CN104076607B - Eurymeric anti-corrosion agent composition - Google Patents

Eurymeric anti-corrosion agent composition Download PDF

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Publication number
CN104076607B
CN104076607B CN201410117221.7A CN201410117221A CN104076607B CN 104076607 B CN104076607 B CN 104076607B CN 201410117221 A CN201410117221 A CN 201410117221A CN 104076607 B CN104076607 B CN 104076607B
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ingredient
agent composition
corrosion agent
diazido
eurymeric anti
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CN104076607A (en
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高桥和树
松本直纯
引田二郎
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention provides that a kind of focusing nargin is big and the eurymeric anti-corrosion agent composition of excellent in resolution.Eurymeric anti-corrosion agent composition of the invention contain relative to 100 mass parts alkali soluble resin (A) be 5~25 mass parts phenolic compounds (B), and range of the eurymeric anti-corrosion agent composition with 100 mass parts of gross mass relative to (A) ingredient and (B) ingredient for 15~40 mass parts contains the mixture (C) of photonasty ingredient, the mixture (C) of the photonasty ingredient includes the carboxylate of 3 kinds or more of diazido quinone, and the eurymeric anti-corrosion agent composition also contains organic solvent (D).

Description

Eurymeric anti-corrosion agent composition
Technical field
The present invention relates to a kind of eurymeric anti-corrosion agent compositions.
Background technique
So far, in the manufacturing field for the liquid crystal display element for having used glass substrate, in order to be formed more Inexpensively and sensitivity, resolving power and the excellent resist pattern of shape, and extensively using for manufacture semiconductor element by The positive-workingresist material of the System forming of linear phenol-aldehyde resin-naphtoquinone compounds containing diazido.
In the manufacture of semiconductor element, maximum uses the circle of 8 inches of diameter (about 200mm)~12 inch (about 300mm) Template silicon wafer, in contrast, in flat-panel monitor (hereinafter, sometimes referred to as FPD.) manufacture in, use large-scale substrate.
In this way, being coated with the substrate of anti-corrosion agent composition naturally in material, vpg connection and silicon in the manufacturing field of FPD Chip is different, and also differs widely in terms of its size with silicon wafer.
Therefore, for the anticorrosive additive material of FPD manufacture, semiconductor element manufacturing field institute is focused on it It is required that microscopic characteristics on, not as good as in the improvement for focusing on macroscopic properties.
As the anticorrosive additive material in the improvement for focusing on macroscopic properties, such as describes and make in patent document 1 With 500 × 600mm2Also there is macroscopic properties in the technique of above large substrate (coating, heating is uneven, development is unequal) Anti-corrosion agent composition.
Existing technical literature
Patent document
Patent document 1: No. 3789926 bulletins of Japanese Patent No.
Summary of the invention
Subject to be solved by the invention
Along with the enlargement etc. of FPD substrate, for the anticorrosive additive material for manufacturing FPD, there is still room for improvement.
In the manufacture of FPD, due to using large substrate, there is the dimensional accuracy caused by the deformation of substrate itself The problem of variation.Therefore, it is necessary to focus the big anticorrosive additive material of nargin (focus margin).
But in the exposure device of large substrate, mainly penetrated using g to improve production capacity (throughput) Line, h ray and i ray mixed wavelengths and not use short wavelength, so that aperture is become smaller, therefore, it is difficult to be stably formed figure Case.Nargin and resolving power are adequately focused that is, being difficult to obtain with previous anticorrosive additive material.In addition, when g ray, h ray or Under the single wavelength of i ray in use, due to making numerical aperture become larger, available resolving power, but it is abundant due to focusing Degree narrows, and therefore, it is difficult to be stably formed fine pattern.
The present invention completes in view of the foregoing, and project, which is to provide, focuses nargin greatly and the eurymeric of excellent in resolution Anti-corrosion agent composition.
Means for solving the problems
The present invention is a kind of eurymeric anti-corrosion agent composition, contains and is relative to the alkali soluble resin (A) of 100 mass parts The phenolic compounds (B) of 5~25 mass parts, and the eurymeric anti-corrosion agent composition is relative to the total of (A) ingredient and (B) ingredient 100 mass parts of quality are the mixture (C) that the range of 15~40 mass parts contains photonasty ingredient, and the photonasty ingredient mixes Close the carboxylate of object (C) comprising diazido quinone shown in following formula (C-1), diazido quinone shown in following formula (C-2) Carboxylate and following formula (C-3) shown in diazido quinone carboxylate, the eurymeric anti-corrosion agent composition also contains organic Solvent (D).
[changing 1]
[in formula, R14Independently indicate the alkyl of carbon atom number 1~5；D separately indicates that hydrogen atom or 1,2- bis- are folded Nitrogen base naphthoquinones -5- sulfonyl, and at least one D indicates 1,2- diazido naphthoquinones -5- sulfonyl；L, m is separately Indicate 1 or 2.]
[changing 2]
[in formula, D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least one D Indicate 1,2- diazido naphthoquinones -5- sulfonyl.]
[changing 3]
[in formula, D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least one D Indicate 1,2- diazido naphthoquinones -5- sulfonyl.]
In the present invention, phenolic compounds (B) is preferably following compounds (b0-1).
[changing 4]
In the present invention, the content of the carboxylate of diazido quinone shown in the above-mentioned formula (C-2) in mixture (C) is preferred For 33 mass % or less.
In the present invention, two nucleomes (there are two the condensation body molecules of phenol core for tool) content of the phenols in (A) ingredient is with GPC (gel permeation chromatography) method meter is preferably 10% or less.In the present invention, (D) ingredient preferably comprises propylene glycol monomethyl ether Ester.In the present invention, the total amount of (A), (B) and (C) ingredient is preferably 30 mass % or less relative to the gross mass of composition.This hair Bright eurymeric anti-corrosion agent composition is preferred for manufacturing flat-panel monitor (FPD).In addition, FPD preferably use will be selected in the present invention It is used from the single light of any two or more mixed light or g ray, h ray or i ray in g ray, h ray and i ray Make the exposure technology of exposure light source to make.
In the present invention, (B) ingredient relative to 100 mass parts of (A) ingredient for 5~20 mass parts is preferably comprised.
