WO2007148574A1 - Resist stripping agent - Google Patents

Resist stripping agent Download PDF

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Publication number
WO2007148574A1
WO2007148574A1 PCT/JP2007/061867 JP2007061867W WO2007148574A1 WO 2007148574 A1 WO2007148574 A1 WO 2007148574A1 JP 2007061867 W JP2007061867 W JP 2007061867W WO 2007148574 A1 WO2007148574 A1 WO 2007148574A1
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WO
WIPO (PCT)
Prior art keywords
resist
acid
stripping
anticorrosion
weight
Prior art date
Application number
PCT/JP2007/061867
Other languages
French (fr)
Japanese (ja)
Inventor
Yasushi Shiraki
Toyozo Fujioka
Shigeru Matsuo
Original Assignee
Idemitsu Kosan Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co., Ltd. filed Critical Idemitsu Kosan Co., Ltd.
Priority to JP2008522407A priority Critical patent/JPWO2007148574A1/en
Publication of WO2007148574A1 publication Critical patent/WO2007148574A1/en

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Classifications

    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3227—Ethers thereof
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/039—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • the present invention relates to a resist stripper.
  • the resist remover of the present invention is excellent in releasability, safe from flammability, and excellent in corrosion resistance that does not corrode the conductor.
  • Integrated circuits such as IC and LSI, display devices such as LCD and EL elements, printed circuit boards, and the like are manufactured using photolithography technology.
  • unnecessary resist photosensitive agent
  • resist stripper unnecessary resist
  • the mainstay is resist strippers containing amine compounds with excellent stripping properties.
  • This amine release agent can be classified into a solvent type and an aqueous type.
  • a solvent based release agent dimethyl sulfoxide (about 30 weight 0/0) + monoethanol ⁇ Min (about 70 weight 0/0) and, like Monoe Tanoruamin + N-methylpyrrolidone is used.
  • an aqueous release agent water (about 20 to 30 wt%) + diethylene glycol monobutyl ether (about 20-30 by weight 0 / o) + monoethanol ⁇ Min (about 30-40 weight 0/0), alkyl benzene sulfonic acid + Functional water (ozone water), acid (sulfuric acid + hydrogen peroxide) + functional water (ozone water) are used.
  • Patent Document 1 discloses a photoresist stripper containing a product obtained by reacting alkanolamine and formaldehyde. This product is produced by reacting an alkanolamine with formaldehyde in a formaldehyde / alkanolamine (molar ratio) at a ratio of 0.8 or less.
  • Patent Document 2 discloses a photoresist stripping composition comprising an alkanolamine compound, a sulfone compound or a sulfoxide compound, and a hydroxy compound.
  • Patent Document 3 discloses a resist remover having a stable pH and containing at least a hydroxycarboxylic acid and water.
  • the hydroxycarboxylic acid contained after the production has a ratio of the condensate of two or more molecules to the hydroxycarboxylic acid monomer (ie, the condensate / monomer) is 1/9 or less. Have been adjusted so that.
  • Patent Document 4 discloses a stripping agent that strips a resist for using an alloy of copper and silver in a wiring process.
  • This resist stripper contains piperazines.
  • Patent Document 5 discloses a resist stripper containing tetraethylenepentamine and ether alcohol.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-219486
  • Patent Document 2 JP 05-281753 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-049438
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-205674
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-205675
  • the technologies described in the above patent documents have been developed for the purpose of improving resist stripping performance and preventing corrosion of conductors (such as wiring made of copper (Cu) or aluminum (A1)). However, there is a problem that these technologies still cannot satisfy both purposes completely.
  • the present invention has been made in view of the above problems, and provides a resist stripper that has excellent releasability, is safe without flammability, and has excellent corrosion resistance that does not corrode conductors. With the goal.
  • the present inventor has made extensive studies in view of the above situation. As a result, a specific novel alkoxyamide compound having high amphiphilic properties was used as a resist stripper. This resist stripper was excellent in anticorrosion properties, and was excellent in both strength and stripping performance. The present invention has been completed in this way.
  • the resist remover of the present invention contains a compound represented by the formula (1).
  • R is an alkyl group having 1 to 18 carbon atoms.
  • R and R are
  • R and R may be the same or different from each other, and
  • the alkoxyamide-based resist stripper has high stripping performance and is extremely excellent in corrosion resistance against copper and aluminum. Further, since this resist stripper is water-soluble, no IPA (isopropyl alcohol) rinse is required, and productivity can be improved.
  • the compound represented by the formula (1) Preferably, about 20 to 100% by weight of the compound represented by the formula (1) and about 0 to 80% by weight of water are included.
  • the resist remover can also be used as a water-mixed resist remover.
  • resist stripping agents can be made non-hazardous by eliminating flammability by using a water mixture. Can be handled.
  • the resist stripper has high stripping performance even at a high water dilution rate, and the amount of resist stripper used can be reduced. Furthermore, even when the resist stripping agent is not a water mixture, the safety can be improved because the alkoxyamide compound itself has a high flash point.
  • the carbon numbers of R and R are:! -4.
  • the resist stripping agent can suppress that the solubility to water falls, and water rinse becomes possible.
  • the carbon number of R and R is 1, and the carbon number of R is:
  • the resist stripper can suppress the decrease in water solubility without decreasing the resist strippability.
  • the carbon number of R and R is 2, and the carbon number of R is:! -6
  • the resist stripper can suppress the decrease in water solubility without decreasing the resist strippability.
  • an anticorrosive agent a chelating agent, a peeling accelerator, a reducing agent, an oxidizing agent, a surfactant, a buffering agent and / or an antioxidant are added.
  • the resist stripper can suppress performance deterioration due to oxidation.
  • FIG. 1 shows Table 1 showing release agent types (composition of the release liquid), release performance and anticorrosion performance for Examples 1 to 15.
  • FIG. 2 shows Table 2 showing the release agent type (composition of the release solution), release performance and anticorrosion performance for Comparative Examples:!
  • the resist remover of the present invention is used in the production of liquid crystal display panels and semiconductor elements. It is. That is, the resist (photosensitive agent) that is no longer necessary in the photolithography process is dissolved and removed.
  • the resist stripper of this embodiment is configured to include an alkoxyamide compound represented by the formula (1).
  • R is an alkyl group having 1 to 18 carbon atoms.
  • R and R are
  • a monovalent hydrocarbon group which may have a hydrogen atom or an ether bond having 1 to 6 carbon atoms.
  • examples of the alkyl group of R include a methylol group, an ethyl group, various propyl groups, and various butylenes.
  • This alkyl group is particularly preferably one having 1 to 6 carbon atoms, preferably one having 1 to 8 carbon atoms.
  • the hydrocarbon group for R and R may be either linear or branched.
  • Saturated hydrocarbon groups are preferred. Examples thereof include a methyl group, an ethyl group, various propyl groups, various butyl groups, a methoxymethyl group, a methoxyethyl group, and an ethoxyethyl group, and the methyl group is the most common.
  • R and R may be the same or different
  • This ring structure may be a heterocyclic structure in which nitrogen is a heteroatom, or may be a heterocyclic structure in which a nitrogen atom and an oxygen atom are heteroatoms.
  • Examples of the group having a heterocyclic structure include a 1_pyrrolidinyl group, a piperidino group, and a morpholino group.
  • alkoxyamide-based compounds examples include 3-methoxy-1-N, N-dimethylpropionamide, 3_butoxy_N, N-dimethylpropionamide, 3-methoxy-1-N, N-jetylpropionamide, 3 -Ethoxy_N, N-Jetylpropionamide can be cited as S [0019]
  • the number of carbon atoms of R and R is 1 to 4, more preferably R and R.
  • the carbon number of R and R is 1, the carbon number of R is preferably 1 to 8.
  • R has 1 to 6 carbon atoms. This will remove the resist
  • R and R may have 1 to 6 carbon atoms.
  • R has 1 to 3 carbon atoms. This will remove the resist
  • R and R have 2 carbon atoms
  • the alkoxyamide compound represented by the above formula (1) is usually mixed with water and used as a water mixed resist remover.
  • This resist stripper can be handled as a non-hazardous material because it is not flammable by using a water mixture.
  • this resist stripper has high stripping performance even at a high water dilution rate, and can reduce the amount of resist stripper used. Furthermore, even when not using a water mixture, it can be used as a resist remover. Further, since the alkoxyamide compound itself is a third petroleum with a high flash point, safety can be improved.
  • the resist stripper contains about 20 to 100% by weight of the compound represented by the formula (1) and about 0 to 80% by weight of water. More preferably, it contains about 25 to 100% by weight of the compound represented by formula (1) and about 0 to 75% by weight of water, and more preferably about 40 to 100% by weight. A compound represented by the formula (1) and 0 to 60% by weight of water are included. In this way, the stripping performance of the resist stripper can be exhibited well.
  • the addition amount is about 5 to 80% by weight, preferably about 20 to 60% by weight. That is, when the compound represented by the formula (1) is less than about 40% by weight or exceeds about 80% by weight, depending on the compound represented by the formula (1), the peeling performance with respect to the resist is lowered. Because there is a worry to do.
  • the amount of water added is preferably about 0 to 80% by weight, more preferably about 0 to 40% by weight. Good. In this way, if the peeling performance with respect to the resist deteriorates, it is possible to prevent problems.
  • the resist stripper of this embodiment is preferably added with an anticorrosive, a chelating agent, a stripping accelerator, a reducing agent, an oxidizing agent, a surfactant, a buffering agent, Z or an antioxidant, and the like.
  • an anticorrosive e.g., a chelating agent, a stripping accelerator, a reducing agent, an oxidizing agent, a surfactant, a buffering agent, Z or an antioxidant, and the like.
  • Toyole e.g., when a surfactant is added, the permeability to fine gaps is improved, and the peelability of the resist can be improved. Moreover, the performance deterioration by oxidation can be suppressed by adding antioxidant as needed.
  • the above anticorrosives, chelating agents, peeling accelerators, reducing agents, oxidizing agents, surfactants and antioxidants can be used alone or in combination of two or more.
  • anticorrosive or chelating agent examples include aromatic hydroxy compounds, acetylene alcohols, carboxyl group-containing organic compounds and anhydrides, triazole compounds, saccharides, and oxime compounds.
  • aromatic hydroxy compounds examples include aromatic hydroxy compounds, acetylene alcohols, carboxyl group-containing organic compounds and anhydrides, triazole compounds, saccharides, and oxime compounds.
  • triazole compounds examples include triazole compounds, saccharides, and oxime compounds.
  • aromatic hydroxy compound phenol, cresol, xylenol, pyro-power teconole, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol Nore, p-hydroxyphenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, ⁇ -hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, Examples include 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, and the like.
  • carboxyl group-containing organic compound and its anhydride formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, gnoretalic acid, maleic acid, fumaric acid, benzoic acid, phthalic acid, 1,2,3_Benzenetricarboxylic acid, glycolic acid, lactic acid, malic acid, succinic acid, acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, salicylic acid, tartaric acid, acrylic acid, ⁇ -linolenic acid, etc. be able to.
  • Examples of the triazole compound include benzotriazole, ⁇ _tolyltriazole, m-tolyltriazole, p_trinortriazolole, carboxybenzotriazole, 1-hydroxybenzazotriazole, nitrobenzotriazole, dihydroxypropylbenzotriazole, And aminotriazole.
  • saccharide examples include sorbitol, xylitol, palatinit, arabitol, mannitol, sucrose, starch and the like.
  • oxime compounds examples include dimethyl darilioxime and diphenyl daroxime.
  • the above anticorrosive or chelating agent may be used either alone or as a mixture thereof.
  • Examples of the release accelerator include benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, or alkylbenzenesulfonic acid such as methyl, propyl, heptyl, octyl, decyl, dodecyl, and the like.
  • the above peeling accelerator may be used either alone or as a mixture thereof.
  • Examples of the reducing agent include hyposulfite, sulfate-based reducing agents, amine-based reducing agents, and other reducing agents.
  • hyposulfite and sulfate-based reducing agent examples include sodium thiosulfate, sodium dithionite, sodium pyrosulfite, and sodium metabisulfite.
  • amine reducing agent examples include hydroxyreamine, monoethanolamine, tryptophan, histidine, methionine, and phenylalanine.
  • reducing agents include ascorbic acid, butynediols, unsaturated ketones, uric acid , Tetraamisole, hydrazines, and derivatives thereof, including strong rubazates, oximes, hydroquinone, pyrogallol, gallic acid, 2,4,5-trihydroxybutyrophenone, tocopheronole, 6-hydroxy -2,5,7,8-tetramethylchroman-2-carboxylic acid, butylated hydroxytoluene (BHT), butylated hydroxybenzene (BHA), 2,6-di-tert-butyl- Four
  • reducing agent may be used either alone or as a mixture thereof.
  • oxidizing agent ozone, hydrogen peroxide, hypochlorous acid or hypochlorite, chlorous acid or chlorite, perchloric acid or perchlorate, hypobromous acid or the following Bromate, bromate or bromate, perbromate or perbromate, hypoiodic acid or hypoiodite, iodic acid or iodate, periodic acid or periodic acid Salt, persulfate or persulfate, peracetic acid or peracetate, perpropionic acid or perpropionate, perbenzoic acid or perbenzoate, tert-ptylnoide oral peroxide, ethylbenzennoide oral peroxide, cumene Examples include Hyde mouth peroxide.
  • the oxidizing agent may be used either alone or as a mixture thereof.
  • surfactant examples include cationic, anionic, nonionic, and fluorine surfactants.
  • Cationic surfactants such as alkyltrimethylammonium salt, alkylamidoamine, alkyldimethylbenzylammonium salt, polyethylenepolyamine cation resin, cetyltrimethylammonium chloride, quaternary ammonium salt, etc.
  • a surfactant may be mentioned.
  • Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene glycol fatty acid ester, polyoxyalkylene sorbite fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid. Listed are ester-based surfactants.
  • an anionic surfactant a group that exhibits anionic properties in water, A group to be formed (hereinafter referred to as a sulfonic acid group), a group to form a sulfate ester (hereinafter referred to as a sulfate ester group), a group to form a phosphate ester (hereinafter referred to as a phosphate ester group), Examples include groups that form carboxylic acids (hereinafter referred to as carboxylic acid groups).
  • Examples of the compound having a sulfonic acid group include alkyl diphenyl ether disulfonic acid, alkylene disulfonic acid, naphthalene sulfonic acid formalin condensate, phenol sulfonic acid formalin condensate, and phenol phenol sulfonic acid formalin condensate.
  • a compound having two or more anionic functional groups in the child structure a compound such as an alkylbenzene sulfonic acid, a dialkyl succinate sulfonic acid, a monoalkyl succinate sulfonic acid, an alkyl phenoxy succinate sulfonic acid, or a salt thereof. Can be mentioned.
  • Examples of the compound having a sulfate ester group include methyl taurines such as alkyl methyl taurine, acyl methyl taurine, fatty acid methyl taurine, polyoxyalkylene alkyl phenolate ester sulfate sulfate, polyoxyalkylene vinyleno quinoleate ester sulfate ester, Examples thereof include compounds such as polyoxyalkylene polycyclic phenyl ether sulfate, polyoxyalkylene aryl ether sulfate, and salts thereof.
