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WO2005114331A1 - Composé de résist et composition de résist - Google Patents

Composé de résist et composition de résist Download PDF

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Publication number
WO2005114331A1
WO2005114331A1 PCT/JP2005/009249 JP2005009249W WO2005114331A1 WO 2005114331 A1 WO2005114331 A1 WO 2005114331A1 JP 2005009249 W JP2005009249 W JP 2005009249W WO 2005114331 A1 WO2005114331 A1 WO 2005114331A1
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WO
WIPO (PCT)
Prior art keywords
group
formula
carbon atoms
compound
resist
Prior art date
Application number
PCT/JP2005/009249
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English (en)
Japanese (ja)
Inventor
Dai Oguro
Masatoshi Echigo
Takeo Hayashi
Original Assignee
Mitsubishi Gas Chemical Company, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Company, Inc. filed Critical Mitsubishi Gas Chemical Company, Inc.
Publication of WO2005114331A1 publication Critical patent/WO2005114331A1/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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/34—Cyanuric or isocyanuric esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
    • C07F9/65505—Phosphonic acids containing oxirane groups; esters thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • Resist compound and resist composition are Resist compound and resist composition
  • the present invention relates to a radiation-sensitive resist composition containing a resist conjugate represented by a specific chemical structural formula, which is useful as a non-polymer resist material, and a resist conjugate used therefor.
  • a radiation-sensitive material that responds to radiation such as ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV), electron beams, and X-rays, it is used in masks for LSI and VLSI production in the electronics field, and has a high-resolution resist pattern.
  • the present invention relates to a resist composition and a resist compound that can be used to manufacture a semiconductor device.
  • resist materials have been polymer materials capable of forming an amorphous thin film.
  • resist ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV), electron beams, X-rays, etc.
  • EUV extreme ultraviolet rays
  • a line pattern of about 0.1 m is formed.
  • non-polymeric resist materials include (1) positive and negative resists induced by fullerene force, (2) positive and negative resists induced by calixarene force, and (3) starburst resist. Positive resist derived from compound, (4) Posi resist which also induces dendrimer marker, (5) Positive resist which induces dendrimer Z calixarene force, (6) Starburst compound with high branching degree Force induced positive resist and (7) trimming Positive resist derived from a starburst-type compound having an ester bond with an acid as a central skeleton; (8) a negative resist capable of inducing cyclic polyphenolic conjugate; and (9) a polyphenolic conjugate. Induced negative resist, and (10) Calixresorcinarane force induced negative resist.
  • Patent Document 1 JP-A-7-134413
  • Patent Document 2 JP-A-9 211862
  • Patent Document 3 JP-A-10-282649
  • Patent Document 4 JP-A-11-143074
  • Patent Document 5 JP-A-11-258796
  • Patent Document 6 JP-A-11-72916
  • Patent Document 7 JP-A-11-322656
  • Patent Document 8 JP-A-9-236919
  • Patent Document 9 JP 2000-305270 A
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2002-99088
  • Patent Document 11 JP-A-2002-99089
  • Patent Document 12 JP-A-2002-49152
  • Patent Document 13 JP 2003-183227 A
  • Patent Document 14 Japanese Patent Application Laid-Open No. 2002-328466
  • Patent Document 15 JP-A-11-153863
  • Patent Document 16 Japanese Patent Application Laid-Open No. 2003-207893
  • Patent Document 17 Japanese Patent Application Laid-Open No. 2004-334106
  • Patent document 18 JP-A-9-236919
  • Patent Document 19 JP 2004-18421A
  • Non-Patent Document 1 Proceedings of SPIE vol.3999 (2000) P1202-1206 Disclosure of Invention
  • An object of the present invention is not only to ultraviolet rays such as i-rays and g-rays but also to radiations such as visible light, excimer laser light such as KrF, extreme ultraviolet (EUV), electron beam, X-ray, and ion beam.
  • An object of the present invention is to provide a radiation-sensitive resist composition that can be used and a resist conjugate used for the composition.
