WO2015146053A1 - Imide sulfonate compound, photoacid generator, and resin composition for photolithography - Google Patents

Imide sulfonate compound, photoacid generator, and resin composition for photolithography Download PDF

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WO2015146053A1
WO2015146053A1 PCT/JP2015/001406 JP2015001406W WO2015146053A1 WO 2015146053 A1 WO2015146053 A1 WO 2015146053A1 JP 2015001406 W JP2015001406 W JP 2015001406W WO 2015146053 A1 WO2015146053 A1 WO 2015146053A1
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PCT/JP2015/001406
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昌明 岡
秀基 木村
卓也 池田
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サンアプロ株式会社
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D223/00Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/14Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D223/18Dibenzazepines; Hydrogenated dibenzazepines
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0046Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition

Abstract

Provided are: a non-ionic photoacid generator including an imide sulfonate compound and having high light sensitivity to an i-line, excellent thermal stability, and excellent solubility in a hydrophobic material; and a resin composition for photolithography including the same. The present invention is an imide sulfonate compound represented by general formula (1). [In formula (1), R1 to R8 is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, etc. At least two of R1 to R8 may be joined to form a ring structure. R9 is a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent (a part or all of the hydrogen may be substituted with fluorine).]

Description

Imide sulfonate compounds, photoacid generator and photolithographic resin composition

The present invention, imide sulfonate compound, an optical acid generating agent and a photolithographic resin composition. More particularly, ultraviolet (i-line) by the action of suitable to generate a strong acid non-ionic photoacid generator, and a photolithographic resin composition containing the same.

Conventionally, in the field of typified by microfabrication in semiconductor manufacturing, photolithography has been widely used with wavelength 365nm i-line as exposure light.
As the resist material used in photolithography process, for example, a carboxylic acid tert- butyl ester group, or a polymer and a resin composition is used containing a photoacid generator having a phenol tert- butyl carbonate group there. As the photoacid generator, triarylsulfonium salts (Patent Document 1), ionic photoacid generators such as phenacyl sulfonium salt having a naphthalene skeleton (Patent Document 2), and an acid generator having an oxime sulfonate structure (Patent Documents 3), a non-ionic acid generators such as acid generator having a sulfonyl diazomethane structure (Patent Document 4) is known. The resist material by irradiating the ultraviolet rays, it generates a strong acid photoacid generator is decomposed. By further performing post exposure bake (PEB), tert- butyl ester groups in the polymer by this strong acid, or tert- butyl carbonate groups is dissociated, carboxylic acid, or a phenolic hydroxyl group is formed, the ultraviolet ray irradiation unit It becomes readily soluble in an alkaline developer. Pattern formation is performed by utilizing this phenomenon.

However accordance photolithography process becomes finer processing, the influence of the swelling patterns of the light unexposed portion is swelled by an alkali developing solution is increased, it is necessary to suppress the swelling of the resist material.
These polymers cycloaliphatic skeleton in the resist material in order to solve, or fluorine-containing backbone, such as that is contained to hydrophobic, a method of suppressing the swelling of the resist materials have been proposed.

However, since the ionic photoacid generators of the alicyclic skeleton, and compatibility with hydrophobic material containing a fluorine-containing backbone such is insufficient, it can exhibit sufficient resist performance for phase separation resist material not, there is a problem that can not be patterned. On the other hand, in the non-ionic photoacid generator is a good compatibility with the hydrophobic material, sensitivity is insufficient problem for i-line, and heat the stability is insufficient to decompose in post exposure baking (PEB) Allowance there is a small problem.

JP-A-50-151997 JP JP-9-118663 discloses JP-06-77433 discloses JP 10-213899 discloses

Therefore it has a high photosensitivity in the i-line, excellent heat stability, and to provide a non-ionic photoacid generator which is excellent in solubility in a hydrophobic material.

The present inventors have, as a result of studies to achieve the above object, the present invention has been attained.
That is, the present invention is an imide sulfonate compound characterized by being represented by the general formula (1).

Figure JPOXMLDOC01-appb-C000001

Wherein (1), R1 ~ R8 are each independently hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group having 1 to 18 carbon atoms having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, carbon an alkynyl group having from 2 to 18, an aryl group having 6 to 18 carbon atoms, a hydroxyl group, a carboxyl group, a silyl group, a nitro group, a cyano group, an amino group, an alkoxy group or aryloxy group represented by R 11 O-, R 12 alkylthio or arylthio group represented by S-, sulfinyl group represented by R 13 SO-, R 14 SO 2 - sulfonyl group represented by, an alkylcarbonyl group or an arylcarbonyl group represented by R 15 CO-, R 16 COO - carbonyloxy group represented by, oxycarbonyl group represented by R 17 OCO-, R8 carbonate group represented by -OCOO-, represents a urethane group represented by R 19 NHCOO-. At least two R1 ~ R8 may be bonded to form a ring structure. R9 represents a hydrocarbon group which may having 1 to 18 carbon atoms which may have a substituent (a portion of the hydrogen or all may be substituted by fluorine). ]

Nonionic photoacid generator containing imide sulfonate compounds of the present invention and which (A) is a nonionic, excellent compatibility with the hydrophobic material than in the ionic acid generator. Also it has a biphenyl structure in which twisted benzene rings, because structure is hard to crystallize, excellent solubility in solvents. Further, since having an imide skeleton is a site of absorption i-line, non-ionic photoacid generator by irradiation of i-ray (A) is easily decomposed, it is possible to generate a sulfonic acid is a strong acid. Further nonionic photoacid generators (A), for having an imide skeleton, excellent heat stability.

Therefore nonionic photoacid generators (A) photolithography resin composition containing the present invention (Q) is a high sensitivity to i-line, also the allowance for post exposure baking (PEB) wide for excellent workability.

Imide sulfonate compounds of the invention represented by the aforementioned general formula (1).

In the formula (1), the halogen atom of R1 ~ R8, fluorine atom, chlorine atom, bromine atom and iodine atom.

The alkyl group of R1 ~ 1 to 18 carbon atoms R8, straight-chain alkyl groups (methyl, ethyl having 1 to 18 carbon atoms, n- propyl, n- butyl, n- pentyl, n- octyl, n- decyl , n- dodecyl, n- tetradecyl, n- hexadecyl and n- octadecyl), branched-chain alkyl group having 1 to 18 carbon atoms (isopropyl, isobutyl, sec- butyl, tert- butyl, isopentyl, neopentyl, tert- pentyl , isohexyl and isooctadecyl), and cycloalkyl groups (cyclopropyl 3 to 18 carbon atoms, cyclobutyl, cyclopentyl, cyclohexyl and 4-decyl cyclohexyl, and the like).
Linear or branched fluoroalkyl group (trifluoromethyl having 1 to 18 carbon atoms, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoro propyl, 2,2,3,3,3-pentafluoro-propyl, 1,1,1,3,3,3-hexafluoro-2-propyl, heptafluoropropyl, 2,2,3,3,4,4 , 4-heptafluorobutyl, perfluorobutyl, nonafluoro -tert- butyl, IH, 1H-nonafluorobutyl pentyl, perfluoro pentyl, IH, 1H-tridecafluorohexyl, perfluorohexyl, IH, 1H-pentadecafluorooctyl , perfluorooctyl, group).

The alkenyl group of the R1 ~ 2-18 carbon atoms in R8, vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl 2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-2 - butenyl, 3-methyl-2-butenyl, 1,2-dimethyl-1-propenyl, 1-decenyl, 2-decenyl, 8-decenyl, 1-dodecenyl, 2-dodecenyl, straight-chain or branched, such as 10-dodecenyl Jo are mentioned.

The alkynyl group of the R1 ~ 2-18 carbon atoms in R8, and the alkynyl group having 2 to 18 carbon atoms, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1 - methyl-2-propynyl, 1-Bae Nchiniru, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1,2-dimethyl-2-propynyl, 1-decynyl, 2-decynyl, 8- decynyl, 1-dodecynyl, 2-dodecynyl, 10-dodecynyl include those straight or branched, such as.

The aryl group of the R1 ~ having 6 to 18 carbon atoms R8, phenyl, tolyl, dimethylphenyl, naphthyl, anthracenyl, biphenyl and pentafluorophenyl and the like.

The silyl group of the R1 ~ R8, for example, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl silyl group, triethylsilyl group, i- propyl dimethylsilyl group, methyldi -i- propyl silyl group, tri -i- propyl silyl group, tert- butyldimethylsilyl group, methyldi -tert- butylsilyl group, tri -tert- butylsilyl group, phenyldimethylsilyl group, a methyl diphenyl silyl group, tricaprate ascorbyl silyl groups such as triphenylsilyl group.

Examples of the amino group of R1 ~ R8, substituted amino group (methylamino amino group (--NH2) and having 1 to 15 carbon atoms, dimethylamino, ethylamino, methylethylamino, diethylamino, n- propylamino, methyl -n - propylamino, ethyl -n- propylamino, n- propylamino, isopropylamino, isopropyl methyl amino, isopropyl ethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n- propyl phenylamino and isopropyl-phenylamino, etc.) and the like.

The alkoxy group represented by R 11 O-of R1 ~ R8, straight or branched alkoxy group having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- butoxy, tert - butoxy, hexyloxy, decyloxy, dodecyloxy and octadecyloxy etc.) or the like, a linear or branched fluoroalkyl group (trifluoromethyl having 1 to 18 carbon atoms, 2,2-difluoroethyl, 2,2,2 fluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoro-propyl, 1,1,1,3,3,3-hexafluoro-2 propyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluoro-butyl, perfluoro Chill, nonafluoro -tert- butyl, IH, 1H-nonafluorobutyl pentyl, perfluoro pentyl, IH, 1H-tridecafluorohexyl, perfluorohexyl, IH, 1H-pentadecafluorooctyl, perfluorooctyl, group), etc. They include alkoxy groups of. The aryloxy group is phenoxy, naphthoxy, Antorokishi, pentafluorophenyloxy, 3-trifluoromethylphenyl oxy, 3,5-bis-trifluoromethylphenyl oxy, and the like.