  • Examples of the compound having a phosphoric ester group include compounds such as polyoxyalkylene alkyl ether phosphoric acid and polyoxyalkylene alkyl phenyl ether phosphoric acid, and salts thereof.
  • Examples of the compound having a carboxylic acid group include sarcosine compounds such as isyl sarcosine and fatty acid sarcosine, fatty acid compounds such as coconut oil, oleic acid, acrylic acid and ⁇ -linolenic acid, and salts thereof.
  • compounds having two different anionic functional groups in the molecular structure include compounds such as alkylsulfosuccinic acid and polyoxyalkylenealkylsulfosuccinic acid, which are compounds having a sulfonic acid group and a carboxylic acid group, or salts thereof.
  • fluorosurfactant examples include a perfluoroalkylethylene oxide adduct, a perfluoroalkyl phosphate ester, and a perfluoroalkylphenylglycine.
  • the above surfactants may be used either alone or as a mixture thereof.
  • Examples of the buffer include inorganic acid salts and organic acid salts.
  • organic acids useful in buffer systems include, but are not limited to, formic acid, trifluoroacetic acid, propionic acid, butyric acid, valeric acid, heptanoic acid, lactic acid, oxalic acid, malic acid, malonic acid, succinic acid, fumaric acid, adipine Examples include acids, benzoic acid, phthalic acid and citrate.
  • Conjugate bases useful in the buffer system of the present invention include organic acid salts, ammonia, tetramethylammonium hydroxide, tetraalkylammonium hydroxide, 2_ (methylamino) ethanol, monoisopropanol.
  • the salt is at least one selected from the group consisting of carboxylate, sulfate, sulfonate, phosphonate, nitrate, hydrochloride and borate. Specifically, ammonium acetate, ammonium citrate, ammonium oxalate, ammonium sulfosuccinate, ammonium sulfate, ammonium methanesulfonate, ammonium phosphonate, ammonium nitrate, ammonium chloride, ammonium tetraborate, ammonium acrylic acid, etc. Is mentioned. Paying attention to cations, in addition to ammonium salt, amin salt or quaternary ammonium salt may be used.
  • amines examples include hydroxylamines such as hydroxylamine, jetylhydroxylamine, anolamines such as ethylamine, propanediamine, dibutylamine, and trimethylamine, monoethanolamine, methylethanolamine, and methyljetanolamine.
  • Alkanolamines such as triethanolamine, monoisopropanolamine, diglycolamine, N, N-dimethyl-1-2- (2-aminoethoxy) ethanol, aromatic amines such as aniline and benzylamine, Morpholines such as ethylmorpholine, hydroxymorpholine, aminopropylone morpholine, 1 _ (2-aminoethyl) piperidine, 1 _ (2 _ Hydroxyethyl) piperazine, 1- (2 aminoethyl) piperazine, 1 (3-aminoprohi.
  • Alkanolamines such as triethanolamine, monoisopropanolamine, diglycolamine, N, N-dimethyl-1-2- (2-aminoethoxy) ethanol, aromatic amines such as aniline and benzylamine, Morpholines such as ethylmorpholine, hydroxymorpholine, aminopropylone morpholine, 1 _ (2-aminoethyl
  • Nore mono-imita, Norole, 1,8-diazabi'cyclo [5.4.0] undec-7 -ene, NN N '-trimethylaminoethanolamine, pentamethyljetylenetriamine and the like.
  • the amine is not particularly limited as long as it exhibits basicity.
  • quaternary ammonium ions that form quaternary ammonium salts include tetramethyl ammonium ion, tetraethyl ammonium ion, triethyl methyl ammonium ion, lauryl trimethyl ammonium ion, and benzyl trimethyl ammonium ion.
  • the above buffering agents may be used either alone or as a mixture thereof.
  • examples thereof include bisphenol compounds such as phenol), 4,4, -methylenebis (2,6 di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tertbutylphenol), and the like.
  • phosphite antioxidants such as triphenyl phosphate, trisnoylphenyl phosphite and tris (mono and di-noylphenyl) phosphate can be mentioned.
  • sulfur-based antioxidants such as dilauryl dipropionate and distearyl thiodipropionate can be mentioned.
  • the above antioxidants may be used either alone or as a mixture thereof. Also acid
  • the amount of antioxidation agent used is preferably about 0.01 to 1.0% by weight based on the resist stripper.
  • the resist remover that is effective in the present embodiment uses the alkoxyamide-based compound represented by the formula (1), so that it has high peeling performance and is anticorrosive against copper, aluminum, and the like. It is very excellent in sex.
  • a water-based release agent it is flammable and safe, and since it has water solubility, it can be rinsed with water and does not require an IPA rinse, thus improving productivity. be able to.
  • FIG. 1 shows Table 1 showing the release agent type (composition of the release solution), release performance, and anticorrosion performance for Examples 1 to 15.
  • FIG. 2 shows Table 2 showing the release agent type (the composition of the release solution), the release performance and the anticorrosion performance for Comparative Examples:!
  • Substrate A film-forming glass (size: about 100 mm X 100 mm) manufactured by Hitachi Metals, Ltd. was used.
  • HPR204 naphthoquinone diazide / Novolac resin
  • Fuji Film Electronics Materials Co., Ltd. was applied and baked in an oven at a predetermined temperature for about 15 minutes. That is, Examples 1, 2, 3, 5-8, 10-: 15 and Comparative Examples 1, 3-6 were baked in an oven at about 130 ° C. for about 15 minutes. In Examples 4 and 9, and Comparative Example 2, those baked in an oven at about 150 ° C. for about 15 minutes were used.
  • ⁇ It takes less than 40 seconds to become transparent.
  • the predetermined temperature when stirring is room temperature (for example, 0-30 ° C). , Usually 20-25 ° C).
  • the predetermined temperature during stirring was set to about 40 ° C.
  • Resist stripping—2 About 5 ml of the stripping agent and the above-prepared resist substrate test piece are placed in a sample bottle of about 30 ml and stirred for about 60se C at a predetermined temperature. Then, the resist substrate was taken out and immediately rinsed with acetone, and then the surface after drying at about 50 ° C. for about 30 minutes was observed and judged as follows.
  • ⁇ There is no cloudy portion on the glass substrate surface, and the resist is completely washed and peeled off.
  • ⁇ The glass substrate surface has a slightly cloudy portion, and the resist is almost removed by washing.
  • the predetermined temperature for stirring for about 60 seconds is the room temperature (for example, 0-30 °). C, usually 20-25 ° C). In Examples 4 and 9, and Comparative Example 2, the predetermined temperature when stirring for about 60 seconds was about 40 ° C.
  • the anticorrosion performance was evaluated by the following two evaluation methods.
  • Anticorrosion-1 Put a release agent in a sample bottle of about 30ml, immerse a copper wire of about 0.5mm in diameter about 100mm in diameter, and observe the degree of coloration after 1 week. It was judged.
  • ⁇ No discoloration at all. ⁇ : Slightly discolored to light blue.
  • Anti-corrosion—2 Make a Mo (molybdenum) / Al / Mo multilayer wiring board, put this test piece (about 10mm x 5mm) into a sample bottle of about 30ml, add about 5ml of release agent, and add about 40 ° Soaked in C for about 5 minutes. Immersion 'After the corrosion operation, observation was made according to the following procedure, and judgment was made as follows.
  • step 1 perform IPA rinse, as step 2, perform acetone rinse, and as step 3, dry at approximately 50 ° C for approximately 30 minutes, and then use SEM (scanning electron microscope) to determine the degree of corrosion of A1. Was observed.
  • SEM scanning electron microscope
  • a resist release agent comprising about 80% by weight of 3-methoxy-N, N dimethylpropionamide (abbreviated as MDMPA as appropriate) and about 20% by weight of water. Prepared. Subsequently, the peeling test and the corrosion test were performed.
  • Resist stripping property-1 ⁇ (Time until the substrate became transparent was 38 seconds.)
  • Resist stripping property 2 :
  • a resist release agent comprising about 60% by weight of 3-methoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • Resist strippability-1 ⁇ (Time until substrate became transparent was 39 seconds.)
  • Resist strippability 2 Anticorrosion 1: 0
  • This resist stripper has a slightly cloudy portion on the glass substrate surface in resist stripping property 2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
  • a release agent according to Example 3 a resist release agent comprising about 100% by weight of 3-methoxy-N, N dimethylpropionamide was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • Resist stripping property-1 ⁇ (Time until the substrate became transparent was 32 seconds.)
  • Resist stripping property 2 :
  • a release agent according to Example 4 a resist release agent composed of about 100% by weight of 3 methoxy-N, N-dimethylpropionamide was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • Resist stripping property-1 ⁇ (Time until the substrate becomes transparent was 35 seconds.)
  • Resist stripping property 2 ⁇
  • a release agent according to Example 5 about 100% by weight of 3_butoxy-N, N-dimethylpropylene was used. A resist stripper made of lopionamide (abbreviated as BDMPA as appropriate) was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • BDMPA lopionamide
  • Resist releasability _ 1 ⁇ (Time until substrate became transparent was 31 seconds.)
  • Resist releasability — 2 ⁇
  • This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is recognized). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
  • a release agent according to Example 6 a resist release agent comprising about 80 wt% of 3 butoxy-N, N dimethylpropionamide and about 20 wt% of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • Resist releasability _ 1 ⁇ (The time until the substrate became transparent was 24 seconds.)
  • Resist releasability — 2 ⁇
  • This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is recognized). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
  • a release agent according to Example 7 a resist release agent comprising about 60% by weight of 3 butoxy-N, N dimethylpropionamide and about 40% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted. The test results are shown in Table 1.
  • Resist strippability-1 (Time until the substrate became transparent was 29 seconds.)
  • Resist stripp 2 (Time until the substrate became transparent was 29 seconds.)
  • a resist release agent comprising about 40% by weight of 3 butoxy-N, N dimethylpropionamide and about 60% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • Resist strippability-1 (Time until the substrate became transparent was 24 seconds.)
  • Resist stripp 2 (Time until the substrate became transparent was 24 seconds.)
  • a resist release agent comprising about 60% by weight of 3_butoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • Resist strippability-1 ⁇ (Time until substrate became transparent was 39 seconds.)
  • Resist strippability 2 :
  • This resist stripper has a slightly cloudy portion on the glass substrate surface in resist stripping property 2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). In addition, this resist stripper is used in other tests for stripping performance and corrosion resistance. It was excellent.
  • a resist release agent comprising about 100% by weight of 3-methoxy-N, N-jetinorepropionamide (abbreviated as MDEPA as appropriate) was prepared. Subsequently, the peeling test and the corrosion test were performed.
  • MDEPA 3-methoxy-N, N-jetinorepropionamide
  • Resist stripping property-1 ⁇ (Time until the substrate becomes transparent was 30 seconds.)
  • Resist stripping property 2 :
  • a resist remover comprising about 80% by weight of 3-methoxy-1-N, N-jetylpropionamide and about 20% by weight of water was prepared as a remover useful for Example 11. Subsequently, the above peeling test and corrosion test were conducted.
  • Resist releasability _ 1 0 (Time until the substrate became transparent was 18 seconds.)
  • Resist releasability — 2 0 (Time until the substrate became transparent was 18 seconds.)
  • a resist stripping agent according to Example 12 a resist stripping agent comprising about 60% by weight of 3-methoxy-N, N-jetylpropionamide and about 40% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • Resist releasability _ 1 0 (Time until the substrate became transparent was 28 seconds.)
  • Resist releasability — 2 0
  • Anticorrosion 1 0
  • a resist stripping agent comprising about 100% by weight of 3 ethoxy N, N jetyl propionamide (abbreviated as EDEPA as appropriate) was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • EDEPA N jetyl propionamide
  • Resist stripping property-1 ⁇ (Time until the substrate became transparent was 19 seconds.)
  • Resist stripping property 2 :
  • This resist stripper has a slightly cloudy portion on the glass substrate surface in resist stripping property 2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
  • a resist stripping agent according to Example 14 a resist stripping agent comprising about 80% by weight of 3_ethoxy_N, N-jetylpropionamide and about 20% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
  • Resist stripping property-1 ⁇ (Time until the substrate became transparent was 19 seconds.)
  • Resist stripping property 2 :
  • Resist releasability _ 1 ⁇ (The time until the substrate became transparent was 29 seconds.)
  • Resist releasability — 2 ⁇
  • This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is recognized). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
  • Resist releasability _ 1 X (Time until the substrate became transparent was 45 seconds.)
  • Resist releasability — 2 ⁇
  • This resist stripper required a long time for stripping in the resist stripping_1, and a small amount of resist residue was observed in the resist stripping_2. In addition, this resist stripper turned slightly light blue in anticorrosion property_1, and further, A1 eluted slightly in anticorrosion property_2, and corrosion was observed.
  • Resist stripping property-1 X (Time until the substrate became transparent was 50 seconds.)
  • Resist stripping property 2 :
  • This resist stripper required a long time for stripping in the resist stripping_1, and a small amount of resist residue was observed in the resist stripping_2. In addition, this resist stripper turned slightly light blue in anticorrosion property_1, and further, A1 eluted slightly in anticorrosion property_2, and corrosion was observed.
  • Resist strippability-1 X (Time until the substrate became transparent was 56 seconds.)
  • Resist strippability-2 X
  • This resist stripper requires a long time for stripping in resist stripping_1, and in resist stripping_2, more than half of the surface of the glass substrate is cloudy, and cleaning stripping is insufficient. The resist remained. In addition, this resist stripper turned slightly light blue in the anticorrosion property_1, and further, in the anticorrosion property_2, A1 was slightly eluted and corrosion was observed.
  • Resist strippability-1 ⁇ (Time to clear the substrate was 38 seconds.)
  • Resist strippability 2 ⁇
  • resist stripper had excellent strippability in resist strippability-1, a small amount of resist residue was observed in resist strippability_2. In addition, this resist stripper clearly turned blue in anticorrosion property 1 and, further, in the anticorrosion property 2, A1 was clearly eluted and severe corrosion was observed.
  • Resist strippability-1 (Time until the substrate became transparent was 24 seconds.)
  • Resist stripp 2 (Time until the substrate became transparent was 24 seconds.)
  • This resist remover was excellent in peelability.
  • this resist stripper clearly turned blue in the anticorrosion property_1, and further, in the anticorrosion property_2, A1 was clearly eluted and severe corrosion was observed.
  • Resist strippability-1 ⁇ (Time until the substrate became transparent was 29 seconds.)
  • Resist strippability 2 :
  • Anticorrosive 1 X
  • Anticorrosion 2 X
  • resist stripper was excellent in stripping property in resist stripping property 1, a small amount of resist residue was observed in resist stripping property 2. In addition, this resist stripper clearly turned blue in anticorrosion property 1 and, further, in the anticorrosion property 2, A1 was clearly eluted and severe corrosion was observed.
  • resist stripper of the present invention has been described with reference to the preferred embodiment, the resist stripper according to the present invention is not limited to the above-described embodiment. Needless to say, it is possible to implement this change.
  • the compound represented by the formula (1) contained in the resist stripper is not limited to one type, for example, a resist stripper containing two or more compounds represented by the formula (1). There may be.
  • liquid crystal / semiconductor resist removers are not limited to liquid crystal / semiconductor resist removers.