  • Still another object of the present invention is to provide a non-polymeric radiation-sensitive resist composition having a high resolution, a high heat resistance and a solvent solubility in a simple manufacturing process, and a resist conjugate used therefor.
  • the present invention provides a resist composition containing one or more resist compounds (A) satisfying all the conditions (a) to (d).
  • the molecule has at least one functional group selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group.
  • Molecular weight force 00-5000.
  • the present invention also provides a resistive conjugate suitable for the resistive conjugate (A).
  • the resist composition of the present invention contains the resist conjugate (A).
  • the resist conjugate (A) in the present invention satisfies all of the following conditions (a) to (d) at the same time.
  • the resist compound can be selectively solvent-insoluble in the exposed portion by the crosslinking reactive group, and is used for a negative resist composition.
  • the cross-linking reaction means a chemical reaction in which a plurality of reaction points in a resist compound are connected by a covalent bond.
  • the number of the cross-linking reactive groups in the molecule is at least 1, preferably 2, more preferably 2 to 15, particularly preferably 3 to 15. With such a range, the resolution and the image performance can be further improved.
  • Examples of the crosslinking reactive group include a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenol group, and a halogenated methyl group.
  • a carbon-carbon multiple bond group, an epoxy group, a methyl halide group and the like are preferable.
  • Examples include a carbon-carbon triple bond such as a pargyl group (CH ⁇ C) and an acetylene group (R 4 —C ⁇ C).
  • a carbon-carbon double bond such as a buryl group, an aryl group, a vinylene group, an atariloyl group, and a metharylyl group, and a carbon-carbon triple bond such as a propargyl group and an acetylene group are more preferable.
  • Atariloyl, methacryloyl, and propargyl groups are most preferred.
  • Examples of the epoxy group include a glycidyl group (CH (-O-) CHCH-).
  • Examples of the halogenated methyl group include, for example,
  • Methyl group (C1CH-), bromomethyl group (BrCH-) and methyl iodide group (ICH-).
  • R 4 is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
  • the molecule has at least one functional group selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group.
  • the resist conjugate (A) has at least one functional group selected from the group consisting of a urea group, an amide group, a urethane group, and an imide group, in particular, a group consisting of a urea group, an amide group, and a urethane group. It is preferable that one or more and at least three functional groups are selected. Further, it may contain a functional group having another nitrogen component.
  • Other functional groups include a tertiary amine group; a quaternary ammonium group; an imino group; an azide group; a function containing a heterocyclic amine such as pyridine, pyrrole, imidazole, indole, quinoline, pyrimidine, triazine, pyrrolidine, and morpholine. But not limited to.
  • a tertiary amine group such as pyridine, pyrrole, imidazole, indole, quinoline, pyrimidine, triazine, pyrrolidine, and morpholine.
  • each of the branched molecular chains in the branched structure has at least one cross-linking reactive group, and each of the molecular chains has an urea bond, a urethane bond, an amide bond, and an imide bond (preferably, , A rare bond, and a urethane bond).
  • the substrate adhesion can be improved, and the resolution can be further improved.
  • the molecular weight is from 500 to 5,000.
  • the molecular weight is 500-5000, preferably ⁇ 600-3000, more preferably ⁇ 700-2000.
  • the content is in the above range, good film-forming properties can be imparted, and the resolution and alkali developing performance can be further improved.
  • the “branched structure” refers to a structure that satisfies at least one of the following (1) to (4).
  • It contains at least one isocyanurate ring.
  • the resist material has excellent film forming properties, light transmittance, solvent solubility, etching resistance, etc. necessary for pattern formation. Has features. Further, since the number of photosensitive groups can be increased, sensitivity can be increased.
  • the resist conjugate (A) satisfies F ⁇ 5 (F represents the total number of atoms Z (the total number of carbon atoms and the total number of oxygen atoms)).
  • F represents the total number of atoms Z (the total number of carbon atoms and the total number of oxygen atoms)
  • performance such as resolution and etching resistance does not deteriorate.
