JP2014199312A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition having a large focus margin and excellent resolution.SOLUTION: The positive resist composition contains 5 to 25 parts by mass of a phenolic compound (B) with respect to 100 parts by mass of an alkali soluble resin (A), and 15 to 40 parts by mass of a photosensitive component mixture (C) comprising three or more quinonediazide esterified compounds with respect to total mass 100 parts by mass of (A) composition and (B) composition, and further contains an organic solvent (D).

Description

  The present invention relates to a positive resist composition.

  In the field of manufacturing liquid crystal display elements using glass substrates, novolaks are used in the manufacture of semiconductor elements because they are relatively inexpensive and can form resist patterns with excellent sensitivity, resolution, and shape. A positive resist material composed of a resin-quinonediazide group-containing compound system is often used.

In the manufacture of semiconductor devices, a disk-type silicon wafer having a maximum diameter of 8 inches (about 200 mm) to 12 inches (about 300 mm) is used, whereas a flat panel display (hereinafter referred to as FPD) may be used. ), A large substrate is used.
As described above, in the field of FPD manufacturing, the substrate to which the resist composition is applied is naturally different in terms of material and shape, but is greatly different from the silicon wafer in terms of its size.
Therefore, the resist material for FPD manufacturing has been focused on improving macro characteristics rather than micro characteristics required in the field of semiconductor element manufacturing.

As a resist material with an emphasis on improving macro characteristics, for example, in Patent Document 1, even in a process using a large substrate of 500 × 600 mm ² or more, macro characteristics (coating properties, heating unevenness, development) A resist material having a non-uniformity is described.

Japanese Patent No. 3789926

With increasing size of FPD substrates, there is still room for improvement in resist materials used in FPD manufacturing.
Since a large substrate is used for manufacturing the FPD, there is a problem of deterioration of dimensional accuracy due to distortion of the substrate itself. For this reason, a resist material having a large focus margin is required.
However, in a large-sized substrate exposure apparatus, a mixed wavelength of g-line, h-line, and i-line is mainly used to improve throughput, and as a result, the aperture becomes small, so that stable pattern formation is achieved. Was difficult. That is, it has been difficult to obtain a sufficient focus margin and resolution with conventional resist materials. In addition, when used with a single wavelength of g-line, h-line or i-line, the numerical aperture is increased, so that the resolution is obtained, but the focus margin is narrowed, so that it is difficult to stably form a fine pattern. there were.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a positive resist composition having a large focus margin and excellent resolution.

  This invention contains 5-25 mass parts phenolic compound (B) with respect to 100 mass parts alkali-soluble resin (A), and with respect to 100 mass parts of total mass of (A) component and (B) component, A quinonediazide esterified product represented by the following formula (C-1), a quinonediazide esterified product represented by the following formula (C-2), and a quinonediazide esterified product represented by the following formula (C-3). It is a positive resist composition containing the photosensitive component mixture (C) in the range of 15 to 40 parts by mass and further containing an organic solvent (D).

［式中、Ｒ^１４は、独立に炭素原子数１〜５のアルキル基を表わし；Ｄは、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表し、；ｌ、ｍは、それぞれ独立に１又は２を表わす。］

[Wherein, R ¹⁴ independently represents an alkyl group having 1 to 5 carbon atoms; D represents each independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group; One represents a 1,2-naphthoquinonediazide-5-sulfonyl group; l and m each independently represent 1 or 2; ]

［式中、Ｄは、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表わす。］

[Wherein, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. ]

［式中、Ｄは、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表わす。］

[Wherein, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. ]

  In the present invention, the phenol compound (B) is preferably the following compound (b0-1).

In the present invention, the content of the quinonediazide esterified product represented by the formula (C-2) in the mixture (C) is preferably 33% by mass or less.
In the present invention, the component (A) has a phenol dinuclear content (condensate molecule having two phenol nuclei) content of 10% or less in the GPC (gel permeation chromatography) method. preferable. In the present invention, the component (D) preferably contains propylene glycol monomethyl ether acetate. In the present invention, the total amount of the components (A), (B) and (C) is preferably 30% by mass or less based on the total mass of the composition. The positive resist composition of the present invention is preferably used for manufacturing a flood panel display (FPD). Further, in the present invention, the FPD uses any two or more kinds of mixed light selected from the group consisting of g-line, h-line and i-line, or single light of g-line, h-line or i-line as an exposure light source. It is preferable that it is made using the conventional exposure process.
In this invention, it is preferable to contain 5-20 mass parts of (B) component with respect to 100 mass parts of (A) component.
In this invention, it is preferable to contain 20-40 mass parts of (C) component with respect to 100 mass parts of total mass of (A) component and (B) component.