  • print board removers for example, print board removers, resist developers, flux cleaners, resin solvents (for example, polyimide resin solvents, polyamides) It is also used as a solvent for resins.
  • resin solvents for example, polyimide resin solvents, polyamides

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Abstract

Disclosed is a resist stripping agent which has excellent stripping properties, which has no flammability and therefore is safe, and which does not cause corrosion of a conductive material and therefore has excellent anti-corrosion properties. The resist stripping agent comprises a compound represented by the formula (1). (1) wherein R3 represents an alkyl group having 1 to 18 carbon atoms, and R1 and R2 independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have an ether bond.

Description

明 細 書  Specification
レジスト剥離剤  Resist stripper
技術分野  Technical field
[0001] 本発明は、レジスト剥離剤に関する。特に、本発明のレジスト剥離剤は、剥離性に 優れ、かつ、引火性がなく安全であり、さらに、導電体を腐蝕させない防食性に優れ ている。  [0001] The present invention relates to a resist stripper. In particular, the resist remover of the present invention is excellent in releasability, safe from flammability, and excellent in corrosion resistance that does not corrode the conductor.
背景技術  Background
[0002] IC, LSIのような集積回路、 LCD, EL素子のような表示機器、プリント基板等は、ホ トリソグラフィー技術を用いて製造されている。このホトリソグラフィー工程において、 不必要となったレジスト (感光剤）は、レジスト剥離剤を用いて除去される。  [0002] Integrated circuits such as IC and LSI, display devices such as LCD and EL elements, printed circuit boards, and the like are manufactured using photolithography technology. In this photolithography process, unnecessary resist (photosensitive agent) is removed using a resist stripper.
[0003] (従来例）  [0003] (Conventional example)
このレジスト剥離工程では、これまで種々のレジスト剥離剤が使用されてきた。しか し、近年、液晶表示パネルや半導体素子のプロセスの微細化や短時間処理に対応 するには能力が低ぐ更なる性能が望まれている。現在では、剥離性に優れたァミン 系化合物を含むレジスト剥離剤が主力となっている。  In the resist stripping process, various resist stripping agents have been used so far. However, in recent years, further performance with low capability has been desired in order to cope with the miniaturization and short-time processing of liquid crystal display panels and semiconductor elements. Currently, the mainstay is resist strippers containing amine compounds with excellent stripping properties.
このアミン系剥離剤は溶剤系と水系に分類できる。たとえば、溶剤系剥離剤として、 ジメチルスルホキシド（約 30重量0 /0) +モノエタノールァミン（約 70重量0 /0)や、モノエ タノールァミン + N—メチルピロリドンなどが使用されている。一方、水系剥離剤として 、水（約 20〜30重量％) +ジエチレングリコールモノブチルエーテル（約 20〜30重 量0 /o) +モノエタノールァミン（約 30〜40重量0 /0)、アルキルベンゼンスルホン酸 + 機能水 (オゾン水）、酸系（硫酸 +過酸化水素） +機能水 (オゾン水)などが使用され ている。 This amine release agent can be classified into a solvent type and an aqueous type. For example, as a solvent based release agent, dimethyl sulfoxide (about 30 weight 0/0) + monoethanol § Min (about 70 weight 0/0) and, like Monoe Tanoruamin + N-methylpyrrolidone is used. Meanwhile, as an aqueous release agent, water (about 20 to 30 wt%) + diethylene glycol monobutyl ether (about 20-30 by weight 0 / o) + monoethanol § Min (about 30-40 weight 0/0), alkyl benzene sulfonic acid + Functional water (ozone water), acid (sulfuric acid + hydrogen peroxide) + functional water (ozone water) are used.
[0004] 近年、水リンスが可能な水系剥離剤の使用が拡大している。この理由は、水系剥離 剤が剥離性に優れ、し力も引火性がなく危険物ではないからである。ところで、水系 剥離剤は、モノエタノールァミンが添加されている。このため、水系剥離剤は、配線な どの導電体への腐食が起こるといった欠点を有している。したがって、実際には剥離 性能と腐食性を考慮して、モノエタノールァミンの含有量を調整する必要がある。そし て、レジスト剥離性能と導電体へのダメージ (腐食）防止を目的として、様々なレジスト 剥離剤が開発されてきた。 [0004] In recent years, the use of water-based release agents capable of water rinsing has expanded. The reason for this is that the water-based release agent is excellent in releasability, has no flammability, and is not a dangerous substance. By the way, monoethanolamine is added to the aqueous release agent. For this reason, the water-based release agent has a drawback that corrosion occurs on conductors such as wiring. Therefore, in actuality, it is necessary to adjust the monoethanolamine content in consideration of peeling performance and corrosivity. And Various resist stripping agents have been developed for the purpose of resist stripping performance and prevention of damage (corrosion) to conductors.
[0005] たとえば、特許文献 1には、アルカノールァミンとホルムアルデヒドを反応させた生 成物を含有するフォトレジスト剥離剤が開示されている。この生成物は、アル力ノール ァミンとホルムアルデヒドを、ホルムアルデヒド/アルカノールァミン（モル比）で、 0. 8 以下の割合で反応させることによって、生成される。  [0005] For example, Patent Document 1 discloses a photoresist stripper containing a product obtained by reacting alkanolamine and formaldehyde. This product is produced by reacting an alkanolamine with formaldehyde in a formaldehyde / alkanolamine (molar ratio) at a ratio of 0.8 or less.
また、特許文献 2には、アルカノールァミン化合物と、スルホン化合物又はスルホキ シド化合物と、ヒドロキシィ匕合物とからなる、フォトレジスト剥離剤組成物が開示されて いる。  Patent Document 2 discloses a photoresist stripping composition comprising an alkanolamine compound, a sulfone compound or a sulfoxide compound, and a hydroxy compound.
さらに、特許文献 3には、少なくともヒドロキシカルボン酸および水を含む、 pHの安 定したレジスト剥離剤が開示されている。このレジスト剥離剤は、製造後に含まれるヒ ドロキシカルボン酸が、二分子以上の縮合体とヒドロキシカルボン酸単量体との比率（ すなわち、縮合体/単量体）が 1/9以下になるように調整されている。  Further, Patent Document 3 discloses a resist remover having a stable pH and containing at least a hydroxycarboxylic acid and water. In this resist stripper, the hydroxycarboxylic acid contained after the production has a ratio of the condensate of two or more molecules to the hydroxycarboxylic acid monomer (ie, the condensate / monomer) is 1/9 or less. Have been adjusted so that.
また、特許文献 4には、銅と銀の合金を配線プロセスに使用するためのレジストを剥 離する剥離剤が開示されている。このレジスト剥離剤は、ピぺラジン類を含んでいる。 さらに、特許文献 5には、テトラエチレンペンタミン及びエーテルアルコールを含む レジスト剥離剤が開示されている。  Patent Document 4 discloses a stripping agent that strips a resist for using an alloy of copper and silver in a wiring process. This resist stripper contains piperazines. Further, Patent Document 5 discloses a resist stripper containing tetraethylenepentamine and ether alcohol.
特許文献 1 :特開 2004— 219486号公報  Patent Document 1: Japanese Patent Application Laid-Open No. 2004-219486
特許文献 2：特開平 05— 281753号公報  Patent Document 2: JP 05-281753 A
特許文献 3 :特開 2005— 049438号公報  Patent Document 3: Japanese Patent Laid-Open No. 2005-049438
特許文献 4：特開 2004— 205674号公報  Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-205674
特許文献 5：特開 2004— 205675号公報  Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-205675
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 上記各特許文献に記載された技術は、レジスト剥離性能の向上と導電体 (銅 (Cu) やアルミニウム (A1)などからなる配線など）の防食を目的として開発された。しかしな がら、これらの技術では、まだ完全に両目的を満足することができないといった問題 があった。 [0007] 本発明は、上記課題に鑑みなされたものであり、剥離性に優れ、かつ、引火性がな く安全であり、さらに、導電体を腐蝕させない防食性に優れたレジスト剥離剤の提供 を目的とする。 [0006] The technologies described in the above patent documents have been developed for the purpose of improving resist stripping performance and preventing corrosion of conductors (such as wiring made of copper (Cu) or aluminum (A1)). However, there is a problem that these technologies still cannot satisfy both purposes completely. [0007] The present invention has been made in view of the above problems, and provides a resist stripper that has excellent releasability, is safe without flammability, and has excellent corrosion resistance that does not corrode conductors. With the goal.
[0008] なお、本発明者は、上記の状況を鑑み、鋭意検討した。この結果、高い両親媒性を もつ特定の新規なアルコキシアミド系化合物を、レジスト剥離剤として使用した。この レジスト剥離剤は、防食性に優れ、し力も剥離性能にも優れていた。本発明は、この ようにして完成したものである。  [0008] The present inventor has made extensive studies in view of the above situation. As a result, a specific novel alkoxyamide compound having high amphiphilic properties was used as a resist stripper. This resist stripper was excellent in anticorrosion properties, and was excellent in both strength and stripping performance. The present invention has been completed in this way.
課題を解決するための手段  Means for solving the problem
[0009] 上記目的を達成するために、本発明のレジスト剥離剤は、式（1)で表される化合物 を含んでいる。 In order to achieve the above object, the resist remover of the present invention contains a compound represented by the formula (1).
[化 1]  [Chemical 1]
Figure imgf000005_0001
Figure imgf000005_0001
ここで、式（1)において、 Rは炭素数 1〜： 18のアルキル基である。 R及び Rは、そ  Here, in the formula (1), R is an alkyl group having 1 to 18 carbon atoms. R and R are
3 1 2 れぞれ独立に水素原子又は炭素数 1〜6のエーテル結合を有してもよい炭化水素基 である。 Rと Rは、互いに同一であっても異なっていてもよぐさらに、互いに結合し  3 1 2 Each independently represents a hydrogen atom or a hydrocarbon group which may have an ether bond having 1 to 6 carbon atoms. R and R may be the same or different from each other, and
1 2  1 2
て環構造を形成してもよい。  To form a ring structure.
このように、アルコキシアミド系のレジスト剥離剤は、高い剥離性能を有するとともに 、銅やアルミに対して防食性に非常に優れている。また、このレジスト剥離剤は、水溶 性を有しているので、 IPA (イソプロピルアルコール）リンスが不要であり、生産性を向 上させることができる。  As described above, the alkoxyamide-based resist stripper has high stripping performance and is extremely excellent in corrosion resistance against copper and aluminum. Further, since this resist stripper is water-soluble, no IPA (isopropyl alcohol) rinse is required, and productivity can be improved.
また、好ましくは、約 20〜： 100重量％の前記式（1)で表される化合物と、約 0〜80 重量％の水とが含まれるとよレ、。  Preferably, about 20 to 100% by weight of the compound represented by the formula (1) and about 0 to 80% by weight of water are included.
このように、レジスト剥離剤は、水混合系のレジスト剥離剤としても使用することがで きる。また、レジスト剥離剤は、水混合物とすることにより引火性をなくし、非危険物と して取り扱うことができる。また、レジスト剥離剤は、高い水希釈率でも高い剥離性能 を有しており、レジスト剥離剤の使用量を低減することができる。さらに、レジスト剥離 剤は、水混合物としない場合であっても、アルコキシアミド系化合物自体の引火点が 高ぐ第三石油類であることから、安全性を向上させることができる。 As described above, the resist remover can also be used as a water-mixed resist remover. In addition, resist stripping agents can be made non-hazardous by eliminating flammability by using a water mixture. Can be handled. In addition, the resist stripper has high stripping performance even at a high water dilution rate, and the amount of resist stripper used can be reduced. Furthermore, even when the resist stripping agent is not a water mixture, the safety can be improved because the alkoxyamide compound itself has a high flash point.
[0011] また、好ましくは、前記 R及び Rの炭素数を、：!〜 4とするとよレ、。 [0011] Preferably, the carbon numbers of R and R are:! -4.
1 2  1 2
このようにすると、レジスト剥離剤は、水への溶解性が低下するのを抑制することが でき、水リンスが可能となる。  If it does in this way, the resist stripping agent can suppress that the solubility to water falls, and water rinse becomes possible.
[0012] また、好ましくは、前記 R及び Rの炭素数を 1とし、かつ、前記 Rの炭素数を:!〜 8 [0012] Preferably, the carbon number of R and R is 1, and the carbon number of R is:
1 2 3  one two Three
とするとよレ、。  And then,
このようにすると、レジスト剥離剤は、レジストの剥離性を低下させずに、水への溶解 性が低下するのを抑制することができる。  In this way, the resist stripper can suppress the decrease in water solubility without decreasing the resist strippability.
[0013] また、好ましくは、前記 R及び Rの炭素数を 2とし、かつ、前記 Rの炭素数を:!〜 6 [0013] Preferably, the carbon number of R and R is 2, and the carbon number of R is:! -6
1 2 3  one two Three
とするとよレ、。  And then,
このようにしても、レジスト剥離剤は、レジストの剥離性を低下させずに、水への溶解 性が低下するのを抑制することができる。  Even in this case, the resist stripper can suppress the decrease in water solubility without decreasing the resist strippability.
[0014] また、好ましくは、防食剤、キレート剤、剥離促進剤、還元剤、酸化剤、界面活性剤 、緩衝剤及び/又は酸化防止剤が添加されるとょレ、。 [0014] Preferably, an anticorrosive agent, a chelating agent, a peeling accelerator, a reducing agent, an oxidizing agent, a surfactant, a buffering agent and / or an antioxidant are added.
このように、たとえば、界面活性剤を添加すると、微細隙間への浸透性が向上し、レ ジストの剥離性を向上させることができる。また、酸化防止剤を添加することにより、レ ジスト剥離剤は、酸化による性能劣化を抑制することができる。  Thus, for example, when a surfactant is added, the permeability to fine gaps is improved, and the peelability of the resist can be improved. In addition, by adding an antioxidant, the resist stripper can suppress performance deterioration due to oxidation.
図面の簡単な説明  Brief Description of Drawings
[0015] [図 1]図 1は、実施例 1〜： 15に対する、剥離剤種 (剥離液の組成）、剥離性能及び防 食性能を表した表一 1を示してレ、る。  [0015] [FIG. 1] FIG. 1 shows Table 1 showing release agent types (composition of the release liquid), release performance and anticorrosion performance for Examples 1 to 15.
[図 2]図 2は、比較例:!〜 6に対する、剥離剤種 (剥離液の組成）、剥離性能及び防食 性能を表した表 2を示してレ、る。  [FIG. 2] FIG. 2 shows Table 2 showing the release agent type (composition of the release solution), release performance and anticorrosion performance for Comparative Examples:!
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0016] [レジスト剥離剤の一実施形態]  [One Embodiment of Resist Stripper]
本発明のレジスト剥離剤は、液晶表示パネルや半導体素子などの製造時に用いら れる。すなわち、ホトリソグラフィー工程において、不必要となったレジスト (感光剤）を 、溶解して除去する。 The resist remover of the present invention is used in the production of liquid crystal display panels and semiconductor elements. It is. That is, the resist (photosensitive agent) that is no longer necessary in the photolithography process is dissolved and removed.
本実施形態のレジスト剥離剤は、式（1)で表されるアルコキシアミド系の化合物を含 む構成としてある。  The resist stripper of this embodiment is configured to include an alkoxyamide compound represented by the formula (1).
