KR100558125B1 - Positive photoresist composition for manufacturing system lcd, manufacturing method for the positive photoresist and formation method of resist pattern - Google Patents

Abstract

A positive type photoresist composition having excellent storage stability is provided, which is suitable for manufacturing a system LCD having an integrated circuit and a liquid crystal display portion formed on one substrate. The positive type photoresist composition for producing this system LCD contains (A) an alkali-soluble resin, (B) an esterification reaction product of a compound represented by the following general formula (I) and a 1,2-naphthoquinone diazidesulfonyl compound. It is obtained by dissolving a naphthoquinone diazide esterified compound, the (C) phenolic hydroxyl group containing compound whose molecular weight is 1000 or less, and (D) reduction inhibitor in the organic solvent.

Description

POSITIVE PHOTORESIST COMPOSITION FOR MANUFACTURING SYSTEM LCD, MANUFACTURING METHOD FOR THE POSITIVE PHOTORESIST AND FORMATION METHOD OF RESIST PATTERN}

FIG. 1 shows the application of a positive photoresist composition to a glass substrate, baked and dried for pattern linearity under low NA conditions, followed by pattern exposure, followed by developer with a slit coater over the developer from substrate end X to Z. Diagram of what was contained.

The present invention relates to a positive type photoresist composition for LCD production, in which an integrated circuit and a liquid crystal display portion are formed on one substrate, a method of producing the positive type photoresist composition, and a method of forming a resist pattern using the positive type photoresist composition.

Conventionally, as a resist material in the manufacture of a semiconductor element or a liquid crystal display device (LCD), especially a TFT, it is suitable for exposure to ghi lines (rays including both g lines, h lines and i lines), and is relatively inexpensive. From the viewpoint of high sensitivity, a novolak-naphthoquinonediazide-based positive photoresist composition using a novolak resin as an alkali-soluble resin and a naphthoquinone diazide group-containing compound as a photosensitive component (hereinafter also referred to as PAC) This has been widely used (see, for example, Japanese Unexamined Patent Publication Nos. 2000-131835, 2001-75272, 2000-181055, and 2000-112120).

In the case of LCD manufacture, since only the pixel part of a display is formed on a board | substrate, the positive type photoresist composition should just have the sensitivity which can form a very rough pattern (for example, about 3-5 micrometers). Therefore, as PAC, although the sensitivity is not high, since it is inexpensive, the esterification reaction product of a benzophenone type phenol compound and a 1, 2- naphthoquinone diazide-5-sulfonyl compound (benzophenone type PAC) This was mainly used. In addition, the benzophenone-based PAC has excellent storage stability, especially little change with sensitivity over time, and the resist pattern formed in LCD production also targets very rough dimensions as described above. For this reason, there has been no particular problem regarding the storage safety of the resist composition.

Recently, however, as a next-generation LCD, an integrated circuit portion such as a driver, a digital-to-analog converter (DAC), an image processor, a video controller, and a RAM is formed on the one glass substrate simultaneously with the display portion, a so-called "system LCD". There is an active development of technology for high performance LCDs (see, for example, Semiconductor FPD World 2001.9, pp.50-67). Hereinafter, in the present specification, an LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate as described above is referred to as a system LCD for convenience.

In such a system LCD, for example, the pattern dimension of the display portion is about 2 to 10 탆, whereas the integrated circuit portion is formed with a fine dimension of about 0.5 to 2.0 탆. Therefore, the resist composition for system LCD manufacture is basically requested | required the ability (high resolution and linearity) which can simultaneously form a fine pattern and a rough pattern in a favorable shape.

In addition, it is expected that low temperature polysilicon, particularly low temperature polysilicon formed in a low temperature process of 600 ° C. or lower, is suitable as a substrate of the system LCD in that the electrical resistance is smaller and the mobility is higher than that of amorphous silicon. Therefore, the development of the system LCD which uses low temperature polysilicon for a board | substrate is active, and the development of the resist composition suitable for manufacture of the system LCD using low temperature polysilicon is desired.

In the production of the system LCD as described above, in order to form a fine resist pattern, it is difficult to apply in the conventional benzophenone PAC suitable for ghi ray exposure, so that the use of a nonbenzophenone PAC suitable for i ray exposure is difficult. It is expected to be suitable. Moreover, since it is necessary to form a fine resist pattern, it is anticipated that the resist composition excellent in the storage stability in which the change with the resist over time is strictly suppressed like the manufacture of the semiconductor element mentioned above is expected.

However, according to the findings of the present inventors, the resist composition containing the non-benzophenone-based PAC is excellent in terms of resolution, but has a difficulty in storage stability and causes a change over time during storage after manufacture, resulting in sensitivity and Changes in resist properties such as resolution have sometimes occurred. Therefore, in the storage of the resist composition, it is necessary to strictly control the storage temperature in a limited temperature range of approximately 0 to 20 ° C. Moreover, even if temperature is controlled in this way, there exists a problem that only storage stability of about 6 months can be obtained. Therefore, it is not suitable for system LCD manufacture, such as the shape of the resist pattern formed by the change with the passage of the resist characteristic over time, or the cost becoming high for precise temperature control.

Accordingly, the present invention is a positive photoresist composition containing non-benzophenone-based PAC as a photosensitive component, which is suitable for the production of a system LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate, and excellent in storage stability, the positive thereof. An object of the present invention is to provide a method for producing a photoresist composition and a method for forming a resist pattern.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject, As a result, as a PAC, the positive type photoresist composition which used the esterification reaction product of the non-benzophenone type polyphenol compound and 1,2-naphthoquinone diazide sulfonyl compound is used. The positive photoresist composition obtained by blending a reducing agent such as benzoquinone is changed over time during bottle storage, and the phenomenon of causing a change over time in the resist properties is suppressed, and storage stability is improved. It was found that the material was suitable for system LCD production, and the present invention was completed.

