WO2005036268A1 - Composition de photoresine - Google Patents

Composition de photoresine Download PDF

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Publication number
WO2005036268A1
WO2005036268A1 PCT/JP2004/014832 JP2004014832W WO2005036268A1 WO 2005036268 A1 WO2005036268 A1 WO 2005036268A1 JP 2004014832 W JP2004014832 W JP 2004014832W WO 2005036268 A1 WO2005036268 A1 WO 2005036268A1
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WO
WIPO (PCT)
Prior art keywords
acid
group
mass
alkali
resist
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Application number
PCT/JP2004/014832
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English (en)
Japanese (ja)
Inventor
Masaki Hosaka
Masatoshi Homma
Original Assignee
Asahi Denka Co., Ltd.
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Publication date
Application filed by Asahi Denka Co., Ltd. filed Critical Asahi Denka Co., Ltd.
Priority to KR1020067007065A priority Critical patent/KR101073417B1/ko
Priority to JP2005514594A priority patent/JP4673222B2/ja
Priority to CN2004800267290A priority patent/CN1853138B/zh
Publication of WO2005036268A1 publication Critical patent/WO2005036268A1/fr

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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
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition

Definitions

  • the present invention relates to a photoresist composition in which scum is reduced in an alkaline developing step of a photoresist.
  • photoresists have been widely used when forming wiring patterns such as printed circuit boards, integrated circuits, and color filters.
  • a film-like or liquid photoresist is laminated or coated on a substrate, and then irradiated with actinic radiation such as ultraviolet rays, X-rays, and electron beams, exposed, and cured. Thereafter, development is performed by removing the uncured photoresist with a developer to form a patterned resist film.
  • an alkaline aqueous solution is usually used, and as the alkaline agent of the developing solution, an inorganic alkaline compound such as an alkali metal carbonate or an alkali metal hydroxide, or an organic alkaline compound such as tetramethylammonium hydroxide is used. Are used.
  • bubbles are generated when air is entrained in the developing solution, but since the developing solution is usually used in circulation, if the generated foam has insufficient defoaming properties, the bubbles may accumulate. Become. In particular, due to the circulating use, as the resist component in the developer increases, the bubbles hardly disappear. Bubbles not only hinder the circulation of the developer but also hinder the contact between the developer and the photoresist, thus causing a problem that the uncured resist is not sufficiently removed and a good resist pattern is not formed.
  • a photoresist which is unlikely to generate scum includes a photopolymer having a polyoxyalkylene group.
  • Photoresists containing compatible compounds see, for example, Patent Documents 1 and 2), compounds that generate an acid upon irradiation with actinic rays or radiation, and are decomposed by the action of an acid to increase solubility in an alkaline developer.
  • a photoresist containing a group-containing resin see, for example, Patent Document 3
  • a phenolic compound are blended to improve the resolution, thereby reducing the amount of additive and the scum due to the photosensitive agent.
  • Photoresist for example, refer to Patent Document 4 is known.
  • a polyoxyalkylene sorbitol fatty acid ester is used in order to improve resolution (for example, see Patent Documents 5 and 6).
  • blending of a polyoxyalkylene sorbite fatty acid ester is effective in dispersing scum and preventing foaming.
  • an alkali developer containing a nonionic surfactant IJ having an HLB of 0 to 4 and a nonionic surfactant having an HLB of 620 and an anionic polymer surfactant for example, Alkaline developer containing an amphoteric surfactant and a nonionic surfactant (see, for example, Patent Literature 8), etc. are known to have excellent scum dispersibility. There was a problem that the liquid foamed a lot.
  • Patent Document 1 JP-A-5-232699
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2003-149809
  • Patent Document 3 JP-A-10_133376
  • Patent Document 4 JP-A-5-204144
  • Patent Document 5 JP-A-1-302349
  • Patent Document 6 JP-A-2002-72461
  • Patent Document 7 JP-A-8-160632
  • Patent Document 8 JP-A-11-352700 Problems the invention is trying to solve
  • an object of the present invention is to provide a photoresist having excellent scum dispersibility and less bubbling of a developer.