  According to the present invention, a positive resist composition having a large focus margin and excellent resolution can be provided.

In the present specification and claims, “aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
The “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
“Fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms.
“Structural unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
“A structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
“Acrylic acid ester” is a compound in which the hydrogen atom at the carboxy group terminal of acrylic acid (CH ₂ ═CH—COOH) is substituted with an organic group.
In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α ) for substituting the hydrogen atom bonded to the α-position carbon atom is an atom or group other than a hydrogen atom, such as an alkyl group having 1 to 5 carbon atoms or a halogenated group having 1 to 5 carbon atoms. Examples thereof include an alkyl group and a hydroxyalkyl group. The α-position carbon atom of the acrylate ester is a carbon atom to which a carbonyl group is bonded unless otherwise specified.
Hereinafter, an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylate ester. Further, the acrylate ester and the α-substituted acrylate ester may be collectively referred to as “(α-substituted) acrylate ester”.
“A structural unit derived from hydroxystyrene or a hydroxystyrene derivative” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene or a hydroxystyrene derivative.
“Hydroxystyrene derivative” is a concept including those in which the hydrogen atom at the α-position of hydroxystyrene is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. The derivatives include those in which the hydrogen atom at the α-position may be substituted with a substituent, the hydrogen atom of the hydroxyl group of hydroxystyrene substituted with an organic group, and the hydrogen atom at the α-position substituted with a substituent. Examples include those in which a substituent other than a hydroxyl group is bonded to a good benzene ring of hydroxystyrene. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same substituents as those mentioned as the substituent at the α-position in the α-substituted acrylic ester.
The “structural unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative” means a structural unit configured by cleavage of an ethylenic double bond of vinyl benzoic acid or a vinyl benzoic acid derivative.
The “vinyl benzoic acid derivative” is a concept including a compound in which the hydrogen atom at the α-position of vinyl benzoic acid is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those obtained by substituting the hydrogen atom of the carboxy group of vinyl benzoic acid with an organic group, which may be substituted with a hydrogen atom at the α-position, and the hydrogen atom at the α-position with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group and a carboxy group is bonded to the benzene ring of vinyl benzoic acid. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
“Styrene” is a concept that includes styrene and those in which the α-position hydrogen atom of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.
“Structural unit derived from styrene” and “structural unit derived from styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.
The alkyl group as a substituent at the α-position is preferably a linear or branched alkyl group, specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Specific examples of the halogenated alkyl group as the substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the substituent at the α-position” are substituted with a halogen atom. It is done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as a substituent at the α-position include a group in which part or all of the hydrogen atoms of the “alkyl group as the substituent at the α-position” are substituted with a hydroxyl group. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.
When it is described as “may have a substituent”, when a hydrogen atom (—H) is substituted with a monovalent group, and when a methylene group (—CH ₂ —) is substituted with a divalent group Including both.
“Exposure” is a concept including general irradiation of radiation.

≪Positive resist composition≫
The resist composition of this invention contains 5-25 mass parts phenolic compound (B) with respect to 100 mass parts alkali-soluble resin (A), and the total mass of (A) component and (B) component is 100 masses. Part, the quinonediazide esterified product represented by the following formula (C-1), the quinonediazide esterified product represented by the following formula (C-2), and the quinonediazide esterified product represented by the following formula (C-3) And a photosensitive resist mixture (C) in the range of 15 to 40 parts by mass, and further containing an organic solvent (D).

［式中、Ｒ^１４は、独立に炭素原子数１〜５のアルキル基を表わし；Ｄは、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表し、；ｌ、ｍは、それぞれ独立に１又は２を表わす。］

[Wherein, R ¹⁴ independently represents an alkyl group having 1 to 5 carbon atoms; D represents each independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group; One represents a 1,2-naphthoquinonediazide-5-sulfonyl group; l and m each independently represent 1 or 2; ]

［式中、Ｄは、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表わす。］

[Wherein, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. ]

［式中、Ｄは、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表わす。］

[Wherein, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. ]

[Alkali-soluble resin (A)]
The alkali-soluble resin as the component (A) is not particularly limited, and can be arbitrarily selected from those that can be usually used as a film-forming substance in a positive photoresist composition. For example, a phenolic resin, an acrylic resin, a copolymer of styrene and acrylic acid, a polymer of hydroxystyrene, polyvinylphenol, poly α-methylvinylphenol, etc., known as a film forming resin for a positive photoresist composition Can be mentioned. Among these, a phenol resin is particularly preferably used, and among them, a novolak resin that is easily dissolved in an alkaline aqueous solution without swelling and excellent in developability is preferable.

