably linearity Excellent system The material suitable for LCD can be obtained.

The molecular weight of the component (C) is preferably 100 or less, preferably 700 or less, substantially 200 or more, and preferably 300 or more, from the viewpoint of the above effects.

As the component (C), phenolic water generally used in a photoresist composition is used. The acid group-containing compound is not particularly limited as long as it satisfies the above-mentioned molecular weight condition, and one or more kinds can be arbitrarily selected and used. In particular, the following general formula (III)

(In the formula, RU to R ¹⁸ each independently represent 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 cycloalkyl group having 3 to 6 carbon atoms. R ^2Q and R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; when R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q ² represents a hydrogen atom; An alkyl group having 1 to 6 carbon atoms or a residue represented by the following chemical formula (IV)

(In the formula, R ²² and R ²³ are each 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 cycloalkyl group having 3 to 6 carbon atoms. the expressed; g a is an integer of 1 to 3), if Q ² is bonded with the terminal of R ¹⁹ is, Q ² is R ^19, and, together with the carbon atoms between Q ² and R ^19, carbon Chain represents a cycloalkyl group of 3 to 6; e, f represents an integer of 1 to 3; h represents 0 Represents an integer of 3 to 3; n represents an integer of 0 to 3]

The phenol compound represented by the following is preferable because it shows the above characteristics well.

Specifically, for example, the phenol compound used in the naphthoquinonediazide esterified product of the phenol compound exemplified in the above-mentioned component (B) can be preferably used. ) Isopropyl]-4-[1,1 _bis (4-hydroxyphenyl) ethyl] benzene is preferred.

The amount of the component (C) is in the range of 10 to 70% by mass, preferably 20 to 60% by mass, based on the component (A) from the viewpoint of the effect. (D) ingredient>

As the component (D), one or more kinds can be selected and used without particular limitation as long as they are general ones used in a photoresist composition, and propylene glycol monoalkyl ether acetate, And those containing Z or 2-heptanone are preferred because they have excellent coatability and excellent uniformity of the thickness of a resist film on a large glass substrate.

It is to be noted that both propylene daricol monoalkyl ether acetate and 21-heptane can be used, but the spin coat method or the like, when used alone or in combination with another organic solvent, is used. In many cases, it is preferable in terms of the uniformity of the film thickness at the time of coating.

The propylene glycol monoalkyl ether acetate preferably contains 50 to 100% by mass of the component (D).

Propylene dalycol monoalkyl ether acetate has, for example, a linear or branched alkyl group having 1 to 3 carbon atoms. Among them, propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) Is particularly preferable because the film thickness of the resist film on the large glass substrate is very excellent.

On the other hand, 2-hepno-non is not particularly limited, but as described above, (B) It is a suitable solvent when combined with a non-benzophenone-based photosensitive component as a futoquinone diester.

2-Heptane-non is a very preferable solvent because it has excellent heat resistance as compared with PGMEA and has the property of giving a resist composition with reduced scum generation. Further, other solvents can be mixed with these preferable solvents. For example, when an alkyl lactate such as methyl lactate or ethyl lactate (preferably ethyl lactate) is blended, a resist pattern having excellent uniformity in the thickness of the resist film and excellent shape can be formed.

When a mixture of propylene glycol monoalkyl ether acetate and alkyl lactate is used, the mass ratio is 0.1 to 10 times, preferably 1 to 5 times the mass ratio of propylene glycol monoalkyl ether acetate to propylene glycol monoalkyl ether acetate. It is desirable to mix twice the amount of alkyl lactate.

Organic solvents such as carboxylactone and propylene glycol monobutyl ether can also be used.

When arptyrolactone is used, it is added in an amount of 0.01 to 1 times by mass, preferably 0.05 to 0.5 times by mass with respect to propylene glycol monoalkyl ether acetate. It is desirable to do.

Specific examples of other organic solvents that can be blended include the following.