That is, this invention (A) alkali-soluble resin, (B) following General formula (I)

[Wherein, R ¹ to R ⁸ 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 ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁹ may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in which case Q ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following general formula (II)

(In formula, R <^12> and R <^13> respectively independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C3-C6 cycloalkyl group. c represents an integer of 1 to 3), or Q ¹ may be bonded to the terminal of R ⁹ , in which case Q ¹ is between R ⁹ and Q ¹ and R ⁹ . Together with a carbon atom, a cycloalkyl group of 3 to 6 carbon atoms is represented; a and b represent the integer of 1-3; d represents an integer of 0 to 3; when a, b or d is 3, R ³ , R ⁶ or R ⁸ are not present; n represents an integer of 0 to 3]. A naphthoquinone diazide esterified product containing the esterification product of the compound represented by the above formula and the 1,2-naphthoquinone diazidesulfonyl compound, and (C) a phenol having a molecular weight of 1000 or less. Positive type photoresist composition for LCD manufacture in which integrated circuit and liquid crystal display part were formed on one board | substrate characterized by obtained by melt | dissolving a hydroxy group containing compound and (D) reducing agent in the organic solvent (Hereinafter, the positive type photoresist of this invention. Also referred to as resist composition).

Moreover, this invention is the manufacturing method of the said positive type photoresist composition which mixes the resin solution in which the said (D) component is mix | blended with the organic solvent solution of the said (A) component, and the said (B) component and (C) component. to provide.

The present invention also provides a process for forming a coating film by (1) applying the positive photoresist composition on a substrate, (2) heating (prebaking) the substrate on which the coating film is formed, and forming a resist film on the substrate, (3) a step of selectively exposing the resist film using a mask on which both a resist pattern forming mask pattern of 2.0 µm or less and a mask pattern for resist pattern formation exceeding 2.0 µm are drawn, (4) the above (5) Process of heat-processing (post exposure bake: PEB) with respect to the resist film after selective exposure, (5) Developing process using alkali aqueous solution is performed to the resist film after the said heat processing, and has a pattern dimension of 2.0 micrometers or less on the said board | substrate. Simultaneously forming a resist pattern for an integrated circuit and a resist pattern for a liquid crystal display portion larger than 2.0 mu m Provides a resist pattern forming method comprising the step.

(Embodiment of the Invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

<< Positive type photoresist composition for LCD manufacture >>

<(A) component>

(A) component is alkali-soluble resin.

The component (A) is not particularly limited, and may be optionally used one or two or more of those which can be normally used as a film forming material in the positive photoresist composition.

For example, phenols (phenol, m-cresol, p-cresol, xenol, trimethylphenol, etc.) and aldehydes (formaldehyde, formaldehyde precursors, propionaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, Novolak resin obtained by condensing 4-hydroxybenzaldehyde and the like) and / or ketones (methyl ethyl ketone, acetone and the like) in the presence of an acidic catalyst;

Hydroxystyrene resins such as homopolymers of hydroxystyrene, copolymers of hydroxystyrene and other styrene monomers, copolymers of hydroxystyrene and acrylic acid or methacrylic acid or derivatives thereof;

Acrylic acid or methacrylic acid resin which is a copolymer of acrylic acid or methacrylic acid, and its derivative (s) is mentioned.

In particular, a furnace obtained by condensation reaction of phenols containing at least two selected from m-cresol, p-cresol, 3,4-xylenol and 2,3,5-trimethylphenol with aldehydes containing formaldehyde Volac resin is suitable for manufacture of a resist material with high sensitivity and excellent resolution.

(A) component can be manufactured according to a conventional method.

Although the polystyrene conversion mass mean molecular weight by gel permeation chromatography of (A) component changes with the kind, it is 2000-100000, Preferably it is 3000-30000 from a sensitivity and a pattern formation surface.

(A) component can be manufactured according to a conventional method.

<(B) component>

Component (B) is a naphthoquinone diazide esterified product, and an esterification reaction product of the phenol compound represented by the general formula (I) and 1,2-naphthoquinone diazidesulfonyl compound (hereinafter referred to as a nonbenzophenone-based compound). PAC). The positive photoresist composition containing the non-benzophenol-based PAC is highly sensitive and high resolution. Moreover, it is suitable for the photolithography using i line | wire, and is also preferable also in the characteristics, such as linearity and a depth of focus (DOF).

In general formula (I), R <^1> -R <^8> is respectively independently a hydrogen atom, a halogen atom, the C1-C6 linear or branched alkyl group, the alkoxy group which has a C1-C6 linear or branched alkyl group, Or a cycloalkyl group having 3 to 6 carbon atoms; R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms; R ⁹ may be a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, in which case Q ¹ represents a hydrogen atom, a straight or branched alkyl group having 1 to 6 carbon atoms, or a residue represented by Formula (II), or Q ¹ may be bonded with the terminal of R ^9, in that case, Q ¹ is and R ^9, together with the carbon atoms between Q ¹ and R ⁹ represents a cycloalkyl group of 3 to 6 carbon chain; a and b represent the integer of 1-3; d represents an integer of 0 to 3; n represents the integer of 0-3.