  • the present inventors have intensively studied the above problem, and by blending a polyetherester having a specific structure into the photoresist, a photoresist having excellent scum dispersibility and less foaming of the developing solution can be obtained.
  • the inventors have found that the present invention can be obtained, and completed the present invention.
  • the present invention provides, as the component (A), the following general formula (1)
  • RCO represents a residue obtained by removing a hydroxyl group from a fatty acid having 6 to 22 carbon atoms
  • X represents a residue obtained by removing a hydroxyl group from a polyol having at least three hydroxyl groups
  • AO and A ′ ′ A represents an oxyalkylene group having 2 to 4 carbon atoms
  • a represents 0 or a number of 1 or more
  • b represents a number of 1 or more
  • m and n represent a number of 1 or more, provided that m and n The total is the same as the number of hydroxyl groups of the polyol.
  • a photoresist composition comprising, as the component (B), an alkali-soluble resin having an anionic group or a modified product thereof.
  • the component (A) of the present invention is a polyetherester represented by the general formula (1).
  • RCO represents a residue obtained by removing a hydroxyl group from a fatty acid having 6 to 22 carbon atoms.
  • the fatty acids having 6 to 22 carbon atoms include hexanoic acid (cabroic acid), heptanoic acid, octanoic acid (force prillic acid), nonanoic acid (pelargonic acid), decanoic acid (force pric acid), pendecane Acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), 12-hydroxyoctadecanoic acid (12 -Linear saturated fatty acids such as hydroxystearic acid), eicosanoic acid (araquinic acid), docosanoic acid (behenic acid); is
  • Branched fatty acids Branched fatty acids; 10-pandecenoic acid, palmitoleic acid, oleic acid, isoleate Phosphate, elaidic acid, linoleic acid, linolenic acid, ricinoleic acid, Gadore phosphate, El force acids, unsaturated fatty acids such as selacholeic acid.
  • fatty acids having 5 or less carbon atoms foaming of the developer increases, and in the case of fatty acids having 23 or more carbon atoms, the dispersibility of scum may be insufficient.
  • fatty acids having 10 to 14 carbon atoms are most preferable, and fatty acids having 8 to 18 carbon atoms are more preferable.
  • a saturated fatty acid is preferable since it has less foaming than an unsaturated fatty acid.
  • X represents a residue obtained by removing a hydroxyl group from a polyol having at least three hydroxyl groups.
  • polyolefins include glycerin, 1,2,3-butanetriol, 1,2,4_butanetriol, 2-hydroxymethinole-1,3_propanediol, and 2- 1,2,3-Pentontriol, 1,3,5_Pentantriol, 2,3,5_Pentantriol, 2—Methino-1,2,4_propanetriol, 2-hydroxymethyi 1,3-butanediol, trimethylolethane, 1,3,5-hexanetriol, 1,2,6-hexanetriol, 3-hydroxymethinol_1,5_pentanediol, 3-methylol Trivalent alcohols such as 1,3,5_pentanetriol, trimethylolpropane, trimethylolbutane, 2,5-dimethyl_1,2,5-hexanetriol and triethanolamine; pentaerythrito
  • Pentahydric alcohols such as aditol, arabitolone, xylitol, and triglycerin; hexavalent alcohols such as diantaerythritol, sonorebitone, mannitore, iditonore, inositotone, danoresitone, talose, arose, etc .; Trihydric alcohols; trivalent such as tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1,3-tris (3-t-butinole-1-hydroxy-6-methylphenylbutane) And the like.
  • glycerin and sorbitan are most preferred, with tri- and hexahydric alcohols being more preferred, and tri- and tetrahydric alcohols being more preferred.
  • AO and AO ′ represent an oxyalkylene group having 2 to 4 carbon atoms, a represents 0 or 1 or more, and b represents 1 or more.