That is, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isoamyl ketone; ethylene glycol, propylene glycol, ethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, and monomers thereof. Polyhydric alcohols such as tyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and methyl acetate, ethyl acetate, butyl acetate, Esters such as methyl ruvinate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. When such a solvent is used, it is desirable that the content is not more than 50% by mass in the component (D).

The positive photoresist composition of the present invention contains compatible additives as necessary, for example, an additional resin and a plasticizer for improving the performance of the resist film, as long as the object of the present invention is not impaired. , Storage stabilizers, surfactants, coloring agents to make the developed image more visible, sensitizers to further improve the sensitizing effect, dyes for preventing halation, adhesion improvers, etc. Conventional additives can be included.

Antihalation dyes include ultraviolet absorbers (eg, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2', 4,1-dihydroxybenzophenone, 5-amino-3- Methyl-11-phenyl-1-41- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-methylethyl-4'-ethoxyazobenzene, 4-ethylethylaminoazobenzene, curcumin Etc.) can be used.

The surfactant can be added, for example, to prevent striation. For example, Florad FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), EFTOP EF 122A, EF 122B, EF 122C, EF 126 (trade name, manufactured by Tochem Products Co., Ltd.) and R-08 (trade name, manufactured by INHIKIN INK CHEMICAL INDUSTRIES, LTD.).

The positive photoresist composition of the present invention is preferably prepared by dissolving the component (A), the component (B), the component (C) and, if necessary, other components in the organic solvent (D). be able to.

The amount of the component (D) is preferably adjusted appropriately so as to dissolve the components (A) to (C) and other components used as necessary, and to obtain a uniform positive photoresist composition. I can do it. Preferably, the solid content [components (A) to (C) and other components used as needed] is 10 to 50% by mass, more preferably 20 to 35% by mass.

[Method of forming resist pattern] An example of a preferred method for forming a resist pattern in the manufacture of an LCD will be described below.

First, the above-mentioned positive photoresist composition of the present invention is applied to a substrate using a spinner or the like to form a coating film. A glass substrate is preferred as the substrate. Amorphous silica is usually used as the glass substrate, but low temperature polysilicon or the like is preferable in the field of system LCD. As the glass substrate, since the composition of the present invention has excellent resolution under low NA conditions, it is large in size of 50 O mm x 60 O mm or more, especially 55 O mm X 65 O mm or more. Substrate can be used.

Next, the glass substrate on which the coating film is formed is subjected to a heat treatment (prebaking) at, for example, 100 to 140 ° C. to remove the residual solvent, thereby forming a resist coating film. As a prebaking method, it is preferable to perform proximity baking in which a gap is provided between the hot plate and the substrate.

Further, the resist film is selectively exposed using a mask on which a mask pattern is drawn.

As a light source, it is preferable to use i-line (365 nm) in order to form a fine pattern. The exposure process employed in this exposure is preferably a low NA exposure process having an NA of 0.3 or less, preferably 0.2 or less, and more preferably 0.15 or less. In the method of forming a resist pattern, when a system LCD is manufactured, in the step of performing the selective exposure, a mask pattern for forming a resist pattern of 2.0 m or less, It is preferable to use a mask on which both the resist pattern forming mask patterns are drawn.

Next, the resist film after the selective exposure is subjected to a heat treatment (post-exposure bake: PEB). As the PEB method, there are a proximity bake where a gap is provided between the hot plate and the substrate, and a direct bake where no gap is provided. Then, in order to obtain a diffusion effect by PEB without causing the substrate to be warped, a method of performing direct baking after performing proximity baking is preferable. The heating temperature is 90 ~: L 40 ° C, especially 110 ~ 130 preferable.