Further, if the Q ¹ and R ⁹ form a cycloalkyl group of 3 to 6 carbon chain taken together with the carbon atoms between Q ¹ and R ⁹ include, in combination is Q ¹ and R ⁹ forms an alkylene group of a carbon number of 2 to 5 Doing.

As a phenolic compound corresponding to general formula (I), tris (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) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethyl Phenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4- Hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclo Hexyl-4-hydroxy- 2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2- Trisphenol-type compounds such as methylphenyl) -2-hydroxyphenylmethane and 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) -4-methylphenol Linear trinuclear phenolic compounds; 1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy- 5-methylbenzyl) -4-hydroxyphenyl] methane, bis [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-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Hydroxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2 -Hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl Linear tetranuclear phenol compounds such as 3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane; 2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxy Hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4 Linear polyphenol compounds such as linear 5-nuclear phenol compounds such as methylphenol;

Bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- ( 2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- ( 3'-fluoro-4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-tri Hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3 ', 5'-dimethylphenyl) Bisphenol-type compounds such as propane; 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl Multinuclear branched compounds such as) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene; Condensation type phenol compounds, such as 1, 1-bis (4-hydroxyphenyl) cyclohexane, etc. are mentioned.

These can be used 1 type or in combination or 2 or more types.

Especially, it is preferable to have a trisphenol-type compound as a main component from a viewpoint of high sensitivity and resolution, and it is especially bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane. [Hereinafter referred to as (B1 ')], and bis (4-hydroxy-2,3,5-trimethyl phenyl) -2-hydroxyphenylmethane [hereinafter referred to as (B3')] are preferable. In addition, for the purpose of producing a resist composition having excellent total balance of resist properties such as resolution, sensitivity, heat resistance, DOF characteristics, and linearity, a linear polyphenol compound, a bisphenol type compound, a multinuclear branched compound, a condensation type phenol compound, and the like can be used. It is preferable to use together with the said trisphenol type compound, Especially, when using a bisphenol type compound especially, bis (2, 4- dihydroxy phenyl) methane [hereinafter, (B2 ')], it is excellent in a total balance. Resist compositions can be prepared.

In addition, the naphthoquinone diazide esterified product of each of said (B1 '), (B2'), (B3 ') is abbreviated as (B1), (B2), (B3).

When using (B1) and (B3), it is preferable that the compounding quantity in (B) component is 10 mass% or more and 15 mass% or more, respectively. Further, each may be 90 mass% or less, preferably 85 mass% or less.

Moreover, when using all of (B1), (B2), and (B3), each compounding quantity is 50-90 mass% of (B1), Preferably it is 60-80 mass%, (B2) from a viewpoint of an effect. The compounding quantity of is 5-25 mass%, Preferably it is 10-15 mass%, The compounding quantity of (B3) becomes 5-25 mass%, Preferably it is 10-15 mass%.

The naphthoquinone diazide sulfonic-acid esterification method of all or one part of the phenolic hydroxyl group of the compound represented by the said General formula (I) can be performed by a conventional method.

For example, it can obtain by condensing naphthoquinone diazide sulfonyl chloride with the compound represented by the said general formula (I).

Specifically, for example, a compound represented by the above general formula (I) and naphthoquinone-1,2-diazide-4 (or 5) -sulfonyl chloride are selected from dioxane, n-methylpyrrolidone, and dimethylacetate. The product obtained by dissolving a predetermined amount in organic solvents, such as an amide and tetrahydrofuran, adding at least 1 type of basic catalysts, such as triethylamine, a triethanolamine, a pyridine, alkali carbonate, and an alkali hydrogen carbonate, wash | cleans with water, It can be prepared by drying.

As the component (B), as described above, in addition to these illustrated preferred naphthoquinone diazide esterates, other naphthoquinone diazide esterates which are generally used as photosensitive components in positive photoresist compositions can also be used. For example, esterification products of phenol compounds such as polyhydroxybenzophenone and alkyl gallate and naphthoquinone diazide sulfonic acid compounds can also be used. These other naphthoquinone diazide esterified products can be used selecting 1 type (s) or 2 or more types arbitrarily.

It is preferable that the usage-amount of these other naphthoquinone diazide esterified products is 80 mass% or less, especially 50 mass% or less in (B) component from a viewpoint of the improvement of the effect of this invention.

The compounding quantity of (B) component in a photoresist composition becomes 20-70 mass% with respect to the total amount of (A) component and the following (C) component, Preferably it is 25-60 mass%.

By making the compounding quantity of (B) component more than the said lower limit, the image faithful to a pattern is obtained and transferability improves. By below the said upper limit carrying out, the degradation of a sensitivity can be prevented, the homogeneity of the resist film formed is improved, and the effect that resolution is improved is acquired.

The resist properties required for the resist composition in system LCD production are as follows.

For example, in the field of LCD manufacturing, including system LCDs, high sensitivity is desired from the viewpoint of throughput improvement and process controllability.

Moreover, in manufacture of LCD, a large glass substrate is used compared with the semiconductor field. Therefore, in order to widen the exposure area, it is considered preferable to use an exposure process with a condition of low NA (numerical aperture of lens). Among them, in the case of system LCDs, since integrated circuit portions are also formed on the substrate in addition to the display portion, the substrate tends to be larger in size, which is lower than that in ordinary LCD manufacture, for example, 0.3 or less, especially It is considered preferable to use an exposure process with a low NA condition of 0.2 or less.