  • Examples of the oxyalkylene group having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxy (methinole) ethylene, oxybutylene, oxy (ethyl) ethylene and the like.
  • the group can be obtained by addition-polymerizing an alkylene oxide having 2 to 4 carbon atoms to the polyol having at least three hydroxyl groups.
  • alkylene oxides examples include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1,4-butylene oxide) and the like.
  • alkylene oxide is polymerized, homopolymerization of one kind of alkylene oxide or the like, random polymerization of two or more kinds of alkylene oxides, block polymerization, random / block polymerization, or the like may be used.
  • ethylene oxide is preferred.
  • one of them is preferably ethylene oxide.
  • the ethylene oxide content is too low, the dispersion of the scum may be insufficient, whereas if the ethylene oxide content is high, the foaming of the developer may increase.
  • the ethylene oxide content of the group represented by (AO) and the group represented by ( ⁇ ') depends on the total
  • fixture 60- 90 mass 0/0 is a 50- 95 mass 0/0 is more preferred instrument 70 to 85 wt%.
  • the total number of a and b is preferably 1 to 50, more preferably 2 to 20 force, and most preferably 4 to 15.
  • n and n are the total number of forces of m and n the same as the number of hydroxyl groups of the polyol 1 Represents the above numbers.
  • the ratio of n to m is preferably 0.5-4 force S, more preferably 0.8-3, and most preferably 1-2.
  • the method for producing the polyetherester represented by the general formula (1) is not particularly limited, and can be produced by a known method. Examples of such a method include (A) a method in which an alkylene oxide is addition-polymerized to a partial ester of a fatty acid and a polyol, and (B) a method in which an alkylene oxide is addition-polymerized to a polyol, and then a fatty acid ester.
  • No. Catalysts for addition polymerization of alkylenoxide include, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide; alkali metal alkoxides such as sodium methylate and potassium butoxide; and trimethyl oxide.
  • Tertiary amine conjugates such as min and triethylamine; and Lewis acids such as stannous salt, stannic chloride and boron trifluoride.
  • esterification may be performed directly with a fatty acid, or esterification may be performed by transesterification using a fatty acid lower alcohol such as fatty acid methyl or fatty acid butyl.
  • a polyetherester having a number of 0 is not obtained, and a polyetherester having the same number of a and b is obtained.
  • a transesterification reaction occurs. May be
  • the content of the polyetherester represented by the general formula (1) is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the photoresist composition of the present invention. More preferably 15 parts by mass, most preferably 5-10 parts by mass. If the content of the polyetherester represented by the general formula (1) is less than 1 part by mass, the dispersibility of the scum may be insufficient. If the content exceeds 20 parts by mass, the adhesion of the resist to the base material may be reduced. This is because the resolution of the resist pattern after alkali development may be reduced.
  • the component (B) of the present invention is an alkali-soluble resin having an anionic group or a modified product thereof.
  • anionic group include a carboxyl group, a sulfonic acid group, an ester sulfate group, a phosphoric ester group, a phenolic hydroxyl group, and the like.
  • Carboxy with preferred hydroxyl groups Sil groups are more preferred.
  • the alkali-soluble resin containing a carboxy group includes a radically polymerizable unsaturated acid such as acrylic acid, methacryloline acid, crotonic acid, fumaric acid, maleic anhydride (anhydride), and itaconic anhydride as an essential component. And a radical polymerizable monomer such as (meth) acrylic acid esters, styrene, acrylonitrile, and (meth) acrylamide.
  • a radical polymerizable monomer such as (meth) acrylic acid esters, styrene, acrylonitrile, and (meth) acrylamide.
  • the acid value of the alkali-soluble resin containing a carboxyl group is preferably 20-300 mgKOH / g, more preferably 40-200 mgKOH / g, and more preferably 60-170 mgK ⁇ H / g. Is most preferred. If the acid value is less than 20 mgK ⁇ H / g, the solubility in the alkaline developer may be insufficient and the developability may decrease. If the acid value exceeds 300 mgK ⁇ H / g, the resolution of the resist pattern after alkali development May decrease.