In the present invention, preferably comprising relative to 100 mass parts of gross mass of (A) ingredient and (B) ingredient is 20~40 mass (C) ingredient of part.
Invention effect
Nargin is focused greatly and the eurymeric anti-corrosion agent composition of excellent in resolution according to the present invention it is possible to provide.
Specific embodiment
In this specification and the claims, " aliphatic " is the concept opposite with aromatic series, and definition refers to not Group, compound with armaticity etc..
As long as no special instructions, " alkyl " refers to the group comprising straight-chain, branched and cricoid 1 valence saturated hydrocarbyl.
As long as no special instructions, " alkylidene " refers to the base comprising straight-chain, branched and cricoid divalent saturated hydrocarbyl Group.Alkyl in alkoxy is also synonymous.
" halogenated alkyl " is part or all of group after being substituted with halogen atoms of the hydrogen atom of alkyl, as the halogen Plain atom can enumerate fluorine atom, chlorine atom, bromine atom, iodine atom.
" fluoro-alkyl " or " fluorianted alkylene " refer to the hydrogen atom of alkyl or alkylidene part or all by fluorine original Group after son substitution.
" Component units " refer to the monomeric unit for constituting high-molecular compound (resin, polymer, copolymer).
" Component units derived from acrylate " refer to the composition list that the ethylenic double bond of acrylate cracks and constitutes Member.
" acrylate " is acrylic acid (CH2=CH-COOH) carboxyl terminal hydrogen atom replaced by organic group after Compound.
The hydrogen atom of the carbon atom bonding with α in acrylate can be substituted with a substituent.Replace the carbon with α Substituent group (the R of the hydrogen atom of atomistic bindingα) it is atom or group other than hydrogen atom, such as the alkane of carbon number 1~5 can be enumerated Base, the halogenated alkyl of carbon number 1~5, hydroxy alkyl etc..It is explained, as long as no special instructions, the carbon of the position α of acrylate is former Son refers to the carbon atom with carbonyl linkage.
Replace hereinafter, the acrylate after being sometimes substituted with a substituent the hydrogen atom of the carbon atom bonding with α is referred to as α Acrylate.In addition, acrylate and α substituted acrylate are referred to as " (α replaces) acrylate " sometimes.
" Component units as derived from hydroxy styrenes or hydroxy styrenes derivative " refer to hydroxy styrenes or hydroxy benzenes The ethylenic double bond of ethene derivatives cracks and the Component units of composition.
The concept of " hydroxy styrenes derivative " includes the hydrogen atom of the position α of hydroxy styrenes by alkyl, halogenated alkyl etc. The derivative of substance and these substances after the substitution of other substituent groups.It as the derivative of these substances, can enumerate: by α The hydrogen atom organic group of the hydroxyl of hydroxy styrenes that can be substituted with a substituent of hydrogen atom replace after substance；To α The substance etc. after substituent group other than the phenyl ring bonding hydroxyl-removal for the hydroxy styrenes that the hydrogen atom of position can be substituted with a substituent. It is explained, as long as no special instructions, α (α carbon atoms) refer to the carbon atom being bonded with phenyl ring.
As the substituent group for replacing the hydrogen atom of the position α of hydroxy styrenes, can enumerate and in above-mentioned α substituted acrylate The identical substituent group of substituent group cited by the middle substituent group as α.
" Component units as derived from vinyl benzoic acid or vinyl benzoic acid derivative " refer to vinyl benzoic acid or The ethylenic double bond of vinyl benzoic acid derivative cracks and the Component units of composition.
The concept of " vinyl benzoic acid derivative " includes the hydrogen atom of the position α of vinyl benzoic acid by alkyl, alkyl halide The derivative of substance and these substances after the substitution of other substituent groups such as base.As the derivative of these substances, can enumerate: Object after the hydrogen atom organic group of the carboxyl for the vinyl benzoic acid that α hydrogen atoms can be substituted with a substituent is replaced Matter；Taking other than hydroxyl-removal and carboxyl is bonded to the phenyl ring for the vinyl benzoic acid that α hydrogen atoms can be substituted with a substituent The substance etc. of Dai Jihou.It is explained, as long as no special instructions, α (α carbon atoms) refer to that the carbon being bonded with phenyl ring is former Son.
The concept of " styrene " include the position α of styrene and styrene hydrogen atom by alkyl, halogenated alkyl etc. other Substance after substituent group substitution.
" as the Component units of styrene derived ", " Component units as derived from styrene derivative " refer to styrene or benzene The ethylenic double bond of ethene derivatives cracks and the Component units of composition.
Alkyl as above-mentioned α of substituent group is preferably the alkyl of straight-chain or branched, specifically, carbon can be enumerated The alkyl (methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, amyl, isopentyl, neopentyl) of number 1~5 Deng.
In addition, the halogenated alkyl of the substituent group as α, specifically, can enumerate above-mentioned " as α substituent groups Alkyl " hydrogen atom part or all of group after being replaced with halogen atom.As the halogen atom, fluorine original can be enumerated Son, chlorine atom, bromine atom, iodine atom etc., particularly preferred fluorine atom.
In addition, the hydroxy alkyl of the substituent group as α, specifically, can enumerate above-mentioned " as α substituent groups Alkyl " hydrogen atom part or all of group after being replaced with hydroxyl.The quantity of hydroxyl in the hydroxy alkyl is preferred It is 1~5, most preferably 1.
When being recorded as " can have substituent group ", include the case where replacing hydrogen atom (- H) with 1 valence group and will be sub- Methyl (- CH2) with divalent group replace the case where.
The concept of " exposure " includes the irradiation of all radioactive ray.
" eurymeric anti-corrosion agent composition "
Anti-corrosion agent composition of the invention is a kind of eurymeric anti-corrosion agent composition, contains the alkali relative to 100 mass parts Soluble resin (A) is the phenolic compounds (B) of 5~25 mass parts, the eurymeric anti-corrosion agent composition with relative to (A) ingredient and (B) 100 mass parts of gross mass of ingredient contain the mixture (C) of photonasty ingredient, the sense for the range of 15~40 mass parts Carboxylate of the mixture (C) of photosensitiveness ingredient comprising diazido quinone shown in following formula (C-1), following formula (C-2) are shown Diazido quinone carboxylate and following formula (C-3) shown in diazido quinone carboxylate, positive-workingresist combination Object also contains organic solvent (D).