Examples of the alkylthio group represented R1 ~ at R 12 S- of R8, straight or branched chain alkylthio group (methylthio having 1 to 18 carbon atoms, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec- butylthio, tert- butylthio, pentylthio, isopentylthio, neopentylthio, tert- pentylthio, octylthio, decylthio, it includes dodecylthio and iso-octadecyl thio, etc.) and the like. The arylthio group, an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2 - bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenyl-thio, 4-hydroxyphenyl-thio, 2-methoxy phenylthio, 4-methoxyphenyl-thio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl ] phenylthio, 4- Phenylthio) phenylthio, 4-benzoyl phenyl thio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenyl-thio, 4-benzoyl-2-methylthiophenyl thio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethyl-benzoyl) phenylthio 4- (p-isopropyl-benzoyl) phenylthio and 4- ( p-tert-butyl-benzoyl) phenylthio etc.) and the like.

The sulfinyl group represented by R 13 SO- said R1 ~ R8, linear or branched sulfinyl group having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propyl sulfinyl, isopropyl sulfinyl, butylsulfinyl, iso-butylsulfinyl, sec- butylsulfinyl, tert- butylsulfinyl, pentylsulfamoyl nyl, iso pentylsulfamoyl alkylsulfinyl, neo pentylsulfamoyl sulfinyl, tert- pentylsulfamoyl alkylsulfinyl, octyl sulfinyl and iso-octadecyl-sulfinyl, etc.), an arylsulfinyl group having 6 to 10 carbon atoms (phenylsulfinyl, tolyl sulfinyl and naphthylsulfinyl etc.) and the like.

Wherein R1 R 14 SO 2 of ~ R8 - The sulfonyl group represented by a straight chain or branched chain alkylsulfonyl group (methylsulfonyl having 1 to 18 carbon atoms, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, iso sulfonyl, sec- butylsulfonyl, tert- butylsulfonyl, pentylsulfonyl, isopentyl sulfonyl, neopentyl sulfonyl, tert- pentyl sulfonyl, octylsulfonyl and octadecylsulfonylamino etc.), an arylsulfonyl group {phenylsulfonyl having 6 to 10 carbon atoms, tolyl sulfonyl (tosyl) and naphthylsulfonyl and the like}.

The alkyl group represented by R 15 CO- said R1 ~ R8, carbon atoms (including the carbonyl carbon) linear or branched alkyl group (acetyl 2-18, propionyl, butanoyl, 2-methyl-propionyl , heptanoyl, 2-methyl butanoyl, 3-methylbutanoyl, octanoyl, decanoyl, include dodecanoyl and octadecanoyl, etc.) and the like. The arylcarbonyl group, and an aryl group of 7-11 (including the carbonyl carbon) carbon atoms (such as benzoyl and naphthoyl).

Examples of the carbonyl group represented by R 16 COO- of R1 ~ R8, linear or branched acyloxy groups (acetoxy having 2 to 19 carbon atoms, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, butylcarbonyloxy , isobutyl carbonyloxy, sec- butylcarbonyloxy, tert- butylcarbonyloxy, hexyl carbonyloxy, 2-ethylhexyl carbonyloxy, octylcarbonyloxy, tetradecyl carbonyloxy and octadecyl carbonyloxy, etc.), etc., an aryl having 6 to 18 carbon atoms carbonyl group (benzoyloxy, naphthoyloxy, pentafluoro benzoyloxy etc.) and the like, a linear or branched fluoroalkyl group (trifluoromethyl having 1 to 8 carbon atoms , 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoro-propyl, 1, 1,1,3,3,3-hexafluoro-2-propyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluoro-butyl, perfluorobutyl, nonafluoro -tert- butyl, 1H , 1H-nonafluorobutyl pentyl, perfluoro pentyl, IH, 1H-tridecafluorohexyl, perfluorohexyl, IH, 1H-pentadecafluorooctyl, perfluorooctyl, and the like carbonyloxy group group).

The oxycarbonyl group represented by R 17 OCO- said R1 ~ R8, straight or branched chain alkoxycarbonyl group (methoxycarbonyl 2-19 (including the carbonyl carbon) carbon atoms, ethoxycarbonyl, propoxycarbonyl, iso propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec- butoxycarbonyl, tert- butoxycarbonyl, Ok Ciro alkoxycarbonyl, tetradecyloxy carbonyl and octadecenyl siloxy carbonyl, etc.), including the number of carbon atoms (the carbonyl carbon) of 7-11 aryloxy etc. carbonyl group (phenoxycarbonyl and naphthoxycarbonyl, etc.).

Wherein R1 The R 18 carbonate group represented by -OCOO- R 18 of ~ R8, straight-chain alkyl groups (methyl of 1 to 18 carbon atoms, ethyl, n- propyl, n- butyl, n- pentyl, n- octyl , n- decyl, n- dodecyl, n- tetradecyl, n- hexadecyl and n- octadecyl), branched-chain alkyl group having 1 to 18 carbon atoms (isopropyl, isobutyl, sec- butyl, tert- butyl, isopentyl, neopentyl , tert- pentyl, isohexyl and isooctadecyl), and cycloalkyl groups (cyclopropyl 3 to 18 carbon atoms, cyclobutyl, cyclopentyl, cyclohexyl and 4-decyl cyclohexyl), linear or branched fluoro having 1 to 8 carbon atoms alkyl groups (trifluoromethyl, 2,2 Jifuruoroe Le, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoro-propyl, 1, 1, 1, 3,3-hexafluoro-2-propyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluoro-butyl, perfluorobutyl, nonafluoro -tert- butyl, IH, 1H-nonafluorobutyl pentyl , perfluoro pentyl, IH, 1H-tridecafluorohexyl, perfluorohexyl, IH, 1H-pentadecafluorooctyl, perfluorooctyl, groups, etc.) and the like.

Wherein R1 The R 19 of the urethane group represented by R 19 NHCOO- of ~ R8, straight-chain alkyl groups (methyl of 1 to 18 carbon atoms, ethyl, n- propyl, n- butyl, n- pentyl, n- octyl , n- decyl, n- dodecyl, n- tetradecyl, n- hexadecyl and n- octadecyl), branched-chain alkyl group having 1 to 18 carbon atoms (isopropyl, isobutyl, sec- butyl, tert- butyl, isopentyl, neopentyl , tert- pentyl, isohexyl and isooctadecyl), and cycloalkyl groups (cyclopropyl 3 to 18 carbon atoms, cyclobutyl, cyclopentyl, cyclohexyl and 4-decyl cyclohexyl), linear or branched fluoro having 1 to 8 carbon atoms alkyl groups (trifluoromethyl, 2,2-difluoro-ethyl , 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoro-propyl, 1,1,1,3,3 , 3-hexafluoro-2-propyl, heptafluoropropyl, 2,2,3,3,4,4,4-heptafluoro-butyl, perfluorobutyl, nonafluoro -tert- butyl, IH, 1H-nonafluorobutyl pentyl, perfluoropentyl, IH, 1H-tridecafluorohexyl, perfluorohexyl, IH, 1H-pentadecafluorooctyl, perfluorooctyl, groups, etc.) and the like.

The fluoroalkyl group having 1 to 18 carbon atoms alkyl or C 1 -C 18, alkenyl groups having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a silyl group , alkoxy or aryloxy group represented by R 11 O-, alkylthio group or arylthio group represented by R 12 S-, a sulfinyl group represented by R 13 SO-, R 14 SO 2 - sulfonyl group represented by, R alkylcarbonyl group or an arylcarbonyl group represented by 15 CO-, carbonyloxy group represented by R 16 COO-, oxycarbonyl group represented by R 17 OCO-, carbonate group represented by R 18 OCOO-, R 19 NHCOO- urethane groups represented in the substituted (T) Good.

The substituent (T), for example, an alkyl group, hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, arylthio group, an acyloxy group, an arylthio group, an alkylthio group, aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, and arylsulfonyl group and a halogen atom. Substituents (T) is may be one, or two or more kinds.

At least two of said R1 ~ R8 is linked together, they may form a ring structure. When they form a ring structure, two meeting adjacent preferable to form an aromatic ring. The ring may contain a hetero atom, an oxo group. And it may have further substituent (T).

Suitable imide sulfonate represented by the formula (1), R1 all hydrogen atoms of ~ R8 or, in at least any one is independent of R1 ~ R8, halogen atom, alkyl group or carbon number of 1 to 18 carbon atoms fluoroalkyl group of 1 to 18, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a hydroxyl group, a carboxyl group, or an alkoxy group represented by R 11 O- an aryloxy group, R 15 CO- alkyl group or aryl group represented by, carbonyloxy group represented by R 16 COO-, oxycarbonyl group represented by R 17 OCO-, or at least 2 of said R1 ~ R8 one is bound to one another, is preferably one but two meet next forming the aromatic ring.

Still preferably imide sulfonates having the formula (1), all of R1 ~ R8 is hydrogen atom or at least one two of the same functional group R1 ~ R8, its functional group, a halogen atom, the number of carbon atoms 1-18 alkyl group or a fluoroalkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a hydroxyl group, a carboxyl radical, R 11 alkoxy group or aryloxy group represented by O-, alkylcarbonyl group or an arylcarbonyl group represented by R 15 CO-, carbonyloxy group represented by R 16 COO-, oxycarbonyl group represented by R 17 OCO- some, or, wherein at least 2 of R1 ~ R8 is linked together, next to meet 2 TsugaKaoru Those which form a ring.

By ultraviolet irradiation is an essential functional group for decomposing the sulphonic acid ester moiety R9, a part or all of hydrocarbon radicals (hydrogen Good 1-18 carbon atoms which may have a substituent is substituted by fluorine it is that may be). Examples of the substituent, those exemplified as the substituents (T) can be used. Examples of the hydrocarbon group having 1 to 18 carbon atoms, an alkyl group, an aryl group and heterocyclic hydrocarbon group.

As the alkyl group, straight-chain alkyl groups (methyl of 1 to 18 carbon atoms, ethyl, n- propyl, n- butyl, n- pentyl, n- octyl, n- decyl, n- dodecyl, n- tetradecyl, n- hexadecyl and n- octadecyl), branched-chain alkyl groups (isopropyl having 1 to 18 carbon atoms, isobutyl, sec- butyl, tert- butyl, isopentyl, neopentyl, tert- pentyl, isohexyl and isooctadecyl), and 3 carbon atoms cycloalkyl group and 18 (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 4-decyl cyclohexyl, 10-camphorsulfonic yl, etc.), and the like.