[化 2]  [Chemical 2]
Figure imgf000007_0001
Figure imgf000007_0001
上記式（1)において、 Rは炭素数 1〜： 18のアルキル基である。 R及び Rは、それ  In the above formula (1), R is an alkyl group having 1 to 18 carbon atoms. R and R are
3 1 2 ぞれ水素原子、又は、炭素数 1〜6のエーテル結合を有してもよい一価の炭化水素 基である。  3 1 2 A monovalent hydrocarbon group which may have a hydrogen atom or an ether bond having 1 to 6 carbon atoms.
[0017] ここで、 Rのアルキル基としては、メチノレ基、ェチル基、各種プロピル基、各種ブチ  Here, examples of the alkyl group of R include a methylol group, an ethyl group, various propyl groups, and various butylenes.
3  Three
ル基、各種ペンチル基、各種へキシル基、各種ォクチル基などが挙げられる。このァ ルキル基は、炭素数 1〜8のものが好ましぐ炭素数 1〜6のものが特に好ましい。 また、 R及び Rの炭化水素基としては、直鎖状、分岐状のいずれであってもよいが Group, various pentyl groups, various hexyl groups, various octyl groups and the like. This alkyl group is particularly preferably one having 1 to 6 carbon atoms, preferably one having 1 to 8 carbon atoms. The hydrocarbon group for R and R may be either linear or branched.
1 2 1 2
、飽和炭化水素基が好ましい。その例としては、メチル基、ェチル基、各種プロピル 基、各種ブチル基、メトキシメチル基、メトキシェチル基、エトキシェチル基などが挙 げられ、メチル基が最も一般的である。 R及び Rは、互いに同一であっても異なって  Saturated hydrocarbon groups are preferred. Examples thereof include a methyl group, an ethyl group, various propyl groups, various butyl groups, a methoxymethyl group, a methoxyethyl group, and an ethoxyethyl group, and the methyl group is the most common. R and R may be the same or different
1 2  1 2
レ、てもよく、さらに、互いに結合して環構造を形成してもよい。この環構造は、窒素を ヘテロ原子とする複素環構造であってもよぐまた、窒素原子と酸素原子をへテロ原 子とする複素環構造であってもよい。この複素環構造を有する基としては、たとえば、 1 _ピロリジニル基、ピぺジリノ基、モルホリノ基などを挙げることができる。  Or may be bonded to each other to form a ring structure. This ring structure may be a heterocyclic structure in which nitrogen is a heteroatom, or may be a heterocyclic structure in which a nitrogen atom and an oxygen atom are heteroatoms. Examples of the group having a heterocyclic structure include a 1_pyrrolidinyl group, a piperidino group, and a morpholino group.
[0018] 上記アルコキシアミド系の化合物として、たとえば、 3—メトキシ一 N， N—ジメチルプ ロピオンアミド、 3 _ブトキシ _N, N—ジメチルプロピオンアミド、 3—メトキシ一 N， N —ジェチルプロピオンアミド、 3—エトキシ _N, N—ジェチルプロピオンアミドなどを 挙げ'ること力 Sできる。 [0019] ここで、好ましくは、 R及び Rの炭素数を、 1〜4とするとよく、より好ましくは、 R及 [0018] Examples of the alkoxyamide-based compounds include 3-methoxy-1-N, N-dimethylpropionamide, 3_butoxy_N, N-dimethylpropionamide, 3-methoxy-1-N, N-jetylpropionamide, 3 -Ethoxy_N, N-Jetylpropionamide can be cited as S [0019] Here, preferably, the number of carbon atoms of R and R is 1 to 4, more preferably R and R.
1 2 1 び Rの炭素数を、 1〜2とするとよレ、。このようにすると、水への溶解性が低下するの Let 1 2 1 and R have 1 to 2 carbon atoms. This will reduce the solubility in water
2 2
を抑制することができ、水リンスが可能となる。  And water rinsing becomes possible.
[0020] また、好ましくは、 R及び Rの炭素数を 1としたとき、 Rの炭素数を 1〜8とするとよく [0020] Preferably, when the carbon number of R and R is 1, the carbon number of R is preferably 1 to 8.
1 2 3  one two Three
、より好ましくは、 Rの炭素数を 1〜6とするとよレ、。このようにすると、レジストの剥離  More preferably, R has 1 to 6 carbon atoms. This will remove the resist
3  Three
性（レジストを溶解する性能を含む。）を低下させずに、水への溶解性を増大させるこ とができる。 R及び Rの炭素数を 1としたとき、 Rの炭素数を 1〜8とするとよい理由  The solubility in water can be increased without reducing the properties (including the ability to dissolve the resist). The reason why R and R should have 1 to 8 carbon atoms
1 2 3  one two Three
は、 Rの炭素数が大きいほど水への溶解性が低下し、水希釈率が低下するとともに The larger the carbon number of R, the lower the solubility in water and the lower the water dilution rate.
3 Three
、水リンスが困難となるからである。  This is because water rinsing becomes difficult.
[0021] また、好ましくは、 R及び Rの炭素数を 2としたとき、 Rの炭素数を 1〜6とするとよく [0021] Further, preferably, when R and R have 2 carbon atoms, R may have 1 to 6 carbon atoms.
1 2 3  one two Three
、より好ましくは、 Rの炭素数を 1〜3とするとよい。このようにすると、レジストの剥離  More preferably, R has 1 to 3 carbon atoms. This will remove the resist
3  Three
性を低下させずに、水への溶解性を増大させることができる。 R及び Rの炭素数を 2  The solubility in water can be increased without reducing the properties. R and R have 2 carbon atoms
1 2  1 2
としたとき、 Rの炭素数を 1〜6とするとよい理由は、 Rの炭素数が大きいほど水への  The reason why the carbon number of R should be 1-6 is that the larger the carbon number of R,
3 3  3 3
溶解性が低下し、水希釈率が低下するとともに、水リンスが困難となるからである。  This is because solubility decreases, water dilution rate decreases, and water rinsing becomes difficult.
[0022] 上記式（1)で表されるアルコキシアミド系の化合物は、通常、水と混合され水混合 系のレジスト剥離剤として使用される。このレジスト剥離剤は、水混合物とすることによ り引火性がないので、非危険物として取り扱うことができる。また、このレジスト剥離剤 は、高い水希釈率でも高い剥離性能を有しており、レジスト剥離剤の使用量を低減 すること力 Sできる。さらに、水混合物としない場合であっても、レジスト剥離剤として使 用すること力 Sできる。また、アルコキシアミド系化合物自体の引火点が高ぐ第三石油 類であることから、安全性を向上させることができる。 [0022] The alkoxyamide compound represented by the above formula (1) is usually mixed with water and used as a water mixed resist remover. This resist stripper can be handled as a non-hazardous material because it is not flammable by using a water mixture. In addition, this resist stripper has high stripping performance even at a high water dilution rate, and can reduce the amount of resist stripper used. Furthermore, even when not using a water mixture, it can be used as a resist remover. Further, since the alkoxyamide compound itself is a third petroleum with a high flash point, safety can be improved.
[0023] ここで、好ましくは、レジスト剥離剤に、約 20〜100重量％の式（1)で表される化合 物と、約 0〜80重量％の水とが含まれるとよレ、。より好ましくは、約 25〜： 100重量％の 式（1)で表される化合物と、約 0〜75重量％の水とが含まれるとよぐさらに好ましく は、約 40〜： 100重量％の式（1)で表される化合物と、 0〜60重量％の水とが含まれ るとよレ、。このようにすると、レジスト剥離剤の剥離性能を良好に発揮することができる [0023] Here, preferably, the resist stripper contains about 20 to 100% by weight of the compound represented by the formula (1) and about 0 to 80% by weight of water. More preferably, it contains about 25 to 100% by weight of the compound represented by formula (1) and about 0 to 75% by weight of water, and more preferably about 40 to 100% by weight. A compound represented by the formula (1) and 0 to 60% by weight of water are included. In this way, the stripping performance of the resist stripper can be exhibited well.
[0024] たとえば、式（1)で表される化合物として、 N, N_ジメチル体を使用する場合、水 添加量は、約 5〜80重量％とするとよぐ好ましくは、約 20〜60重量％とするとよい。 すなわち、式（1)で表される化合物が、約 40重量％未満であったり、あるいは、約 80 重量％を超えると、式（1)で表される化合物によっては、レジストに対する剥離性能が 低下する心配があるからである。また、式（1)で表される化合物として、 N， N—ジェ チル体を使用する場合、水添加量は、約 0〜80重量％とするとよぐ好ましくは、約 0 〜40重量％とするとよい。このようにすると、レジストに対する剥離性能が低下すると レ、つた不具合を防止することができる。 [0024] For example, when an N, N_dimethyl form is used as the compound represented by the formula (1), The addition amount is about 5 to 80% by weight, preferably about 20 to 60% by weight. That is, when the compound represented by the formula (1) is less than about 40% by weight or exceeds about 80% by weight, depending on the compound represented by the formula (1), the peeling performance with respect to the resist is lowered. Because there is a worry to do. In addition, when an N, N-ethyl derivative is used as the compound represented by the formula (1), the amount of water added is preferably about 0 to 80% by weight, more preferably about 0 to 40% by weight. Good. In this way, if the peeling performance with respect to the resist deteriorates, it is possible to prevent problems.
[0025] また、本実施形態のレジスト剥離剤は、好ましくは、防食剤、キレート剤、剥離促進 剤、還元剤、酸化剤、界面活性剤、緩衝剤及び Z又は酸化防止剤などが添加される とよレ、。このように、たとえば、界面活性剤を添加すると、微細隙間への浸透性が向上 し、レジストの剥離性を向上させることができる。また、必要に応じて、酸化防止剤を 添加することにより、酸化による性能劣化を抑制することができる。上記防食剤、キレ ート剤、剥離促進剤、還元剤、酸化剤、界面活性剤、酸化防止剤は、単独でも使用 でき、また、 2種以上を組み合わせても使用できる。  [0025] Further, the resist stripper of this embodiment is preferably added with an anticorrosive, a chelating agent, a stripping accelerator, a reducing agent, an oxidizing agent, a surfactant, a buffering agent, Z or an antioxidant, and the like. Toyole. Thus, for example, when a surfactant is added, the permeability to fine gaps is improved, and the peelability of the resist can be improved. Moreover, the performance deterioration by oxidation can be suppressed by adding antioxidant as needed. The above anticorrosives, chelating agents, peeling accelerators, reducing agents, oxidizing agents, surfactants and antioxidants can be used alone or in combination of two or more.
[0026] 防食剤、あるいは、キレート剤として、芳香族ヒドロキシ化合物、アセチレンアルコー ノレ、カルボキシル基含有有機化合物及びその無水物、トリァゾール化合物、糖類及 びォキシム系化合物などが挙げられる。上記各防食剤、あるいは、キレート剤は、単 独でも使用でき、また、 2種以上を組み合わせても使用できる。  [0026] Examples of the anticorrosive or chelating agent include aromatic hydroxy compounds, acetylene alcohols, carboxyl group-containing organic compounds and anhydrides, triazole compounds, saccharides, and oxime compounds. Each of the above anticorrosives or chelating agents can be used alone or in combination of two or more.
[0027] 芳香族ヒドロキシ化合物として、フエノール、クレゾール、キシレノール、ピロ力テコー ノレ、レゾルシノール、ヒドロキノン、ピロガロール、 1 , 2, 4—ベンゼントリオール、サリ チルアルコール、 p—ヒドロキシベンジルアルコール、 o—ヒドロキシベンジルアルコー ノレ、 p—ヒドロキシフエネチルアルコール、 p—アミノフエノール、 m—ァミノフエノール、 ジァミノフエノール、アミノレゾルシノール、 ρ—ヒドロキシ安息香酸、 o—ヒドロキシ安息 香酸、 2, 4—ジヒドロキシ安息香酸、 2， 5—ジヒドロキシ安息香酸、 3, 4—ジヒドロキ シ安息香酸、 3, 5 _ジヒドロキシ安息香酸、没食子酸等を挙げることができる。  [0027] As an aromatic hydroxy compound, phenol, cresol, xylenol, pyro-power teconole, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol Nore, p-hydroxyphenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, ρ-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, Examples include 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, and the like.
[0028] アセチレンアルコールとして、 2—ブチン一1 , 4—ジオール、 3， 5—ジメチル一 1 _ へキシン _ 3 _オール、 2 _メチル _ 3—ブチン _ 2 _オール、 3 _メチル_ 1 _ぺン チン _ 3 _オール、 3， 6—ジメチル一 4—ォクチン一 3， 6—ジオール、 2, 4， 7, 9 _ テトラメチルー 5—デシン一4, 7—オール、 2, 5—ジメチルー 3—へキシン一2, 5— ジオール等を挙げることができる。 [0028] As acetylene alcohol, 2-butyne mono-1,4-diol, 3,5-dimethyl mono 1_hexyne_3_ol, 2_methyl_3-butyne_2_ol, 3_methyl_1_ Pentin _ 3 _ol, 3, 6-dimethyl 1-octyne 3,6-diol, 2, 4, 7, 9 _ And tetramethyl-5-decyne-1,4,7-ol, 2,5-dimethyl-3-hexyne-1,2,5-diol, and the like.
[0029] カルボキシル基含有有機化合物及びその無水物として、蟻酸、酢酸、プロピオン酸 、酪酸、イソ酪酸、シユウ酸、マロン酸、コハク酸、グノレタル酸、マレイン酸、フマル酸、 安息香酸、フタル酸、 1， 2, 3 _ベンゼントリカルボン酸、グリコール酸、乳酸、リンゴ 酸、クェン酸、無水酢酸、無水フタル酸、無水マレイン酸、無水コハク酸、サリチル酸 、酒石酸、アクリル酸、 γ—リノレン酸等を挙げることができる。 [0029] As the carboxyl group-containing organic compound and its anhydride, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, gnoretalic acid, maleic acid, fumaric acid, benzoic acid, phthalic acid, 1,2,3_Benzenetricarboxylic acid, glycolic acid, lactic acid, malic acid, succinic acid, acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, salicylic acid, tartaric acid, acrylic acid, γ-linolenic acid, etc. be able to.
[0030] トリァゾール化合物としては、ベンゾトリァゾール、 ο _トリルトリァゾール、 m—トリルト リアゾール、 p _トリノレトリァゾーノレ、カルボキシベンゾトリアゾール、 1—ヒドロキシベン ゾトリァゾール、ニトロべンゾトリァゾール、ジヒドロキシプロピルべンゾトリァゾール、ァ ミノトリァゾール等を挙げることができる。 [0030] Examples of the triazole compound include benzotriazole, ο_tolyltriazole, m-tolyltriazole, p_trinortriazolole, carboxybenzotriazole, 1-hydroxybenzazotriazole, nitrobenzotriazole, dihydroxypropylbenzotriazole, And aminotriazole.
また、糖類として、ソルビトール、キシリトール、パラチニット、ァラビトール、マンニト ール、蔗糖、澱粉等を挙げることができる。  Examples of the saccharide include sorbitol, xylitol, palatinit, arabitol, mannitol, sucrose, starch and the like.
また、ォキシム系化合物としては、ジメチルダリオキシム、ジフエニルダリオキシム等 を挙げることができる。  Examples of oxime compounds include dimethyl darilioxime and diphenyl daroxime.