  • the resistive conjugate (A) in the present invention is preferably represented by the following formula (1).
  • E is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, or a substituted alkylene group having 1 to 12 carbon atoms;
  • s, t, and u each independently represent an integer of 0 to 3, and a plurality of E, X, Z, and Y may be the same or different.
  • R 1 is a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 3 carbon atoms.
  • R 1 is a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 3 carbon atoms.
  • To 12 one-branched alkyl radicals, which are selected substituents;
  • ⁇ is a hydrogen atom or a substituent selected from the group consisting of an aryloxy group, an atariloyloxy group, a glycidyloxy group and a chloromethyloxy group, and at least one of A is an aryloxy group, Atalyloyloxy, glycidyloxy, and chloromethyloxy groups which are selected substituents;
  • Ar is an aromatic hydrocarbon group having 6 to 12 carbon atoms
  • Y is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, a substituted alkylene group having 1 to 12 carbon atoms, or a single bond;
  • Z represents a single bond or a substituent selected from the group consisting of O, —S, and —NH;
  • al is an integer from 1 to 9;
  • rl is an integer from 0 to 8.
  • n 1
  • A, Ar, al, rl may be the same or different Good. )]
  • linear hydrocarbon group having 1 to 12 carbon atoms examples include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, Hexyl, octyl, decyl, dodecyl and the like;
  • Examples of the cyclic hydrocarbon group having 3 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclododecyl and the like;
  • alkoxy group having 1 to 12 carbon atoms examples include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
  • Examples of the one-branched alkyl group having 3 to 12 carbon atoms include isopropyl, sec-butyl, t-butyl, 1,1-dimethylpropyl, 1-methylbutyl, 1,1-dimethylbutyl, and 1-methyl And a didecane group;
  • Examples of the divalent acyclic hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propylene group, a dimethylmethylene group, a trimethylene group, a tetramethylene group, a t-butylene group, a hexylene group, an otathylene group, Dodecylene groups and the like;
  • Examples of the divalent cyclic hydrocarbon group having 3 to 12 carbon atoms include a phenylene group, a tolylene group, a naphthylene group, a cyclopentylene group, a cyclohexylene group, and a cyclododecylene group;
  • Examples of the substituted alkylene group having 1 to 12 carbon atoms include an aminomethylene group, a hydroxylmethylene group, a carboxylmethylene group, a chloromethylene group, a bromomethylene group, an odomethylene group, a methoxymethylene group, an ethoxymethylene group, a propoxymethylene group, Butoxymethylene group, acetylmethylene group, cyanomethylene group, nitromethylene group, etc .;
  • Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group. And a biphenyl group.
  • the compound of the formula (1) is an isocyanurate derived from diisocyanate, After the reaction of phenols or hydroxyalkylphenols, a crosslinking reaction occurs by irradiation with visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray, or ion beam, or a chemical reaction induced by the irradiation.
  • Cross-linking reactive group introduction It is manufactured by reacting a reagent.
  • the method for producing the resist conjugate (A) used in the present invention is not particularly limited.
  • polyisocyanates having three or more isocyanate groups, aminophenols or hydroxyalkylphenols are used.
  • a crosslinking reactive group-introducing reagent that causes a crosslinking reaction by irradiation with visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, or ion beam, or a chemical reaction induced by the irradiation is used as a base.
  • EUV extreme ultraviolet light
  • the production method of reacting in the presence of a catalyst is preferred because all the steps can be produced in the same reaction vessel, which is simpler and more practical.
  • the isocyanurate is not particularly limited, but is tolylene diisocyanate, bis (isocyanate phenyl) methane, bis (isocyanate cyclohexyl) methane, phenylene diisocyanate, cyclohexanediisocyanate.
  • Isophorone diisocyanate hexamethylene diisocyanate, bis (isocyanatemethyl) cyclohexane, metaxylene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, lysine
  • it is either diisocyanate, tetramethylxylene diisocyanate, or isocyanurate derived from trimethylhexamethylene diisocyanate.