[changing 5]
[in formula, R14Independently indicate the alkyl of carbon atom number 1~5；D separately indicates that hydrogen atom or 1,2- bis- are folded Nitrogen base naphthoquinones -5- sulfonyl, and at least one D indicates 1,2- diazido naphthoquinones -5- sulfonyl；L, m is separately Indicate 1 or 2.]
[changing 6]
[in formula, D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least one D Indicate 1,2- diazido naphthoquinones -5- sulfonyl.]
[changing 7]
[in formula, D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least one D Indicate 1,2- diazido naphthoquinones -5- sulfonyl.]
[alkali soluble resin (A)]
As the alkali soluble resin of (A) ingredient, there is no particular restriction, can lead to from positive light anti-etching agent composition It often can be as carrying out any selection in the alkali soluble resin that overlay film forming material uses.Such as it can enumerate photic as eurymeric The overlay film formation resin of anti-corrosion agent composition and known phenolic resin, acrylic resin, styrene and acrylic acid are total to Polymers, the polymer of hydroxy styrenes, polyvinylphenol, poly- Alpha-Methyl vinylphenol etc..Wherein, it particularly preferably uses Phenolic resin, wherein it is non-swelling, be easy to be dissolved in aqueous alkali and developability it is excellent linear phenol-aldehyde resin it is more particularly suitable.
It as the example of phenolic resin, can enumerate: the condensation of the condensation reaction product, phenols and ketone of phenols and aldehydes Reaction product, vinyl phenol based polymer, isopropenyl phenol based polymer, these phenolic resin hydrogenation product Deng.
It as the phenols of the above-mentioned phenolic resin of formation, such as can enumerate: phenol, metacresol, paracresol, o-cresol, 2,3- The diformazans phenols such as dimethlbenzene, 2,5- dimethlbenzene, 3,5- dimethlbenzene, 3,4- dimethlbenzene；M-ethylphenol, to second Base phenol, o-ethyl phenol, 2,3,5- pseudocuminol, 2,3,5- triethyl group phenol, 4-TBP, 3- tert-butyl The induced by alkyl hydroxybenzene such as phenol, 2-TBP, 2- tert-butyl-4-methyl-Phenol, 2- tert-butyl -5- methylphenol；It is right Metoxyphenol, meta-methoxy phenol, to thanatol, m-oxethyl phenol, to propoxyl group phenol, propoxyl group phenol etc. Alkoxylated phenols；Adjacent isopropenyl phenol, to isopropenyl phenol, 2- methyl -4- isopropenyl phenol, 2- ethyl - The isopropenyls phenols such as 4- isopropenyl phenol；The aryl phenols such as phenylphenol；4,4 '-dihydroxybiphenyls, bisphenol-A, isophthalic Polyhydroxy phenols such as diphenol, hydroquinone, pyrogallol etc..These phenols can be used alone or be applied in combination two or more. In these phenols, particularly preferred metacresol, paracresol, 2,5- dimethlbenzene, 3,5- dimethlbenzene, 2,3,5- trimethyls Phenol.
It as above-mentioned aldehydes, such as can enumerate: formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionic aldehyde, butyraldehyde, trimethyl second Aldehyde, methacrylaldehyde, crotonaldehyde, hexamethylene aldehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, ethylalbenzene, α-phenyl Propionic aldehyde, beta-phenyl propionic aldehyde, salicylaldhyde, m-hydroxybenzaldehyde, parahydroxyben-zaldehyde, o-tolualdehyde, methylbenzene Formaldehyde, p-tolyl aldehyde, o-chlorobenzaldehyde, m chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamic acid etc..These aldehydes can be independent Using or be applied in combination two or more.It is heat-resisting in order to improve from the easiness obtained, preferably formaldehyde in these aldehydes Property, and hydroxy benzaldehyde class and formaldehyde is particularly preferably applied in combination.
As above-mentioned ketone, such as acetone, methyl ethyl ketone, metacetone, diphenylketone can be enumerated etc..These ketones can be single It solely uses or is applied in combination and is two or more.In the combination of phenols and ketone, the combination of particularly preferred pyrogallol and acetone.
The condensation reaction product of phenols and aldehydes or ketone can utilize well known side in the presence of acidic catalysts Method manufactures.As acidic catalyst at this time, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-methyl benzenesulfonic acid etc. can be used.To such Obtained condensation product removes resulting substance behind low molecule region by implementing the processing such as separation, excellent heat resistance, Therefore it is preferred that.The processing such as separation can be then injected by the way that the resin for utilizing condensation reaction to obtain is dissolved in good solvent Carry out the methods of its precipitating in water, wherein the good solvent is for example are as follows: the alcohol such as methanol, ethyl alcohol；The ketone such as acetone, methyl ethyl ketone； Ethylene glycol monomethyl ether acetate, tetrahydrofuran etc..
In above-mentioned phenolic resin of the invention, first particularly preferably is used to the mixed phenol containing paracresol and metacresol The linear phenol-aldehyde resin that aldehyde is 2000~8000 as the conversion of polystyrene synthesized by condensing agent weight average molecular weight (Mw), In, contain in the mixed phenol and the paracresol of 60 moles of % or more is calculated as with ingredient proportion (molar ratio) and (is rubbed with ingredient proportion That ratio) it is calculated as the metacresol of 30 moles of % or more.
When paracresol system repetitive unit is lower than 60 moles of %, easily cause relative to temperature unevenness when heating Sensitivity variation, and when metacresol system repetitive unit is lower than 30 moles of %, it is therefore unexcellent there are the tendency that sensitivity is deteriorated Choosing.
It is explained, diformazan phenol system repetitive unit, trimethyl phenol system can be contained in alkali soluble resin of the invention Other phenol system repetitive units such as repetitive unit, but be most preferably comprising being calculated as 60~70 moles of %'s with ingredient proportion (molar ratio) Paracresol and be calculated as with ingredient proportion (molar ratio) metacresol of 40~30 moles of % 2 ingredient systems linear phenol-aldehyde resin, It can two nucleomes containing phenols in alkali soluble resin of the invention (there are two the condensation body molecules of phenol core for tool).