  Examples of phenol resins include condensation reaction products of phenols and aldehydes, condensation reaction products of phenols and ketones, vinyl phenol polymers, isopropenyl phenol polymers, and hydrogen of these phenol resins. Examples include addition reaction products.

  Examples of phenols that form the phenol resin include phenol, m-cresol, p-cresol, o-cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and the like. Xylenols; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2 Alkylphenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol , P-p Alkoxyphenols such as poxyphenol and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol Arylphenols such as phenylphenol; polyhydroxyphenols such as 4,4′-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, and the like. These may be used alone or in combination of two or more. Among these phenols, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, and 2,3,5-trimethylphenol are particularly preferable.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropyl. Aldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p- Chlorobenzaldehyde, cinnamon Examples include aldehyde. These may be used alone or in combination of two or more. Among these aldehydes, formaldehyde is preferable because it is easily available. In particular, in order to improve heat resistance, it is preferable to use a combination of hydroxybenzaldehydes and formaldehyde.

  Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, and diphenyl ketone. These may be used alone or in combination of two or more. In the combination of phenols and ketones, the combination of pyrogallol and acetone is particularly preferable.

  The condensation reaction product of phenols and aldehydes or ketones can be produced by a known method in the presence of an acidic catalyst. In this case, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic acid, etc. can be used as the acidic catalyst. The condensation product obtained in this manner is preferably a product obtained by cutting a low molecular region by performing a treatment such as fractionation, because it is excellent in heat resistance. In the treatment such as fractionation, the resin obtained by the condensation reaction is dissolved in a good solvent, for example, alcohol such as methanol or ethanol, ketone such as acetone or methyl ethyl ketone, ethylene glycol monoethyl ether acetate, tetrahydrofuran or the like, and then poured into water. It is carried out by a method such as precipitation.

  In the present invention, among the above, p-cresol and m-cresol are mixed in a proportion (molar ratio) containing 60 mol% or more of p-cresol and 30 mol% or more of m-cresol. A novolak resin having a polystyrene-converted weight average molecular weight (Mw) of 2000 to 8000 synthesized using phenol and formaldehyde as a condensing agent is preferable.

  If the p-cresol repeating unit is less than 60 mol%, the sensitivity is likely to change due to temperature unevenness during the heat treatment, and if the m-cresol repeating unit is less than 30 mol%, the sensitivity tends to be inferior.

The alkali-soluble resin of the present invention may contain other phenol-based repeating units such as a xylenol-based repeating unit and a trimethylphenol-based repeating unit, but most preferably, a charging ratio (molar ratio). Is a two-component novolak resin comprising 60-70 mol% of p-cresol and 40-30 mol% of m-cresol, and a binuclear compound of phenols (condensate molecule having two phenol nuclei) It may contain.
A novolak resin having a low content of low molecular weight phenols such as a content of 10% or less, preferably 5% or less in the GPC (gel permeation chromatography) method is preferred. The dinuclear body sublimates during pre-baking or post-baking at a high temperature (for example, 130 ° C.) to contaminate the top plate of the furnace, and further stains the glass substrate coated with the resist, thereby reducing the yield. Because. Further, the low molecular weight substance such as the dinuclear body tends to remain on the surface of the glass substrate even after the development processing, and as a result, the resolution is lowered.

[Phenol compound (B)]
In this invention, although a phenol compound is not specifically limited, For example, it is preferable that it is a phenol compound represented by the following general formula (b0).

［式中、Ｒ^１〜Ｒ^８はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又は炭素原子鎖３〜６のシクロアルキル基を表し；Ｒ^９〜Ｒ^１１はそれぞれ独立に水素原子又は炭素原子数１〜６のアルキル基を表し；Ｑは水素原子、炭素原子数１〜６のアルキル基、Ｒ^９と結合して炭素原子鎖３〜６のシクロアルキル基を形成する基、又は化学式（ｂ０−ｒ）で表される基（式中、Ｒ^１２及びＲ^１３はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又は炭素原子鎖３〜６のシクロアルキル基を表し；ｃは１〜３の整数を示す）を表し；ａ、ｂは１〜３の整数を表し；ｄは０〜３の整数を表し；ｎは０〜３の整数を表す。］

[Wherein R ^{1 to} R ⁸ 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. R ^{9 to} R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom bonded to R ^9. A group forming a cycloalkyl group having a chain of 3 to 6 or a group represented by the chemical formula (b0-r) (wherein R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 6 Represents an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, or a cycloalkyl group of 3 to 6 carbon atoms; c represents an integer of 1 to 3; and a and b are integers of 1 to 3 D represents an integer of 0 to 3; n represents an integer of 0 to 3 ]

In formula (b0-r), R ^{1 to} R ⁸ 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 chain 3 to 6 carbon atoms. Of the cycloalkyl group.
As the alkyl group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Examples thereof include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group.
The alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group, and examples thereof include a methoxy group and an ethoxy group.
Examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
In the present invention, R ^{1 to} R ⁸ are each independently preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen element.