The aryl group, an aryl group having 6 to 10 carbon atoms (phenyl, tolyl, dimethylphenyl, naphthyl, and pentafluorophenyl and the like) and the like.

The heterocyclic hydrocarbon group, a heterocyclic hydrocarbon group (thienyl having 4 to 18 carbon atoms, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl , quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, Kisantoniru include Chiokisantoniru and dibenzofuranyl, etc.) and the like.

The group partially or entirely substituted with fluorine hydrogen hydrocarbon group may having 1 to 18 carbon atoms which may have a substituent, and an electron-withdrawing large CxFy.
Electron-withdrawing large CxFy is a functional group consisting of carbon atoms 1 ~ 8 (x = 1 ~ 8), and fluorine atoms 3 ~ 17 (y = 3 ~ 17).
If it is 1 or more carbon atoms are readily synthesized in strong acid, excellent heat stability if 8 or less. If the number of fluorine atoms is 3 or more can act as a strong acid, it is easy to synthesize the strong acid if 17 or less.
CxFy in nonionic acid generator (A) may be used alone or in combination of two or more thereof.

The CxFy, a hydrogen atom straight chain alkyl group substituted with a fluorine atom (RF1), branched-chain alkyl group (RF2), a cycloalkyl group (RF3), and the like aryl group (RF4).

The linear alkyl group in which a hydrogen atom is substituted with a fluorine atom (RF1), for example, a trifluoromethyl group (x = 1, y = 3), a pentafluoroethyl group (x = 2, y = 5), nona fluoro butyl group (x = 4, y = 9), perfluorohexyl group (x = 6, y = 13), and perfluorooctyl group (x = 8, y = 17), and the like.

The branched-chain alkyl group in which hydrogen atoms are substituted with fluorine atom (RF2), for example, perfluoro isopropyl group (x = 3, y = 7), perfluoro -tert- butyl group (x = 4, y = 9 ), and perfluoro-2-ethylhexyl group (x = 8, y = 17), and the like.

The cycloalkyl group in which hydrogen atoms are substituted with fluorine atom (RF3), for example, perfluoro cyclobutyl group (x = 4, y = 7), perfluorocyclopentyl group (x = 5, y = 9), par fluorocyclohexyl group (x = 6, y = 11), and perfluoro (1-cyclohexyl) methyl (x = 7, y = 13), and the like.

The aryl group in which a hydrogen atom is substituted with a fluorine atom (RF4), for example, pentafluorophenyl group (x = 6, y = 5), and 3-trifluoromethyl-tetrafluorophenyl group (x = 7, y = 7), and the like.

Of R9, preferably greater CxFy electron-withdrawing, of CxFy, ease of availability, and in view of the decomposition of the sulfonic acid ester moiety, preferably a linear alkyl group (RF1), branched alkyl group (RF2), and an aryl group (RF4), more preferably a linear alkyl group (RF1), and an aryl group (RF4), particularly preferably trifluoromethyl group (x = 1, y = 3), pentafluoro ethyl group (x = 2, y = 5), heptafluoropropyl group (x = 3, y = 7), nonafluorobutyl group (x = 4, y = 9), and pentafluorophenyl group (x = 6, y = 5) is.

Preferred specific examples of the general formula (1) imide sulfonate compound represented by the ease of synthesis, absorption wavelength adjustment region, and heat but below the stability point of view but are not limited thereto.

Figure JPOXMLDOC01-appb-C000002

Figure JPOXMLDOC01-appb-C000003

Figure JPOXMLDOC01-appb-C000004

Figure JPOXMLDOC01-appb-C000005

Figure JPOXMLDOC01-appb-C000006

Figure JPOXMLDOC01-appb-C000007

The method of synthesizing the imide sulfonate compounds of the present invention is not particularly limited as long synthesize the desired product, for example, the precursor N- hydroxy imide compound (P1) (R9-SO 2 ) sulfonic acid anhydride represented by 2 O possible synthesis reaction, or by reaction with a salt and R9-SO 2 Cl sulfonic acid chloride represented the N- hydroxy imide compound (P1) of the object.

Nonionic photoacid generator (A) of the present invention containing the imide sulfonate compounds.
Nonionic photoacid generator (A) of the present invention, in order to facilitate the dissolution of the resist material, may be previously dissolved in a solvent which does not inhibit the advance reaction.

As the solvent, carbonate (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate); esters (ethyl acetate, ethyl lactate, beta-propiolactone, beta-butyrolactone, .gamma.-butyrolactone, [delta] - valerolactone and ε- caprolactone, etc.), ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether); and ether esters ( ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Fine diethylene glycol monobutyl ether acetate, etc.) and the like.

When a solvent is used, the proportion of the solvent, relative to 100 parts by weight of nonionic photoacid generator of the present invention is preferably 15 to 1,000 parts by weight, more preferably 30 to 500 parts by weight.

Photolithographic resin composition of the present invention (Q) is because it contains non-ionic photoacid generators of the (A) as an essential component, by performing UV irradiation and post-exposure heating (PEB), exposed and unexposed the difference in solubility arrive in the developing solution parts. Nonionic photoacid generators (A) may be used in combination singly, or two or more.
The photolithographic resin composition (Q), a mixture of negative-type chemically amplified resin (QN) and nonionic photoacid generators and (A); and a chemically amplified positive resin (QP) and non-ionic photoacid mixture of generator (a).

The negative-type chemically amplified resin (QN), composed of a phenolic hydroxyl group-containing resin (QN1) and the crosslinking agent (QN2).

The phenolic hydroxyl group-containing resin (QN1) is not particularly limited as long as it is a resin containing a phenolic hydroxyl group, for example, novolak resin, polyhydroxystyrene, copolymer of hydroxystyrene, co-hydroxy styrene and styrene heavy coalescence, hydroxystyrene, copolymers of styrene and (meth) acrylic acid derivatives, phenol - xylylene glycol condensation resin, a cresol - xylylene glycol condensation resin, a polyimide containing a phenolic hydroxyl group, polyamic acid containing a phenolic hydroxyl group phenol - dicyclopentadiene condensation resin or the like is used. Among these, a novolac resin, polyhydroxystyrene, copolymer of polyhydroxystyrene, a copolymer of hydroxystyrene and styrene, hydroxystyrene, copolymers of styrene and (meth) acrylic acid derivatives, phenol - xylylene glycol condensation resin is preferable. Incidentally, these phenolic hydroxyl group-containing resin (QN1) may be used singly or may be used in combination of two or more.

The above novolak resins may, for example, a phenol and an aldehyde can be obtained by condensing in the presence of a catalyst.
Examples of the phenols include phenol, o- cresol, m- cresol, p- cresol, o- ethylphenol, m- ethylphenol, p- ethylphenol, o- butylphenol, m- butylphenol, p- butylphenol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5 trimethylphenol, catechol, resorcinol, pyrogallol, alpha-naphthol, beta-naphthol.
Further, examples of the aldehyde formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

Specific novolak resins, such as phenol / formaldehyde condensation novolak resin, a cresol / formaldehyde novolac resins, phenol - naphthol / formaldehyde condensate novolak resins.

Moreover, the above phenolic hydroxyl group-containing resin (QN1) is low molecular weight phenolic compounds may be included as part of the component.
Examples of the low molecular weight phenolic compounds, e.g., 4,4'-dihydroxydiphenyl methane, 4,4'-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- phenyl ethane, tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1 - methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4 - [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane, 1,1,2,2-tetra (4-hydroxy Phenyl) ethane, 4,4 '- {1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene} bisphenol and the like. These low molecular weight phenolic compounds may be used singly or may be used in combination of two or more.

The content of phenolic hydroxyl group-containing resin (QN1) in the low molecular weight phenolic compounds, when a phenolic hydroxyl group-containing resin (QN1) and 100 wt%, preferably 40 wt% or less, more preferably 1 to 30% by weight.

The weight average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is the resolution of the obtained insulating film, thermal shock resistance, heat resistance, from the viewpoint of film residual rate, preferably 2,000 or more, more preferably 2000 it is about to 20000.
Further, it the content of the phenolic hydroxyl group-containing resin (QN1) in the negative-type chemically amplified resin (QN) is, when the entire composition excluding the solvent is 100% by weight, 30 to 90 wt% by weight, more preferably 40 to 80 wt%. If the proportion of the phenolic hydroxyl group-containing resin (QN1) is 30 to 90 wt%, the film formed using the photosensitive insulating resin composition has a sufficient developability with an aqueous alkali solution for preferred.

As the crosslinking agent (QN2), not particularly limited as long as it is a compound capable of crosslinking the phenolic hydroxyl group-containing resin (QN1) by strong acid generated from the non-ionic photoacid generators (A).

As the crosslinking agent (QN2), for example, bisphenol A type epoxy compound, bisphenol F epoxy compounds, bisphenol S-based epoxy compounds, novolak resin-based epoxy compounds, resol resin-based epoxy compounds, poly (hydroxystyrene) epoxy compound, oxetane compounds, methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenol compounds, alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group containing phenol compound, carboxymethyl group-containing melamine resins, carboxymethyl group-containing benzoguanamine resins, carboxymethyl group-containing urea Fat, carboxymethyl group-containing phenol resin, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, mention may be made of carboxymethyl group-containing urea compounds and carboxymethyl group-containing phenol compounds and the like.

Of these crosslinking agents (QN2), methylol group-containing phenol compound, methoxymethyl group-containing melamine compounds, methoxymethyl group-containing phenol compound, methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds and acetoxymethyl group-containing phenol compound it is preferred, more preferably a methoxymethyl group-containing melamine compounds (e.g., hexamethoxymethylmelamine, etc.), methoxymethyl group-containing glycoluril compounds and methoxymethyl group-containing urea compounds. Methoxymethyl group-containing melamine compounds, CYMEL300, CYMEL301, CYMEL303, CYMEL305 the trade names such as (Mitsui Cyanamid Co., Ltd.), methoxymethyl group-containing glycoluril compound CYMEL1174 (manufactured by Mitsui Cyanamid Co.) trade names such as in and methoxymethyl group-containing urea compounds are commercially available under the trade names of MX290 (manufactured by Sanwa Chemical Co.).

The content of the crosslinking agent (QN2), a reduction in residual film rate, in terms of meandering and swelling and development of the pattern, the total acidic functional groups in the phenolic hydroxyl group-containing resin (QN1), usually, 5 - 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%.