It is preferred that as content with GPC (gel permeation chromatography) method is calculated as 10% or less, two cores of preferably 5% phenols below The poor linear phenol-aldehyde resin of the low-molecular weight of phenols as body.This is because: above-mentioned two nucleome high temperature (such as 130 DEG C) prebake or it is rear bake in distil and pollute the cover board etc. of furnace, and further pollution is coated with the glass base of resist Plate leads to its decrease in yield.In addition, the low-molecular weights such as above-mentioned two nucleome are also easy to remain in glass base after development treatment As a result plate surface causes resolving power to decline.
[phenolic compounds (B)]
Phenolic compounds in the present invention is not particularly limited, such as preferably phenolic compounds shown in the following general formula (b0).
[changing 8]
[in formula, R1~R8Separately indicate hydrogen atom, halogen atom, the alkyl of carbon atom number 1~6, carbon atom number 1 ~6 alkoxy or the naphthenic base of carbon atom chain 3~6；R9~R11Separately indicate hydrogen atom or carbon atom number 1~6 Alkyl；Q indicates the alkyl and R of hydrogen atom, carbon atom number 1~69Be bonded and formed the naphthenic base of carbon atom chain 3~6 group, Or group shown in chemical formula (b0-r) (in formula, R12And R13Separately indicate hydrogen atom, halogen atom, carbon atom number 1 The naphthenic base of~6 alkyl, the alkoxy of carbon atom number 1~6 or carbon atom chain 3~6；C indicates 1~3 integer)；A, b is indicated 1~3 integer；D indicates 0~3 integer；N indicates 0~3 integer.]
In formula (b0-r), R1~R8Separately indicate hydrogen atom, halogen atom, the alkyl of carbon atom number 1~6, carbon The alkoxy of atomicity 1~6 or the naphthenic base of carbon atom chain 3~6.
As the alkyl of carbon atom number 1~6, the preferably alkyl of the straight-chain or branched of carbon number 1~6, specifically, can Enumerate methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, amyl, isopentyl, neopentyl, hexyl etc..
As the alkoxy of carbon number 1~6, can enumerate methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, Tert-butoxy etc., preferably methoxyl group, ethyoxyl.
As the naphthenic base of carbon atom chain 3~6, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc. can be enumerated.
In the present invention, R1~R8It is separately preferably hydrogen atom or methyl, particularly preferably protium.
In formula (b0-r), R9~R11It is separately hydrogen atom or the alkyl of carbon atom number 1~6.About R9~R11In Carbon atom number 1~6 alkyl explanation and above-mentioned R1~R8In explanation it is identical.
In the present invention, R9~R11It is separately preferably hydrogen atom or methyl, particularly preferably protium.
In formula (b0-r), Q is the alkyl and R of hydrogen atom, carbon atom number 1~69It is bonded and forms carbon atom chain 3~6 Group shown in the group or chemical formula (b0-r) of naphthenic base.Alkyl and R about the carbon atom number 1~6 in Q9Bonding and The explanation of the naphthenic base of the carbon atom chain 3~6 of formation and above-mentioned R1~R8In explanation it is identical.
R when Q is group shown in chemical formula (b0-r), in formula (b0-r)12And R13Separately indicate that hydrogen is former The naphthenic base of son, halogen atom, the alkyl of carbon atom number 1~6, the alkoxy of carbon atom number 1~6 or carbon atom chain 3~6, c table Show 1~3 integer.About the alkyl of the carbon atom number 1~6 in formula (b0-r), the alkoxy or carbon atom of carbon atom number 1~6 The explanation of the naphthenic base of chain 3~6 and above-mentioned R1~R8In explanation it is identical.
In the present invention, Q is preferably group shown in formula (b0-r), in formula (b0-r), R12、R13It is separately excellent It is selected as hydrogen atom or methyl, c is preferably 1 or 2.
In formula (b0), a, b indicate that 1~3 integer, d indicate that 0~3 integer, n indicate 0~3 integer.
It as the example of (B) ingredient, can enumerate: three (4- hydroxy phenyl) methane, bis- (4- hydroxy-3-methyl benzene Base) -2- hydroxy phenyl methane, bis- (4- hydroxyl -2,3,5- trimethylphenyl) -2- hydroxy phenyl methane, bis- (4- hydroxyls Base -3,5- 3,5-dimethylphenyl) -4- hydroxy phenyl methane, bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) -3- hydroxy benzenes Methylmethane, bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) -2- hydroxy phenyl methane, bis- (4- hydroxyl -2,5- dimethyl Phenyl) -4- hydroxy phenyl methane, bis- (4- hydroxyl -2,5- 3,5-dimethylphenyl) -3- hydroxy phenyl methane, bis- (4- hydroxyls Base -2,5- 3,5-dimethylphenyl) -2- hydroxy phenyl methane, bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) -3,4- dihydroxies Base phenylmethane, bis- (4- hydroxyl -2,5- 3,5-dimethylphenyl) -3,4- dihydroxy benzenes methylmethanes, it is bis- (hydroxyl -2 4-, 5- 3,5-dimethylphenyl) -2,4- dihydroxy benzenes methylmethane, bis- (4- hydroxy phenyl) -3- methoxyl group -4- hydroxy phenyl first Alkane, bis- (5- cyclohexyl -4- hydroxy-2-methyl phenyl) -4- hydroxy phenyl methane, bis- (5- cyclohexyl -4- hydroxyls Base -2- aminomethyl phenyl) -3- hydroxy phenyl methane, bis- (5- cyclohexyl -4- hydroxy-2-methyl phenyl) -2- hydroxyls Base phenylmethane, bis- (5- cyclohexyl -4- hydroxy-2-methyl phenyl) -3,4- dihydroxy benzenes methylmethanes, 1- [1- (4- hydroxy phenyl) isopropyl] -4- [bis- (4- hydroxy phenyl) ethyls of 1,1-] benzene, 1- [1- (3- methyl -4- hydroxyl Base phenyl) isopropyl] -4- [bis- (3- methyl -4- hydroxy phenyl) ethyls of 1,1-] benzene, 2- (2,3,4- trihydroxy benzene Base) -2- (2 ', 3 ', 4 '-trihydroxy phenyl) propane, 2- (2,4- dihydroxy phenyl) -2- (2 ', 4 '-dihydroxy benzenes Base) propane, 2- (4- hydroxy phenyl) -2- (4 '-hydroxy phenyl) propane, 2- (3- fluoro -4- hydroxy phenyl) - 2- (3 '-fluoro -4 '-hydroxy phenyl) propane, 2- (2,4- dihydroxy phenyl) -2- (4 '-hydroxy phenyl) propane, 2- (2,3,4- trihydroxy phenyl) -2- (4 '-hydroxy phenyl) propane, 2- (2,3,4- trihydroxy phenyl) -2- (4 '-hydroxyls -3 ', 5 ' -3,5-dimethylphenyls) propane, bis- (2,3,4- trihydroxy phenyl) methane, bis- (2,4- dihydroxy benzenes Base) methane, 2,3,4- trihydroxy phenyl -4 '-hydroxy phenyl methane, 1,1- bis- (4- hydroxy phenyl) hexamethylene, 2,4- Bis- [1- (4- hydroxy phenyl) isopropyl] -5- hydroxyl phenols etc..