Moreover, in the case of the exposure process in the low NA conditions as mentioned above, although the resolution tends to worsen, in system LCD, although the pattern dimension of a display part is about 2-10 micrometers, for example, an integrated circuit part Since silver is formed in the fine dimension about 0.5-2.0 micrometers, the high resolution which can form a fine resist pattern is also desired.

In addition, it is also desired that the linearity characteristic and the like which can accurately form the resist pattern of the display portion and the integrated circuit portion of the display portion having largely different dimensions at the same time are desired.

In the present invention, as the component (B), by using an esterification reaction product of a specific phenol compound represented by the general formula (I) and 1,2-naphthoquinone diazidesulfonyl compound, it is highly sensitive, for example, low A positive type photoresist composition having high resolution and good characteristics such as linearity even under NA conditions is obtained.

<(C) component>

(C) component is a phenolic hydroxyl group containing compound. By using this (C) component, the positive type photoresist composition suitable for system LCD which is excellent in a sensitivity improvement effect, and also high sensitivity, high resolution, and also linearity excellent also in the i line | wire exposure process in low NA conditions is obtained. .

It is preferable from the viewpoint of the said effect that the molecular weight of (C) component is 1000 or less, Preferably it is 700 or less, substantially 200 or more, Preferably it is 300 or more.

(C) As a component, as a sensitivity improving agent or a sensitizer, it is a phenolic hydroxyl group containing compound generally used for a resist composition, Preferably there is no restriction | limiting in particular if it satisfy | fills the conditions of the said molecular weight, One type or two or more types It can be chosen arbitrarily. And especially, the following general formula (III)

[Wherein, R ²¹ to R ²⁸ 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 ³⁰ and R ³¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ²⁹ may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in which case Q ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a residue represented by the following general formula (IV):

(In formula, R <^32> and R <^33> respectively independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C3-C6 cycloalkyl group. ; g represents an integer of 0 to 3) and Q ² or may be bonded to the terminal of R ^29, in that case, Q ² is burnt together with the carbon atoms between R ²⁹ and, Q ² and R ²⁹ A cycloalkyl group of small chains 3 to 6 is represented; e and f represent the integer of 1-3; h represents an integer of 0 to 3; when e, f or h is 3, R ²³ , R ²⁶ or R ²⁸ are not present; m represents an integer of 0 to 3].

More specifically, bis (3-methyl-4-hydroxyphenyl) other than the phenolic compound represented by general formula (I) used by the naphthoquinone diazide esterified product illustrated, for example in the said (B) component 4-isopropylphenylmethane, bis (3-methyl-4-hydroxyphenyl) -phenylmethane, bis (2-methyl-4-hydroxyphenyl) -phenylmethane, bis (3-methyl-2-hydroxy Phenyl) -phenylmethane, bis (3,5-dimethyl-4-hydroxyphenyl) -phenylmethane, bis (3-ethyl-4-hydroxyphenyl) -phenylmethane, bis (2-methyl-4-hydroxy Trisphenyl type compounds, such as phenyl) -phenylmethane and bis (2-tert- butyl-4, 5- dihydroxyphenyl) -phenylmethane, can be used suitably. Among them, bis (2-methyl-4-hydroxyphenyl) -phenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) Ethyl] benzene is preferred.

The compounding quantity of (C) component is 10-70 mass% with respect to (A) component from a viewpoint of an effect, Preferably it is the range of 20-60 mass%.

<(D) component>

(D) component is a reduction inhibitor. By using a reducing agent, the positive type photoresist composition excellent in storage stability and suitable for system LCD is obtained.

The present inventors are one of the causes of inferior storage stability of conventional resist compositions using non-benzophenone-based PACs. Non-benzophenone-based PACs have lower acidity compared to benzophenone-based PACs, and therefore, Since the acidity is also relatively low, the reducing action tends to proceed in the resist composition, and it is found that deterioration of resist characteristics over time, in particular over time, of sensitivity occurs during bottle storage. The problem of storage stability was solved by mix | blending the material which prevents the reducing effect.

As a reduction inhibitor, what is generally used as a inhibitor of a free radical chain reaction can be used, for example.

As such a reduction inhibitor, the compound of Unexamined-Japanese-Patent No. 10-232489 is mentioned, for example, A quinone type compound, such as benzoquinone and a naphthoquinone, can be illustrated. Especially, benzoquinone is used suitably.

As benzoquinone, o-benzoquinone, p-benzoquinone, etc. are mentioned, Preferably it is p-benzoquinone.

Examples of naphthoquinone include 1,2-naphthoquinone, 1,4-naphthoquinone, 2,6-naphthoquinone, and the like, and preferably 1,4-naphthoquinone.

The compounding quantity of (D) component in a positive photoresist composition shows an effect in about 0.1-1.0 mass% with respect to all solid content other than the (D) component contained in a resist composition.

In addition, the reducing agent used in the present invention itself is reduced in the positive photoresist composition during the storage period. For this reason, in the resist composition, instead of the reducing agent, a reducing agent corresponding to the reducing agent is present, and the amount thereof increases with the storage time.

As the reducing agent, for example, hydroquinone is applicable when the reducing agent is benzoquinone.

There is no reason for actively adding a reducing agent such as hydroquinone to the positive photoresist composition, and therefore, the positive photoresist composition of the present invention is used even when the positive photoresist composition containing the reducing agent does not contain a reducing agent. It can be said that it was obtained by the manufacturing method of the positive photoresist composition of this invention.

<Organic solvent>

Although the organic solvent can be used 1 type or 2 types or more without a restriction | limiting in particular if it is a general thing used for a photoresist composition, The thing containing propylene glycol monoalkyl ether acetate and / or 2-heptanone is excellent in applicability | paintability, It is preferable at the point which is excellent in the film thickness uniformity of the resist film on a large glass substrate.