When the resist film after PEB is subjected to a developing treatment using a developing solution, for example, an alkaline aqueous solution such as a 1 to 10% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), the exposed portions are dissolved and removed. Thus, a resist pattern is formed. When a mask on which both the resist pattern forming mask pattern of 2.0 or less and the resist pattern forming mask pattern of more than 2.0 m are drawn is used, the resist pattern for the integrated circuit and the liquid crystal are formed on the substrate. A resist pattern for the display portion is simultaneously formed.

Further, the resist pattern can be formed by washing the developing solution remaining on the resist pattern surface with a rinse solution such as pure water.

Since the positive photoresist composition for LCD of the present invention has excellent linearity, a resist pattern that faithfully reproduces both rough and fine mask patterns can be obtained. Therefore, when a step of simultaneously forming a resist pattern using a mask on which both are drawn is performed, a resist pattern for an integrated circuit having a pattern size of 2.0 m or less and a resist pattern of more than 2.0 m are formed on the substrate. The resist pattern for the liquid crystal display portion can be formed at the same time.

As described above, the positive photoresist composition of the present invention is suitable for an exposure process under low NA conditions. It is also suitable for i-line exposure processes. Therefore, in the manufacture of LCD, a resist pattern of at least a display portion can be obtained with high resolution.

Further, since the positive photoresist composition of the present invention is excellent in linearity under low NA conditions, a rough pattern and a fine pattern can be formed on one substrate under the same exposure conditions. Therefore, even under a low NA condition, a resist pattern for a display portion of a system LCD and a finer integrated circuit portion can be obtained at a high resolution at the same time, which is suitable for manufacturing a system LCD. In addition, by using an alcohol-soluble nopolak resin containing 3,4-xylenol as the component (A), heat resistance is improved, and the residual film property after alkali development is improved. Furthermore, since the resolution is good, the system Suitable for LCD.

Furthermore, high sensitivity can also be realized by a combination of phenols in the essential alcohol-soluble novolak resin.

It also has the effect of reducing scum generation.

In addition, in the positive photoresist composition for LCD, it is necessary that the width of the depth of focus (DOF) is large to some extent from the viewpoint of production efficiency, easy control of production conditions, and the like. The positive photoresist composition for LCD can realize a range of depth of focus (for example, 15 / m or more) that can be practically used for LCD.

Note that good linearity is not equivalent to high resolution characteristics, and a positive resist composition may have poor linearity even if resolution is good.

In contrast, the positive photoresist composition for LCDs of the present invention can provide high resolution under low NA conditions (a uniform and good resolution can be obtained even when a large area is exposed) and a linearity. It is also preferable, and can be preferably used as a general positive photoresist composition for LCDs, and is particularly suitable for system LCDs.

Further, according to the method for forming a resist pattern of the present invention using the above positive photoresist composition having excellent resolution under low NA conditions, throughput in the production of LCD is improved.

Further, according to the method for forming a resist pattern of the present invention, a high-resolution resist pattern can be formed even in an exposure process under a low NA condition suitable for LCD production. In particular, a resist pattern for an integrated circuit with a pattern size of 2.0 m or less, for example, and a resist pattern for a liquid crystal display portion with a pattern size of more than 2.0 m, for example, can be simultaneously formed on a substrate. It can be used favorably in the manufacture of LCDs. Example

Next, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to this.

[Method for evaluating positive photoresist composition]

The following physical properties of the positive photoresist compositions of the following Examples or Comparative Examples

The evaluation methods (1) to (5) are described below.

(1) Linearity evaluation:

Glass substrate (55 OmmX 65 Omm) on which a Ti film is formed using a positive photoresist composition by a resist coating device for large substrates (apparatus name: TR3600 manufactured by Tokyo Ohka Kogyo Co., Ltd.) After application on top, the temperature of the hot plate is set to 100 ° C, the first drying is performed for 90 seconds by a proximity bake with an interval of about lmm, and then the temperature of the hot plate is set to 90 ° C The second drying was performed for 90 seconds by a proximity bake with an interval of 0.5 mm to form a resist film having a thickness of 1.5 τη.