  • isocyanurate derived from tolylene diisocyanate, bis (isocyanate phenyl) methane, isophorone diisocyanate, bis (isocyanatemethyl) cyclohexane, and meta-xylene diisocyanate Particularly preferred are tolylene diisocyanate, bis (isocyanate phenyl) methane, isophorone diisocyanate, and isocyanurate derived from bis (isocyanatemethyl) cyclohexane.
  • the aminophenols or hydroxyalkylphenols are not particularly limited as long as they have a functional group having higher reactivity with isocyanate than phenolic hydroxyl groups.
  • the aminophenols include p-aminophenol, m-aminophenol, o-aminophenol, 4 aminocatechol, 3 aminocatechol, 2 aminoresorcinol, 4 aminoresorcinol, 5 aminoresorcinol, 2 aminohydroquinone, 4-aminopyrogallol, 5-aminopyrogallol, 2-aminomethylphenol, 3-aminomethylphenol, 4-aminomethylphenol, 4-aminomethylcatechol, 3-aminomethylcatechol, 2-aminomethylresorcinol, 4-aminomethylresorcinol, 5 aminomethylresorcinol, 2aminomethylhydroquinone, 4-aminomethylpyrogallol, 5aminomethylpyrogallol, 5aminomethylpyrogallol, 5aminomethyl
  • hydroxyalkylphenols examples include 4-hydroxymethylphenol, 3-hydroxymethylphenol, 2-hydroxymethylphenol, 4-hydroxymethylcatechol, 3-hydroxymethylcatechol, 2-hydroxymethylresorcinol, and 4-hydroxymethylresorcinol. , 5-hydroxymethylresorcinol, 2-hydroxymethylhydroquinone, 4-hydroxymethylpyrogallol, 5-hydroxymethylpyrogallol and the like. In particular, 4-hydroxymethylphenol and 5-hydroxymethylresorcinol are preferred!
  • the reaction of the isocyanurate with an aminophenol or a hydroxyalkylphenol and a crosslinking reactive group-introducing agent is carried out by dissolving an aminophenol or a hydroxyalkylphenol in an aprotic polar solvent, and then dissolving the aminophenol or the hydroxyalkylphenol in the aprotic polar solvent.
  • the compound having three or more isocyanate groups is a liquid, it does not have to be dissolved in an aprotic solvent.
  • the solution it is preferable to drop the solution at a temperature of about 5 ° C to 100 ° C over about 1 to 150 minutes. Thereby, it selectively reacts with an amino group or a hydroxyalkyl group isocyanate group. Although the reaction proceeds without a catalyst, the reaction speed may increase when one or more base catalysts are used.
  • a cross-linking reactive group such as an atalyloyl group in the same reaction vessel
  • a cross-linking reactive group-introducing agent such as an atalyl-based iuclide is introduced in the presence of the above-mentioned base catalyst such as triethylamine. And at room temperature for 2-4 hours. Distilled water is added to the reaction solution to precipitate crystals, which are then washed with distilled water, purified by Z or column chromatography, high-performance liquid chromatography, etc., and dried to obtain the resist-bonded product (A).
  • the crosslinking reactive group-introducing agent referred to herein includes an acid, an acid chloride, an acid anhydride, a carboxylic acid derivative compound such as dicarbonate, an alkyl halide, an epihalohydrin, etc. having a crosslinking reactive group.
  • the crosslinking reactive group includes a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenol group, a chloromethyl group, and the like.
  • aprotic polar solvent used in the above reaction, a compound having three or more isocyanate groups, an aminophenol or a hydroxyalkylphenol, a reagent for introducing a cross-linking reactive group, and a product such as resist
  • a conventionally known aprotic polar solvent which is not particularly limited, can be used.
  • dimethylformamide, dimethylacetamide and the like can be mentioned. These may be used alone or in combination of two or more.