In formula (b0-r), R ^{9 to} R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The explanation for the alkyl group having 1 to 6 carbon atoms in R ^{9 to} R ¹¹ is the same as the explanation for R ^{1 to} R ⁸ .
In the present invention, R ^{9 to} R ¹¹ are each independently preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen element.

In the formula (b0-r), Q represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a group that combines with R ⁹ to form a cycloalkyl group having 3 to 6 carbon atoms, or a chemical formula (b0-r) ). The explanation for the alkyl group having 1 to 6 carbon atoms in Q and the cycloalkyl group having 3 to 6 carbon atoms formed by bonding to R ⁹ are the same as those for R ^{1 to} R ⁸ .
When Q is a group represented by the chemical formula (b0-r), in the formula (b0-r), 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 is represented, and c represents an integer of 1 to 3. The description of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, or the cycloalkyl group having 3 to 6 carbon atoms in the formula (b0-r) is the same as in R ^{1 to} R ⁸ . It is the same as the description.

In the present invention, Q is preferably a group represented by the formula (b0-r). In the formula (b0-r), R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group. Preferably, c is 1 or 2.

  In formula (b0), a and b represent an integer of 1 to 3, d represents an integer of 0 to 3, and n represents an integer of 0 to 3.

  Examples of the component (B) include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, and bis (4-hydroxy-2,3,5-trimethyl). Phenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethyl) Phenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenol) ) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxy Phenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4) -Hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methyl) Phenyl) -2-hydroxyphenylmethane, bis (5-si Rohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] Benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, 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 B-4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4 '-Hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3', 5'-dimethylphenyl) propane, bis (2,3,4-trihydroxy) Phenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4′-hydroxyphenylmethane, 1,1-di (4-hydroxyphenyl) cyclohexane, 2,4-bis [1- (4-hydroxyphenyl) isopropyl] -5-hydroxyphenol and the like.

  Among these, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxy are particularly excellent in sensitivity improvement effect. Phenylmethane, 2,4-bis [1- (4-hydroxyphenyl) isopropyl] -5-hydroxyphenol, 1,1-di (4-hydroxyphenyl) cyclohexane, 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and the like are preferable.

In the field of FPD production, improvement in throughput is a very large problem, but blending the phenol compound is preferable because high sensitivity is achieved and contribution to improvement in throughput.
Also, by blending the phenol compound, a poorly surface-solubilized layer is strongly formed on the resist film, so that the amount of unexposed resist film loss during development is small, and development unevenness occurs due to differences in development time. Is considered to be suppressed.

  Among the phenol compounds, a compound represented by the above formula (b0-1) (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene) And the compound represented by the following formula (b0-2) (bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane) has high sensitivity, high residual film ratio, and linearity. It is particularly preferable in that it has an excellent improvement effect.

(B) When mix | blending a component with the composition of this invention, the content is 5-25 mass parts with respect to 100 mass parts of alkali-soluble resin which is (A) component, Preferably it selects in the range of 10-20 mass parts. It is.
Below this range, the effect of improving sensitivity and increasing the residual film ratio cannot be obtained sufficiently, and if it exceeds this range, residues are likely to be generated on the substrate surface after development, and the raw material cost also increases. It is not preferable.

  When using the positive resist composition of this invention for manufacture of FPD, it is preferable to contain 5-20 mass parts of (B) component with respect to 100 mass parts of (A) component, Preferably it is 7-15 mass parts. . This is because, in the pattern formation with different dimensions, the effect of improving the sensitivity and the remaining film ratio can be sufficiently obtained within this range.

[Mixture of photosensitive components (C)]
In the present invention, the mixture (C) of photosensitive components is a quinonediazide esterified product represented by the following formula (C-1), a quinonediazide esterified product represented by the following formula (C-2), and the following formula (C -3) and a quinonediazide esterified product.

［式中、Ｒ^１４は、独立に炭素原子数１〜５のアルキル基を表わし；Ｄは、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表し、；ｌ、ｍは、それぞれ独立に１又は２を表わす。］

[Wherein, R ¹⁴ independently represents an alkyl group having 1 to 5 carbon atoms; D represents each independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group; One represents a 1,2-naphthoquinonediazide-5-sulfonyl group; l and m each independently represent 1 or 2; ]

［式中、Ｄは、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表わす。］

[Wherein, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. ]

［式中、Ｄは、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表わす。］

[Wherein, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. ]

In formula (C-1), R ¹⁴ is independently an alkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, or an n-butyl group. , Isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. In the present invention, each R ¹⁴ is preferably independently a methyl group or an ethyl group, and more preferably a methyl group.