In addition, although both propylene glycol monoalkyl ether acetate and 2-heptanone can be used, respectively, when using individually or in mixture with another organic solvent is preferable from a viewpoint of the film thickness uniformity at the time of application | coating using a spin coat method etc. There are many.

It is preferable to contain 50-100 mass% of propylene glycol monoalkyl ether acetates in all the organic solvents.

Propylene glycol monoalkyl ether acetate has, for example, a linear or branched alkyl group having 1 to 3 carbon atoms, and among them, propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMEA) is a resist on a large glass substrate. It is especially preferable because the film thickness uniformity of the film is very excellent.

On the other hand, 2-heptanone is not particularly limited, but as described above, (B) naphthoquinone diazide esterified product is a suitable solvent when combined with a nonbenzophenone-based photosensitive component.

2-heptanone is excellent in heat resistance compared to PGMEA and has the property of providing a resist composition with reduced scum generation, and is a very preferred solvent.

When using 2-heptanone individually or in mixture with another organic solvent, it is preferable to contain 50-100 mass% in all the organic solvents.

Moreover, you may use it, mixing another solvent with these preferable solvents.

For example, when alkyl lactate, such as methyl lactate and ethyl lactate (preferably ethyl lactate), is mix | blended, it is preferable because it is excellent in the film thickness uniformity of a resist film, and can form the resist pattern excellent in shape.

When using a mixture of propylene glycol monoalkyl ether acetate and alkyl lactate, it is preferable to mix | blend 0.1-10 times, preferably 1-5 times the amount of alkyl lactate with respect to propylene glycol monoalkyl ether acetate.

Moreover, organic solvents, such as (gamma) -butyrolactone and a propylene glycol monobutyl ether, can also be used.

When using gamma -butyrolactone, it is preferable to mix | blend in the range of 0.01-1 time, preferably 0.05-0.5 time by mass ratio with respect to propylene glycol monoalkyl ether acetate.

Moreover, as an organic solvent which can be mix | blended other, the following are mentioned specifically ,, for example.

Namely, ketones, such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isoamyl ketone; Ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate or polyhydric compounds such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Alcohols and derivatives thereof; Cyclic ethers such as dioxane; And esters such as methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate.

When using these solvents, it is preferable that they are 50 mass% or less in all the organic solvents.

The usage-amount of the organic solvent is suitably adjusted so that a uniform positive photoresist composition may be obtained when dissolving the solid content ((A) to (D) components and other components to be used later, as necessary). . Preferably, it is used so that solid content concentration may be 10-50 mass%, More preferably, it is 20-35 mass%. In addition, solid content of a positive photoresist composition is corresponded to the sum total of (A)-(D) component and the other component used as needed.

In the positive photoresist composition of the present invention, additives, plasticizers, storage stabilizers, etc., for improving the performance of a compatible additive, for example, a resist film, etc., as necessary, within a range that does not impair the object of the present invention, Common additives such as a surfactant, a coloring agent for making the developed image more visible, a sensitizer for improving the sensitizing effect, a dye for preventing halation, and an adhesion improving agent may be contained.

As a dye for prevention of halation, an ultraviolet absorber (for example, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2', 4'-dihydroxybenzophenone, 5-amino 3-Methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4-di Ethylaminoazobenzene, curcumin, etc.) may be used.

Surfactants can be added, for example, for the prevention of striation, etc., for example, fluoride FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), F-top EF122A, EF122B, EF122C, EF126 ( Fluorine-based surfactants, such as a brand name and the Tochem Products Co., Ltd. product, XR-104, Megapack R-08 (brand name, Dainippon Ink Chemical Co., Ltd. product), etc. can be used.

It is preferable that the positive photoresist composition of this invention is manufactured so that Mw (henceforth a resist molecular weight) of solid content contained in this resist composition may exist in the range of 5000-30000, More preferable Mw is 6000-10000. . By setting the resist molecular weight within the above range, a positive photoresist composition can be obtained without sacrificing sensitivity and having excellent linearity and DOF characteristics and excellent heat resistance.

If the resist molecular weight is smaller than the above range, resolution, linearity, DOF characteristics, and heat resistance will be insufficient, and if it exceeds the above range, the decrease in sensitivity will be remarkable, and the applicability of the resist composition may be impaired.

In this specification, the value measured using the following GPC system is used as a resist molecular weight.

Device name: SYSTEM 11 (Product name, manufactured by Showa Electric Works)

Precolumn: KF-G (trade name, manufactured by Shodex)

Column: KF-805, KF-803, KF-802 (product name, manufactured by Shodex)

Detector: UV41 (trade name, manufactured by Shodex), measured at 280 nm.

Solvent and the like: Tetrahydrofuran was poured at a flow rate of 1.0 ml / min and measured at 35 ° C.

Measurement sample preparation method: The photoresist composition to be measured is manufactured so that a solid content concentration may be 30 mass%, this is diluted with tetrahydrofuran, and the measurement sample whose solid content concentration is 0.1 mass% is created.

20 µl of the measurement sample is injected into the apparatus and measured.

In system LCD manufacturing, instead of the g line (436 nm) exposure conventionally used for the manufacture of LCD, there is a tendency to use a photolithography technique using a shorter wavelength i line (365 nm) exposure to increase the resolution. have. In contrast, the positive photoresist composition of the present invention, in particular using a non-benzophenone-based compound as component (B) and optionally as component (C), absorbs i-rays by component (B) and component (C). Since is suppressed, it is suitable for an i line | wire exposure process and can implement | achieve a high resolution further more.