  • alkali-soluble resin having a phenolic hydroxyl group examples include, for example, a novolak resin obtained by polycondensation of a phenol compound and an aldehyde with an acid catalyst, and copolymerization of hydroxystyrene and another radical polymerizable monomer. Polybutylphenol resin and the like.
  • Aldehydes used in the novolak resin include, for example, phenol, m-cresol, o-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcinol, pyrogallol, bisphenol, bisphenol A , Ethyl phenol, propyl phenol, butyl phenol and the like.
  • examples of the aldehydes used in the novolak resin include honolemuanolaldehyde, acetoaldehyde, propionaldehyde, and the like.
  • the molecular weight of the alkali-soluble resin is preferably 1,000 to 1,000,000, more preferably 2,000 to 100,000, and most preferably 3,000 to 50,000 in terms of weight average molecular weight.
  • the weight average molecular weight is less than 1000, the viscosity may be too low to form a film having a thickness usable for photoresist, and when the weight average molecular weight exceeds 1,000,000, the viscosity may be too high to apply easily.
  • the glass transition temperature (Tg) is 0 ° C. or higher, particularly in the range of 510 ° C. to 70 ° C., it is preferable because the coating film does not show tackiness.
  • the photoresist composition of the present invention may be a negative resist or a positive resist.
  • the negative resist include a photo-radical polymerization type resist, a chemically amplified type resist, and a photo-ionization type resist.
  • a negative resist for example, Non-diazide resists, chemically amplified resists, and the like can be used.
  • a photo-radical polymerization type resist is preferred because of good scum dispersibility of the developer and little bubbling.
  • the photo-radical polymerization type negative resist is an alkali-soluble resin in which the component (B) has an anionic group, and further contains a poly (meth) acrylate of a polyhydric alcohol and a photopolymerization initiator. Or a modified product in which a component (B) is an alkali-soluble resin having an anionic group, in which a part of the anionic group is substituted with a radical polymerizable group. Contained photoresist.
  • polyhydric alcohol of poly (meth) acrylate of polyhydric alcohol examples include neopentyl glycol, hexylene glycol, glycerin, trimethylolpropane, (poly) ethylene glycol, (poly) propylene glycol, Oxyethylene polyoxypropylene glycol, alkylene oxide adducts of bisphenol A, and the like can be mentioned.
  • Examples of the photopolymerization initiator include, for example, aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzylxanthone, thioxanthone, and anthraquinone; acetophenone, propiophenone, disease-hydroxyisobutyl phenone, ⁇ , float quote—Dicronoleate 4-phenoxyacetophenone, 1-hydroxy-1-cyclohexynoleacetophenone, diacetinoleacetophenone, acetofenone, etc .; Organic peroxides such as _ethylhexanoate, t_butylhydroxide peroxide, di-t-butyldiperoxyisophthalate, 3,3 ', 4,4 and tetra (t_butylperoxycarbonyl) benzophenone Jifuji Diphenyl enohalonium salts such as levothy
  • the modified product in which a part of the anionic group of the alkali-soluble resin having an anionic group is substituted with a radical polymerizable group is obtained by adding glycidyl acrylate or glycidyl methacrylate to the alkali-soluble resin having an anionic group.
  • glycidyl group-containing unsaturated compounds such as aryl glycidyl ether.
  • the content of the radical polymerizable group is preferably from 200 to 3000, more preferably from 230 to 1500, most preferably from 250 to 750, in terms of unsaturated resin equivalent weight of the resin.
  • the peelability of the resist pattern after alkali development may be insufficient. If it exceeds 3,000, the resist pattern after alkali development may be insufficient. This is because developability may be insufficient.
  • the chemically amplified negative resist is a photoresist in which the component (B) is an alkali-soluble resin having a phenolic hydroxyl group, and further contains a photoacid generator and a crosslinking agent.