上記防食剤、あるいは、キレート剤は、単独またはそれらの混合物のいずれで用い てもよい。  The above anticorrosive or chelating agent may be used either alone or as a mixture thereof.
[0031] 剥離促進剤として、ベンゼンスルホン酸、トルエンスルホン酸、キシレンスルホン酸、 フエノールスルホン酸、あるいはメチル、プロピル、ヘプチル、ォクチル、デシル、ドデ シル等のアルキルベンゼンスルホン酸などが挙げられる。  [0031] Examples of the release accelerator include benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, or alkylbenzenesulfonic acid such as methyl, propyl, heptyl, octyl, decyl, dodecyl, and the like.
上記剥離促進剤は、単独またはそれらの混合物のいずれで用いてもよい。  The above peeling accelerator may be used either alone or as a mixture thereof.
[0032] 還元剤としては、次亜硫酸、硫酸塩系還元剤、アミン系還元剤、あるいは、その他 の還元剤が挙げられる。 [0032] Examples of the reducing agent include hyposulfite, sulfate-based reducing agents, amine-based reducing agents, and other reducing agents.
上記次亜硫酸、硫酸塩系還元剤として、チォ硫酸ナトリウム、亜ニチオン酸ナトリウ ム、ピロ亜硫酸ナトリウム、メタ重亜硫酸ナトリウムなどが挙げられる。  Examples of the hyposulfite and sulfate-based reducing agent include sodium thiosulfate, sodium dithionite, sodium pyrosulfite, and sodium metabisulfite.
アミン系還元剤として、ヒドロキシノレアミン、モノエタノールァミン、トリプトファン、ヒシ チジン、メチォニン、フエ二ルァラニンなどが挙げられる。  Examples of the amine reducing agent include hydroxyreamine, monoethanolamine, tryptophan, histidine, methionine, and phenylalanine.
その他の還元剤として、ァスコルビン酸、ブチンジオール類、不飽和ケトン類、尿酸 、テトラアミソール、ヒドラジン類、及びその誘導体類であって、力ルバゼート類、ォキ シム類、ヒドロキノン、ピロガロール、没食子酸、 2, 4,5-トリヒドロキシブチロフエノン、ト コフェローノレ、 6-ヒドロキシ -2,5, 7, 8-テトラメチルクロマン- 2-カルボン酸、ブチル化ヒ ドロキシトルエン (BHT)、ブチル化ヒドロキシァ二ソ―ル (BHA)、 2,6-ジ-第三ブチル -4Other reducing agents include ascorbic acid, butynediols, unsaturated ketones, uric acid , Tetraamisole, hydrazines, and derivatives thereof, including strong rubazates, oximes, hydroquinone, pyrogallol, gallic acid, 2,4,5-trihydroxybutyrophenone, tocopheronole, 6-hydroxy -2,5,7,8-tetramethylchroman-2-carboxylic acid, butylated hydroxytoluene (BHT), butylated hydroxybenzene (BHA), 2,6-di-tert-butyl- Four
-ヒドロキシメチルフエノール、チオール類、サリチノレアノレデヒド、 4 -ヒドロキシベンズァ ルデヒド及びグリコールアルデヒドジアルキルァセタール類及びそれらの混合物など が挙げられる。 上記還元剤は、単独またはそれらの混合物のいずれで用いてもよい。 -Hydroxymethylphenol, thiols, salicinoleanolide, 4-hydroxybenzaldehyde and glycolaldehyde dialkylacetals and mixtures thereof. The reducing agent may be used either alone or as a mixture thereof.
[0033] 酸化剤として、オゾン、過酸化水素、次亜塩素酸または次亜塩素酸塩、亜塩素酸ま たは亜塩素酸塩、過塩素酸または過塩素酸塩、次亜臭素酸または次亜臭素酸塩、 亜臭素酸または亜臭素酸塩、過臭素酸または過臭素酸塩、次亜ヨウ素酸または次亜 ヨウ素酸塩、亜ヨウ素酸または亜ヨウ素酸塩、過ヨウ素酸または過ヨウ素酸塩、過硫酸 または過硫酸塩、過酢酸または過酢酸塩、過プロピオン酸または過プロピオン酸塩、 過安息香酸または過安息香酸塩、 tert—プチルノヽイド口パーォキシド、ェチルベン ゼンノヽイド口パーォキシド、キュメンハイド口パーォキシドなどが挙げられる。 [0033] As an oxidizing agent, ozone, hydrogen peroxide, hypochlorous acid or hypochlorite, chlorous acid or chlorite, perchloric acid or perchlorate, hypobromous acid or the following Bromate, bromate or bromate, perbromate or perbromate, hypoiodic acid or hypoiodite, iodic acid or iodate, periodic acid or periodic acid Salt, persulfate or persulfate, peracetic acid or peracetate, perpropionic acid or perpropionate, perbenzoic acid or perbenzoate, tert-ptylnoide oral peroxide, ethylbenzennoide oral peroxide, cumene Examples include Hyde mouth peroxide.
上記酸化剤は、単独またはそれらの混合物のいずれで用いてもよい。  The oxidizing agent may be used either alone or as a mixture thereof.
[0034] 界面活性剤として、カチオン系、ァニオン系、非イオン系、あるいは、フッ素系など の界面活性剤が挙げられる。 [0034] Examples of the surfactant include cationic, anionic, nonionic, and fluorine surfactants.
カチオン系界面活性剤として、アルキルトリメチルアンモニゥム塩系、アルキルアミド アミン系、アルキルジメチルベンジルアンモニゥム塩系、ポリエチレンポリアミン系カチ オン樹脂、セチルトリメチルアンモニゥムクロライド、第 4級アンモニゥム塩などの界面 活性剤が挙げられる。  Cationic surfactants such as alkyltrimethylammonium salt, alkylamidoamine, alkyldimethylbenzylammonium salt, polyethylenepolyamine cation resin, cetyltrimethylammonium chloride, quaternary ammonium salt, etc. A surfactant may be mentioned.
ノニオン系界面活性剤として、ポリオキシアルキレンアルキルエーテル系、ポリオキ シアルキレンアルキルフエニルエーテル系、ポリオキシアルキレングリコール脂肪酸 エステル系、ポリオキシアルキレンソルビット脂肪酸エステル系、ソルビタン脂肪酸ェ ステル系、ポリオキシアルキレンソルビタン脂肪酸エステル系などの界面活性剤が挙 げられる。  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene glycol fatty acid ester, polyoxyalkylene sorbite fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid. Listed are ester-based surfactants.
ァニオン系界面活性剤として、水中でァニオン性を示す基であって、スルホン酸を 形成する基（以下、スルホン酸基と記す。）、硫酸エステルを形成する基（以下、硫酸 エステル基と記す。）、リン酸エステルを形成する基（以下、リン酸エステル基と記す。 )、カルボン酸を形成する基（以下、カルボン酸基と記す。）などが挙げられる。 As an anionic surfactant, a group that exhibits anionic properties in water, A group to be formed (hereinafter referred to as a sulfonic acid group), a group to form a sulfate ester (hereinafter referred to as a sulfate ester group), a group to form a phosphate ester (hereinafter referred to as a phosphate ester group), Examples include groups that form carboxylic acids (hereinafter referred to as carboxylic acid groups).
[0035] 上記スルホン酸基を有する化合物として、アルキルジフヱニルエーテルジスルホン 酸、アルキレンジスルホン酸、ナフタレンスルホン酸ホルマリン縮合物、フヱノールス ルホン酸ホルマリン縮合物、フヱユルフェノールスルホン酸ホルマリン縮合物等の分 子構造中にァニオン系官能基を 2つ以上有する化合物、アルキルベンゼンスルホン 酸、ジアルキルサクシネートスルホン酸、モノアルキルサクシネートスルホン酸、アル キルフエノキシェトキシェチルスルホン酸等の化合物又はその塩などが挙げられる。 硫酸エステル基を有する化合物として、アルキルメチルタウリン、ァシルメチルタウリ ン、脂肪酸メチルタウリンなどのメチルタウリン類、ポリオキシアルキレンアルキルフエ ニノレエーテノレ硫酸エステノレ、ポリオキシァノレキレンァノレキノレエーテノレ硫酸エステノレ、 ポリオキシアルキレン多環フエニルエーテル硫酸エステル、ポリオキシアルキレンァリ ールエーテル硫酸エステル等の化合物又はその塩などが挙げられる。  [0035] Examples of the compound having a sulfonic acid group include alkyl diphenyl ether disulfonic acid, alkylene disulfonic acid, naphthalene sulfonic acid formalin condensate, phenol sulfonic acid formalin condensate, and phenol phenol sulfonic acid formalin condensate. A compound having two or more anionic functional groups in the child structure, a compound such as an alkylbenzene sulfonic acid, a dialkyl succinate sulfonic acid, a monoalkyl succinate sulfonic acid, an alkyl phenoxy succinate sulfonic acid, or a salt thereof. Can be mentioned. Examples of the compound having a sulfate ester group include methyl taurines such as alkyl methyl taurine, acyl methyl taurine, fatty acid methyl taurine, polyoxyalkylene alkyl phenolate ester sulfate sulfate, polyoxyalkylene vinyleno quinoleate ester sulfate ester, Examples thereof include compounds such as polyoxyalkylene polycyclic phenyl ether sulfate, polyoxyalkylene aryl ether sulfate, and salts thereof.
リン酸エステル基を有する化合物として、ポリオキシアルキレンアルキルエーテルリ ン酸、ポリオキシアルキレンアルキルフエニルエーテルリン酸などの化合物またはそ の塩などが挙げられる。  Examples of the compound having a phosphoric ester group include compounds such as polyoxyalkylene alkyl ether phosphoric acid and polyoxyalkylene alkyl phenyl ether phosphoric acid, and salts thereof.
カルボン酸基を有する化合物として、ァシルサルコシン、脂肪酸サルコシンなどの サルコシン類化合物、やし油、ォレイン酸、アクリル酸、 γ—リノレン酸などの脂肪酸 類化合物またはその塩などが挙げられる。  Examples of the compound having a carboxylic acid group include sarcosine compounds such as isyl sarcosine and fatty acid sarcosine, fatty acid compounds such as coconut oil, oleic acid, acrylic acid and γ-linolenic acid, and salts thereof.
さらに、分子構造中に異なった 2つのァニオン系官能基を有する化合物として、ス ルホン酸基及びカルボン酸基を有する化合物であるアルキルスルホコハク酸、ポリオ キシアルキレンアルキルスルホコハク酸などの化合物またはその塩などが挙げられる  Furthermore, compounds having two different anionic functional groups in the molecular structure include compounds such as alkylsulfosuccinic acid and polyoxyalkylenealkylsulfosuccinic acid, which are compounds having a sulfonic acid group and a carboxylic acid group, or salts thereof. Be mentioned
[0036] フッ素系界面活性剤として、パーフルォロアルキルエチレンォキシド付加物、パー フルォロアルキルりん酸エステル、パーフルォロアルキルフエニルグリシンなどが挙げ られる。 [0036] Examples of the fluorosurfactant include a perfluoroalkylethylene oxide adduct, a perfluoroalkyl phosphate ester, and a perfluoroalkylphenylglycine.
上記界面活性剤は、単独またはそれらの混合物のいずれで用いてもよい。 [0037] 緩衝剤としては、無機酸塩系や有機酸塩系などが挙げられる。 The above surfactants may be used either alone or as a mixture thereof. [0037] Examples of the buffer include inorganic acid salts and organic acid salts.
例えば、緩衝系で有用な有機酸として、限定しないが、ギ酸、トリフルォロ酢酸、プ ロピオン酸、酪酸、吉草酸、ヘプタン酸、乳酸、シユウ酸、リンゴ酸、マロン酸、コハク 酸、フマル酸、アジピン酸、安息香酸、フタル酸およびクェン酸などが挙げられる。 また、本発明の緩衝系において有用な共役塩基として、有機酸の塩、アンモニア、 テトラメチルアンモニゥム水酸化物、テトラアルキルアンモニゥム水酸化物、 2 _ (メチ ルァミノ）エタノール、モノイソプロパノールァミン、ジグリコールァミン、 N， N—ジメチ ノレ一 2 _ (2—アミノエトキシ）エタノール、 1 _ (2—アミノエチル）ピぺリジン、 1 _ (2 _ ヒドロキシェチル）ピぺラジン、 1 _ (2—アミノエチル）ピぺラジン、 1 _ (3—ァミノプロ ピル）一イミダゾール、 1 , 8—ジァザビシクロ [5. 4. 0]— 7—ゥンデセン、 N. N. N， —トリメチルアミノエタノールアミン、ペンタメチルジェチレントリアミン、ェチルモルホリ ン、ヒドロキシモルホリン、ァミノプロピロンモルホリン、トリエタノールァミンおよびメチ ルジェタノールァミンなどが挙げられる。また、有用な共役塩基は、上記例示に限定 されない。  For example, organic acids useful in buffer systems include, but are not limited to, formic acid, trifluoroacetic acid, propionic acid, butyric acid, valeric acid, heptanoic acid, lactic acid, oxalic acid, malic acid, malonic acid, succinic acid, fumaric acid, adipine Examples include acids, benzoic acid, phthalic acid and citrate. Conjugate bases useful in the buffer system of the present invention include organic acid salts, ammonia, tetramethylammonium hydroxide, tetraalkylammonium hydroxide, 2_ (methylamino) ethanol, monoisopropanol. Min, diglycolamine, N, N-dimethylol 2_ (2-aminoethoxy) ethanol, 1_ (2-aminoethyl) piperidine, 1_ (2_hydroxyethyl) piperazine, 1 _ (2-aminoethyl) piperazine, 1 _ (3-aminopropyl) monoimidazole, 1,8-diazabicyclo [5. 4. 0] —7-undecene, NN N, —trimethylaminoethanolamine, pentamethyl Jetylenetriamine, ethylmorpholine, hydroxymorpholine, aminominopyrone morpholine, triethanolamine, methyljetanolamine, etc. It is below. In addition, useful conjugate bases are not limited to the above examples.
[0038] また、カルボン酸塩、硫酸塩、スルホン酸塩、ホスホン酸塩、硝酸塩、塩酸塩および 硼酸塩からなる群より選ばれる 1種以上の塩であることが望ましい。具体的には、酢 酸アンモニゥム、クェン酸アンモニゥム、シユウ酸アンモニゥム、スルホコハク酸アンモ 二ゥム、硫酸アンモニゥム、メタンスルホン酸アンモニゥム、ホスホン酸アンモニゥム、 硝酸アンモニゥム、塩化アンモニゥム、四硼酸アンモニゥム、アクリル酸アンモニゥム などが挙げられる。陽イオンに注目するとアンモニゥム塩以外にもァミン塩でも第四級 アンモニゥム塩でもよい。  [0038] Further, it is desirable that the salt is at least one selected from the group consisting of carboxylate, sulfate, sulfonate, phosphonate, nitrate, hydrochloride and borate. Specifically, ammonium acetate, ammonium citrate, ammonium oxalate, ammonium sulfosuccinate, ammonium sulfate, ammonium methanesulfonate, ammonium phosphonate, ammonium nitrate, ammonium chloride, ammonium tetraborate, ammonium acrylic acid, etc. Is mentioned. Paying attention to cations, in addition to ammonium salt, amin salt or quaternary ammonium salt may be used.