  • the base catalyst used in the above reaction may be any alkaline conjugate, such as mono, di- or trialkylamines, mono-, di- or trialkanolamines, and heterocyclic compounds. It is preferable to use at least one of an alkali compound such as amines, tetramethylammonium hydroxide (TMAH) and choline, and a metal compound such as an alkylammonium salt and an alcoholate. Among them, trialkylamines such as triethylamine, triisopropylamine, and tributylamine are preferred, and triethylamine is particularly preferred.
  • TMAH tetramethylammonium hydroxide
  • a metal compound such as an alkylammonium salt and an alcoholate.
  • trialkylamines such as triethylamine, triisopropylamine, and tributylamine are preferred, and triethylamine is particularly preferred.
  • the reaction is carried out at normal pressure and room temperature for 2 to 4 hours in the presence of the base catalyst. Distilled water is added to the reaction solution to precipitate crystals, which are then washed with distilled water, purified by Z or column chromatography, high-performance liquid chromatography, or the like, and dried to obtain the resisted conjugate (A).
  • the reaction solution is crystallized by adding it to a large amount of water, and the filtered crystals are dissolved in acetone. Then, it is again added to a large amount of water and crystallized to obtain a polyphenol conjugate as an intermediate.
  • a crosslinking reactive group-introducing agent such as 3-bromopropene is introduced with potassium carbonate and iodide in order to introduce a crosslinking reactive group such as an aryl group and the like.
  • the reaction is carried out at normal pressure and room temperature for 2 to 40 hours in the presence of a catalyst such as sodium. After removing the salt from the reaction solution and concentrating the solvent, the residue is washed with distilled water, purified by Z or column chromatography, high performance liquid chromatography or the like, and dried to obtain the resist-bonded product (A).
  • the compounds of the formulas (4) to (6) are reacted with isocyanurate derived from diisocyanate and an aminophenol or hydroxyalkylphenol, and then reacted with visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV ), Electron beam, X-ray and ion beam irradiation, or a chemical reaction induced by the irradiation, or a cross-linking reactive group-introducing reagent which causes a cross-linking reaction.
  • isocyanurate derived from diisocyanate a branched polyphenol conjugate having a branched structure can be easily obtained.
  • the isocyanurate derived from diisocyanate the above compounds can be used.
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • the reaction of an isocyanurate derived from diisocyanate with an aminophenol or a hydroxyalkylphenol and a reagent for introducing a crosslinking reactive group is carried out by reacting the above compound having three or more isocyanate groups with an aminophenol or Hydroxyalkylpheno
  • the reaction can be carried out in the same manner as in the reaction with the reactive group and the reagent for introducing a crosslinking reactive group.
  • the compounds of formulas (4) to (6) of the corresponding monomers can be selectively obtained by separation by column chromatography or by using monomeric isocyanurate as a raw material. It comes out.
  • the resist conjugate (A) in the present invention is more preferably one represented by the following formula (2).
  • X is the same as described above, and a plurality of Xs may be the same or different.
  • V represents an integer of 3 to 15.
  • R is a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and carbon
  • R 3 is a hydrogen atom, a hydroxyl group, a non-cyclic hydrocarbon group having 1 to 12 carbon atoms, and a cyclic carbon group having 3 to 12 carbon atoms.
  • E 2 is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, and a divalent hydrocarbon group having 3 to 12 carbon atoms. Or a substituted alkylene group having 1 to 12 carbon atoms.
  • E ′ may be the same or different and each independently represents a single bond, a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, 3 to 12 carbon atoms. And a substituted alkylene group having 1 to 12 carbon atoms, wherein X in the formula (2) is bonded to E ′.
  • the alkyl group, the divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, the divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, and the substituted alkylene group having 1 to 12 carbon atoms are the same as those in the formula (1). Can be exemplified.
  • Examples of the substituted alkyl group having 1 to 12 carbon atoms include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a chloromethyl group, and a bromomethyl group.
  • the compound of the formula (2) is produced by reacting an oligomer of monoisocyanate or triisocyanate with an aminophenol or a hydroxyalkylphenol.
  • an oligomer of monoisocyanate or triisocyanate By using a monoisocyanate oligomer or triisocyanate, a branched polyphenol conjugate can be easily obtained.