Wherein, the aspect especially excellent from sensitivity improvement effect, preferably bis- (4- hydroxy-3-methyl benzene Base) -2- hydroxy phenyl methane, bis- (4- hydroxyl -2,3,5- trimethylphenyl) -2- hydroxy phenyl methane, 2,4- be bis- [1- (4- hydroxy phenyl) isopropyl] -5- hydroxyl phenol, 1,1- bis- (4- hydroxy phenyl) hexamethylene, 1- [1- (4- Hydroxy phenyl) isopropyl] -4- [bis- (4- hydroxy phenyl) ethyls of 1,1-] benzene etc..
In the manufacturing field of FPD, the raising of production capacity is very big problem, but by cooperating the phenolate to close Object facilitates the raising of production capacity to reach high sensitivity, therefore it is preferred that.
In addition, to be stably formed surface difficulty deliquescent layer on resist film, therefore being recognized by cooperating the phenolic compounds Film reduction amount for the resist film of unexposed portion in development is small, can inhibit the development generated by the difference of developing time Uneven generation.
It is excellent in the improvement effect of high sensitivity, high residual film ratio and the linearity (linearity) in the phenolic compounds Different aspect, particularly preferred above-mentioned formula (b0-1) compound represented (1- [1- (4- hydroxy phenyl) isopropyl] -4- [bis- (4- hydroxy phenyl) ethyls of 1,1-] benzene) and following formula (b0-2) compound represented (bis- (2,3,5- trimethyls- 4- hydroxy phenyl) -2- hydroxy phenyl methane).
[changing 9]
By (B) components matching, when composition of the invention, content can be can relative to the alkali as (A) ingredient 100 mass parts of soluble resin are 5~25 mass parts, are selected in the range of preferably 10~20 mass parts.
If the content of (B) ingredient is lower than the range, it is unable to fully obtain high sensitivity, the raising effect of high residual film ratio Fruit, if the content of (B) ingredient is higher than the range, substrate surface after development is easy to produce residue, and cost of material Also it gets higher, is undesirable in this regard.
When eurymeric anti-corrosion agent composition of the invention to be used for the manufacture purposes of FPD, preferably comprise relative to (A) ingredient 100 mass parts are (B) ingredient of 5~20 mass parts, (B) ingredient of further preferably 7~15 mass parts.This is because: even if In the different pattern of size is formed, as long as making (B) ingredient in the range, high sensitivity, high residual film ratio can be sufficiently obtained The improvement effect of change.
[mixture (C) of photonasty ingredient]
In the present invention, the mixture (C) of photonasty ingredient includes the esterification of diazido quinone shown in following formula (C-1) The esterification of diazido quinone shown in the carboxylate and following formula (C-3) of diazido quinone shown in object, following formula (C-2) Object.
[changing 10]
[in formula, R14Independently indicate the alkyl of carbon atom number 1~5；D separately indicates that hydrogen atom or 1,2- bis- are folded Nitrogen base naphthoquinones -5- sulfonyl, and at least one D indicates 1,2- diazido naphthoquinones -5- sulfonyl；L, m is separately Indicate 1 or 2.]
[changing 11]
[in formula, D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least one D Indicate 1,2- diazido naphthoquinones -5- sulfonyl.]
[changing 12]
[in formula, D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least one D Indicate 1,2- diazido naphthoquinones -5- sulfonyl.]
In formula (C-1), R14It independently is the alkyl of carbon atom number 1~5.
The alkyl of carbon number 1~5 is preferably the straight-chain of carbon number 1~5 or the alkyl of branched, specifically, first can be enumerated Base, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, amyl, isopentyl, neopentyl etc..In the present invention, R14Respectively It is independently preferably methyl or ethyl, more preferably methyl.
In formula (C-1), D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least One D indicates 1,2- diazido naphthoquinones -5- sulfonyl, and l, m are separately 1 or 2.
The D of the carboxylate of diazido quinone shown in above-mentioned formula (C-1) is 1,2- diazido naphthoquinones -5- sulfonyl When average proportions (average esterification rate) be preferably 40~60%, more preferably 50~55%.It is lower than 40% in the average proportions When, the film after being easy to produce development is reduced, and is easy that residual film ratio is made to be lower.In addition, being deposited if the average proportions are more than 60% In the tendency that sensitivity is significantly deteriorated.
In formula (C-2), D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least One D indicates 1,2- diazido naphthoquinones -5- sulfonyl.
The D of the carboxylate of diazido quinone shown in above-mentioned formula (C-2) is 1,2- diazido naphthoquinones -5- sulfonyl When average proportions (average esterification rate) be preferably 65~85%, more preferably 70~75%.It is lower than 65% in the average proportions When, the film after being easy to produce development is reduced, and is easy that residual film ratio is made to be lower.In addition, being deposited if the average proportions are more than 85% In the tendency that sensitivity is significantly deteriorated.
In formula (C-3), D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least One D indicates 1,2- diazido naphthoquinones -5- sulfonyl.
The D of the carboxylate of diazido quinone shown in above-mentioned formula (C-3) is 1,2- diazido naphthoquinones -5- sulfonyl When average proportions (average esterification rate) be preferably 50~70%, more preferably 57~62%.It is lower than 50% in the average proportions When, the film after being easy to produce development is reduced, and is easy that residual film ratio is made to be lower.In addition, being deposited if the average proportions are more than 70% In the tendency that storage stability reduces.