The chemically amplified positive resin (QP), a part of the phenolic hydroxyl group, a hydrogen atom of a carboxyl group, or an acidic functional group of the alkali-soluble resin (QP1) containing 1 or more acidic functional groups such as sulfonyl group or all, protecting group introduction resins substituted with an acid dissociable group (QP2) and the like.
Incidentally, the acid-dissociable group is a group capable of dissociating in the presence of a strong acid generated from the non-ionic photoacid generators (A).
Protecting group introducing resin (QP2) as per se is insoluble or scarcely soluble in alkali.

The alkali-soluble resin (QP1), for example, a phenolic hydroxyl group-containing resin (QP11), carboxyl group-containing resin (QP12), and sulfonic acid group-containing resin (QP13) and the like.
The phenolic hydroxyl group-containing resin (QP11), the same thing can be used as the phenolic hydroxyl group-containing resin (QN1).

Examples of the carboxyl group-containing resin (QP12), not particularly limited as long as the polymer der having a carboxyl group, for example, vinyl polymer and a carboxyl group-containing vinyl monomers (Ba), and a hydrophobic group-containing vinyl monomer (Bb) if necessary obtained by.

Examples of the carboxyl group-containing vinyl monomers (Ba), for example, unsaturated monocarboxylic acid [(meth) acrylic acid, crotonic acid and cinnamic acid], unsaturated polyvalent (divalent to tetravalent) carboxylic acid [(anhydrous) maleic acid, itaconic acid, fumaric acid, and citraconic acid, (alkyl group having 1 to 10 carbon atoms) esters [maleic acid monoalkyl esters unsaturated polycarboxylic acid alkyl, such as fumaric acid monoalkyl ester and citraconic acid monoalkyl ester ], and their salts [alkali metal salts (sodium salts and potassium salts), alkaline earth metal salts (calcium salts and magnesium salts), amine salts and ammonium salts, etc.] and the like.
Preferred among these polymerizable and unsaturated monocarboxylic acids from the viewpoint of ease of availability, more preferred are (meth) acrylic acid.

The hydrophobic group-containing vinyl monomer (Bb), and (meth) acrylic acid ester (Bb1), and aromatic hydrocarbon monomer (Bb2) or the like.

(Meth) acrylic acid ester (Bb1), for example, alkyl having 1 to 20 carbon atoms alkyl (meth) acrylates [such as methyl (meth) acrylate, ethyl (meth) acrylate, n- propyl (meth) acrylate, isopropyl (meth) acrylate, n- butyl (meth) acrylate, n- hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, etc.] and alicyclic group-containing (meth) acrylate [dicyclopentanyl (meth) acrylate, Siji black pentenyl (meth) acrylate and isobornyl (meth) acrylate, etc.] and the like.

The aromatic hydrocarbon monomer (Bb2), for example, hydrocarbon monomers [for example, styrene having a styrene skeleton, alpha-methyl styrene, vinyl toluene, 2,4-dimethylstyrene, ethylstyrene, isopropyl styrene, butyl styrene, phenyl styrene and cyclohexyl styrene and benzyl styrene], and vinyl naphthalene.

At the carboxyl group-containing resin (QP12), charged monomer mole ratio of (Ba) / (Bb) is usually 10 to 100 / 0-90, from the viewpoint of developability, preferably from 10 to 80/20 to 90, more preferably it is a 25-85 / 15 to 75.

The sulfonic acid group-containing resin (QP13), is not particularly limited as long as it is a polymer having a sulfonic acid group, for example, a sulfonic acid group-containing vinyl monomer (Bc), and a hydrophobic group-containing vinyl monomer (Bb) if necessary obtained by vinyl polymerization.
The hydrophobic group-containing vinyl monomer (Bb), same as above can be used.

The sulfonic acid group-containing vinyl monomer (Bc), for example, vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, alpha-methyl styrene sulfonic acid, 2- (meth) acryloyl-2- methylpropane sulfonic acid and salts thereof. Alkali metal (sodium and potassium) salt as the salt, alkaline earth metal (calcium and magnesium) salts, primary to tertiary amine salts, such as ammonium salts and quaternary ammonium salts.

In sulfonic acid group-containing resin (QP13), charged monomer mole ratio of (Bc) / (Bb) is usually 10 to 100 / 0-90, from the viewpoint of developability, preferably from 10 to 80/20 to 90, more preferably is 25-85 / 15 to 75.

HLB value of the alkali-soluble resin (QP1) is the preferred range varies depending resin skeleton of the alkali-soluble resin (QP1), is preferably 4-19, more preferably 5-18, particularly preferably 6-17.
When the HLB value for development if 4 or more, the developing property is further improved, water resistance of the cured product if 19 or less is even better.

Incidentally, HLB in the present invention is a HLB value by Oda method, the hydrophilic - and that hydrophobic balance value can be calculated from the ratio of the organic values ​​and inorganic values ​​of organic compounds.
HLB ≒ 10 × inorganic / organic Moreover, the value of the inorganic values ​​and organic property, document "Synthesis and Application of Surfactants" (Maki Shoten, Oda, Teramura Author) 501 pages; or " new surfactant Getting Started "(Takehiko Fujimoto al., Sanyo Chemical Industries, issued Co., Ltd.) are described in detail in the 198 pages of.

The acid dissociable group for protecting groups introduced in the resin (QP2), for example, substituted methyl group, 1-substituted ethyl group, 1-branched alkyl group, silyl group, germyl group, alkoxycarbonyl group, acyl group and cyclic acid dissociable group can be given. These may be used singly, or may be used in combination of two or more.

The 1-substituted methyl group, e.g., methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, Metokishifena sill group, methylthio phenacyl group, alpha-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n- propoxycarbonylmethyl group, i- propoxycarbonyl methyl group, n- butoxycarbonyl methyl group, tert- Bed Alkoxycarbonylmethyl group, and the like.

The 1-substituted ethyl group, for example, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-ethoxypropyl, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-phenoxyethyl group, 1-benzyloxyethyl group, 1-benzyl-thio ethyl group, 1-cyclopropylethyl group, 1-phenylethyl, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonyl ethyl group , 1-isopropoxycarbonyl ethyl group, 1-n-butoxycarbonylethyl group, 1-tert Butoxycarbonyl ethyl group and the like.

The 1-branched alkyl group, for example, i- propyl group, sec- butyl group, tert- butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, there may be mentioned 1,1-dimethylbutyl group, etc. it can.

The silyl group such as trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl silyl group, triethylsilyl group, i- propyl dimethylsilyl group, methyldi -i- propyl silyl group, tri -i- propyl silyl group, tert- butyl butyldimethylsilyl group, methyldi -tert- butylsilyl group, tri -tert- butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, and a tricaprate ascorbyl silyl groups such as triphenylsilyl group.

The germyl group, for example, trimethylgermyl group, ethyldimethylgermyl germyl group, methyl diethyl germyl group, triethylsilyl germyl group, an isopropyl dimethyl germyl group, methyldi -i- propyl germyl group, tri -i- propyl gel mill group, tert- butyldimethyl germyl group, methyldi -tert- Buchirugerumiru group, tri -tert- Buchirugerumiru group, phenyl dimethyl germyl group, methyl diphenyl germyl group, a tricaprate ascorbyl germyl groups such as triphenyl germyl group it can be mentioned.

The alkoxycarbonyl group includes, for example, methoxycarbonyl group, ethoxycarbonyl group, i- propoxycarbonyl group, a tert- butoxycarbonyl group.

Examples of the acyl group include acetyl group, a propionyl group, a butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoyl group, sebacoyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, campholoyl group, benzoyl group , phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, Isonikochi Yl group, p- toluenesulfonyl group, and mesyl group.

The cyclic acid-dissociable group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, cyclohexenyl group, 4-methoxy cyclohexyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 3-bromo-tetrahydropyranyl group, 4-methoxy tetrahydropyranyl group, 4-methoxy tetrahydrothiopyranyl group, and a 3-tetrahydrothiophene-1,1-dioxide group.

Of these acid-dissociable group, tert- butyl group, a benzyl group, a 1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group, tert- butoxycarbonyl group, tert- butoxycarbonyl methyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, and tetrahydrothiofuranyl group, and the like are preferable.

Ratio of the number of acid-dissociable groups to the total number of the unprotected acidic functional groups and acid-dissociable group introduction rate {protecting group introducing resin (QP2) of the acid dissociable group for protecting group introducing resin (QP2) } it is not be specified in the flatly on the type of the alkali-soluble resin acid-dissociable group and the base is introduced, and preferably from 10 to 100%, more preferably 15 to 100%.

Polystyrene-reduced weight average molecular weight measured by gel permeation chromatography (GPC) of a protecting group introduced resin (QP2) (hereinafter. Referred to as "Mw") is preferably from 1,000 to 150,000, more preferably 3, it is 000 to 100,000.

Further, Mw polystyrene reduced number average molecular weight measured by gel permeation chromatography (GPC) of a protecting group introduced resin (QP2) (hereinafter, referred to as. "Mn") ratio of (Mw / Mn) is usually 1 to 10, preferably 1-5.

Photolithographic resin composition (Q) of the based on the weight of solids nonionic photoacid generator content of (A) is preferably 0.001 to 20 wt%, more preferably from 0.01 to 15 weight %, particularly preferably 0.05 to 7 wt%.
If 0.001% by weight or more sensitivity can be more satisfactorily exhibited to ultraviolet light, the physical properties of the insoluble portion can be better exerted against an alkali developer if 20 wt% or less.

Resists using photolithography resin composition (Q) of the present invention, for example, dissolved in a predetermined organic solvent (dispersion and when containing inorganic fine particles is dissolved) resin solution, spin coating, curtain coating, roll coating, spray coating, after application to the substrate using a screen printing or the like known method can be formed by drying the solvent by blowing heating or hot air.

As the organic solvent for dissolving photolithographic resin composition (Q), it can dissolve the resin composition, in particular as long as the resin solution can be adjusted to the applicable physical properties (viscosity, etc.) to spin coating Limited not. For example, N- methylpyrrolidone, N, N- dimethylformamide, dimethyl sulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, known solvents such as acetone and xylene There can be used.
Of these solvents, from the viewpoint of drying temperature, boiling point of 200 ° C. or less (toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, acetone and xylene) are preferred, it can also be used in alone or in combination of two or more kinds.
When using organic solvent, the amount of the solvent is not particularly limited, based on the weight of solids photolithographic resin composition (Q), is usually preferably 30 to 1,000% by weight, more preferably 40-900% by weight, particularly preferably 50-800% by weight.