In the production of the positive photoresist composition of the present invention, as a method for producing the resist molecular weight to be in the above-mentioned suitable range, for example, (1) before mixing so that Mw after mixing all the components becomes the above range (A ) A method of adjusting the Mw of the component (A) to an appropriate range in advance, for example, by performing a classification operation on the component, (2) A plurality of (A) components having different Mw are prepared, and this is appropriately blended to obtain the Mw of the solid content. And the like in the above range.

Among these production methods, in particular, the production method according to the above (2) is more preferable from the viewpoint of easy adjustment of the resist molecular weight and sensitivity adjustment.

<< Production method of positive type photoresist composition for system LCD manufacture >>

The positive photoresist composition of the present invention is preferably prepared by dissolving the component (A), the component (B), the component (C), the component (D), and other components in an organic solvent, if necessary. Although this manufacture can mix | blend the component (D) with the other component at the time of manufacture of a positive type photoresist composition, More preferably, the organic solvent solution of (A) component which the (D) component was mix | blended is used. The method for producing a positive photoresist composition for producing a system LCD of the present invention for producing a positive photoresist composition is preferably used.

The manufacturing method of the positive type photoresist composition for system LCD manufacture of this invention mixes the resin solution which the said (D) component is mix | blended with the organic solvent solution of the said (A) component, and the said (B) component and (C) component Way.

According to the investigation by the present inventors, in the manufacture of the positive type photoresist composition for producing the system LCD of the present invention, simply by blending the component (D) in an organic solvent containing the component (A) or the like, It was found that the change over time of quality could not be prevented, and even the same product may cause the variation of the characteristics between lots. As a result of further studies by the present inventors, it has been conventionally considered that only PAC deterioration causes deterioration of the photoresist composition. It has been found that this is the cause of variation in resist characteristics between the lots.

That is, when (A) component is preserve | saved in the state of the organic solvent solution, it will deteriorate with time and this has produced the variation of the resist characteristic between lots.

Therefore, in the manufacturing method of the positive photoresist composition of this invention, the organic solvent solution (solution (I)) of (A) component is obtained first. Although the density | concentration of (A) component in this solution (I) is not specifically limited, Usually, it is common to set it as 20-60 mass%, especially 35-55 mass%, and also it is preferable.

Next, the organic solvent solution (solution (II)) containing (A) component and (D) component is obtained by mix | blending (D) component with respect to solution (I) manufactured as mentioned above.

It is preferable to mix | blend component (D) with the same means as the following 1-2, in order to avoid the problem of particle generation after resist manufacture.

1. At room temperature (20-25 degreeC), (D) component is mix | blended with the organic solvent same as the organic solvent used for solution (I) so that it may become 10-20 mass% concentration, and it stirred for 10 minutes or more, and made it melt | dissolve completely. Solution.

2. The solution of component (D) is added to the solution (I) in small portions to obtain the solution (II).

Subsequently, (B) component and (C) component are added to solution (II), a ultraviolet absorber, surfactant, etc. are added as needed, if necessary, a solvent is added again and concentration adjustment is carried out, and it is set as a uniform solvent (III), The positive photoresist composition of the invention is obtained. The kind of solvent added may be the same as or different from the organic solvent used for solution (I), (II), etc. Moreover, the obtained solution (III) can also be filtered with a membrane filter etc.

In addition, in this invention, what is remarkable is that the solution (II) is prepared by adding the component (D) in the amount required for stability of the component (A) in the solution (I), and the solution (II) is positive. Only by manufacturing a type | mold photoresist composition, a stable positive type photoresist composition is obtained. That is, it is not necessary to add a stabilizer etc. newly, such as addition of (D) component with respect to the newly added (B) component.

As described above, in the production method of the present invention, as a result of maintaining the storage stability of the component (A), the storage stability of the positive photoresist composition using the same is also maintained.

<< formation method of a resist pattern >>

Below, an example of the suitable formation method of the resist pattern at the time of manufacturing a system LCD using the positive photoresist composition of this invention is shown.

First, the positive type photoresist composition of this invention mentioned above is apply | coated to a board | substrate with a spinner etc., and a coating film is formed. As a board | substrate, a glass substrate is preferable. Amorphous silica is usually used as the glass substrate, but in the field of system LCD, a glass substrate having a low temperature polysilicon layer or the like is considered to be preferable. As this glass substrate, since the positive photoresist composition of this invention is excellent in the resolution under low NA conditions, a large size board | substrate of 500 mm x 600 mm or more, especially 550 mm x 650 mm or more can be used.

Subsequently, the glass substrate in which this coating film was formed is heat-processed (prebaked) at 100-140 degreeC, for example, and a residual solvent is removed and a resist film is formed. As a prebaking method, it is preferable to perform a proximity baking with a space | interval between a hotplate and a board | substrate.

In addition, the resist film is subjected to selective exposure using a mask on which a mask pattern is drawn.

As a light source, in order to form a fine pattern, it is preferable to use i line (365 nm). Moreover, it is preferable that the exposure process employ | adopted by this exposure is the exposure process of the low NA condition whose NA is 0.3 or less, Preferably it is 0.2 or less, More preferably, it is 0.15 or less.

Next, heat treatment (post exposure bake: PEB) is performed on the resist film after selective exposure. Examples of the PEB method include a proximal bake with a gap between the hot plate and the substrate, and a direct bake without a gap. The method of performing direct baking is preferable. Moreover, heating temperature is 90-150 degreeC, especially 100-140 degreeC is preferable.