ァミンとしては、ヒドロキシルァミンゃジェチルヒドロキシルァミンなどのヒドロキシルァ ミン類、ェチルァミン、プロパンジァミン、ジブチルァミン、トリメチルァミンなどのァノレ キノレアミン類、モノエタノールァミン、メチルエタノールァミン、メチルジェタノールアミ ン、トリエタノールァミン、モノイソプロパノールァミン、ジグリコールァミン、 N, N—ジメ チル一 2 _ (2—アミノエトキシ）エタノールなどのアルカノールァミン類、ァニリン、ベ ンジルァミンなどの芳香族ァミン類、ェチルモルホリン、ヒドロキシモルホリン、アミノプ 口ピロンモルホリンなどのモルフオリン類、 1 _ (2—アミノエチル）ピぺリジン、 1 _ (2 _ ヒドロキシェチル）ピぺラジン、 1一（2 アミノエチル）ピぺラジン、 1 （3 ァミノプロ ヒ。ノレ）一イミタ、、ノーノレ、 1 , 8—ジァザビ'シクロ [5. 4. 0] undec- 7 - ene, N. N. N' -トリメチルアミノエタノールアミン、ペンタメチルジェチレントリァミンなどが挙げられ る。また、上記アミンは、塩基性を示すものであればよぐ特に限定されるものではな レ、。 Examples of such amines include hydroxylamines such as hydroxylamine, jetylhydroxylamine, anolamines such as ethylamine, propanediamine, dibutylamine, and trimethylamine, monoethanolamine, methylethanolamine, and methyljetanolamine. , Alkanolamines such as triethanolamine, monoisopropanolamine, diglycolamine, N, N-dimethyl-1-2- (2-aminoethoxy) ethanol, aromatic amines such as aniline and benzylamine, Morpholines such as ethylmorpholine, hydroxymorpholine, aminopropylone morpholine, 1 _ (2-aminoethyl) piperidine, 1 _ (2 _ Hydroxyethyl) piperazine, 1- (2 aminoethyl) piperazine, 1 (3-aminoprohi. Nore) mono-imita, Norole, 1,8-diazabi'cyclo [5.4.0] undec-7 -ene, NN N '-trimethylaminoethanolamine, pentamethyljetylenetriamine and the like. The amine is not particularly limited as long as it exhibits basicity.
第四級アンモニゥム塩を形成する第四級アンモニゥムイオンとして、テトラメチルァ ンモニゥムイオン、テトラエチルアンモニゥムイオン、トリェチルメチルアンモニゥムィ オン、ラウリルトリメチルアンモニゥムイオン、ベンジルトリメチルアンモニゥムイオンな どが挙げられる。  Examples of quaternary ammonium ions that form quaternary ammonium salts include tetramethyl ammonium ion, tetraethyl ammonium ion, triethyl methyl ammonium ion, lauryl trimethyl ammonium ion, and benzyl trimethyl ammonium ion.
上記緩衝剤は、単独またはそれらの混合物のいずれで用いてもよい。  The above buffering agents may be used either alone or as a mixture thereof.
上記酸化防止剤として、 2, 6—ジ tert ブチル _4_メチルフエノール、 2， 5 _ ジ一 tert—ブチルヒドロキノン、 2， 6 _ジ一 tert—ブチル一ひ一ジメチルァミノ一 p _ タレゾール等のモノフエノール系化合物を挙げることができる。また、 4, 4 '—ビス（2， 6—ジ tert ブチルフエノール）、 4, 4'ーメチレン ビス（2,6 ジ tert ブチノレ フエノール）、 2, 2 ' メチレン一ビス（4—メチル 6— tert ブチルフエノール）、 4, 4，ーメチレン ビス（ 2， 6 ジー tert ブチルフエノール）、 4 , 4 'ーブチリデンービス (3—メチルー 6— tert ブチルフエノール）等のビスフエノール化合物を挙げること ができる。また、 4, 4 'ーチォビス（3—メチルー 6—tert ブチルフエノール）、 2, 2 ' ーチォビス（6— tert ブチルー o クレゾ一ル）、 2, 2，ーチォビス（4ーメチルー 6— tert ブチルフエノール）等のチォビスフエノール系化合物を挙げることができる。ま た、テトラキス [メチレン一 3— (3, 5—ジ一 tert ブチル 4—ヒドロキシフエニル）プ 口ピオネート]メタン、トリス（2—メチル _4—ヒドロキシ一 5 _tert_ブチル一フエノー ノレ）ブタン等のトリスフヱノール系化合物を挙げることができる。また、トリフエ二ルフォ スフアイト、トリスノユルフェ二ルフォスファイト、トリス（モノ及びジ一ノユルフェニル）ホ スフアイト等のホスファイト系酸化防止剤を挙げることができる。また、ジラウリルジプロ ピオネート、ジステアリルチオジプロピオネート等の硫黄系酸化防止剤を挙げることが できる。  Monophenols such as 2,6-di-tert-butyl_4_methylphenol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-diethyl dimethylamino-p_taresol Examples of such compounds are listed. In addition, 4, 4'-bis (2, 6-di tert butyl phenol), 4, 4'-methylene bis (2,6 di tert butynole phenol), 2, 2 'methylene bis (4-methyl 6- tert butyl) Examples thereof include bisphenol compounds such as phenol), 4,4, -methylenebis (2,6 di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tertbutylphenol), and the like. Also, 4, 4'-thiobis (3-methyl-6-tertbutylphenol), 2,2'-thiobis (6-tertbutyl-o-cresol), 2,2, -thiobis (4-methyl-6-tertbutylphenol), etc. Mention may be made of thiobisphenol compounds. In addition, tetrakis [methylene-3- (3,5-di-tert-butyl 4-hydroxyphenyl) propionate] methane, tris (2-methyl-4-hydroxy-5-tert_butyl-phenol) butane, etc. Mention may be made of trisphenol compounds. Further, phosphite antioxidants such as triphenyl phosphate, trisnoylphenyl phosphite and tris (mono and di-noylphenyl) phosphate can be mentioned. In addition, sulfur-based antioxidants such as dilauryl dipropionate and distearyl thiodipropionate can be mentioned.
上記酸化防止剤は単独またはそれらの混合物のいずれで用いてもよい。また、酸 化防止剤の使用量は、レジスト剥離剤に対して約 0. 01〜： 1. 0重量％の添加が好ま しい。 The above antioxidants may be used either alone or as a mixture thereof. Also acid The amount of antioxidation agent used is preferably about 0.01 to 1.0% by weight based on the resist stripper.
[0040] このように本実施形態に力かるレジスト剥離剤は、式（1)で表されるアルコキシアミド 系の化合物を用いることにより、高い剥離性能を有するとともに、銅やアルミなどに対 する防食性に非常に優れている。また、水系剥離剤とすることにより、引火性がなく安 全であり、さらに、水溶性を有しているので、水リンスが可能であり、かつ、 IPAリンス が不要なので、生産性を向上させることができる。  [0040] As described above, the resist remover that is effective in the present embodiment uses the alkoxyamide-based compound represented by the formula (1), so that it has high peeling performance and is anticorrosive against copper, aluminum, and the like. It is very excellent in sex. In addition, by using a water-based release agent, it is flammable and safe, and since it has water solubility, it can be rinsed with water and does not require an IPA rinse, thus improving productivity. be able to.
次に、上記レジスト剥離剤の実施例及び比較例について、図 1の表一 1及び図 2の 表一 2を参照して説明する。  Next, Examples and Comparative Examples of the resist stripping agent will be described with reference to Table 1 in FIG. 1 and Table 1 in FIG.
実施例 1  Example 1
[0041] 図 1は、実施例 1〜： 15に対する、剥離剤種 (剥離液の組成）、剥離性能及び防食性 能を表した表 1を示してレ、る。  [0041] FIG. 1 shows Table 1 showing the release agent type (composition of the release solution), release performance, and anticorrosion performance for Examples 1 to 15.
また、図 2は、比較例：!〜 6に対する、剥離剤種 (剥離液の組成）、剥離性能及び防 食性能を表した表 2を示してレ、る。  FIG. 2 shows Table 2 showing the release agent type (the composition of the release solution), the release performance and the anticorrosion performance for Comparative Examples:!
まず、実施例：!〜 15と比較例:!〜 6に対する、共通のレジスト剥離性能評価法（レジ スト基板、剥離試験及び腐蝕試験)などについて説明する。  First, a common resist stripping performance evaluation method (resist substrate, stripping test and corrosion test) for Examples:! To 15 and Comparative Examples:! To 6 will be described.
[0042] <レジスト基板 > [0042] <Resist substrate>
基板：日立金属株式会社製の成膜ガラス（サイズ約 100mm X 100mm)を使用し た。  Substrate: A film-forming glass (size: about 100 mm X 100 mm) manufactured by Hitachi Metals, Ltd. was used.
レジスト：富士フィルムエレクトロニクスマテリアルズ (株)の HPR204 (ナフトキノンジ アジド/ノボルトラック樹脂）を塗布し、所定の温度にて約 15分間オーブン中でベー キングしたものを使用した。すなわち、実施例 1、 2、 3、 5〜8、 10〜： 15、及び、比較 例 1、 3〜6は、約 130°Cにて約 15分間オーブン中でベーキングしたものを使用した 。また、実施例 4、 9、及び、比較例 2は、約 150°Cにて約 15分間オーブン中でベー キングしたものを使用した。  Resist: An HPR204 (naphthoquinone diazide / Novolac resin) manufactured by Fuji Film Electronics Materials Co., Ltd. was applied and baked in an oven at a predetermined temperature for about 15 minutes. That is, Examples 1, 2, 3, 5-8, 10-: 15 and Comparative Examples 1, 3-6 were baked in an oven at about 130 ° C. for about 15 minutes. In Examples 4 and 9, and Comparative Example 2, those baked in an oven at about 150 ° C. for about 15 minutes were used.
なお、剥離性を評価する場合は、上記レジスト基板を約 10mm X 5mmに切断した 試験片を用いた。  When evaluating peelability, a test piece obtained by cutting the resist substrate into about 10 mm × 5 mm was used.
[0043] <剥離試験 > 剥離性能は下記の 2つの評価法で評価した。 [0043] <Peel test> The peeling performance was evaluated by the following two evaluation methods.
レジスト剥離性— 1：約 30mlのサンプノレ瓶に、剥離剤約 5mlと上記作製したレジスト 基板の試験片を 1枚入れ、所定の温度で攪拌しながら液中のガラス基板が無色透明 になるまでの時間を測定し、下記のように判断した。  Resist stripping—1: Put about 5 ml of stripping agent and one test piece of the above-prepared resist substrate into a 30 ml Sampnole bottle and stir at the specified temperature until the glass substrate in the solution becomes colorless and transparent. Time was measured and judged as follows.
〇 ：透明になるまでの時間が 40sec未満。  ○: It takes less than 40 seconds to become transparent.
X ：透明になるまでの時間が 40sec以上。  X: It takes 40 seconds or more to become transparent.
なお、実施例 1、 2、 3、 5〜8、 10〜15、及び、比較例 1、 3〜6は、撹拌する際の上 記所定の温度を室温（たとえば、 0〜30°Cであり、通常、 20〜25°C)とした。また、実 施例 4、 9、及び、比較例 2は、撹拌する際の上記所定の温度を約 40°Cとした。  In Examples 1, 2, 3, 5-8, 10-15, and Comparative Examples 1, 3-6, the predetermined temperature when stirring is room temperature (for example, 0-30 ° C). , Usually 20-25 ° C). In Examples 4 and 9, and Comparative Example 2, the predetermined temperature during stirring was set to about 40 ° C.
[0044] レジスト剥離性— 2：約 30mlのサンプル瓶に、剥離剤約 5mlと上記作製したレジスト 基板の試験片を:!枚入れ、所定の温度で約 60seC間攪拌し、剥離させた後、レジスト 基板を取り出し即アセトンリンス後、約 50°C下にて約 30分乾燥後の表面を観察し、 下記のように判断した。 [0044] Resist stripping—2: About 5 ml of the stripping agent and the above-prepared resist substrate test piece are placed in a sample bottle of about 30 ml and stirred for about 60se C at a predetermined temperature. Then, the resist substrate was taken out and immediately rinsed with acetone, and then the surface after drying at about 50 ° C. for about 30 minutes was observed and judged as follows.
〇 ：ガラス基板表面に全く曇り部分がなくレジストが完全に洗浄剥離されている。 △ ：ガラス基板表面に僅かに曇り部分があり、ほぼレジストが洗浄剥離されてい る。  ◯: There is no cloudy portion on the glass substrate surface, and the resist is completely washed and peeled off. Δ: The glass substrate surface has a slightly cloudy portion, and the resist is almost removed by washing.
X ：ガラス基板表面の半分以上に曇りがあり、洗浄剥離が不十分で、かなりレジ ストが残存している。  X: More than half of the surface of the glass substrate is cloudy, cleaning and peeling are insufficient, and a considerable amount of resist remains.
なお、実施例 1、 2、 3、 5〜8、 10〜： 15、及び、比較例 1、 3〜6は、約 60sec間撹拌 する際の上記所定の温度を室温（たとえば、 0〜30°Cであり、通常、 20〜25°C)とし た。また、実施例 4、 9、及び、比較例 2は、約 60sec間撹拌する際の上記所定の温度 を約 40°Cとした。  In Examples 1, 2, 3, 5-8, 10-: 15, and Comparative Examples 1, 3-6, the predetermined temperature for stirring for about 60 seconds is the room temperature (for example, 0-30 °). C, usually 20-25 ° C). In Examples 4 and 9, and Comparative Example 2, the predetermined temperature when stirring for about 60 seconds was about 40 ° C.
[0045] <腐食試験 > [0045] <Corrosion test>
防食性能は下記の 2つの評価法で評価した。  The anticorrosion performance was evaluated by the following two evaluation methods.
防食性— 1 :約 30mlのサンプル瓶に、剥離剤を入れ、その中に直径約 0. 5mmの 銅線約 100mmを丸めて浸漬させ、 1週間後の着色度合いを観察し、下記のように判 断した。  Anticorrosion-1: Put a release agent in a sample bottle of about 30ml, immerse a copper wire of about 0.5mm in diameter about 100mm in diameter, and observe the degree of coloration after 1 week. It was judged.
〇 ：全く変色無し。 Δ ：僅かに淡青色に変色。 ○: No discoloration at all. Δ: Slightly discolored to light blue.
X ：明らかに青色に変色。  X: Clearly blue.
防食性— 2： Mo (モリブデン) /Al/Moの積層配線基板を作製し、この試験片 (約 10mm X 5mm)を約 30mlのサンプル瓶に入れ、剥離剤約 5mlを添加し、約 40°Cに て約 5分間浸漬させた。浸漬 '腐食操作後、下記の手順で観察し、下記のように判断 した。  Anti-corrosion—2: Make a Mo (molybdenum) / Al / Mo multilayer wiring board, put this test piece (about 10mm x 5mm) into a sample bottle of about 30ml, add about 5ml of release agent, and add about 40 ° Soaked in C for about 5 minutes. Immersion 'After the corrosion operation, observation was made according to the following procedure, and judgment was made as follows.