Drying conditions of the resin solution after coating varies depending on the solvent to be used preferably is carried out in the range of 2 to 30 minutes at 50 ~ 200 ° C., photolithography resin composition after drying residual solvent amount of (Q) ( appropriately determined in% by weight), and the like.

After forming a resist on a substrate, it is irradiated with light of the wiring pattern. Then, after post-exposure heating (PEB), perform alkali development to form a wiring pattern.

As a method of light irradiation by actinic light through a photomask having a wiring pattern, a method can be cited for exposing the resist. As the active rays used for the irradiation is not particularly limited as long as it can decompose the nonionic photoacid generator in photolithography resin composition of the present invention (Q) (A).
As the active ray, a low-pressure mercury lamp, medium pressure mercury lamps, high pressure mercury lamp, ultra-high pressure mercury lamp, xenon lamp, metal halide lamp, an electron beam irradiation apparatus, X-rays irradiation device, laser (argon laser, a dye laser, nitrogen laser, LED, helium there is a cadmium laser, and the like), and the like. Of these, preferably a high pressure mercury lamp and ultra-high pressure mercury lamp.

The temperature of the post exposure baking (PEB), a normal 40 ~ 200 ° C., preferably 500 ~ 190 ° C., more preferably 60 ~ 180 ° C.. The deprotection reaction is less than 40 ° C., or the crosslinking reaction can not be sufficiently, can not be insufficient difference in solubility of the ultraviolet irradiation unit and the ultraviolet non-irradiation part pattern formation, problems productivity drops higher than 200 ° C. there is.
The heating time is a usually 0.5 to 120 minutes, preferably from 1 to 90 minutes, more preferably 2 to 90 minutes. Is less than 0.5 minutes is difficult to control the time and temperature, there is a problem of lowered productivity and larger 120 minutes.

As a method of alkali development, and a method of dissolving and removing the wiring pattern using an alkaline developer. As the alkali developing solution is not particularly limited as long as conditions that can differences in solubility of the ultraviolet irradiation unit and the ultraviolet non-irradiation part of the photolithographic resin composition (Q).
As the alkali developing solution an aqueous solution of sodium hydroxide, aqueous potassium hydroxide, sodium hydrogen carbonate and tetramethylammonium salt solution or the like.
The alkali developer may be added a water-soluble organic solvent. The water-soluble organic solvent, methanol, ethanol, isopropyl alcohol, tetrahydrofuran, N- methylpyrrolidone and the like.

As a developing method, dipping method using an alkaline developing solution, a shower method, and there is a spray system, who spray method is preferred.
The temperature of the developing solution is preferably used in 25 ~ 40 ° C.. Development time is appropriately determined according to the thickness of the resist.

Hereinafter, further illustrate the present invention through examples and comparative examples, the present invention is not limited thereto. Hereinafter, unless particularly specified, percentages are by weight%, the numbers represent weight ratios in parts.

Production Example 1
Synthesis diphenic anhydride N- hydroxy-2,2'-dicarboximide [Intermediate (1)] 11.2g (0.050mol), hydroxylamine hydrochloride 4.9 g (0.070 mol), pyridine (50mL the mixture) was stirred at 100 ° C. 10 hours. The reaction solution was poured into 1N hydrochloric acid After cooling to room temperature, the precipitate was collected by filtration to give the title compound Intermediate (1)] was obtained 20.5 g. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, DMSO-d6, δ (ppm): 11.7 (s, 1H), 8.5 (d, 1H), 8.3 (d, 1H), 8.2 (d, 1H), 7.9 (t, 1H), 7.6 (t, 1H), 7.4 (t, 1H), 7.3 (d, 1H), 7.2 (t, 1H)}

Production Example 2
N- hydroxy-4-methoxy-biphenyl-2,2'-dicarboximide [Intermediate (2) Synthesis of 20% aqueous sodium carbonate (65 g), dioxane (250 g) were mixed was placed in a reaction vessel, 1 hour nitrogen It was allowed to vent. To this solution, 2-bromo-5-methoxy toluene (24.5 g), 2-methylphenyl boronic acid (25 g), was added tetrakis (triphenylphosphine) palladium (1.4 g), under a nitrogen atmosphere with stirring in temperature was raised to 60 ° C., and allowed to react for 12 hours. After returning the reaction solution to room temperature, the reaction solution was added hydrogen chloride until acidic and extracted with methylene chloride. The extract was washed with water separation, was concentrated by an evaporator to give an orange solid (8.5 g). The resulting solid (5.0 g), was dissolved in pyridine (150 g), it was previously mixed in a separate reaction vessel, water (500 mL), potassium permanganate (37 g), sodium hydroxide (38 g) It was added dropwise over a period of 1 hour. Stirring was heated to 80 ° C. while the solids were removed by filtration after reacting for 2 hours. To the resulting filtrate, until acidic hydrogen chloride was added, the precipitate to have solid was collected and washed ethanol, with water. The resulting solid was dissolved in acetic anhydride (30 g), after reacting for 2 hours under reflux, it was evaporated acetic anhydride in the vacuum. Residue was dissolved by adding pyridine (10 g), further added hydroxylamine hydrochloride (4.9 g), and stirred at 100 ° C. 10 hours. The reaction solution was poured into 1N hydrochloric acid (300 mL) after cooling to room temperature, the precipitate was collected by filtration to give the title compound Intermediate (2)]. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, DMSO-d6, δ (ppm): 11.7 (s, 1H), 8.8 (s, 1H), 8.3 (d, 1H), 8.2 (d, 1H), 7.9 (t, 1H), 7.4 (t, 1H), 7.3 (d, 1H), 7.2 (t, 1H), 3.7 (s, 3H)}

Production Example 3
N- hydroxy-5,5'-difluoro-2,2'-dicarboximide [Intermediate (3)] Synthesis of 2-bromo-4-fluoro-benzoic acid methyl (5.6 g) N, N- dimethyl was dissolved in formamide (30 mL), copper powder (6.1 g) was added and reacted for 15 hours with stirring 130 ° C.. After cooling to room temperature, the solid was removed by filtration, water (20 mL), was added sodium hydroxide (15 g), and reacted for 3 hours at 60 ° C.. With stirring 1N hydrochloric acid (100 mL) in a beaker and the reaction solution was added, the it has been precipitated solid was collected by filtration. The resulting solid was dissolved in acetic anhydride (30 g), after reacting for 2 hours under reflux, it was evaporated acetic anhydride in the vacuum. Residue was dissolved by adding pyridine (10 g), further added hydroxylamine hydrochloride (4.9 g), and stirred at 100 ° C. 10 hours. The reaction solution was poured into 1N hydrochloric acid (300 mL) after cooling to room temperature, the precipitate was collected by filtration to give the title compound Intermediate (3)]. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, DMSO-d6, δ (ppm): 11.7 (s, 1H), 8.4-8.2 (m, 3H), 7.3 over 7.6 (m, 3H ), 19 F-NMR: 300MHz , DMSO-d6, δ (ppm), - 98 (m, 1F), - 114 (m, 1F)}

Production Example 4
N- hydroxy-4,4'-dimethyl-2,2'-dicarboximide [Intermediate (4) Synthesis of 2-bromo-4-fluorobenzoate (5.6 g) of 2-bromo -5 - was changed to methyl benzoate (5.7 g), in the same manner as in production example 3, to give the title compound intermediate (4)] and. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, DMSO-d6, δ (ppm): 11.7 (s, 1H), 8.3 (d, 1H), 8.2 (d, 1H), 8.1 (s, 1H), 7.6 (d, 1H), 7.1 (s, 1H), 7.0 (d, 1H), 2.5 (s, 3H), 2.4 (s, 3H)}

Production Example 5
N- hydroxy-6,6'-dimethyl-2,2'-dicarboximide [Intermediate (5)] Synthesis of 2-bromo-4-fluorobenzoate with (5.6 g) of 2-bromo -3 - was changed to methyl benzoate (5.7 g), in the same manner as in production example 3, the title compound was obtained [intermediate (5)]. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, DMSO-d6, δ (ppm): 11.7 (s, 1H), 8.1 (d, 1H), 7.7 (d, 1H), 7.5 (t, 1H), 7.3 (t, 1H), 7.1 (d, 1H), 7.0 (d, 1H), 2.4 (s, 3H), 2.3 (s, 3H)}

Production Example 6
N- hydroxy-4,4'-dimethoxy-2,2'-dicarboximide [Intermediate (6)] 2-bromo-5 Synthesis of 2-bromo-4-fluorobenzoate with (5.6 g) of - was changed to methyl-methoxybenzoic acid (5.9 g), in the same manner as in production example 3, the title compound was obtained [intermediate (6)]. The product 1 H-NMR was identified by {1 H-NMR: 300MHz, DMSO-d6, δ (ppm): 11.7 (s, 1H), 8.3 (d, 1H), 8.2 ( d, 1H), 7.6 (s, 1H), 7.4 (d, 1H), 6.9s, 1H), 6.8 (d, 1H), 3.9 (s, 3H), 3. 4 (s, 3H)}

Production Example 7
N- hydroxy-4,4'-dicarboxylate-2,2'-dicarboximide [Intermediate (7)] Synthesis of 2-bromo-4-fluorobenzoate (5.6 g) of 4-bromo isophthalic was changed to dimethyl (7.5 g), in the same manner as in production example 3, the title compound was obtained [intermediate (7)]. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, DMSO-d6, δ (ppm): 12.4 (s, 1H), 12.2 (s, 1H), 11.7 (s, 1H), 8.3 (d, 1H), 8.2 (d, 1H), 8.1 (s, 1H), 7.6 (d, 1H), 7.1 (s, 1H), 7.0 (d, 1H)}

Production Example 8
N- hydroxy-4,4 ', 5,5'-tetramethoxy-2,2'-dicarboximide [Intermediate (8) Synthesis of 2-bromo-4-fluorobenzoate (5.6 g) it was changed to 2-bromo-4,5-dimethoxybenzoic acid methyl (7.5 g), in the same manner as in production example 3, the title compound was obtained [intermediate (8)]. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, DMSO-d6, δ (ppm) 11.4 (s, 1H), 7.7 (s, 1H), 7.7 (s, 1H), 7.6 (s, 1H ), 6.8 (s, 1H), 4.1 (s, 3H), 3.9 (s, 3H), 3.8 (s, 3H), 3.7 (s, 3H)}