When the development process using the developing solution, for example, alkaline aqueous solution, such as 1-10 mass% tetramethylammonium hydroxide aqueous solution, is performed with respect to the resist film after the said PEB, an exposure part will melt | dissolve and remove, and the resist for integrated circuits on a board | substrate will be carried out. The pattern and the resist pattern for the liquid crystal display portion are simultaneously formed.

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

In this method of forming a resist pattern, when producing a system LCD, a mask pattern for forming a resist pattern of 2.0 µm or less and a mask for forming a resist pattern exceeding 2.0 µm are used as the mask in the step of performing the selective exposure. You can use a mask with both sides of the pattern drawn.

And since the positive photoresist composition for LCDs of this invention is excellent in resolution, the resist pattern which faithfully reproduced the fine pattern of a mask pattern is obtained. Therefore, in the step of simultaneously forming the resist pattern, it is possible to simultaneously form a resist pattern for integrated circuits having a pattern dimension of 2.0 μm or less and a resist pattern for liquid crystal display portions exceeding 2.0 μm on the substrate.

As described above, since the positive photoresist composition of the present invention contains non-benzophenone PAC, it is highly sensitive, suitable for i-ray exposure, and the like, and has high resolution even under low NA conditions.

In addition, since the reducing agent is blended, the phenomenon that changes over time during long-term storage in a bottle and changes in resist characteristics (sensitivity, dimension, film thickness, etc.) occurs over time is suppressed, and storage is prevented. Excellent stability In addition, conventionally, in order to prevent the change over time, it was necessary to strictly manage the storage temperature within a range of, for example, 0 to 20 ° C. The permissible range is wide and can be managed within the range of, for example, -10 to + 25 ° C. Moreover, the characteristics, such as linearity and DOF, are also favorable, and are suitable for system LCD manufacture.

(Example)

Hereinafter, an Example is shown and this invention is demonstrated in detail.

The following (1)-(3) were evaluated using the positive photoresist composition manufactured by the following Examples 1-3 and Comparative Example 1.

Assessment Methods

(1) Storage stability evaluation: evaluation of dimensions over time

Regarding the positive photoresist composition prepared in the following Examples or Comparative Examples, samples (i) stored at 25 ° C. for 6 months and samples (ii) stored at 6 ° C. for 6 months were prepared. .

In the case where the resist pattern is similarly formed using the said sample (i) in the Eop exposure amount (exposure amount (mJ) which can reproduce 1.5 micrometers L & S resist pattern faithfully) when the said sample (ii) is used, The dimensional change rate of 1.5 micrometer L & S pattern was calculated | required.

In addition, the resist pattern was formed as follows.

The sample was apply | coated on the silicon wafer using a spinner, and it dried on 90 degreeC for 90 second on the hotplate, and obtained the resist film with a film thickness of 1.05 micrometer. The film was selectively exposed to an i-ray exposure apparatus (product name "FX702J", manufactured by Nikon Corporation NA = 0.14), treated with PEB (post-exposure heating) at 110 ° C for 90 seconds, and then a TMAH aqueous solution having a concentration of 2.38% by mass (product name). `` NMD-3 '', manufactured by Tokyo Kogyo Co., Ltd., was developed at 23 ° C. for 90 seconds, and then rinsed for 30 seconds with pure water, followed by a drying step to obtain a 1.5 μm L & S pattern. Formed.

(2) Resolution Evaluation:

The limit resolution using the said sample (i) in the Eop exposure amount at the time of using the said sample (ii) was calculated | required.

(3) Linearity Evaluation:

Each sample (i) was applied onto a glass substrate (550 mm x 650 mm) on which a Ti film was formed using a resist coating apparatus for large substrates (apparatus name: TR36000, manufactured by Tokyo Kogyo Co., Ltd.), and then hot The temperature of a plate is 100 degreeC, the 1st drying for 90 second is carried out by the proximity baking which spaced about 1 mm, and then the temperature of a hotplate is 90 degreeC, and the clearance of 0.5 mm spaced The 2nd drying for 90 second was performed by baking, and the resist film with a film thickness of 1.5 micrometers was formed.

Subsequently, the i-line exposure apparatus (device name: FX-702J, through a test chart mask (reticle) on which a mask pattern for reproducing a resist pattern of 3.0 µm line and space (L & S) and a 1.5 µm L & S was simultaneously drawn. Using Nikon Corporation; NA = 0.14), selective exposure was performed at an exposure amount (Eop exposure amount) that can faithfully reproduce 1.5 µm L & S.

Subsequently, the temperature of the hotplate was set to 120 ° C, spaced 0.5 mm, heat treatment was performed by proximity bake for 30 seconds, and then heat treatment was performed for 60 seconds by direct bake without spacing at the same temperature.

Subsequently, as shown in FIG. 1, a 23 ° C., 2.38% by mass TMAH aqueous solution was used with a developing apparatus having a slit coater nozzle (device name: TD-39000 Demonstrator, manufactured by Toyo Kogyo Co., Ltd.). After passing from Y to Z, the solution was held on the substrate for 10 seconds, 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 with the SEM (scanning electron microscope) photograph, and the reproducibility of the resist pattern of 3.0 micrometers L & S was evaluated. The dimension change rate is less than +/- 10%, and A and more than 10%, 15% or less, and B and more than 15% are represented by C.

(Example 1)

The following were prepared as (A)-(D) component.