Then, through a test chart mask (reticle) on which a mask pattern for reproducing the 3.0 m line-and-space (L & S) and 1.5 L & S resist patterns was drawn simultaneously, an i-line exposure device (device name: FX- Selective exposure was carried out using an exposure dose (Eop exposure dose) that can faithfully reproduce 3.0 tmL & S, using 7002J, manufactured by Nicon Corporation; NA = 0.14).

Next, the temperature of the hot plate is set to 120 ° C, a heat treatment is performed for 30 seconds by a proximity bake at intervals of 0.5 mm, and then a direct bake is performed at the same temperature without any space. Heat treatment was performed for 60 seconds.

Next, a 23.degree. C., 2.38 mass% TMAH aqueous solution was developed using a developing device (device name: TD-3900, demonstration machine, manufactured by Tokyo Ohka Kogyo Co., Ltd.) having a slit nozzle. As shown in 1, from the substrate end portion X to Y through Z, it took 10 seconds to pour the liquid on the substrate, held for 55 seconds, washed with water for 30 seconds, and spin-dried. Then, the cross-sectional shape of the obtained resist pattern was observed by SEM (scanning electron microscope) photograph, and the reproducibility of the 1.5 mL & S resist pattern was evaluated.

(2) Sensitivity evaluation:

The above Eop exposure amount was used as an index for sensitivity evaluation. (3) Evaluation of resolution:

The limiting resolution at the above E op exposure was determined.

(4) DOF characteristics evaluation:

In the above Eop exposure amount, the focus was shifted up and down as appropriate, and the width of the depth of focus (DOF) obtained in 1.5 mL & S within the range of the dimensional change rate of 10% of the soil was obtained in units of / zm.

(5) Scum rating:

At the above Eop exposure amount, the substrate surface on which 1.5 mL & S was drawn was observed with an SEM to check for scum.

(6) Heat resistance evaluation:

At the above Eop exposure amount, the substrate on which 1.5 mL & S is drawn is left on a hot plate set at 140 for 300 seconds, and then left in an oven set at 200 ° C for 30 minutes. did. As a result, ◎ indicates that the dimensional change rate of 1.5 mL & S was more than 100% to 105% or less, 105 indicates that the dimensional change rate was more than 105% to 110% or less, and X indicates that the rate of change was more than 110%. expressed.

(Example 1)

The following components were prepared as components (A) to (D).

(A) 100 parts by mass of alkali-soluble nopolak resin

A1: [M-cresol Z3,4-xylenol = 9Z1 (molar ratio) 1 mole of mixed phenol and propionaldehyde Z formaldehyde = 0.83 mole of mixed aldehyde of 1/3 (molar ratio) Nopolak resin of Mw = 4750, Mw / Mn (dispersion degree) = 2.44, synthesized by a method] (B) Naphthoquinonediazide ester 40 mass 咅 β

Naphthoquinonediazide esterified compound of B1 / B2 / B3 mixed with 6Z1Z1 (mass ratio)

Β1: モル 1'1 mole and 1,2-naphthoquinonediazide-5-sulfonic acid Mouth ride (hereinafter referred to as “5-NQD”) Esterification reaction product with 2 moles

B 2: Esterification reaction product of 1 mol of B 2 ′ and 4 mol of 5-NQD B 3: Esterification reaction product of 1 mol of B 3 ′ and 2 mol of 5—NQD (C) phenolic hydroxyl group Compound 25 parts by mass

C 1: 1- [1- (4-hydroxyphenyl) isopropyl] —4 -— [1,1-bis (4-hydroxyphenyl) ethyl] benzene

(D) Organic solvent

D1: PGMEA surfactant (product name "R-08"; equivalent to 450 ppm based on the total weight of components (A) to (C) and components (A) to (C)) (Nippon Dainippon Ink and Chemicals Co., Ltd.) is dissolved in PGMEA, which is the component (D), and the solid content [total of (A) to (C) components] is adjusted to 25 to 28% by mass. This was filtered using a membrane filter having a pore size of 0.2 to prepare a positive photoresist composition.