Production Example 9
N- hydroxy-1,1'-binaphthalene-2,2'-dicarboximide [Intermediate (9)] The synthesis of 2-bromo-4-fluorobenzoate (5.6 g) of 1-bromo-2- was changed to methyl naphthalene carboxylic acid (7.8 g), in the same manner as in production example 3, the title compound was obtained [intermediate (9)]. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, DMSO-d6, δ (ppm) 11.7 (s, 1H), 8.3-6.8 (m, 10H)}

Example 1
N- trifluoromethanesulfonyloxy-2,2'-dicarboximide [nonionic photoacid generator (A-1)] Synthesis of
Was dissolved in obtained in Production Example 1 [Intermediate (1)] (3.0g) in pyridine (20 ml), while stirring at 0 ° C., trifluoromethane sulfonic anhydride (12.3 g) was charged dropwise . After 8 hours of stirring at 25 ° C., the reaction mixture dichloromethane - After extraction with water, to give an orange oil by removing the solvent and the organic layer under reduced pressure. Furthermore I title compound which recrystallized from methanol [nonionic photoacid generator (A-1)] was obtained. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.6 (d , 1H), 8.5 (d, 1H), 8.2 (d, 1H), 8.0 (d, 1H) , 7.9 (t, 1H), 7.7-7.6 (m, 3H), 19 F-NMR: 300MHz, deuterochloroform, δ (ppm) -75 (s , 3F)}

Example 2
Obtained in Production Example 1 of N- trifluoromethanesulfonyloxy-4-methoxy-biphenyl-2,2'-dicarboximide [nonionic photoacid generator (A-1)] [Intermediate (1)] (3.0 g) was obtained in production example 2 was changed to intermediate (2)] (3.4g), in the same manner as in example 1, the title compound [nonionic photoacid generator (a-2)] was obtained. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.8 (s , 1H), 8.3 (d, 1H), 8.2 (d, 1H), 7.9 (t, 1H) , 7.4 (t, 1H), 7.3 (d, 1H), 7.2 (t, 1H), 3.7 (s, 3H), 19 F-NMR: 300MHz, deuterochloroform, [delta] (ppm ) -75 (s, 3F)}

Example 3
Obtained in Production Example 1 of N- trifluoromethanesulfonyloxy-5,5'-difluoro-2,2'-dicarboximide [nonionic photoacid generator (A-3)] [Intermediate ( 1)] (obtained in production example 3 to 3.0 g) [intermediate (3)] was changed to (3.5 g), in the same manner as in example 1, the title compound [nonionic light acid generator was obtained (a-3)]. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.3 (d , 1H), 8.1-8.0 (m, 3H), 7.6-7.5 (m, 2H), 19 F-NMR: 300MHz, deuterochloroform, δ (ppm) -75 (s , 3F), - 98 (m, 1F), - 114 (m, 1F)}

Example 4
Obtained in Production Example 1 of N- trifluoromethanesulfonyloxy-4,4'-dimethyl-2,2'-dicarboximide [nonionic photoacid generator (A-4)] [Intermediate ( 1)] (a 3.0 g) obtained in production example 4 [intermediate (4)] was changed to (3.4 g), in the same manner as in example 1, the title compound [nonionic light acid generator was obtained (a-4)]. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.4 (d , 1H), 8.3 (d, 1H), 7.9 (s, 1H), 7.8 (s, 1H) , 7.7 (d, 1H), 7.5 (s, 1H), 2.6 (s, 3H), 2.5 (s, 3H), 19 F-NMR: 300MHz, deuterochloroform, [delta] (ppm ) -75 (s, 3F)}

Example 5
Obtained in Production Example 1 of N- trifluoromethanesulfonyloxy-6,6'-dimethyl-2,2'-dicarboximide [nonionic photoacid generator (A-5)] [Intermediate ( 1)] (a 3.0 g) obtained in production example 5 [intermediate (5)] was changed to (3.4 g), in the same manner as in example 1, the title compound [nonionic light acid generator (a-5)] was obtained. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.1 (d , 1H), 7.7 (d, 1H), 7.5 (t, 1H), 7.3 (t, 1H) , 7.1 (d, 1H), 7.0 (d, 1H), 2.6 (s, 3H), 2.5 (s, 3H), 19 F-NMR: 300MHz, deuterochloroform, [delta] (ppm ) -75 (s, 3F)}

Example 6
Obtained in Production Example 1 of N- trifluoromethanesulfonyloxy-4,4'-dimethoxy-2,2'-dicarboximide [nonionic photoacid generator (A-6)] [Intermediate ( 1)] (obtained in production example 6 3.0 g) [intermediate (6)] was changed to (3.8 g), in the same manner as in example 1, the title compound [nonionic light acid generator (a-6)] was obtained. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.4 (d , 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.4 (d, 1H) , 7.3s, 1H), 7.2 ( d, 1H), 4.0 (s, 3H), 3.9 (s, 3H), 19 F-NMR: 300MHz, deuterochloroform, δ (ppm) - 75 (s, 3F)}

Example 7
Obtained in Production Example 1 of N- trifluoromethanesulfonyloxy-4,4'-carboxymethyl-2,2'-dicarboximide [nonionic photoacid generator (A-7)] [Intermediate (1)] obtained in production example 7 (3.0 g) [intermediate (7)] was changed to (4.1 g), in the same manner as in example 1, the title compound [nonionic give photoacid generator (a-7)]. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 12.7 (s , 1H), 12.4 (s, 1H), 8.3 (d, 1H), 8.2 (d, 1H) , 8.1 (s, 1H), 7.6 (d, 1H), 7.1 (s, 1H), 7.0 (d, 1H), 19 F-NMR: 300MHz, deuterochloroform, [delta] (ppm ) -75 (s, 3F)}

Example 8
N- trifluoromethanesulfonyloxy-4,4 ', obtained in Preparation 1 5,5'-tetramethoxy-2,2'-dicarboximide [nonionic photoacid generator (A-8)] obtained except for changing into the intermediate (1)] obtained in production example 8 (3.0 g) [intermediate (8)] (3.8 g), in the same manner as in example 1, the title compound [nonionic photoacid generator (a-8)] was obtained. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 7.6 (s , 1H), 7.5 (s, 1H), 7.4 (s, 1H), 7.3 (s, 1H) , 4.2 (s, sH), 4.1 (s, 3H), 4.0 (s, 3H), 3.9 (s, 3H), 19 F-NMR: 300MHz, deuterochloroform, [delta] (ppm ) -75 (s, 3F)}

Example 9
N- obtained in Production Example 1 of trifluoromethanesulfonyloxy-1,1'-binaphthalene-2,2'-dicarboximide [nonionic photoacid generator (A-9)] [Intermediate (1 )] (obtained in production example 9 3.0 g) [intermediate (9)] was changed to (4.3 g), in the same manner as in example 1, the title compound [nonionic photoacid was obtained generator (a-9)]. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.3-6.8 (m , 10H), 19 F-NMR: 300MHz, deuterochloroform, δ (ppm) -75 (s , 3F)}

Example 10
Obtained in Synthesis Example 7 N- trifluoromethanesulfonyloxy-4,4'-carbonyl-oxy-methyl-2,2'-dicarboximide [nonionic photoacid generator (A-10)] [ nonionic photoacid generator (a-7)] (4.6g), was dissolved in thionyl chloride (30 g), was allowed to react for one hour at 60 ° C., and the vacuum at 60 ° C., generated with thionyl chloride It was distilled off hydrogen chloride and. The residue was dissolved in acetonitrile (15 mL), methanol was added to (2.5 g), while cooling in an ice bath, was added dropwise over 30 min pyridine (2.3 g), 3 at room temperature (25 ° C.) It was time reaction. While stirring the water (150 mL) in a beaker and the reaction solution was poured, it precipitated white solid was separated by filtration has, washed, to give the title compound [nonionic photoacid generator (A-10)] to . The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.3 (d , 1H), 8.2 (d, 1H), 8.1 (s, 1H), 7.6 (d, 1H) , 7.1 (s, 1H), 7.0 (d, 1H), 2.5 (s, 3H), 2.4 (s, 3H), 19 F-NMR: 300MHz, deuterochloroform, [delta] (ppm ) -75 (s, 3F)}

Example 11
N- trifluoromethanesulfonyloxy-4,4'-dihydroxy-2,2'-dicarboximide [nonionic photoacid generator (A-11)] [Non-ionic obtained in Synthesis Example 6 photoacid generator (a-6)] (4.3g) was dissolved in dichloromethane (20 mL) under a nitrogen atmosphere and cooled to -78 ° C., added dropwise boron tribromide (12.5 g) with stirring and the reaction was allowed to proceed for 6 hours. The reaction solution was poured into saturated aqueous ammonium chloride solution (100 mL), then extracted with methylene chloride (50 mL), the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, the solvent was removed by an evaporator, the title compound [ to obtain a non-ionic photoacid generators (a-11)]. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.4 (d , 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.4 (d, 1H) , 7.3s, 1H), 7.2 ( d, 1H), 5.3 (s, 1H), 5.1 (s, 1H), 19 F-NMR: 300MHz, deuterochloroform, δ (ppm) - 75 (s, 3F)}

Example 12
Obtained in Synthesis Example 11 of N- trifluoromethanesulfonyloxy-4,4'-dibutyl acryloyloxy-2,2'-dicarboximide [nonionic photoacid generator (A-12)] [Non ionic photoacid generating agent (a-11)] (4.0g), was dissolved in acetonitrile (15 mL), added butyroyloxymethyl chloride (2.7 g), while cooling in an ice bath, pyridine (2.5g ) was added dropwise over 30 minutes and reacted for 3 hours at room temperature (25 ° C.). While stirring the water (150 mL) in a beaker and the reaction solution was poured, it precipitated white solid was separated by filtration has, washed, to give the title compound [nonionic photoacid generator (A-12)] to . The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.4 (d , 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.4 (d, 1H) , 7.3s, 1H), 7.2 (d, 1H), 2.4 (d, 2H), 1.7 (m, 2H), 1.2 (m, 2H), 0.9 (t, 3 H), 19 F-NMR : 300MHz, deuterochloroform, δ (ppm) -75 (s , 3F)}