  • the photoacid generator include bis (sulfonyl) diazomethanes such as bis (p-toluenesulfonyl) diazomethane; p-tonoleenesulfonic acid; nitrobenzyl derivatives such as 2-nitrobenzyl; methanesulfonic acid of pyrogallol Pyrogallol and aliphatic or aromatic sulfonic esters such as benzenesulfonate of esters and pyrogallol; onium salts such as diphenyl iodonium hexafluorophosphate and triphenylsulfonium trifluoromethane sulfate; henzointosylate and the like Benzoin tos
  • the negative resist of the photovoltaic thione polymerization type is a photoresist in which the component (B) is an alkali-soluble resin having a phenolic hydroxyl group, and further contains a cationic polymerizable compound and a photoacid generator.
  • the cationic polymerizable compound include p-diisopropylbenzene, m-diisopropylbenzene, diphenylethylene, indenone, and acena.
  • the quinonediazide-based positive resist is a photoresist in which the component (B) is an alkali-soluble resin having a phenolic hydroxyl group and further contains a quinonediazide compound, and is insoluble in an alkaline developer before exposure. However, after exposure, the quinonediazide compound becomes alkali-soluble by becoming an indene carboxylic acid compound.
  • the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid ester and 1,2-benzoquinonediazidesulfonic acid ester of a phenolic hydroxyl group-containing compound.
  • phenolic hydroxyl group-containing compound examples include, in addition to the above-mentioned phenols, 11-naphthol, 2-naphthol, dihydroxynaphthalene, gallic acid, gallic acid ester and the like.
  • the chemically amplified positive resist is a photoresist in which the component (B) is an alkali-soluble resin having an anionic group, and further contains a dissolution inhibitor having an acid-decomposable group and a photoacid generator;
  • the photoresist is a modified product in which the component (B) is a modified product of an alkali-soluble resin having an anionic group in which the anionic group is protected with an acid-decomposable group, and further contains a photoacid generator.
  • the dissolution inhibitor having an acid-decomposable group is a compound having a property of reducing the dissolution of an alkali-soluble resin having an anionic group in a developer.
  • a phenol compound is a Compounds modified with butoxycarbonyl ether, tetrahydroviranyl ether, 3-bromotetrahydrovilaninoleatenoate, 1-methoxycyclohexinoleatenoate, t-butynoleatel, trimethylsilyl ether, triethylsilyl ether, etc. .
  • t-butoxycarbonyl ether of polybutylphenol is preferred.
  • the photoacid generator include those mentioned for the chemically amplified negative resist.
  • An anionic group of an alkali-soluble resin having an anionic group is protected by an acid-decomposable group.
  • modified products include a resin in which a carboxyl group of an alkali-soluble resin having a carboxy group is protected with an acid-decomposable group, and a phenolic hydroxyl group of an alkali-soluble resin having a phenolic hydroxyl group in which an phenolic hydroxyl group is an acid-decomposable group. And the like.
  • Examples of such an acid-decomposable group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, a benzyloxymethyl group, a phenoxymethinole group, a 1-methoxyethyl group, a t-butyl group, and a benzyl group.
  • the photoresist composition of the present invention may contain various additives such as a solvent, a photosensitizer (dye), a radical polymerization inhibitor, a thermal crosslinking compound, a coating improver, It may contain a property improver and the like.
  • Examples of the solvent include glycol solvents such as methoxyethanol, ethoxyethanol, butoxyethanol, methoxy-2-propanol, ethoxymethoxy-2-propanol; and methoxyethanol acetate, ethoxyethanol acetate, methoxy-2-propanol acetate, and the like.
  • Ether acetate solvents such as ethyl acetate, butyl acetate, and ethyl 2-hydroxypropionate (ethyl ethyl lactate); alcohol solvents such as hexanol, cyclohexanol, diacetone alcohol; cyclohexanone; Ketone-based solvents such as methylethanol ketone and methyl isobutyl ketone; and hydrocarbon solvents such as cyclohexane, toluene and xylene.