  • the oligomer of monoisocyanate or triisocyanate is not particularly limited, but oligomers of isocyanate methane, tris (isocyanate phenyl) methane, tris (isocyanate phenyl) thiophosphate, mesitylene trimethane Isocyanate, triisocyanate benzene, lysine ester triisocyanate, 1,6,11- decanetriisocyanate, 1,8 diisocyanate 4 isocyanate methyloctane, 1,3,6 hexamethylene tri It is preferred that the isocyanate or the bicycloheptane triisocyanate be selected. Among them, oligomers of isocyanate methane, tris (isocyanate phenol) methane, and tris (isocyanate phenyl) thiophosphate are particularly preferred. preferable.
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • the reaction of the oligomer of monoisocyanate or triisocyanate with the aminophenols or hydroxyalkylphenols and the reagent for introducing a cross-linking reactive group is carried out by the above-mentioned isocyanurate derived from diisocyanate, and aminophenol.
  • the reaction can be carried out in the same manner as in the reaction with a compound or a hydroxyalkylphenol and a crosslinking reactive group introduction reagent.
  • Compounds of the formula (9) include tris (isocyanate phenyl) methane and amino phenols.
  • a hydroxyalkylphenol and a crosslinking reactive group-introducing agent By using tris (isocyanatephenyl) methane, a branched polyphenol conjugate can be easily obtained.
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • the reaction between tris (isocyanate phenol) methane and an amino phenol or a hydroxyalkyl phenol is carried out by the above-mentioned isocyanurate derived from diisocyanate, an amino phenol or a hydroxyalkyl phenol and a crosslinking reactive group.
  • the reaction can be carried out in the same manner as in the reaction with the introduced reagent.
  • the compound of the formula (10) includes tris (isocyanate phenyl) thiophosphate, It is produced by reacting phenols or hydroxyalkylphenols. By using tris (isocyanatephenyl) thiophosphate, a branched polyphenol compound can be easily obtained.
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • the reaction between tris (isocyanatephenol) thiophosphate and an aminophenol or a hydroxyalkylphenol is carried out by reacting the above-mentioned isocyanurate derived from diisocyanate with an aminophenol or a hydroxyalkylphenol. This can be done in a similar way.
  • the compound of the formula (11) is produced by reacting an oligomer of isocyanate phenol, an aminophenol or a hydroxyalkylphenol, and a reagent for introducing a crosslinking reactive group.
  • an oligomer of isocyanate phenol By using an oligomer of isocyanate phenol, a branched polyphenol conjugate can be easily obtained.
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • the reaction between an oligomer of isocyanate phenol and an aminophenol or a hydroxyalkylphenol is carried out by reacting the isocyanurate derived from the diisocyanate with an aminophenol or a hydroxyalkylphenol and crosslinking reactivity.
  • the reaction can be performed in the same manner as in the reaction with the group introduction reagent.
  • the compound of the formula (12) is produced by reacting mesitylene triisocyanate, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group-introducing agent.
  • mesitylene triisocyanate By using mesitylene triisocyanate, a branched polyphenol compound can be easily obtained.
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • mesitylene triisocyanate and an aminophenol or a hydroxyalkylphenol is carried out in the same manner as the reaction between the isocyanurate derived from diisocyanate and the aminophenol or a hydroxyalkylphenol. With Wear.
  • the compound of the formula (13) is produced by reacting triisocyanate benzene, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group introduction reagent.
  • triisocyanate benzene By using triisocyanate benzene, a branched polyphenol conjugate can be easily obtained.
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • the reaction of triisocyanate benzene with an aminophenol or hydroxyalkylphenol is carried out by reacting the isocyanurate derived from diisocyanate with an aminophenol or hydroxyalkylphenol and a reagent for introducing a crosslinking reactive group. This can be performed in the same manner as described above.
  • the compound of the formula (14) is produced by reacting cyclohexanetriisocyanate, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group introduction reagent.
  • cyclohexanetriisocyanate By using cyclohexanetriisocyanate, a branched polyphenol conjugate can be easily obtained.