手順 1として、 IPAリンスを行レ、、手順 2として、アセトンリンスを行レ、、手順 3として、 約 50°Cにて約 30分乾燥し、 SEM (走查電子顕微鏡)で A1の腐食具合を観察した。  As step 1, perform IPA rinse, as step 2, perform acetone rinse, and as step 3, dry at approximately 50 ° C for approximately 30 minutes, and then use SEM (scanning electron microscope) to determine the degree of corrosion of A1. Was observed.
〇 ：全く変化なし。  ○: No change at all.
△ ：僅かに A1が溶出し、腐食が観察された。  Δ: A1 was slightly eluted and corrosion was observed.
X ：明らかに A1が溶出し、激しい腐食が観察された。  X: A1 was clearly eluted and severe corrosion was observed.
なお、実施例 1〜 15と比較例：!〜 10に対する結果を表一 1及び表一 2に示した。  The results for Examples 1 to 15 and Comparative Examples:! To 10 are shown in Tables 1 and 2.
[0046] 実施例 1にかかる剥離剤として、約 80重量％の 3—メトキシ— N, N ジメチルプロ ピオンアミド（適宜、 MDMPAと略称する。）と約 20重量％の水とからなるレジスト剥 離剤を用意した。続いて、上記剥離試験及び腐蝕試験を行った。 [0046] As the release agent according to Example 1, a resist release agent comprising about 80% by weight of 3-methoxy-N, N dimethylpropionamide (abbreviated as MDMPA as appropriate) and about 20% by weight of water. Prepared. Subsequently, the peeling test and the corrosion test were performed.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 38秒であった。 ) レジスト剥離性 2 :〇  Resist stripping property-1: 〇 (Time until the substrate became transparent was 38 seconds.) Resist stripping property 2::
防食性 1 :〇  Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、剥離性能及び防食性能に優れていた。 実施例 2  Met. This resist stripper was excellent in stripping performance and anticorrosion performance. Example 2
[0047] 実施例 2にかかる剥離剤として、約 60重量％の 3—メトキシ— N, N—ジメチルプロ ピオンアミドと約 40重量％の水とからなるレジスト剥離剤を用意した。続いて、上記剥 離試験及び腐蝕試験を行った。  [0047] As a release agent according to Example 2, a resist release agent comprising about 60% by weight of 3-methoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 39秒であった。 ) レジスト剥離性 2 :△ 防食性 1 :〇 Resist strippability-1: ○ (Time until substrate became transparent was 39 seconds.) Resist strippability 2:: Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、レジスト剥離性 2において、ガラス基板表面に 僅かに曇り部分があり、ほぼレジストが洗浄剥離されている（微量のレジスト残渣が認 められる）。また、このレジスト剥離剤は、他の試験においては、剥離性能及び防食性 肯 に優れていた。  Met. This resist stripper has a slightly cloudy portion on the glass substrate surface in resist stripping property 2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
実施例 3  Example 3
[0048] 実施例 3にかかる剥離剤として、約 100重量％の 3—メトキシ— N, N ジメチルプ ロピオンアミドからなるレジスト剥離剤を用意した。続いて、上記剥離試験及び腐蝕試 験を行った。  [0048] As a release agent according to Example 3, a resist release agent comprising about 100% by weight of 3-methoxy-N, N dimethylpropionamide was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 32秒であった。 ) レジスト剥離性 2 :〇  Resist stripping property-1: ○ (Time until the substrate became transparent was 32 seconds.) Resist stripping property 2::
防食性 1 :〇  Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、剥離性能及び防食性能に優れていた。 実施例 4  Met. This resist stripper was excellent in stripping performance and anticorrosion performance. Example 4
[0049] 実施例 4にかかる剥離剤として、約 100重量％の 3 メトキシ— N, N—ジメチルプ ロピオンアミドからなるレジスト剥離剤を用意した。続いて、上記剥離試験及び腐蝕試 験を行った。  [0049] As a release agent according to Example 4, a resist release agent composed of about 100% by weight of 3 methoxy-N, N-dimethylpropionamide was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 35秒であった。 ) レジスト剥離性 2 :〇  Resist stripping property-1: ○ (Time until the substrate becomes transparent was 35 seconds.) Resist stripping property 2: ○
防食性 1 :〇  Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、剥離性能及び防食性能に優れていた。 実施例 5  Met. This resist stripper was excellent in stripping performance and anticorrosion performance. Example 5
[0050] 実施例 5にかかる剥離剤として、約 100重量％の 3 _ブトキシ— N， N—ジメチルプ ロピオンアミド (適宜、 BDMPAと略称する。）からなるレジスト剥離剤を用意した。続 レ、て、上記剥離試験及び腐蝕試験を行った。 [0050] As a release agent according to Example 5, about 100% by weight of 3_butoxy-N, N-dimethylpropylene was used. A resist stripper made of lopionamide (abbreviated as BDMPA as appropriate) was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性 _ 1 :〇（基板が透明になるまでの時間は、 31秒であった。 ) レジスト剥離性— 2 :△  Resist releasability _ 1: ○ (Time until substrate became transparent was 31 seconds.) Resist releasability — 2: △
防食性— 1 :〇  Anticorrosion-1: 0
防食性— 2 :〇  Anticorrosion-2: ○
であった。このレジスト剥離剤は、レジスト剥離性— 2において、ガラス基板表面に 僅かに曇り部分があり、ほぼレジストが洗浄剥離されている（微量のレジスト残渣が認 められる）。また、このレジスト剥離剤は、他の試験においては、剥離性能及び防食性 肯 に優れていた。  Met. This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is recognized). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
実施例 6  Example 6
[0051] 実施例 6にかかる剥離剤として、約 80重量％の 3 ブトキシ— N, N ジメチルプロ ピオンアミドと約 20重量％の水とからなるレジスト剥離剤を用意した。続いて、上記剥 離試験及び腐蝕試験を行った。  [0051] As a release agent according to Example 6, a resist release agent comprising about 80 wt% of 3 butoxy-N, N dimethylpropionamide and about 20 wt% of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表一 1に示すように、  The test results are shown in Table 1-1.
レジスト剥離性 _ 1 :〇（基板が透明になるまでの時間は、 24秒であった。 ) レジスト剥離性— 2 :△  Resist releasability _ 1: ○ (The time until the substrate became transparent was 24 seconds.) Resist releasability — 2: △
防食性— 1 :〇  Anticorrosion-1: 0
防食性— 2 :〇  Anticorrosion-2: ○
であった。このレジスト剥離剤は、レジスト剥離性— 2において、ガラス基板表面に 僅かに曇り部分があり、ほぼレジストが洗浄剥離されている（微量のレジスト残渣が認 められる）。また、このレジスト剥離剤は、他の試験においては、剥離性能及び防食性 肯 に優れていた。  Met. This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is recognized). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
実施例 7  Example 7
[0052] 実施例 7にかかる剥離剤として、約 60重量％の 3 ブトキシ— N, N ジメチルプロ ピオンアミドと約 40重量％の水とからなるレジスト剥離剤を用意した。続いて、上記剥 離試験及び腐蝕試験を行った。 試験結果は、表 1に示すように、 [0052] As a release agent according to Example 7, a resist release agent comprising about 60% by weight of 3 butoxy-N, N dimethylpropionamide and about 40% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted. The test results are shown in Table 1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 29秒であった。 ) レジスト剥離性 2 :〇  Resist strippability-1: (Time until the substrate became transparent was 29 seconds.) Resist stripp 2:
防食性— 1 :〇  Anticorrosion-1: 0
防食性— 2 :〇  Anticorrosion-2: ○
であった。このレジスト剥離剤は、剥離性能及び防食性能に優れていた。 実施例 8  Met. This resist stripper was excellent in stripping performance and anticorrosion performance. Example 8
[0053] 実施例 8にかかる剥離剤として、約 40重量％の 3 ブトキシ— N, N ジメチルプロ ピオンアミドと約 60重量％の水とからなるレジスト剥離剤を用意した。続いて、上記剥 離試験及び腐蝕試験を行った。  [0053] As a release agent according to Example 8, a resist release agent comprising about 40% by weight of 3 butoxy-N, N dimethylpropionamide and about 60% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 24秒であった。 ) レジスト剥離性 2 :〇  Resist strippability-1: (Time until the substrate became transparent was 24 seconds.) Resist stripp 2:
防食性 1 :〇  Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、剥離性能及び防食性能に優れていた。 実施例 9  Met. This resist stripper was excellent in stripping performance and anticorrosion performance. Example 9
[0054] 実施例 9にかかる剥離剤として、約 60重量％の 3 _ブトキシ— N， N—ジメチルプロ ピオンアミドと約 40重量％の水とからなるレジスト剥離剤を用意した。続いて、上記剥 離試験及び腐蝕試験を行った。  [0054] As a release agent according to Example 9, a resist release agent comprising about 60% by weight of 3_butoxy-N, N-dimethylpropionamide and about 40% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 39秒であった。 ) レジスト剥離性 2 :△  Resist strippability-1: ○ (Time until substrate became transparent was 39 seconds.) Resist strippability 2::
防食性 1 :〇  Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、レジスト剥離性 2において、ガラス基板表面に 僅かに曇り部分があり、ほぼレジストが洗浄剥離されている（微量のレジスト残渣が認 められる）。また、このレジスト剥離剤は、他の試験においては、剥離性能及び防食性 肯 に優れていた。 Met. This resist stripper has a slightly cloudy portion on the glass substrate surface in resist stripping property 2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). In addition, this resist stripper is used in other tests for stripping performance and corrosion resistance. It was excellent.
実施例 10  Example 10
[0055] 実施例 10にかかる剥離剤として、約 100重量％の 3—メトキシ— N, N—ジェチノレ プロピオンアミド（適宜、 MDEPAと略称する。）からなるレジスト剥離剤を用意した。 続いて、上記剥離試験及び腐蝕試験を行った。  [0055] As a release agent according to Example 10, a resist release agent comprising about 100% by weight of 3-methoxy-N, N-jetinorepropionamide (abbreviated as MDEPA as appropriate) was prepared. Subsequently, the peeling test and the corrosion test were performed.
試験結果は、表一 1に示すように、  The test results are shown in Table 1-1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 30秒であった。 ) レジスト剥離性 2 :〇  Resist stripping property-1: ○ (Time until the substrate becomes transparent was 30 seconds.) Resist stripping property 2::
防食性 1 :〇  Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、剥離性能及び防食性能に優れていた。 実施例 11  Met. This resist stripper was excellent in stripping performance and anticorrosion performance. Example 11
[0056] 実施例 11に力かる剥離剤として、約 80重量％の 3—メトキシ一 N, N—ジェチルプ ロピオンアミドと約 20重量％の水とからなるレジスト剥離剤を用意した。続いて、上記 剥離試験及び腐蝕試験を行った。  [0056] A resist remover comprising about 80% by weight of 3-methoxy-1-N, N-jetylpropionamide and about 20% by weight of water was prepared as a remover useful for Example 11. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表一 1に示すように、  The test results are shown in Table 1-1.
レジスト剥離性 _ 1 :〇（基板が透明になるまでの時間は、 18秒であった。 ) レジスト剥離性— 2 :〇  Resist releasability _ 1: 0 (Time until the substrate became transparent was 18 seconds.) Resist releasability — 2: 0
防食性 1 :〇  Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、剥離性能及び防食性能に優れていた。 実施例 12  Met. This resist stripper was excellent in stripping performance and anticorrosion performance. Example 12
[0057] 実施例 12にかかる剥離剤として、約 60重量％の 3—メトキシ— N, N—ジェチルプ ロピオンアミドと約 40重量％の水とからなるレジスト剥離剤を用意した。続いて、上記 剥離試験及び腐蝕試験を行った。  [0057] As a stripping agent according to Example 12, a resist stripping agent comprising about 60% by weight of 3-methoxy-N, N-jetylpropionamide and about 40% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表一 1に示すように、  The test results are shown in Table 1-1.
レジスト剥離性 _ 1 :〇（基板が透明になるまでの時間は、 28秒であった。 ) レジスト剥離性— 2 :〇 防食性 1 :〇 Resist releasability _ 1: 0 (Time until the substrate became transparent was 28 seconds.) Resist releasability — 2: 0 Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、剥離性能及び防食性能に優れていた。 実施例 13  Met. This resist stripper was excellent in stripping performance and anticorrosion performance. Example 13
[0058] 実施例 13にかかる剥離剤として、約 100重量％の 3 エトキシ N， N ジェチル プロピオンアミド (適宜、 EDEPAと略称する。）からなるレジスト剥離剤を用意した。続 レ、て、上記剥離試験及び腐蝕試験を行った。  [0058] As a stripping agent according to Example 13, a resist stripping agent comprising about 100% by weight of 3 ethoxy N, N jetyl propionamide (abbreviated as EDEPA as appropriate) was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 19秒であった。 ) レジスト剥離性 2 :△  Resist stripping property-1: ○ (Time until the substrate became transparent was 19 seconds.) Resist stripping property 2::
防食性 1 :〇  Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、レジスト剥離性 2において、ガラス基板表面に 僅かに曇り部分があり、ほぼレジストが洗浄剥離されている（微量のレジスト残渣が認 められる）。また、このレジスト剥離剤は、他の試験においては、剥離性能及び防食性 肯 に優れていた。  Met. This resist stripper has a slightly cloudy portion on the glass substrate surface in resist stripping property 2, and the resist is almost cleaned and stripped (a small amount of resist residue is observed). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
実施例 14  Example 14
[0059] 実施例 14にかかる剥離剤として、約 80重量％の 3 _エトキシ _N, N—ジェチルプ ロピオンアミドと約 20重量％の水とからなるレジスト剥離剤を用意した。続いて、上記 剥離試験及び腐蝕試験を行った。  [0059] As a stripping agent according to Example 14, a resist stripping agent comprising about 80% by weight of 3_ethoxy_N, N-jetylpropionamide and about 20% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 19秒であった。 ) レジスト剥離性 2 :〇  Resist stripping property-1: ○ (Time until the substrate became transparent was 19 seconds.) Resist stripping property 2::
防食性 1 :〇  Anticorrosion 1: 0
防食性 2 :〇  Anticorrosion 2:
であった。このレジスト剥離剤は、剥離性能及び防食性能に優れていた。 実施例 15  Met. This resist stripper was excellent in stripping performance and anticorrosion performance. Example 15
[0060] 実施例 15にかかる剥離剤として、約 60重量％の 3 _エトキシ _N, N—ジェチルプ ロピオンアミドと約 40重量％の水とからなるレジスト剥離剤を用意した。続いて、上記 剥離試験及び腐蝕試験を行った。 [0060] As a release agent according to Example 15, about 60 wt% of 3_ethoxy_N, N-jetylp A resist stripper composed of lopionamide and about 40% by weight of water was prepared. Subsequently, the above peeling test and corrosion test were conducted.
試験結果は、表 1に示すように、  The test results are shown in Table 1.