Eurymeric anti-corrosion agent composition of the invention contains the photonasty ingredient of the carboxylate comprising above-mentioned 3 kinds of diazido quinones Mixture (C), it is thus regarded that can obtain adequately focusing nargin and resolving power.
In the present invention, in the mixture (C) of photonasty ingredient, the carboxylate of diazido quinone shown in formula (C-2) contains Measuring relative to 100 mass parts of mixture (C) of photonasty ingredient is preferably 33 mass % or less.It is assumed that passing through formula (C- 2) carboxylate of diazido quinone shown in is above-mentioned content, to make development contrast improve, and resolving power is excellent.
In addition, the esterification of diazido quinone shown in the carboxylate of diazido quinone shown in formula (C-1), formula (C-2) The mixed proportion of the carboxylate of diazido quinone shown in object and formula (C-3) is particularly preferably 1:1:2.
In the present invention, to be the model of 15~40 mass parts relative to 100 mass parts of gross mass of (A) ingredient and (B) ingredient The mixture (C) containing photonasty ingredient is enclosed, and preferably selects the mixing of photonasty ingredient in the range of 10~25 mass parts Object (C).
In addition, when eurymeric anti-corrosion agent composition of the invention to be used for the manufacture purposes of FPD, preferably comprise relative to (A) 100 mass parts of gross mass of ingredient and (B) ingredient are (C) ingredient of 20~40 mass parts, further preferably 20~35 mass (C) ingredient of part.
(A)~(C) ingredient and various adding ingredients are preferably dissolved in as the following of organic solvent by the present composition (D) ingredient and use as a solution.
[organic solvent (D)]
About (D) ingredient (organic solvent)
The example of organic solvent used in the present invention can be enumerated: acetone, methyl ethyl ketone, cyclohexanone, methyl isopentyl The ketones such as ketone, 2-HEPTANONE；Ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol acetate, Propylene glycol monoacetate, diethyl two The polyalcohols such as alcohol monoacetate or their monomethyl ether, single ethylether, single propyl ether, single-butyl ether or single phenyl ether and Its derivative；The ring type ethers as dioxanes；And ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, acetone The esters such as sour methyl esters, ethyl pyruvate, methoxy methyl propionate, ethoxyl ethyl propionate.These organic solvents can individually make With or be used in mixed way two or more.
Wherein, excellent coating is being assigned, to against corrosion on large-size glass substrate to anti-corrosion agent composition of the present invention Agent overlay film assigns the aspect of excellent film thickness uniformity, preferably propylene glycol monomethyl ether (PGMEA).
PGMEA is used most preferably in the form of single solvent, PGMEA can also be mixed with the solvent in addition to PGMEA It uses.As such solvent, such as ethyl lactate, gamma-butyrolacton, glycol monobutyl ether, hexylene glycol can be enumerated etc..
When using ethyl lactate, it is generally desirable to according to mass ratio meter to be 0.1~10 times of amount, preferably 1 relative to PGMEA The range fit ethyl lactate of~5 times of amounts.
In addition, when using gamma-butyrolacton, it is generally desirable to according to mass ratio meter with relative to PGMEA for 0.01~1 times Amount, preferably 0.05~0.5 times range fit gamma-butyrolacton measured.
In the manufacturing field of liquid crystal display element, it usually needs with 0.5~2.5 μm, especially 1.0~2.0 μm of film thickness Resist overlay film is formed on the glass substrate, therefore for the excellent liquid crystal display element manufacture resist material of coating is made For material, it is preferred to use these organic solvents by the total amount of above-mentioned (A)~(C) ingredient in composition be adjusted to relative to The gross mass of composition reaches 30 mass % or less, preferably 20~28 mass %.
At this time it is contemplated that the amount of arbitrarily used following (E) ingredients, and make the usage amount of solvent (D) relative to combination The gross mass of object is preferably 65~85 mass %, more preferably 70~75 mass %.
About (E) ingredient (other additives)
Can add and contain within the scope without prejudice to the object of the present invention in the present invention: the ultraviolet light for antihalation is inhaled Receive agent, such as 2,2',4,4'-tetrahydroxybenzophenone, 4- dimethylamino -2 ', 4 '-dihydroxy benaophenonels, 5- ammonia Base-3- methyl-1-phenyl-4- (4- hydroxyphenyl azo) pyrazoles, 4- dimethylamino-4 '-hydroxyazobenzene, 4- diethylamino -4 '-ethyoxyl azobenzene, 4- diethylaminoazobenzene, curcumin (curcumin) etc.；For preventing The only surfactant of striation (striation), such as FLUORAD FC-430, FC431 (trade name, Sumitomo 3M (strain) system Make), F-TOP EF122A, the fluorine such as EF122B, EF122C, EF126 (trade name, Tochem Products Co., Ltd. manufacture) It is surfactant；Benzoquinones, naphthoquinones, p-methyl benzenesulfonic acid etc. save stabilization agent；And be added as needed resin, plasticising The common additives such as agent, stabilization agent, contrast enhancer.
Eurymeric anti-corrosion agent composition of the invention for example can be used for the manufacture purposes of flat-panel monitor, at this point, usually It needs to form resist overlay film on substrate with the film thickness of 0.5~2.5 μm, especially 1.0~2.0 μm.Therefore, in order to make coating It is excellent, it is preferred to use above-mentioned organic solvent by the total amount of above-mentioned (A)~(C) ingredient in composition be adjusted to relative to The gross mass of composition reaches 30 mass % or less, preferably 10~25 mass %.
At this time it is contemplated that the amount of arbitrarily used above-mentioned (E) ingredient, and make the usage amount of solvent (D) relative to combination The gross mass of object is preferably 65~85 mass %, more preferably 70~75 mass %.
Eurymeric anti-corrosion agent composition of the invention is preferred for the manufacture purposes of flat-panel monitor (FPD).Make during fabrication Preferably being used with the FPD of eurymeric anti-corrosion agent composition of the invention will be selected from any two kind in g ray, h ray and i ray The single light of above mixed light or g ray, h ray or i ray is used as the exposure technology of exposure light source to make.