  • ester solvents such as ethyl acetate, butyl acetate, and ethyl 2-hydroxypropionate (ethyl ethyl lactate)
  • alcohol solvents such as hexanol, cyclohexanol, diacetone alcohol; cyclohexanone; Ketone-based solvents such as methylethanol ketone and methyl isobutyl ketone; and hydrocarbon solvents such as cycl
  • Examples of the photosensitizer include thioxanthenes, xanthenes, ketones, thiopyridinium salts, basestyryls, merocyanines, 3_substituted coumarins, 3.4_substituted coumarins, and cyanines. And athalidine, thiazine, phenothiazine, anthracene, corone, benzanthracene, perylene, merocyanine, ketocoumarin, fumaline, and borate dyes.
  • radical polymerization inhibitor examples include p-methoxyphenol, hydroquinone, catechol, resorcinol, naphthylamine, t-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4- Methyl-6_t_butylphenol), 2,2 methylene Bis (4-ethyl-6_t_butylphenol) and the like.
  • the photosensitive resin composition of the present invention contains additives such as a colorant (dye or pigment), a color former (a dye that develops a color when irradiated with light), a plasticizer, a flame retardant, an adhesion promoter, and an organic solvent. If necessary, it may be added.
  • a photoresist pattern of the present invention When a photoresist pattern of the present invention is used to form a resist pattern on a copper-clad laminate, silicon resin, a glass plate, or the like, the photoresist composition is roll-coated, After coating by a knife coating method, a spray coating method, or the like, drying is performed as necessary, drawing is performed with an irradiation force through a desired mask pattern, an electron beam, and development processing is performed using an alkali developing solution.
  • the photoresist composition of the present invention can be suitably used as a dry film resist after being coated on a polymer film and dried.
  • a polymer film is capable of transmitting active light and can be easily removed from the applied and dried resist composition later.
  • examples of such a polymer film include polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polyvinyl chloride, polyvinyl chloride copolymer, polyvinylidene chloride, polyvinyl chloride copolymer, and polymethacryl.
  • Polyethylene terephthalate is preferred among the powers including a film composed of methyl acid copolymer, polystyrene, polystyrene copolymer, polyacrylonitrile, polyamide and the like.
  • the thickness of the polymer film is preferably 5-100 m, more preferably 10-30 m.
  • the thickness of the resist composition applied and dried on the polymer film varies depending on the application. If the thickness is too small, the film strength will be low. If the thickness is too large, the resolution will be low. One lOOm is preferred 5-60'm is more preferred.
  • a protective film may be laminated on the surface of the photopolymerized layer.
  • films such as polyethylene and polypropylene are preferable.
  • Examples of the method of applying the photosensitive resin composition include a roll coating method, a knife coating method, a spray coating method and the like, and the drying temperature and time are usually from 110 to 130 ° C for 110 minutes.
  • the film thickness of the photopolymerized layer in the photosensitive element of the present invention varies depending on the application. Too thin a film reduces the film strength, while too thick reduces the resolution. Then 1 lOO 'm is preferred 5-60' m is more preferred Good.
  • the alkali developing solution used in the developing step is not particularly limited, and a conventionally known alkali developing solution can be used.
  • the alkali agent of such an alkali developer include alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; alkali metal bicarbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; Alkali metal borates such as lithium borate, sodium borate and potassium borate; alkali metal silicates such as lithium silicate, sodium silicate and potassium silicate; lithium hydroxide, sodium hydroxide, and hydroxide
  • Inorganic alkaline compounds such as alkali metal hydroxides such as potassium; ethylenediamine, propylenediamine, piperidine, morpholine, piperazine, tetramethylammonium hydroxide, tetraethynoleammonium hydroxide, trimethyl (2- Organic alcohols such as hydroxyethy
  • the concentration of the alkaline agent in the developer varies depending on the type of the alkaline agent used and the photoresist, but in the case of an alkali metal carbonate, 0.1 to 5 parts by mass of water is used. It is more preferably 0.3 to 3 parts by mass, most preferably 0.5 to 2 parts by mass.