In formula (C-1), each D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. In the formula, l and m are each independently 1 or 2.
The average ratio (average esterification ratio) in which D of the quinonediazide esterified product represented by the above formula (C-1) is a 1,2-naphthoquinonediazide-5-sulfonyl group is preferably 40 to 60%, more preferably 50. ~ 55%. If it is less than 40%, film loss after development tends to occur and the remaining film ratio tends to be low. On the other hand, if it exceeds 60%, the sensitivity tends to be remarkably inferior.

In formula (C-2), each D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. Represent.
The average ratio (average esterification ratio) in which D of the quinonediazide esterified product represented by the formula (C-2) is a 1,2-naphthoquinonediazide-5-sulfonyl group is preferably 65 to 85%, more preferably 70. ~ 75%. If it is less than 65%, film loss after development tends to occur, and the remaining film ratio tends to be low. Moreover, when it exceeds 85%, there exists a tendency for a sensitivity to be remarkably inferior.

In formula (C-3), each D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. Represent.
The average ratio (average esterification ratio) in which D of the quinonediazide esterified product represented by the above formula (C-3) is a 1,2-naphthoquinonediazide-5-sulfonyl group is preferably 50 to 70%, more preferably 57. ~ 62%. If it is less than 50%, film loss after development tends to occur and the remaining film ratio tends to be low. Moreover, when it exceeds 70%, there exists a tendency for storage stability to fall.

  When the positive resist composition of the present invention contains the mixture (C) of the photosensitive component composed of the above three kinds of quinonediazide esterified products, a sufficient focus margin and resolution can be obtained. Conceivable.

In the present invention, in the photosensitive component mixture (C), the content of the quinonediazide esterified product represented by the formula (C-2) is 33% by mass or less based on 100 parts by mass of the photosensitive component mixture (C). It is preferable that By making the quinonediazide esterified product represented by the formula (C-2) to have the above content, it is presumed that the development contrast is improved and the resolution is excellent.
The mixing ratio of the quinonediazide esterified product represented by the formula (C-1), the quinonediazide esterified product represented by the formula (C-2), and the quinonediazide esterified product represented by the formula (C-3) is: Particularly preferred is 1: 1: 2.

  In the present invention, the mixture (C) of the photosensitive component is contained in the range of 15 to 40 parts by mass, preferably 10 to 25 parts by mass with respect to 100 parts by mass of the total mass of the components (A) and (B). It is better to be selected within the range.

  Moreover, when using the positive resist composition of this invention for manufacture of FPD, (C) component is 20-40 mass parts with respect to 100 mass parts of total mass of (A) component and (B) component, Preferably It is preferable to contain 20-35 mass parts.

  The composition of the present invention is preferably used in the form of a solution by dissolving the components (A) to (C) and various additive components in the following component (D) which is an organic solvent.

[Organic solvent (D)]
Regarding component (D) (organic solvent):
Examples of the organic solvent used in the present invention include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol mono Acetate or polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and ethyl lactate, methyl acetate, ethyl acetate Esters such as butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate. Rukoto can. These may be used alone or in combination of two or more.

Among them, propylene glycol monomethyl ether acetate (PGMEA) is preferable in that it provides excellent coating properties to the resist composition of the present invention and excellent film thickness uniformity on a resist film on a large glass substrate.
PGMEA is most preferably used as a single solvent, but solvents other than PGMEA can also be used as a mixture. Examples of such a solvent include ethyl lactate, γ-butyrolactone, propylene glycol monobutyl ether, hexylene glycol and the like.

In the case of using ethyl lactate, it is desirable to blend in an amount of 0.1 to 10 times, preferably 1 to 5 times the mass ratio of PGMEA.
Moreover, when using (gamma) -butyrolactone, it is desirable to mix | blend in 0.01-1 times amount by mass ratio with respect to PGMEA, Preferably it is 0.05-0.5 times amount.

In the field of liquid crystal display device production, it is usually necessary to form a resist film on a glass substrate with a film thickness of 0.5 to 2.5 μm, particularly 1.0 to 2.0 μm. Using an organic solvent, the total amount of the components (A) to (C) in the composition is adjusted to 30% by mass or less, preferably 20 to 28% by mass with respect to the total mass of the composition. Is preferable as a resist material for producing a liquid crystal display element having excellent coating properties.
In consideration of the amount of the following component (E) optionally used in this case, the amount of the solvent (D) used is 65 to 85% by mass, preferably 70 to 75% by mass, based on the total mass of the composition. It is preferable.