(Examples 2 to 6), (Comparative Examples 1 to 5)

A positive photoresist composition was prepared in the same manner as in Example 1 except that the components (A) to (D) were changed to those shown in Table 1 below. table 1

(A) (B) (C) (D)

(Mass ratio)

1 A1 C 1 D 1

Out

Example 2 A2 Same as above Same as above Same as above

3 A3 Same as above Same as above 4 A4 Same as above Same as above

5 A1 Same as above Same as above D2

6 Same as above Same as above D 3

1 A5 Same as above D 1

Ratio 2 A6 Same as above Same as above Same as above

Comparison 3 A7 Same as above Same as above Same as above

Example 4 A8 Same as above Same as above Same as above

5 A 1 Same as above C 2 Same as above Note that Al, B1 to 3, C1 and D1 in Table 1 are as described above.

For component (B), B 1 / B 2 / B 3 (6/1/1) means that B 1 / B 2 / B 3 is mixed at a mass ratio of 6/1/1 as described above. Indicates that it was used.

A2-8, C2, and D2-3 are as follows.

A 2: m-cresol Z 3,4 Using 1 mole of a mixed phenol of 97/3 (molar ratio) and 0.86 mole of a mixed aldehyde of propionaldehydenoformaldehyde = 1/3 (molar ratio) Nopolak resin of Mw = 7000, Mw / Mn = 3.5 synthesized by a conventional method

A3: Synthesized by a conventional method using 1 mol of a mixed phenol of m-cresol / 3,4-monoxylenol = 64 (molar ratio) and 0.86 mole of a mixed aldehyde of propionaldehyde formaldehyde = 1Z3 (molar ratio). Nopolak resin with Mw = 4000, Mw / Mn = 2.5

A 4: m-cresol Z 3,4 1-xylenol / 2,5-1-xylenol = 1 mole of a mixed phenol 60/15/25 (molar ratio) and formaldehyde / salicylaldehyde = 4/1 (molar ratio) mixed aldehyde Nopolak resin with Mw = 7000 and Mw / Mn = 3.5 synthesized by a conventional method using 0.85 mol

A 5: m-cresol Zp-cresol 2,3,5-trimethylphenol (1 mol) mixed with 45/35/25 (molar ratio) and formaldehyde Z salicylaldehyde = 2 Z1 (mol Nopolak resin of Mw = 5000, Mw / Mn = 3.5, synthesized using 0.85 mol of a mixed aldehyde of the following ratio: A 6: m-cresol Zp-cresol Z 2,3,5-trimethylphenol = Mw = 4000 synthesized by a conventional method using 1 mol of a mixed phenol at 90/5/5 (molar ratio) and 0.85 mol of a mixed aldehyde of formaldehyde / crotonaldehyde = 2/1 (molar ratio). , Mw / Mn = 3.05 nopolak resin

A7: Nopolak resin of Mw = 7050, Mw / Mn = 3.5 synthesized by a conventional method using 1 mol of m-cresol and 0.85 mol of formaldehyde

A8: m-cresol / p-cresolno 2,3,5-trimethylphenol =

1 mole of a mixed phenol at 45/35/25 (molar ratio) and 0.

Nopolak resin of Mw = 2500, Mw / Mn = 1.9 synthesized by conventional method using 85 mol

C 2: Nopolak low molecular weight compound with Mw = 1300 synthesized using m-cresol and formaldehyde

D 2: 2—Hep Yu Non

D 3: Ethyl lactate

Table 2

High resolution under low NA conditions is required for a positive photoresist composition for LCD.

In addition, linearity is required for system LCDs.

Heat resistance and sensitivity are commonly required for LCDs and system LCDs.