Example 13
N- pentafluoro benzene sulfonyloxy-2,2'-dicarboximide [nonionic photoacid generator (A-13)] Synthesis of trifluoromethanesulfonic acid anhydride (12.3 g) and pentafluorobenzenesulfonyl chloride it was changed to (11.4 g), in the same manner as in example 1 to obtain the title compound [nonionic photoacid generator (a-13)] to. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.6 (d , 1H), 8.5 (d, 1H), 8.2 (d, 1H), 8.0 (d, 1H) , 7.9 (t, 1H), 7.7-7.6 (m, 3H), 19 F-NMR: 300MHz, deuterochloroform, δ (ppm) -125 (m , 2F), - 133 (m, 1F), - 151 (m, 2F)}

Example 14
N- pentafluoro benzene sulfonyloxy-6,6'-dimethyl-2,2'-dicarboximide [nonionic photoacid generator (A-14)] Synthesis of trifluoromethanesulfonic anhydride (12.3 g ) was changed to penta-fluorobenzenesulfonyl chloride (11.4 g) and, in the same manner as in example 5 to give the title compound [nonionic photoacid generator (a-14)] to. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.1 (d , 1H), 7.7 (d, 1H), 7.5 (t, 1H), 7.3 (t, 1H) , 7.1 (d, 1H), 7.0 (d, 1H), 2.6 (s, 3H), 2.5 (s, 3H), 19 F-NMR: 300MHz, deuterochloroform, [delta] (ppm ) -125 (m, 2F), - 133 (m, 1F), - 151 (m, 2F)}

Example 15
N- pentafluoro benzene sulfonyloxy-4,4'-dimethoxy-2,2'-dicarboximide [nonionic photoacid generator (A-15)] Synthesis of trifluoromethanesulfonic anhydride (12.3 g ) was changed to penta-fluorobenzenesulfonyl chloride (11.4 g) and, in the same manner as in example 6 to give the title compound [nonionic photoacid generator (a-15)] to. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.4 (d , 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.4 (d, 1H) , 7.3s, 1H), 7.2 ( d, 1H), 4.0 (s, 3H), 3.9 (s, 3H), 19 F-NMR: 300MHz, deuterochloroform, δ (ppm) - 125 (m, 2F), - 133 (m, 1F), - 151 (m, 2F)}

Example 16
N- pentafluoro benzene sulfonyloxy-4,4 ', 5,5'-tetramethoxy-2,2'-dicarboximide [nonionic photoacid generator (A-16)] Synthesis of trifluoromethanesulfonic acid except for changing anhydride (12.3 g) in pentafluorobenzenesulfonyl chloride (11.4 g), in the same manner as in example 8, the title compound [nonionic photoacid generator (a-16)] to Obtained. The product was identified by 1 H-NMR, 19 F- NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 7.6 (s , 1H), 7.5 (s, 1H), 7.4 (s, 1H), 7.3 (s, 1H) , 4.2 (s, sH), 4.1 (s, 3H), 4.0 (s, 3H), 3.9 (s, 3H), deuterated chloroform, δ (ppm) -125 (m, 2F ), - 133 (m, 1F), - 151 (m, 2F)}

Example 17
N - (+) - 10- camphorsulfonic sulfonyloxy - 2,2'-dicarboximide [nonionic photoacid generator (A-17)] Synthesis of trifluoromethanesulfonic acid anhydride of (12.3 g) (+) - 10 was changed to camphor sulphonyl chloride (11.0 g), in the same manner as in example 1 to obtain the title compound [nonionic photoacid generator (a-17)] to. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) {1 H -NMR: 300MHz, deuterochloroform, δ (ppm) 8.6 (d , 1H), 8.5 (d, 1H), 8. 2 (d, 1H), 8.0 (d, 1H), 7.9 (t, 1H), 7.7-7.6 (m, 3H), 3.0 (d, 1H), 2.5 (m, 2H), 2.3 (m, 1H), 1.9-1.7 (m, 3H), 1.4-1.2 (m, 2H), 1.0 (s, 3H), 0.8 (s, 3H)}

Example 18
N - (+) - 10- camphorsulfonic sulfonyloxy 6,6'-dimethyl-2,2'-dicarboximide [nonionic photoacid generator (A-18)] Synthesis of trifluoromethanesulfonic anhydride the (12.3g) (+) - except for changing 10 to camphor sulphonyl chloride (11.0 g), in the same manner as in example 5, the title compound [nonionic photoacid generator (a-18) ] was obtained. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.1 (d , 1H), 7.7 (d, 1H), 7.5 (t, 1H), 7.3 (t, 1H) , 7.1 (d, 1H), 7.0 (d, 1H), 3.0 (d, 1H), 2.6 (s, 3H), 2.5 (s, 3H), 2.5 ( m, 2H), 2.3 (m, 1H), 1.9-1.7 (m, 3H), 1.4-1.2 (m, 2H), 1.0 (s, 3H), 0 .8 (s, 3H)}

Example 19
N - (+) - 10- camphorsulfonic sulfonyloxy-4,4'-dimethoxy-2,2'-dicarboximide [nonionic photoacid generator (A-19)] Synthesis of trifluoromethanesulfonic anhydride the (12.3g) (+) - except for changing 10 to camphor sulphonyl chloride (11.0 g), in the same manner as in example 6, the title compound [nonionic photoacid generator (a-19) ] was obtained. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 8.4 (d , 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.4 (d, 1H) , 7.3s, 1H), 7.2 (d, 1H), 4.0 (s, 3H), 3.9 (s, 3H), 3.0 (d, 1H), 2.5 (m, 2H), 2.3 (m, 1H), 1.9-1.7 (m, 3H), 1.4-1.2 (m, 2H), 1.0 (s, 3H), 0.8 (s, 3H)}

Example 20
N - (+) - 10- camphorsulfonic sulfonyloxy-4,4 ', 5,5'-tetramethoxy-2,2'-dicarboximide [nonionic photoacid generator (A-20)] Synthesis of trifluoromethanesulfonic anhydride (12.3g) (+) - 10- was changed to camphor sulphonyl chloride (11.0 g), in the same manner as in example 8, the title compound [nonionic photoacid generator give agent (a-20)]. The product was identified by 1 H-NMR.{1 H-NMR: 300MHz, deuterochloroform, δ (ppm) 7.6 (s , 1H), 7.5 (s, 1H), 7.4 (s, 1H), 7.3 (s, 1H) , 4.2 (s, sH), 4.1 (s, 3H), 4.0 (s, 3H), 3.9 (s, 3H), 3.0 (d, 1H), 2.5 ( m, 2H), 2.3 (m, 1H), 1.9-1.7 (m, 3H), 1.4-1.2 (m, 2H), 1.0 (s, 3H), 0 .8 (s, 3H)}

Comparative Example 1
N- trifluoromethanesulfonyloxy-1,8-naphthalic acid imide [nonionic photoacid generator (A'-1)] Synthesis of

Figure JPOXMLDOC01-appb-C000008

Diphenic anhydride 11.2g of (0.050 mol), except for changing 1,8-naphthalic anhydride (3.0 g, 0.050 mmol) in, in the same manner as in Example 1, represented by the above formula that the title of the nonionic photoacid generator (A'-1) (3.5g, 0.010mol) was obtained.

Comparative Example 2
<Synthesis of ionic photoacid generators (A'-2)>

Figure JPOXMLDOC01-appb-C000009

Diphenyl sulfoxide (12.1 g), with stirring diphenylsulfide (9.3 g) and methanesulfonic acid (43.0 g), which was added dropwise acetic anhydride 7.9 (g), 5 hours at 40 ~ 50 ° C. after reaction, the reaction mixture was cooled to 25 ° C., was charged the reaction solution in fluoride methanesulfonic acid aqueous solution of potassium (121g), and stirred for 8 hours at 50 ° C., somewhat viscous yellow oil was precipitated. The oil was extracted with ethyl acetate, and the organic layer was washed several times with water, distilling off the solvent from the organic layer, was dissolved by adding toluene to the resulting residue, hexane was added, 10 ° C. in was allowed to stand and the mixture was stirred well for one hour. After 1 hour, the solution for separated into two layers, except for the upper layer by separation. The remaining lower layer Hexane was added, mixed well to the pale yellow crystals were precipitated at 25 ° C.. This was filtered off and dried under reduced pressure to obtain ionic photoacid generator represented by the above formula (A'-2).

Comparative Example 3
N- pentafluoro benzene sulfonyloxy-1,8-naphthalic acid imide [nonionic photoacid generator (A'-3)] Synthesis of trifluoromethanesulfonic anhydride (7.4 g, 26 mmol) and pentafluorobenzenesulfonyl chloride (6.9 g, 26 mmol) was changed to, in the same manner as in Comparative example 1, the title compound was obtained [nonionic photoacid generator (A'-3)].

Comparative Example 4
<Synthesis of ionic photoacid generators (A'-4)>
Trifluoperazine methanesulfonic acid aqueous potassium was changed to an aqueous solution of potassium pentafluorobenzenesulfonic acid, in the same manner as in Comparative Example 2, to give the ionic photoacid generator (A'-4).

Comparative Example 5
N - 10-camphor-sulfonyloxy-1,8-naphthalic acid imide [nonionic photoacid generator (A'-5)] Synthesis of trifluoromethanesulfonic anhydride (7.4g, 26mmol) - (+) (+) - obtained 10-camphor sulfonyl chloride (6.5 g, 26 mmol) was changed to, in the same manner as in Comparative example 1, the title compound [nonionic photoacid generator (A'-5)] the It was.

Comparative Example 6
<Synthesis of ionic photoacid generators (A'-6)>
Trifluoperazine methanesulfonic acid aqueous solution of potassium (+) - was changed to 10-camphorsulfonic acid aqueous solution of potassium in the same manner as in Comparative Example 2, to give the ionic photoacid generator (A'-6).

Figure JPOXMLDOC01-appb-T000001

<Performance Evaluation>
As the performance evaluation of the photoacid generator, the resulting non-ionic photoacid generators (A-1) ~ (A20), a non-ionic photoacid generator (A'-1), (A'-3), (A'-5), an ion-based acid generator (A'-2), (A'-4) and molar extinction coefficient of (A'-6), resist curing, thermal decomposition temperature, and solvent solubility, for amine resistance was evaluated by the following method.