About (E) component (other additives) In this invention, in the range which does not impair the objective of this invention, ultraviolet absorbers for halation prevention, 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-diethylaminoazobenzene, curcumin and the like, and surfactants for preventing striation, such as Fluorad FC-430, FC431 (trade name, manufactured by Sumitomo 3M Ltd.), Ftop EF122A , EF122B, EF122C, EF126 (trade name, TO Fluorosurfactants such as Chem Products), storage stabilizers such as benzoquinone, naphthoquinone, and p-toluenesulfonic acid, and additional resins, plasticizers, stabilizers, and contrast improvers as necessary Conventional additives such as the above can be added and contained within a range that does not hinder the object of the present invention.

The positive resist composition of the present invention is used, for example, for the production of flat panel displays. In that case, the resist film is usually 0.5 to 2.5 μm, particularly 1.0 to 2.0 μm in thickness. It must be formed on a substrate. For this purpose, the total amount of the components (A) to (C) in the composition is 30% by mass or less, preferably 10 to 25% by mass, based on the total mass of the composition, using the organic solvent. It is preferable to adjust so as to be excellent in applicability.
In consideration of the amount of the component (E) optionally used in this case, the amount of the solvent (D) used is 65 to 85% by mass, preferably 70 to 75% by mass, based on the total mass of the composition. It is preferable.

The positive resist composition of the present invention is preferably used for manufacturing a flat panel display (FPD). The FPD used in the production of the positive resist composition of the present invention has two or more kinds of mixed light selected from the group consisting of g-line, h-line and i-line, or g-line, h-line or i-line. It is preferable that the light source is produced using an exposure process using single light as an exposure light source.
In this specification, the exposure process using any two or more kinds of mixed light selected from the group consisting of g-line, h-line, and i-line as an exposure light source is g-line (436 nm), h-line (405 nm). , An exposure process using mixed light including a plurality of exposure wavelengths of i-line (365 nm) as an exposure light source. The mixed light including a plurality of exposure wavelengths may be any two types of mixed light selected from the group consisting of g-line, h-line, and i-line, and three types of g-line, h-line, and i-line. It is preferable that the mixed light.
Although the exposure time tends to be longer with the increase in size of the substrate such as FPD, the intensity of the light source can be increased and the exposure time can be shortened by using the above mixed wavelength. The spectral intensity of each light beam can be appropriately selected depending on the type of substrate.

≪Resist pattern formation method≫
An example of a suitable method for forming a resist pattern for FPD production using the composition of the present invention will be described. First, a solution prepared by dissolving the components (A) to (C) and the additive component (E) used as necessary in a suitable solvent (D) as described above is applied onto a glass square substrate with a spinner or the like. To form a coating film. Glass substrate 500 × 600 mm ² or more used at this time, in particular can be a 550～650Mm ² or larger plate.

  If the composition of the present invention is used, a resist pattern excellent in coatability and the like can be obtained even in the production of FPD using such a large glass substrate.

  Next, the glass substrate on which the coating film is formed is heated and dried (prebaked) at about 100 to 140 ° C. to form a photosensitive layer. Next, selective exposure is performed through a desired mask pattern using a light source that emits ultraviolet light, such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, or a xenon lamp. The FPD used in the production of the positive resist composition emits mixed light of two or more selected from the group consisting of g-line, h-line and i-line, or single light of g-line, h-line or i-line. It is preferable that it is made using the exposure process used for the exposure light source.

In the manufacture of an FPD or the like, this selective exposure is performed using a mask on which a resist pattern forming mask pattern having a different pattern dimension is drawn, and a resist pattern having a different pattern dimension is simultaneously formed on the glass substrate. Can be formed.
For example, this selective exposure is performed using a mask (reticle) on which a resist pattern forming mask pattern having a pattern size of 0.5 to 2.5 μm and a resist pattern forming mask pattern having a pattern size of 3 to 10 μm are drawn. I can do it. The resist composition of the present invention also exhibits an excellent linearity effect when simultaneously forming patterns having different dimensions.

  Next, this exposed resist-coated glass substrate is swelled with a developing solution, for example, an alkaline aqueous solution such as an aqueous solution of 1 to 10% by mass of tetramethylammonium hydroxide (TMAH) from one end of the substrate to the other end, Alternatively, the developing solution is spread over the entire surface of the substrate from the developing droplet lower nozzle installed near the center.

  And it develops by leaving still for about 50 to 90 second, and forms a resist pattern on the said glass substrate. Thereafter, a rinsing process is performed in which the developer remaining on the resist pattern surface is washed away with a rinse solution such as pure water.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.