As is clear from the results shown in Table 2, the compositions of Example 18 all satisfied the conditions.

In addition, there was no scum and the depth of focus (DOF) was wide, and these points were favorable.

On the other hand, in the composition of Comparative Example 1, since the component (A) was different from that of the present invention, the evaluation of linearity, sensitivity, and resolution was good, but scum was observed. Therefore, the material was difficult to commercialize as a product.

The composition of Comparative Example 2 has a very low sensitivity of 100 mJ because the component (A) is different from that of the present invention, and is adopted in the field of LCD manufacturing where high sensitivity of about 5 OmJ is required. Was a very difficult material.

The composition of Comparative Example 3 has a linearity because the component (A) is different from that of the present invention. Was bad.

The composition of Comparative Example 4 was inferior in linearity and narrow in the depth of focus (DOF) because the component (A) was different from that of the present invention. Industrial applicability

In the method of producing a positive photoresist composition for LCD and a resist pattern according to the present invention, good resolution can be obtained even under low NA conditions. Also, since it has excellent linearity under low NA conditions, it is suitable for the production of system LCD.

Claims

1. (A) an alkali-soluble resin component containing an alkali-soluble nopolak resin which can be synthesized by a condensation reaction of a phenol containing 3,4-xylenol with an aldehyde,

C) a phenolic hydroxyl group-containing compound having a molecular weight of 100 or less,

(D) an organic solvent,

A di-type photoresist composition for LCD production, comprising:

2. The method according to claim 1, wherein the alcohol-soluble nopolak resin contains an alkali-soluble nopolak resin which can be synthesized using a phenol containing 3-surrounding, 4-xylenol and m-cresol. Positive photoresist composition for LCD production. 3. The alkali-soluble nopolak resin is

3,4-Xylenol 5 to 30 mol%, m-cresol 95 to 40 mol%, and other phenols 0 to 30 mol% can be synthesized using phenols. 3. The positive photoresist composition for producing an LCD according to claim 2, wherein the composition is a soluble nopolak resin.

4. The positive photoresist according to claim 1, wherein the alkali-soluble nopolak resin is an alkali-soluble nopolak resin which can be synthesized using an aldehyde containing propionaldehyde and formaldehyde. Composition. 5. The content of propylene daricol monoalkyl ether acetate in the above component (D) is

2. The positive photoresist composition for producing an LCD according to claim 1, wherein the content is 50 to 100% by mass.

6. The positive photoresist composition for producing LCD according to claim 1, wherein the content of 2-heptanone in the component (D) is 50 to 100% by mass.

7. The positive photoresist composition for LCD production according to claim 1, which is used for an i-ray exposure process.

8. The positive photoresist composition for producing an LCD according to claim 1, which is used for an exposure process having an NA of 0.3 or less.

9. The positive photoresist composition according to claim 1, which is used for manufacturing an LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate.

10. (1) a step of applying the positive photoresist composition according to claim 1 onto a substrate to form a coating film,

(3) Selective exposure is performed on the above resist film using a mask on which both a mask pattern for forming a resist pattern of 2.0 or less and a mask pattern for forming a resist pattern of more than 2.0 m are drawn. Process,

(4) subjecting the resist film after the selective exposure to a heat treatment (post-exposure bake);

(5) The resist film after the above-mentioned heat treatment is subjected to a development treatment using an alkaline aqueous solution, and a resist pattern for an integrated circuit having a pattern size of 2. Simultaneously forming a resist pattern for the liquid crystal display part of

(6) A method for forming a resist pattern, comprising: rinsing the developer remaining on the surface of the resist pattern.

11. The method for forming a resist pattern according to claim 10, wherein the step (3) of performing selective exposure is performed by an exposure process using i-line as a light source.

12. The method of forming a resist pattern according to claim 10, wherein the step (3) of performing the selective exposure is performed by an exposure process under a low NA condition of NA of 0.3 or less.