<Molar extinction coefficient>
The synthesized photoacid generator was diluted to 0.25 mmol / L acetonitrile, UV-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-2550) with a 1cm cell length absorbance in the range from 200nm to 500nm It was measured. From the following equation was calculated i-line molar extinction coefficient (365nm) (ε 365).
ε 365 (L · mol -1 · cm -1) = A 365 /(0.00025mol/L×1cm)
Wherein, A 365 represents the 365nm absorbance. ]

<Resist-curing>
Phenolic resin (DIC Corp., "Phenolite TD431") 75 parts of a melamine curing agent (Mitsui Cyanamid Co., Ltd., "Cymel 300") 25 parts of synthesized photoacid generator 1 part, and propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA.) 200 parts of the resin solution was applied under the conditions of 10 seconds at 1000rpm using a spin coater 10cm each glass substrate. Then dried in vacuum for 5 minutes at 25 ° C., followed by drying for 3 minutes at 80 ° C. on a hot plate to form a resist having a thickness of about 3 [mu] m.
Ultraviolet to resist ultraviolet irradiation device (Oak Seisakusho, HMW-661F-01) using, L-34 with limited wavelengths by the filter (Co. Kenko Optical Co., filter cuts light below 340 nm) It exposed light to a predetermined amount over the entire surface. Incidentally integrated exposure amount was measured wavelength of 365 nm.
Then, after exposure for 10 minutes heating (PEB) was performed at fair wind dryer at 120 ° C., and developed by immersing for 30 seconds with 0.5% potassium hydroxide solution was performed immediately washed, and dried.
The film thickness of the resist shape measuring microscope (an ultradeep shape measuring microscope VK-8550, LTD Keyence) was used for the measurement.
From the lowest exposure amount change in film thickness before and after development the resist here is within 10%, the resist curability was evaluated by the following criteria.
○: minimum exposure amount 250 mJ / cm 2 or less △: Minimum exposure amount greater than 250mJ / cm 2, 500mJ / cm 2 or less ×: Minimum exposure amount is greater than 500 mJ / cm 2

<Thermal decomposition temperature>
Synthesized differential thermal-thermogravimetric simultaneous measurement apparatus photoacid generator was (SII Co., TG / DTA6200) using a nitrogen atmosphere, the weight change in the temperature-raising condition 10 ° C. / min from 30 ° to 500 ° C. measured, the point at which 2% weight was reduced and the thermal decomposition temperature.

<Solvent solubility>
The synthesized photoacid generator taken to 0.1g tube, an organic solvent under 25 ° C. temperature control (butyl acetate, toluene, and PGMEA) 0.2 g was added in portions, photoacid generator was added until complete dissolution. Note that if not completely dissolve be added 20g was evaluated as not dissolved.

<Amine-resistant>
The synthesized photoacid generator, an amine (pyridine, triethylamine) at a concentration of 0.25 mmol / L was diluted to 0.25 mmol / L acetonitrile which was dissolved in advance to calculate the purity by HPLC analysis. The solution 25 ° C. and after 24 hours storage in the dark conditions, calculates the purity again by HPLC analysis, the rate of decrease in purity before and after storage was evaluated by the following criteria amine resistance.

◎: Purity reduction rate is less than 0.1% ○: purity decrease ratio is less than 0.1% to 1.0% △: decreased purity of less than 1.0% - 10% × the: rate of decrease in purity but more than 10%

Nonionic photoacid generator of the present invention prepared in Example (A-1) ~ (A20), a non-ionic photoacid generators for comparison produced in Comparative Example (A'-1), (A '-3), (A'-5), an ion-based acid generator (A'-2), (molar extinction coefficient of A'-4) and (A'-6), thermal decomposition temperature, solvent solubility, the results of the amine resistance was measured by the method described above are shown in Table 2.

Figure JPOXMLDOC01-appb-T000002

As apparent from Table 2, the non-ionic photoacid generators of Examples 1-20 (A) of the present invention have sufficient molar extinction coefficient at the i-line (365 nm), the resist curability is good there it can be seen. Moreover, has excellent solubility in a solvent, handling property in the case of a resist is understood to be good. Furthermore, the thermal decomposition temperature is 220 ° C. or higher, and has a sufficient stability. Moreover, due to the high amine resistance, in the case of a resist, it can be seen that choice of amines which can be used as a quencher is wide.
On the other hand, in Comparative Examples 2, 4 and 6 were used acid ion generation systems known from the prior art, low sensitivity to i-line resist curability is not sufficient. Also, non-ionic photoacid generators in Comparative Examples 1, 3 and 5 solubility in a solvent is insufficient. Also, non-ionic photoacid generators in Comparative Examples 1, 3 and 5 are also insufficient amine resistance, in the case of a resist, by using the relatively pKa high alkylamines such as triethylamine, at the time of storage there is a possibility that the acid generator is aging and degradation.

Imide sulfonate compounds of the present invention is suitable positive resist, resist film, liquid resist, a negative resist, MEMS resist, photosensitive material, nano-imprint material, as a photo acid generator used in micro-stereolithography material or the like . Further, photolithography resin composition of the present invention (Q) is suitable for the applications mentioned above.

Claims (5)

  1. Imide sulfonate compound characterized by being represented by the general formula (1).
    Figure JPOXMLDOC01-appb-C000010
    Wherein (1), R1 ~ R8 are each independently hydrogen atom, a halogen atom, an alkyl group or a fluoroalkyl group having 1 to 18 carbon atoms having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, carbon an alkynyl group having from 2 to 18, an aryl group having 6 to 18 carbon atoms, a hydroxyl group, a carboxyl group, a silyl group, a nitro group, a cyano group, an amino group, an alkoxy group or aryloxy group represented by R 11 O-, R 12 alkylthio or arylthio group represented by S-, sulfinyl group represented by R 13 SO-, R 14 SO 2 - sulfonyl group represented by, an alkylcarbonyl group or an arylcarbonyl group represented by R 15 CO-, R 16 COO - carbonyloxy group represented by, oxycarbonyl group represented by R 17 OCO-, R8 carbonate group represented by -OCOO-, represents a urethane group represented by R 19 NHCOO-. At least two R1 ~ R8 may be bonded to form a ring structure. R9 represents a hydrocarbon group which may having 1 to 18 carbon atoms which may have a substituent (a portion of the hydrogen or all may be substituted by fluorine). ]
  2. In the general formula (1), R1 ~ or all hydrogen atoms of R8, R1 to at least any one is independent of ~ R8, halogen atom, alkyl group or fluoroalkyl having 1 to 18 carbon atoms having 1 to 18 carbon atoms group, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group or aryloxy group represented by R 11 O-, R 15 alkylcarbonyl group or an arylcarbonyl group represented by CO-, carbonyloxy group represented by R 16 COO-, imide sulfonate compound of claim 1 which is oxycarbonyl group represented by R 17 OCO-.
  3. In the general formula (1), R9 is represented by CxFy, carbon atoms 1 ~ 8 (x = 1 ~ 8), and in claim 1 or 2 fluorine atoms 3 ~ 17 (y = 3 ~ 17) imide sulfonate compounds described.
  4. Nonionic photoacid generator containing an imide sulfonate compound according to any one of claims 1 ~ 3 (A).
  5. Photolithographic resin composition comprising a non-ionic photoacid generator of claim 4 (A) (Q).
PCT/JP2015/001406 2014-03-24 2015-03-13 Imide sulfonate compound, photoacid generator, and resin composition for photolithography WO2015146053A1 (en)

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Citations (8)

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JPH02100054A (en) * 1988-10-07 1990-04-12 Fuji Photo Film Co Ltd Positive type photosensitive composition
JPH112901A (en) * 1996-04-25 1999-01-06 Fuji Photo Film Co Ltd Positive photosensitive composition
JP2004217748A (en) * 2003-01-14 2004-08-05 Konica Minolta Holdings Inc Active ray-curable ink composition, method of image formation using the same, and ink jet printer using the same
JP2005314633A (en) * 2003-09-26 2005-11-10 Dainippon Printing Co Ltd Photo-radical generator, photosensitive resin composition, and article
JP2008266495A (en) * 2007-04-23 2008-11-06 Osaka Prefecture Univ Photo acid-generating agent, production method thereof and resin composition for photo lithography
WO2011087011A1 (en) * 2010-01-13 2011-07-21 株式会社Adeka Novel sulfonic acid derivative compound and novel naphthalic acid derivative compound
US20110229821A1 (en) * 2008-09-15 2011-09-22 Centre National De La Recherche Scientifique-Cnrs Method of Photochemical Hydrolysis-Polycondensation of Cross-Linkable Chromophores with Steric Hindrance, Catalysed by a Photogenerated Acid, and the Applications Thereof
JP2013001821A (en) * 2011-06-17 2013-01-07 San Apro Kk Photoacid generator and resin composition for photolithography

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02100054A (en) * 1988-10-07 1990-04-12 Fuji Photo Film Co Ltd Positive type photosensitive composition
JPH112901A (en) * 1996-04-25 1999-01-06 Fuji Photo Film Co Ltd Positive photosensitive composition
JP2004217748A (en) * 2003-01-14 2004-08-05 Konica Minolta Holdings Inc Active ray-curable ink composition, method of image formation using the same, and ink jet printer using the same
JP2005314633A (en) * 2003-09-26 2005-11-10 Dainippon Printing Co Ltd Photo-radical generator, photosensitive resin composition, and article
JP2008266495A (en) * 2007-04-23 2008-11-06 Osaka Prefecture Univ Photo acid-generating agent, production method thereof and resin composition for photo lithography
US20110229821A1 (en) * 2008-09-15 2011-09-22 Centre National De La Recherche Scientifique-Cnrs Method of Photochemical Hydrolysis-Polycondensation of Cross-Linkable Chromophores with Steric Hindrance, Catalysed by a Photogenerated Acid, and the Applications Thereof
WO2011087011A1 (en) * 2010-01-13 2011-07-21 株式会社Adeka Novel sulfonic acid derivative compound and novel naphthalic acid derivative compound
JP2013001821A (en) * 2011-06-17 2013-01-07 San Apro Kk Photoacid generator and resin composition for photolithography

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