レジスト剥離性 _ 1 :〇（基板が透明になるまでの時間は、 29秒であった。 ) レジスト剥離性— 2 :△  Resist releasability _ 1: ○ (The time until the substrate became transparent was 29 seconds.) Resist releasability — 2: △
防食性— 1 :〇  Anticorrosion-1: 0
防食性— 2 :〇  Anticorrosion-2: ○
であった。このレジスト剥離剤は、レジスト剥離性— 2において、ガラス基板表面に 僅かに曇り部分があり、ほぼレジストが洗浄剥離されている（微量のレジスト残渣が認 められる）。また、このレジスト剥離剤は、他の試験においては、剥離性能及び防食性 肯 に優れていた。  Met. This resist stripper has a slightly cloudy portion on the surface of the glass substrate in resist stripping property-2, and the resist is almost cleaned and stripped (a small amount of resist residue is recognized). In addition, this resist stripper was excellent in stripping performance and corrosion resistance in other tests.
比較例 1  Comparative Example 1
[0061] 比較例 1にかかる剥離剤として、約 30重量％のジメチルスルホキシド（適宜、 DMS Oと略称する。）と、約 70重量％のモノエタノールァミン (適宜、 MEAと略称する。）と 力 なるレジスト剥離剤を用意した。続いて、上記剥離試験及び腐蝕試験を行った。 試験結果は、表一 2に示すように、  [0061] As the release agent according to Comparative Example 1, about 30% by weight of dimethyl sulfoxide (appropriately abbreviated as DMS O) and about 70% by weight of monoethanolamine (appropriately abbreviated as MEA), respectively. A powerful resist stripper was prepared. Subsequently, the peeling test and the corrosion test were performed. The test results are shown in Table 1-2.
レジスト剥離性 _ 1 : X (基板が透明になるまでの時間は、 45秒であった。 ) レジスト剥離性— 2 :△  Resist releasability _ 1: X (Time until the substrate became transparent was 45 seconds.) Resist releasability — 2: △
防食性一：!：△  Anticorrosion I:!: △
防食性一 2 :△  Anticorrosion 1 2: △
であった。このレジスト剥離剤は、レジスト剥離性 _ 1において、剥離に長い時間を 必要とし、さらに、レジスト剥離性 _ 2において、微量のレジスト残渣が認められた。ま た、このレジスト剥離剤は、防食性 _ 1において、僅かに淡青色に変色し、さらに、防 食性 _ 2において、僅かに A1が溶出し、腐食が観察された。  Met. This resist stripper required a long time for stripping in the resist stripping_1, and a small amount of resist residue was observed in the resist stripping_2. In addition, this resist stripper turned slightly light blue in anticorrosion property_1, and further, A1 eluted slightly in anticorrosion property_2, and corrosion was observed.
比較例 2  Comparative Example 2
[0062] 比較例 2にかかる剥離剤として、約 30重量％のジメチルスルホキシド（適宜、 DMS Oと略称する。）と、約 70重量％のモノエタノールァミン (適宜、 MEAと略称する。）と 力 なるレジスト剥離剤を用意した。続いて、上記剥離試験及び腐蝕試験を行った。 試験結果は、表 2に示すように、 [0062] As the release agent according to Comparative Example 2, about 30% by weight of dimethyl sulfoxide (appropriately abbreviated as DMS O) and about 70% by weight of monoethanolamine (appropriately abbreviated as MEA), respectively. A powerful resist stripper was prepared. Subsequently, the peeling test and the corrosion test were performed. The test results are shown in Table 2.
レジスト剥離性ー1 : X (基板が透明になるまでの時間は、 50秒であった。 ) レジスト剥離性 2 :△  Resist stripping property-1: X (Time until the substrate became transparent was 50 seconds.) Resist stripping property 2::
防食性一：!：△  Anticorrosion I:!: △
防食性一 2 :△  Anticorrosion 1 2: △
であった。このレジスト剥離剤は、レジスト剥離性 _ 1において、剥離に長い時間を 必要とし、さらに、レジスト剥離性 _ 2において、微量のレジスト残渣が認められた。ま た、このレジスト剥離剤は、防食性 _ 1において、僅かに淡青色に変色し、さらに、防 食性 _ 2において、僅かに A1が溶出し、腐食が観察された。  Met. This resist stripper required a long time for stripping in the resist stripping_1, and a small amount of resist residue was observed in the resist stripping_2. In addition, this resist stripper turned slightly light blue in anticorrosion property_1, and further, A1 eluted slightly in anticorrosion property_2, and corrosion was observed.
比較例 3  Comparative Example 3
[0063] 比較例 3にかかる剥離剤として、約 34重量0 /0のジエチレングリコールモノブチルェ 一テルと、約 46重量％のモノエタノールァミンと、約 20重量％の水と力 なるレジスト 剥離剤を用意した。続いて、上記剥離試験及び腐蝕試験を行った。 [0063] As such a release agent in Comparative Example 3, and diethylene glycol monobutyl E one ether of about 34 weight 0/0, and monoethanolamine § Min about 46%, about 20% by weight of water and power becomes resist stripper Prepared. Subsequently, the peeling test and the corrosion test were performed.
試験結果は、表 2に示すように、  The test results are shown in Table 2.
レジスト剥離性ー1 : X (基板が透明になるまでの時間は、 56秒であった。 ) レジスト剥離性— 2 : X  Resist strippability-1: X (Time until the substrate became transparent was 56 seconds.) Resist strippability-2: X
防食性一：!：△  Anticorrosion I:!: △
防食性一 2 :△  Anticorrosion 1 2: △
であった。このレジスト剥離剤は、レジスト剥離性 _ 1において、剥離に長い時間を 必要とし、さらに、レジスト剥離性 _ 2において、ガラス基板表面の半分以上に曇りが あり、洗浄剥離が不十分で、力、なりレジストが残存していた。また、このレジスト剥離剤 は、防食性 _ 1において、僅かに淡青色に変色し、さらに、防食性 _ 2において、僅 かに A1が溶出し、腐食が観察された。  Met. This resist stripper requires a long time for stripping in resist stripping_1, and in resist stripping_2, more than half of the surface of the glass substrate is cloudy, and cleaning stripping is insufficient. The resist remained. In addition, this resist stripper turned slightly light blue in the anticorrosion property_1, and further, in the anticorrosion property_2, A1 was slightly eluted and corrosion was observed.
比較例 4  Comparative Example 4
[0064] 比較例 4にかかる剥離剤として、約 26重量0 /0のジエチレングリコールモノブチルェ 一テルと、約 34重量％のモノエタノールァミンと、約 40重量％の水と力 なるレジスト 剥離剤を用意した。続いて、上記剥離試験及び腐蝕試験を行った。 [0064] As the release agent according to Comparative Example 4, and diethylene glycol monobutyl E one ether of about 26 weight 0/0, about 34 wt% of monoethanolamine § Min and about 40 wt% of water and power becomes resist stripper Prepared. Subsequently, the peeling test and the corrosion test were performed.
試験結果は、表一 2に示すように、 レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 38秒であった。 ) レジスト剥離性 2 :△ The test results are shown in Table 1-2. Resist strippability-1: ○ (Time to clear the substrate was 38 seconds.) Resist strippability 2: △
防食性 1 : X  Anticorrosive 1: X
防食性一 2 : X  Anticorrosive 1: X
であった。このレジスト剥離剤は、レジスト剥離性— 1において、剥離性が優れてい たものの、レジスト剥離性 _ 2において、微量のレジスト残渣が認められた。また、この レジスト剥離剤は、防食性一 1において、明らかに青色に変色し、さらに、防食性一 2 において、明らかに A1が溶出し、激しい腐食が観察された。  Met. Although this resist stripper had excellent strippability in resist strippability-1, a small amount of resist residue was observed in resist strippability_2. In addition, this resist stripper clearly turned blue in anticorrosion property 1 and, further, in the anticorrosion property 2, A1 was clearly eluted and severe corrosion was observed.
比較例 5  Comparative Example 5
[0065] 比較例 5にかかる剥離剤として、約 17重量0 /0のジエチレングリコールモノブチルェ 一テルと、約 23重量％のモノエタノールァミンと、約 60重量％の水と力 なるレジスト 剥離剤を用意した。続いて、上記剥離試験及び腐蝕試験を行った。 [0065] As the release agent according to Comparative Example 5, and diethylene glycol monobutyl E one ether of about 17 weight 0/0, about 23 wt% of monoethanolamine § Min and about 60 wt% water and force becomes resist stripper Prepared. Subsequently, the peeling test and the corrosion test were performed.
試験結果は、表 2に示すように、  The test results are shown in Table 2.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 24秒であった。 ) レジスト剥離性 2 :〇  Resist strippability-1: (Time until the substrate became transparent was 24 seconds.) Resist stripp 2:
防食性一 1 : X  Anticorrosive 1: X
防食性一 2 : X  Anticorrosive 1: X
であった。このレジスト剥離剤は、剥離性が優れていた。また、このレジスト剥離剤は 、防食性 _ 1において、明らかに青色に変色し、さらに、防食性 _ 2において、明らか に A1が溶出し、激しい腐食が観察された。  Met. This resist remover was excellent in peelability. In addition, this resist stripper clearly turned blue in the anticorrosion property_1, and further, in the anticorrosion property_2, A1 was clearly eluted and severe corrosion was observed.
比較例 6  Comparative Example 6
[0066] 比較例 6にかかる剥離剤として、約 9重量％のジエチレングリコールモノブチルエー テノレと、約 11重量％のモノエタノールァミンと、約 80重量％の水と力 なるレジスト剥 離剤を用意した。続いて、上記剥離試験及び腐蝕試験を行った。  [0066] As a stripping agent according to Comparative Example 6, about 9% by weight of diethylene glycol monobutyl ether, about 11% by weight of monoethanolamine, and about 80% by weight of water and a resist stripping agent having power are prepared. did. Subsequently, the peeling test and the corrosion test were performed.
試験結果は、表 2に示すように、  The test results are shown in Table 2.
レジスト剥離性ー1 :〇（基板が透明になるまでの時間は、 29秒であった。 ) レジスト剥離性 2 :△  Resist strippability-1: ○ (Time until the substrate became transparent was 29 seconds.) Resist strippability 2::
防食性一 1 : X 防食性 2 : X Anticorrosive 1: X Anticorrosion 2: X
であった。このレジスト剥離剤は、レジスト剥離性 1において、剥離性が優れてい たものの、レジスト剥離性 2において、微量のレジスト残渣が認められた。また、この レジスト剥離剤は、防食性一 1において、明らかに青色に変色し、さらに、防食性一 2 において、明らかに A1が溶出し、激しい腐食が観察された。  Met. Although this resist stripper was excellent in stripping property in resist stripping property 1, a small amount of resist residue was observed in resist stripping property 2. In addition, this resist stripper clearly turned blue in anticorrosion property 1 and, further, in the anticorrosion property 2, A1 was clearly eluted and severe corrosion was observed.
[0067] 上記各実施例の試験結果から、全ての実施例において、防食性能が優れているこ とを確認できた。また、剥離性能においては、実施例 2， 5, 6, 9, 13， 15において、 微量のレジスト残渣が認められたものの、他の実施例においては、剥離性能も優れ ていることを確認できた。 [0067] From the test results of the above examples, it was confirmed that the anticorrosion performance was excellent in all examples. In addition, with regard to the stripping performance, a small amount of resist residue was observed in Examples 2, 5, 6, 9, 13, and 15. However, it was confirmed that the stripping performance was excellent in other Examples. .
また、上記各比較例の試験結果から、全ての比較例において、剥離性能及び防食 性能の両方を満足することができなかった。  Further, from the test results of the above comparative examples, it was not possible to satisfy both the peeling performance and the anticorrosion performance in all the comparative examples.
[0068] 以上、本発明のレジスト剥離剤について、好ましい実施形態を示して説明したが、 本発明に係るレジスト剥離剤は、上述した実施形態にのみ限定されるものではなぐ 本発明の範囲で種々の変更実施が可能であることは言うまでもない。 [0068] Although the resist stripper of the present invention has been described with reference to the preferred embodiment, the resist stripper according to the present invention is not limited to the above-described embodiment. Needless to say, it is possible to implement this change.
例えば、レジスト剥離剤に含まれる式（1)で表される化合物は、一種類に限定され るものではなぐたとえば、式（1)で表される二以上の化合物が含まれたレジスト剥離 剤であってもよい。  For example, the compound represented by the formula (1) contained in the resist stripper is not limited to one type, for example, a resist stripper containing two or more compounds represented by the formula (1). There may be.
また、本発明の用途としては、液晶 ·半導体用レジスト剥離剤に限定されるものでは なぐたとえば、プリント基板用剥離剤、レジスト現像液、フラックス洗浄剤、樹脂溶剤（ たとえば、ポリイミド樹脂用溶剤、ポリアミド樹脂用溶剤）などとしても用いられる。  Further, the use of the present invention is not limited to liquid crystal / semiconductor resist removers. For example, print board removers, resist developers, flux cleaners, resin solvents (for example, polyimide resin solvents, polyamides) It is also used as a solvent for resins.

Claims

請求の範囲 The scope of the claims
式（1)で表される化合物を含むことを特徴とするレジスト剥離剤  A resist remover comprising a compound represented by the formula (1)
Figure imgf000027_0001
Figure imgf000027_0001
ここで、式（1)において、 Rは炭素数 1〜： 18のアルキル基であり、 R及び Rは、そ Here, in the formula (1), R is an alkyl group having 1 to 18 carbon atoms, and R and R are
3 1 2 れぞれ独立に水素原子又は炭素数 1〜6のエーテル結合を有してもよい炭化水素基 であり、互いに同一であっても異なっていてもよぐさらに、互いに結合して環構造を 形成してもよい。  3 1 2 Each independently represents a hydrogen atom or a hydrocarbon group which may have an ether bond having 1 to 6 carbon atoms, which may be the same or different from each other. A structure may be formed.
[2] 20〜： 100重量％の前記式（1)で表される化合物と、 0〜80重量％の水とが含まれ ることを特徴とする請求項 1に記載のレジスト剥離剤。  [2] The resist stripping agent according to claim 1, comprising 20 to 100% by weight of the compound represented by the formula (1) and 0 to 80% by weight of water.
[3] 前記 R及び Rの炭素数を、 1〜4としたことを特徴とする請求項 1又は 2に記載のレ [3] The label according to claim 1 or 2, wherein R and R have 1 to 4 carbon atoms.
1 2  1 2
ジスト剥離剤。  Gist stripping agent.
[4] 前記 R及び Rの炭素数を 1とし、かつ、前記 Rの炭素数を 1〜8としたことを特徴と  [4] The carbon number of R and R is 1, and the carbon number of R is 1-8.
1 2 3  one two Three
する請求項 1又は 2に記載のレジスト剥離剤。  The resist remover according to claim 1 or 2.
[5] 前記 R及び Rの炭素数を 2とし、かつ、前記 Rの炭素数を 1〜6としたことを特徴と [5] The carbon number of R and R is 2, and the carbon number of R is 1-6.
1 2 3  one two Three
する請求項 1又は 2に記載のレジスト剥離剤。  The resist remover according to claim 1 or 2.
[6] 防食剤、キレート剤、剥離促進剤、還元剤、酸化剤、界面活性剤、緩衝剤及び Z又 は酸化防止剤が添加されたことを特徴とする請求項 1〜5のいずれか一項に記載の レジスト剥離剤。 [6] The anticorrosive agent, chelating agent, peeling accelerator, reducing agent, oxidizing agent, surfactant, buffering agent, and Z or antioxidant are added. The resist remover according to item.
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