  • the concentration of the alkali agent in the developer is preferably 0.5 to 25 parts by mass with respect to 100 parts by mass of water, and is 1 to 15 parts by mass. More preferably, it is most preferably 1.5 to 10 parts by mass.
  • the temperature of the developer is preferably from 15 to 50 ° C, more preferably from 20 to 40 ° C, and most preferably from 25 to 35 ° C. If the temperature of the developer is lower than 15 ° C, the dissolution of the uncured resist may be insufficient, and if it exceeds 50 ° C, the cured resist may peel off. .
  • a glass flask equipped with a stirrer, thermometer and nitrogen gas inlet tube was charged with 207 g (0.5 mol) of a polyether compound, 219 g (0.5 mol) of coconut oil fatty acid, and 0.5 g of methanesulfonic acid as a catalyst. And reacted at 180 ° C. for 5 hours to obtain polyetherester A-11 of the present invention:
  • R residue obtained by removing a carboxy group from coconut oil fatty acid (a mixture of C12, C14, C16 and having a main component of C12);
  • R a residue obtained by removing a carboxyl group from lauric acid
  • R a residue obtained by removing a carboxy group from oleic acid
  • R residue obtained by removing the carboxy group from tallow fatty acid (a mixture of C16, C18, C20 having a main component of C18);
  • B_l Polyether compound which is an intermediate of A-1 (glycerin ethylene oxide
  • Component (A) used in the composition of the present invention 7 parts by mass of A—11—A—5 or comparative product B_l—B_5, mass ratio of methyl methacrylate / methyl methacrylate / ethyl acrylate / ethyl methacrylate 22Z45Z27Z6 copolymer (Alkali-soluble resin: weight average molecular weight 100,000) 23 parts by weight, polyethylene glycol (number average molecular weight 400) dimethallate 20 parts by weight, tripropylene glycol dimethatalylate 20 parts by weight, benzophenone 7 parts by weight, and 4 Then, 0.7 parts by mass of bis (dimethylamino) benzophenone was dissolved in 40 parts by mass of a mixed solvent of 60 parts by mass of 2-methoxyethanol and 40 parts by mass of Z tonolene to prepare a photoresist composition.
  • Component (A) used in the composition of the present invention 7 parts by mass of A—11—A—5 or comparativ
  • This photoresist composition is uniformly applied to a 25-m-thick polyethylene terephthalate film and dried for 10 minutes with a hot air convection dryer at 100 ° C to form a 50-m-thick photopolymerizable layer. Then, a 35'm polyethylene film is laminated on the surface of the photopolymerizable layer.
  • the surface of the copper-clad laminate on which 35'm rolled copper foil is laminated is polished by wet puff-roll (Scotchbright SF, manufactured by 3LEM Co., Ltd., twice), and the photosensitive layer is peeled off by a hot roll laminator while peeling off the polyethylene film of the laminated film. Laminated with C.
  • the photopolymerizable layer of the copper-clad laminate laminated with the dry film resist was exposed at 60 mj / cm 2 with a 3 kW high-pressure mercury lamp (HMW-201B manufactured by Oak Manufacturing Co., Ltd.). After peeling off the polyethylene terephthalate film, a 1% aqueous solution of sodium carbonate (developer) at 30 ° C. was sprayed for 60 seconds to dissolve and remove unexposed portions, washed with water, dried and developed. Using the substrate after the development, the adhesion was evaluated by the following cross cut test. Table 1 shows the results.
  • the resist was evaluated for adhesion based on the following criteria.
  • ⁇ Bubbling test >> The polyethylene terephthalate film is peeled off from the copper-clad laminate on which the dry film resist is laminated, and without exposure, a 1% aqueous solution of sodium carbonate (developer) at 30 ° C is sprayed for 60 seconds to remove the uncured resist. A developer solution containing 1% by mass was prepared. Using this developer, foaming was evaluated by the following method. Table 1 shows the results.