Example 1
Component (A): Alkali-soluble resin 100 parts by mass [weight average molecular weight 4500 (Mw) obtained by condensation reaction of oxalic acid and formaldehyde added to a mixture of 35 mol% of m-cresol and 65 mol% of p-cresol, phenol A cresol novolac resin having a binuclear content of about 6% was used. The dinuclear content of phenols was measured by GPC measurement using the following equipment and conditions. ]

Apparatus name: SYSTEM11 (made by Showa Denko) Precolumn: KF-G (made by SHODEX) Column: KF-802 (made by SHODEX)
Detector: UV41 (measured at 280 nm)
Conditions such as solvent: Tetrahydrofuran was allowed to flow at a flow rate of 1.0 ml / min, and measurement was performed at 35 ° C.

(B) component: The following phenol compound (b0-1): 15 mass parts

(C) Component: Compound represented by the following formula (C-1-1) / Compound represented by the following formula (C-2-1) / Compound represented by the following formula (C-3-1) = 22 parts by weight of a mixture of 1/1/2 photosensitive component. In the following formulas (C-1-1) to (C-3-1), D represents H or a 1,2-naphthoquinonediazido 5-sulfonyl group, but the number of substitutions and substitution positions vary depending on each molecule. Therefore, the average ratio (average esterification rate (%)) in which D is 1,2-naphthoquinonediazido5-sulfonyl group is shown.
(D) Component: Solvent (PGMEA): 423 parts by mass

［上記式（Ｃ−１−１）中、ＤはＨまたは１，２−ナフトキノンジアジドー５−スルホニル基であり、Ｄの１，２−ナフトキノンジアジドー５−スルホニル基による平均エステル化率は５４．７％である。］

[In the above formula (C-1-1), D is H or 1,2-naphthoquinonediazido5-sulfonyl group, and the average esterification rate of D by 1,2-naphthoquinonediazido5-sulfonyl group is 54. 0.7%. ]

［上記式（Ｃ−２−１）中、ＤはＨまたは１，２−ナフトキノンジアジドー５−スルホニル基であり、Ｄの１，２−ナフトキノンジアジドー５−スルホニル基による平均エステル化率は７２．１％である。］

[In the above formula (C-2-1), D is H or 1,2-naphthoquinonediazido5-sulfonyl group, and the average esterification rate of D by 1,2-naphthoquinonediazido5-sulfonyl group is 72. .1%. ]

［上記式（Ｃ−３−１）中、ＤはＨまたは１，２−ナフトキノンジアジドー５−スルホニル基であり、Ｄの１，２−ナフトキノンジアジドー５−スルホニル基による平均エステル化率は５９．９％である。］

[In the above formula (C-3-1), D is H or 1,2-naphthoquinonediazido5-sulfonyl group, and the average esterification rate of D by 1,2-naphthoquinonediazido5-sulfonyl group is 59. .9%. ]

(Comparative Example 1)
Component (A): 100 parts by mass of alkali-soluble resin [weight average molecular weight (Mw) 4500 obtained by adding oxalic acid and formaldehyde to a mixture of 35 mol% of m-cresol and 65 mol% of p-cresol and a condensation reaction, phenol A cresol novolac resin having a binuclear content of about 6% was used. In addition, the dinuclear content of phenols was measured by GPC measurement using the above apparatus and conditions. ]
(B) component: The following phenol compound (b0-2): 15 mass parts

Component (C): 26 parts by mass of a compound represented by the following formula (C-1-1) / a compound represented by the following formula (C-3-1) = 1/1 photosensitive component.
(D) Component: Solvent (PGMEA): 423 parts by mass

［上記式（Ｃ−１−１）中、ＤはＨまたは１，２−ナフトキノンジアジドー５−スルホニル基であり、Ｄの１，２−ナフトキノンジアジドー５−スルホニル基による平均エステル化率は５４．７％である。］

[In the above formula (C-1-1), D is H or 1,2-naphthoquinonediazido5-sulfonyl group, and the average esterification rate of D by 1,2-naphthoquinonediazido5-sulfonyl group is 54. 0.7%. ]

［上記式（Ｃ−３−１）中、ＤはＨまたは１，２−ナフトキノンジアジドー５−スルホニル基であり、Ｄの１，２−ナフトキノンジアジドー５−スルホニル基による平均エステル化率は５９．９％である。］

[In the above formula (C-3-1), D is H or 1,2-naphthoquinonediazido5-sulfonyl group, and the average esterification rate of D by 1,2-naphthoquinonediazido5-sulfonyl group is 59. .9%. ]

After (A) to (D) were uniformly dissolved, this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive resist composition.