(A) Ingredient:

(A1): Mw = 20000, Mw / Mn = synthesized by a conventional method using 1 mol of mixed phenols of m-cresol / 3,4-xylenol = 8/2 (molar ratio) and 0.82 mol of formaldehyde. 5.2, novolak resin

(B) Ingredients:

(B1): 1 mol of bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane (B1 ') and 1,2-naphthoquinone diazide-5-sul Phenylchloride [hereinafter referred to as (5-NQD)] 2 moles of esterification reaction product

(B2): esterification product of 1 mol of bis (2,4-dihydroxyphenyl) methane (B2 ') with 2 mol of 5-NQD

(B3): esterification product of 1 mol of bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane (B3 ') with 2 mol of 5-NQD

(C) Ingredients:

(C1): bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane

(D) Ingredients:

(D1): p-benzoquinone

Organic solvents:

(E1): PGMEA

(Examples 1-3 and Comparative Example 1)

The said (A) component of the compounding quantity (mass part) of the following Table 1 was melt | dissolved in the organic solvent (E1), and the compound (D) component of the compounding quantity (mass part) of the following Table 1 was mix | blended and melt | dissolved here, Got it. To the solution, the component (B) and the component (C) of the compounding amount (mass part) shown in Table 1 were added and dissolved, and the resultant was filtered using a membrane filter having a pore diameter of 0.2 µm to form a positive photoresist composition. Prepared. The resist molecular weight of the obtained positive photoresist composition is written together in Table 1.

Each item of said (1)-(3) was evaluated about the obtained positive photoresist composition, respectively. The results are shown in Table 2 below.

(A) Component (Amount) (B) Component (mixing ratio) (mixing amount) (C) Component (Combination Amount) (D) Component (Amount of Compound) (E) Component (Amount of Compound) Resist molecular weight Example 1 A1 (15) B1 / B2 / B3 (mixing ratio 6/1/1) (mixing amount 5.5) C1 (4.5) D1 (0.3) E1 (75) 10000 Example 2 Same as above Same as above Same as above D1 (0.1) Same as above Same as above Example 3 Same as above Same as above Same as above D1 (0.5) Same as above Same as above Comparative Example 1 Same as above Same as above Same as above none Same as above Same as above

Evaluation of dimensions over time (%) Resolution Evaluation (μm) Linearity evaluation Example 1 -1.1 1.2 A Example 2 +2.0 1.2 A Example 3 -3.3 1.2 A Comparative Example 1 +3.6 ^{Note 1)} 1.4 A  Note 1) Result at 25 ° C and 1 month

The positive photoresist compositions of Examples 1 to 3 were superior to the resist composition of Comparative Example 1 in which no reducing agent was added, and were excellent in evaluation over time in the dimensions, and were good in storage stability. In addition, even in low NA conditions (NA = 0.14), resolution was good and linearity was also good.

As described above, the positive photoresist composition of the present invention is excellent in storage stability and suitable for system LCD manufacture.

Claims (7)

(A) Alkali-soluble resin, (B) following General formula (I)

[Wherein, R ¹ to R ⁸ 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 ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁹ may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in which case Q ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following general formula (II)

(In formula, R <^12> and R <^13> respectively independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C3-C6 cycloalkyl group. c represents an integer of 1 to 3), or Q ¹ may be bonded to the terminal of R ⁹ , in which case Q ¹ is between R ⁹ and Q ¹ and R ⁹ . Together with a carbon atom, a cycloalkyl group of 3 to 6 carbon atoms is represented; a and b represent the integer of 1-3; d represents an integer of 0 to 3; when a, b or d is 3, R ³ , R ⁶ or R ⁸ are not present; n represents an integer of 0 to 3]. A naphthoquinone diazide esterified product containing the esterification product of the compound represented by the above formula and the 1,2-naphthoquinone diazidesulfonyl compound, and (C) a phenol having a molecular weight of 1000 or less. The positive type photoresist composition for LCD manufacture in which the integrated circuit and the liquid crystal display part were formed on one board | substrate characterized by obtained by melt | dissolving a hydroxy group containing compound and (D) reduction inhibitor in the organic solvent. The positive type photoresist composition of Claim 1 containing the reducing body corresponding to the said (D) component. The positive type photoresist composition according to claim 1, wherein the component (D) is benzoquinone. The positive type photoresist composition of claim 2, wherein the reducing agent is hydroquinone. Positive in any one of Claims 1-4 which mix | blend the resin solution in which the said (D) component is mix | blended with the organic solvent solution of the said (A) component, and the said (B) component and (C) component. Method for producing a photoresist composition. (1) applying the positive photoresist composition according to any one of claims 1 to 4 on a substrate to form a coating film; (2) heat treating (prebaking) the substrate on which the coating film is formed; Process of forming resist film, (3) Selective exposure is performed to the said resist film using the mask in which both the mask pattern for resist pattern formation of 2.0 micrometers or less and the mask pattern for resist pattern formation exceeding 2.0 micrometers are drawn. And (4) heat treatment (post exposure bake: PEB) to the resist film after the selective exposure, and (5) developing treatment using an aqueous alkali solution to the resist film after the heat treatment, and onto the substrate. Resist patterns for integrated circuits with a pattern dimension of 2.0 μm or less and resists for liquid crystal display portions exceeding 2.0 μm Method of forming a resist pattern comprises a step of forming a pattern at the same time. The resist pattern forming method according to claim 6, wherein the step (3) of performing selective exposure is performed by using an i-line as a light source and an exposure process under a low NA condition where NA is 0.3 or less.

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