In this specification, any two or more mixed light in g ray, h ray and i ray is used as exposure light The exposure technology in source refers to: will include multiple exposure wavelengths of g ray (436nm), h ray (405nm), i ray (365nm) Mixed light is used as the exposure technology of exposure light source.It can be to be penetrated selected from g ray, h as the mixed light comprising multiple exposure wavelengths Any two kinds of mixed light in line and i ray, but preferably these three mixed light of g ray, h ray and i ray.
With the enlargement of the substrate of FPD etc., there are the time for exposure also elongated tendency, by using above-mentioned mixed recharge It is long, so as to improve the intensity of light source, and the time for exposure can be shortened.The spectral intensity of each light can be according to substrate Type etc. is suitably selected.
" forming method of resist pattern "
Be exemplified below an example indicate using composition of the invention FPD manufacture resist pattern it is suitable Forming method.Firstly, using the coatings such as rotator by (A)~(C) ingredient and used as needed on glass angular substrate Adding ingredient (E) is dissolved in solution made of solvent (D) appropriate as described above, forms film.The glass base used at this time Plate can be 500 × 600mm2Above, especially 550~650mm2Above large plate.
If using composition of the invention, even if in the manufacture of this FPD for having used large-scale glass substrate, It can obtain the excellent resist pattern such as coating.
Then, the glass substrate for being formed with the film is thermally dried (preliminary drying with 100~140 DEG C or so of temperature Roasting), form it into photosensitive layer.Then, using issue ultraviolet light light source for example low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, Xenon lamp etc. carries out selective exposure across required mask pattern.Use the FPD of eurymeric anti-corrosion agent composition excellent during fabrication Choosing uses will be selected from any two or more mixed light or g ray, h ray or i ray in g ray, h ray and i ray Single light be used as the exposure technology of exposure light source and make.
It is explained, in the manufacture of FPD etc., due to using description to there is the different resist pattern of pattern dimension to be formed with covering The mask of mould pattern exposes to carry out the selectivity, therefore it is different to be formed simultaneously pattern dimension on above-mentioned glass substrate Resist pattern.
For example, the resist pattern described and have pattern dimension to be 0.5~2.5 μm, which can be used, in selectivity exposure forms use The resist pattern that mask pattern and pattern dimension are 3~10 μm formed the mask (graticule (reticle)) of mask pattern come It carries out.When forming the different pattern of this size at the same time, anti-corrosion agent composition of the present invention also plays the excellent linearity Effect.
Then, glass substrate is coated to the resist exposed, be covered with from an end of substrate to another end Alkaline aqueous solution as developer solution such as 1~10 mass % tetramethylammonium hydroxide (TMAH) aqueous solution, or from setting Developer solution in the top of immediate vicinity is added dropwise nozzle and sprays developer solution to entire substrate surface.
Develop moreover, standing 50~90 seconds or so, and forms resist pattern on above-mentioned glass substrate.Later, Elution process is carried out, the leacheates such as described elution process pure water rush the developer solution for remaining in the resist pattern surface It washes.
Embodiment
Hereinafter, being further illustrated using embodiment to the present invention, but the present invention is not limited by following embodiment.
(embodiment 1)
(A) ingredient: 100 mass parts of alkali soluble resin
It [has used and oxalic acid and formaldehyde is added and carries out in the mixture of metacresol 35 moles of % and 65 moles of % of paracresol The obtained weight average molecular weight 4500 (Mw) of condensation reaction, phenols two nucleome contents be about 6% cresol novolac resin.Give Illustrate, two nucleome contents of phenols are utilized to be measured based on the GPC of following device and condition.]
Device name: SYSTEM11 (manufacture of Showa electrician company) pre-column (precolumn): KF-G (SHODEX corporation Make) column: KF-802 (manufacture of SHODEX company)
Detector: UV41 (is measured) at 280nm
The conditions such as solvent: tetrahydrofuran is flowed into the flow of 1.0ml/min, is determined at 35 DEG C.
(B) ingredient: following phenolic compounds (b0-1): 15 mass parts
[changing 13]
(C) ingredient: following formula (C-1-1) compound represented/following formula (C-2-1) compound represented/following 22 mass parts of mixture of the photonasty ingredient of compound represented=1/1/2 formula (C-3-1).Following formula (C-1-1)~ (C-3-1) in, D indicate H or 1,2- diazido naphthoquinones -5- sulfonyl, made according to the difference of each molecule replace number or The position of substitution, which exists, to be changed, and therefore, the average proportions being shown respectively when D is 1,2- diazido naphthoquinones -5- sulfonyl are (flat Equal esterification yield (%)).
(D) ingredient: solvent (PGMEA): 423 mass parts
[changing 14]
[in above-mentioned formula (C-1-1), D be H or 1,2- diazido naphthoquinones -5- sulfonyl, D based on 1,2- bis- The average esterification rate that azido naphthoquinones -5- sulfonyl obtains is 54.7%.]
[changing 15]
[in above-mentioned formula (C-2-1), D be H or 1,2- diazido naphthoquinones -5- sulfonyl, D based on 1,2- bis- The average esterification rate that azido naphthoquinones -5- sulfonyl obtains is 72.1%.]
[changing 16]
[in above-mentioned formula (C-3-1), D be H or 1,2- diazido naphthoquinones -5- sulfonyl, D based on 1,2- bis- The average esterification rate that azido naphthoquinones -5- sulfonyl obtains is 59.9%.]
(comparative example 1)
(A) ingredient: 100 mass parts of alkali soluble resin
It [has used and oxalic acid and formaldehyde is added and carries out in the mixture of metacresol 35 moles of % and 65 moles of % of paracresol The obtained weight average molecular weight of condensation reaction (Mw) is the cresol novolac resin that two nucleome contents of 4500, phenols are about 6%.It gives With explanation, two nucleome contents of phenols are utilized to be measured based on the GPC of following device and condition.]
(B) ingredient: following phenolic compounds (b0-2): 15 mass parts
[changing 17]
(C) ingredient: compound represented=1/1 following formula (C-1-1) compound represented/following formula (C-3-1) Photonasty ingredient 26 mass parts of mixture.
(D) ingredient: solvent (PGMEA): 423 mass parts
[changing 18]
[in above-mentioned formula (C-1-1), D be H or 1,2- diazido naphthoquinones -5- sulfonyl, D based on 1,2- bis- The average esterification rate that azido naphthoquinones -5- sulfonyl obtains is 54.7%.]