(1) Focus margin After applying the sample onto a 6-inch Si wafer using a spinner (TR-6132U [trade name, manufactured by Tatsumo Co., Ltd.], the sample was dried at 110 ° C. for 90 seconds with a direct hot plate (DHP). A resist film having a thickness of 1.5 μm was formed.
Next, a mask pattern for realizing a 2.0 μm line-and-space pattern is drawn, and through a test chart mask (reticle) capable of focusing in the range of 40 to +40 μm, the mirror projection aligner MPA-600FA ( Using a trade name, manufactured by Canon Inc., NA = 0.083), selective exposure was performed with an exposure amount capable of reproducing a 2.0 μm line and space pattern according to the dimensions with a focus of 0 μm.
Subsequently, it was brought into contact with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. for 65 seconds, washed with water for 30 seconds, and spin-dried.
Thereafter, the shape of the obtained resist pattern was observed with an SEM (scanning electron microscope) photograph, and a focus range in which the pattern dimension was 1.80 to 2.20 μm (2.00 ± 0.20 μm) was confirmed. . The results are shown in Table 1 as DOF (± 10%).

(2) Resolution The sample was applied on a 6-inch Si wafer using a spinner (TR-6132U [trade name, manufactured by Tatsumo Co., Ltd.], and then dried at 110 ° C. for 90 seconds with a direct hot plate (DHP). A resist film having a thickness of 1.5 μm was formed.
Next, the mirror projection aligner MPA-600FA (ghi line exposure apparatus) is passed through a test chart mask (reticle) on which a mask pattern for reproducing a 2.0-3.0 μm line-and-space resist pattern is drawn. Using a trade name, manufactured by Canon Inc., NA = 0.083), selective exposure was performed with an exposure amount capable of reproducing a 3.0 μm line and space according to dimensions.
Subsequently, it was brought into contact with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. for 65 seconds, washed with water for 30 seconds, and spin-dried.
Thereafter, the shape of the obtained resist pattern was observed with a SEM (scanning electron microscope) photograph, and the cross-sectional shapes of the line and space patterns of 2.0, 2.5, and 3.0 μm were observed with a SEM (scanning electron microscope). Observed with photographs. The results are shown in Table 1 as “shape”.
In Table 1 below, ◯, Δ, and × are the following evaluations.
○: Resolved and a dimensional difference of less than ± 10% with respect to the MASK dimension.
Δ: Resolution is a dimensional difference of ± 10% or more with respect to the MASK dimension.
X: Not resolved.

As shown in the above results, the positive resist composition of the present invention was superior in DOF (focus margin) and resolution compared to the comparative example.

Claims (10)

For 100 parts by mass of the alkali-soluble resin (A),
5 to 25 parts by mass of the phenol compound (B) is contained,
For 100 parts by mass of the total mass of component (A) and component (B),
A quinonediazide esterified product represented by the following formula (C-1), a quinonediazide esterified product represented by the following formula (C-2), and a quinonediazide esterified product represented by the following formula (C-3). A positive resist composition containing the mixture (C) of photosensitive components in the range of 15 to 40 parts by mass and further containing an organic solvent (D).

[Wherein, R ¹⁴ independently represents an alkyl group having 1 to 5 carbon atoms; D represents each independently a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group; One represents a 1,2-naphthoquinonediazide-5-sulfonyl group; l and m each independently represent 1 or 2; ]

[Wherein, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. ]

[Wherein, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group. ] The positive resist composition according to claim 1, wherein the phenol compound (B) is the following compound (b0-1).

  The positive resist composition according to claim 1 or 2, wherein the content of the quinonediazide esterified product represented by the formula (C-2) in the mixture (C) is 33% by mass or less.   Component (A) is characterized in that the content of dinuclear phenols (condensate molecules having two phenolic nuclei) is 10% or less in the GPC (gel permeation chromatography) method. Item 2. The positive resist composition according to Item 1.   5. The positive resist composition according to claim 1, comprising propylene glycol monomethyl ether acetate as component (D).   The positive resist according to any one of claims 1 to 5, wherein the total amount of the components (A), (B) and (C) is 30% by mass or less based on the total mass of the composition. Composition.   The positive resist composition according to any one of claims 1 to 6, which is used for producing a flat panel display (FPD).   The FPD uses an exposure process that uses any two or more kinds of mixed light selected from the group consisting of g-line, h-line, and i-line, or single light of g-line, h-line, or i-line as an exposure light source. The positive resist composition according to claim 7, wherein the positive resist composition is formed by:   The positive resist composition according to claim 7 or 8, comprising 5 to 20 parts by mass of the component (B) with respect to 100 parts by mass of the component (A).   The positive component according to any one of claims 7 to 9, comprising 20 to 40 parts by mass of the component (C) with respect to 100 parts by mass of the total mass of the component (A) and the component (B). Type resist composition.