  • the amount of foam is less than 20 mL and the foaming property is low.
  • the amount of foam is 20 mL or more and less than 40 mL, and the foaming property is somewhat large.

Abstract

composition de photorésine caractérisée en ce qu'elle comprend : un polyétherester représenté par la formule générale {RCOO(AO)a}mX{O(AO')bH}n (1) (dans laquelle RCO représente le résidu formé par suppression du groupe hydroxy d'un acide gras C6-22; X représente le résidu formé par la suppression des groupes hydroxy d'un polyol comprenant au moins trois groupes hydroxy; AO et AO' représentent chacun un oxyalkylène en C2-4; a vaut 0, 1 ou plus; b vaut 1 ou plus; et m et n valent chacun 1 ou plus, à condition que la somme de m et de n soit identique au nombre de groupes hydroxy contenus dans le polyol) en tant qu'ingrédient (A); et une résine soluble dans l'alcali comportant des groupes anioniques ou une modification de la résine en tant qu'ingrédient (B).
PCT/JP2004/014832 2003-10-14 2004-10-07 Composition de photoresine WO2005036268A1 (fr)

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KR1020067007065A KR101073417B1 (ko) 2003-10-14 2004-10-07 포토 레지스트 조성물
JP2005514594A JP4673222B2 (ja) 2003-10-14 2004-10-07 ドライフィルムレジスト
CN2004800267290A CN1853138B (zh) 2003-10-14 2004-10-07 光致抗蚀剂组合物

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JP2012529163A (ja) * 2009-06-04 2012-11-15 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 二成分エッチング
KR101779652B1 (ko) * 2006-03-28 2017-09-18 메르크 파텐트 게엠베하 네가티브 포토레지스트 조성물
EP3287551A4 (fr) * 2015-04-22 2018-10-03 Nissan Chemical Corporation Fibres photosensibles et procédé de formation d'un modèle de fibres
EP3392708A1 (fr) 2017-04-17 2018-10-24 Shin-Etsu Chemical Co., Ltd. Stratifié de film à résistance positive et procédé de formation de motifs

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KR102146095B1 (ko) 2017-09-15 2020-08-19 주식회사 엘지화학 화학증폭형 포토레지스트 조성물, 포토레지스트 패턴, 및 포토레지스트 패턴 제조방법
KR102475952B1 (ko) * 2018-06-22 2022-12-09 메르크 파텐트 게엠베하 포토레지스트 조성물, 및 포토레지스트 코팅, 에칭된 포토레지스트 코팅 및 에칭된 Si 함유 층(들)의 제조방법, 및 이들을 사용하는 디바이스의 제조방법

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JP2012529163A (ja) * 2009-06-04 2012-11-15 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 二成分エッチング
EP3287551A4 (fr) * 2015-04-22 2018-10-03 Nissan Chemical Corporation Fibres photosensibles et procédé de formation d'un modèle de fibres
EP3392708A1 (fr) 2017-04-17 2018-10-24 Shin-Etsu Chemical Co., Ltd. Stratifié de film à résistance positive et procédé de formation de motifs
KR20180116757A (ko) 2017-04-17 2018-10-25 신에쓰 가가꾸 고교 가부시끼가이샤 포지티브형 레지스트 필름 적층체 및 패턴 형성 방법
US10719015B2 (en) 2017-04-17 2020-07-21 Shin-Etsu Chemical Co., Ltd. Positive resist film laminate and pattern forming process

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TW200517779A (en) 2005-06-01
CN1853138B (zh) 2011-06-15
JP4673222B2 (ja) 2011-04-20
TWI346836B (en) 2011-08-11
KR101073417B1 (ko) 2011-10-17
JPWO2005036268A1 (ja) 2007-11-22
KR20070017962A (ko) 2007-02-13

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