[changing 19]
[in above-mentioned formula (C-3-1), D be H or 1,2- diazido naphthoquinones -5- sulfonyl, D based on 1,2- bis- The average esterification rate that azido naphthoquinones -5- sulfonyl obtains is 59.9%.]
After dissolving (A)~(D) equably, it is filtered with the molecular filter in 0.2 μm of aperture, it is against corrosion to be prepared into eurymeric Agent composition.
(1) nargin is focused
Sample is coated on 6 inches of Si chip using rotator (TR-6132U [trade name, TAZMO company manufacture]) On, it is later, 90 seconds dry with 110 DEG C with plate (DHP) is directly heated, form 1.5 μm of film thickness of resist overlay film.
Then, across describe have for realizing 2.0 μm of line width and the mask pattern of line-spacing pattern and can -40~ The test chart mask (graticule (reticle)) of+40 μm of range changing focal length (focus) is directed at exposer using mirror surface projection (mirror projection aligner) MPA-600FA (trade name, Canon Inc.'s manufacture, NA=0.083), in focal length 2.0 μm of line width can be reappeared according to size under 0 μm and the light exposure of line-spacing pattern has carried out selective exposure.
Then, it contacts it 65 seconds with 23 DEG C, 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solutions, and washes 30 After second, rotarily dried.
Later, the shape of resulting resist pattern is observed by SEM (scanning electron microscope) photo, really Recognize the range for the focal length that pattern dimension is 1.80~2.20 μm (2.00 ± 0.20 μm).Using its result as DOF (± 10%) It is shown in Table 1.
(2) exploring power
Sample is coated on 6 inches of Si chip using rotator (TR-6132U [trade name, TAZMO company manufacture]) On, it is later, 90 seconds dry with 110 DEG C with plate (DHP) is directly heated, form 1.5 μm of film thickness of resist overlay film.
Then, there is the mask pattern for reappearing 2.0~3.0 μm of line width and the resist pattern of line-spacing across description Test chart mask (graticule (reticle)), the mirror surface projection used as ghi x ray exposure x device are directed at exposer MPA- 600FA (trade name, Canon Inc.'s manufacture, NA=0.083), the exposure of 3.0 μm of line widths and line-spacing can be reappeared according to size Amount has carried out selective exposure.
Then, it contacts it 65 seconds with 23 DEG C, 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solutions, and washes 30 After second, rotarily dried.
Later, the shape of resulting resist pattern is observed by SEM (scanning electron microscope) photo, and 2.0,2.5,3.0 μm of line width and the section shape of line-spacing pattern are carried out by SEM (scanning electron microscope) photo Observation.It is shown in Table 1 its result as " shape ".
In following table 1, zero, △, × be evaluation below.
Zero: exploring and to be poor less than ± 10% size for MASK size.
△: poor for ± 10% or more size for MASK size although exploring.
×: non-exploring.
[table 1]
As shown in the above results, compared with comparative example, the DOF of eurymeric anti-corrosion agent composition of the invention (focusing nargin) and Resolving power is excellent.

Claims (10)

1. a kind of eurymeric anti-corrosion agent composition, containing alkali soluble resin (A), relative to the alkali-soluble tree of 100 mass parts Rouge (A) is the phenolic compounds (B) of 5~25 mass parts, and
The eurymeric anti-corrosion agent composition is with 100 mass parts of gross mass relative to (A) ingredient and (B) ingredient for 15~40 mass The range of part contains the mixture (C) of photonasty ingredient, and the mixture (C) of the photonasty ingredient includes following formula (C-1) institute Shown in the carboxylate and following formula (C-3) of diazido quinone shown in the carboxylate of the diazido quinone shown, following formula (C-2) Diazido quinone carboxylate, the eurymeric anti-corrosion agent composition also contains organic solvent (D),
In formula (C-1), R14Independently indicate the alkyl of carbon atom number 1~5；D separately indicates hydrogen atom or 1,2- bis- Azido naphthoquinones -5- sulfonyl, and at least one D indicates 1,2- diazido naphthoquinones -5- sulfonyl；I, m is independently Ground indicates 1 or 2,
In formula (C-2), D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least one D indicates 1,2- diazido naphthoquinones -5- sulfonyl,
In formula (C-3), D separately indicates hydrogen atom or 1,2- diazido naphthoquinones -5- sulfonyl, and at least one D indicates 1,2- diazido naphthoquinones -5- sulfonyl.
2. eurymeric anti-corrosion agent composition according to claim 1, wherein the phenolic compounds (B) is following compounds (b0-1)
3. eurymeric anti-corrosion agent composition according to claim 1 or 2, wherein the formula (C- in the mixture (C) 2) content of the carboxylate of diazido quinone shown in is 33 mass % or less.
4. eurymeric anti-corrosion agent composition according to claim 1, which is characterized in that two nucleomes of the phenols in (A) ingredient Content is calculated as 10% or less with GPC method, wherein two nucleomes of phenols are tool there are two the condensation body molecule of phenol core, and GPC is gel Permeation chromatography.
5. eurymeric anti-corrosion agent composition according to claim 1 or 2, which is characterized in that as (D) ingredient, contain the third two Alcohol monomethyl ether acetate.
6. eurymeric anti-corrosion agent composition according to claim 1 or 2, which is characterized in that (A), (B) and (C) ingredient it is total Measuring relative to the gross mass of composition is 30 mass % or less.
7. eurymeric anti-corrosion agent composition according to claim 1 or 2 is used to manufacture flat-panel monitor FPD.
8. eurymeric anti-corrosion agent composition according to claim 7, wherein the FPD using will selected from g ray, h ray and The single light of any two or more mixed light or g ray, h ray or i ray in i ray is used as the exposure of exposure light source Technique makes.
9. eurymeric anti-corrosion agent composition according to claim 7, which is characterized in that it contains relative to 100 matter of (A) ingredient Measure (B) ingredient that part is 5~20 mass parts.
10. eurymeric anti-corrosion agent composition according to claim 7, which is characterized in that its contain relative to (A) ingredient and (B) 100 mass parts of gross mass of ingredient are (C) ingredient of 20~40 mass parts.
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