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • the reaction of cyclohexanetriisocyanate with an aminophenol or a hydroxyalkylphenol is carried out by reacting the isocyanurate derived from the diisocyanate with an aminophenol or a hydroxyalkylphenol and a reagent for introducing a crosslinking reactive group. Can be carried out in the same manner as in the above reaction.
  • R 3 is a group comprising a hydrogen atom, an acyclic hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, and a substituted alkyl group having 1 to 12 carbon atoms.
  • X, E 2 and k are the same as described above;
  • E 1 and E 1 ′ may be the same or different and each independently represents a single bond or a divalent hydrocarbon group having 1 to 11 carbon atoms. However, the total number of carbon atoms of E 1 and E 1 is 0 to: L 1.
  • J is a substituent selected from —O—, —S—, —NH— and a single bond. However, multiple B, E 1 ′, E 2 , and J may be the same or different. ]
  • a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, and a substituted alkylene group having 1 to 12 carbon atoms are represented by the formula: The same as (1) can be exemplified.
  • Examples of the divalent hydrocarbon group having 1 to 11 carbon atoms 1 , E 1 ′) include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, decylene, pendecylene, and the like.
  • the compound of the formula (3) is produced by reacting a burette derivative, an allohanate derivative, or a urethane derivative derived from diisocyanate, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group introduction reagent. Is done.
  • a burette an allohanate or a urethane derivative derived from diisocyanate, a branched polyphenol conjugate can be easily obtained.
  • the burette form, allohanate form, or urethane form derived from diisocyanate is not particularly limited, but tolylene diisocyanate, bis (isocyanate phenyl) methane, bis (isocyanatecyclohexyl) Methane, phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanatemethyl) cyclohexane, meta-xylene diisocyanate, Any burette, allohanate, or urethane derivative derived from norbornane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, or trimethylhexamethylene diisocyanate. In the preferred to be either. Among them, a buret derivative derived from he
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • the reaction of a burette, allohanate, or urethane derivative derived from diisocyanate with an aminophenol or hydroxyalkylphenol is carried out by reacting the above-described isocyanurate derived from diisocyanate with an aminophenol or hydroxyalkanol.
  • the reaction can be carried out in the same manner as in the reaction with a kilnphenol and a reagent for introducing a crosslinking reactive group.
  • Equation (8) X, J and k are the same as above. However, a plurality of, E 2 , X, J Each may be the same or different.
  • the compound of the formula (8) is produced by reacting a urethane compound derived from diisocyanate, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group introduction reagent.
  • a urethane derivative derived from diisocyanate By using a urethane derivative derived from diisocyanate, a branched polyphenol conjugate can be easily obtained.
  • the urethane form derived from diisocyanate is not particularly limited, but is tolylene diisocyanate, bis (isocyanate phenyl) methane, bis (isocyanate cyclohexyl) methane, phenylene diisocyanate, cyclohexane.
  • urethane derivatives derived from tolylene diisocyanate are particularly preferred.
  • the above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.
  • the reaction between the urethane compound derived from diisocynate and the aminophenol or hydroxyalkylphenol is carried out by the above-described isocyanurate derived from diisocyanate, the aminophenol or hydroxyalkylphenol, and the crosslinking.
  • the reaction can be carried out in the same manner as in the reaction with the reactive group introduction reagent.
  • the compound of the formula (7) is produced by reacting a burette derivative derived from diisocyanate, an aminophenol or a hydroxyalkylphenol, and a reagent for introducing a crosslinking reactive group.
  • a burette derivative derived from diisocyanate By using a burette derivative derived from diisocyanate, a branched polyphenol conjugate can be easily obtained.
  • the burette form derived from diisocyanate is not particularly limited, but is tolylene diisocyanate, bis (isocyanate phenyl) methane, bis (isocyanate cyclohexyl) methane, phenylene isocyanate, cyclo Hexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanate methyl) cyclohexane, metaxylene diisocyanate, norbornane diisocyanate, tolidine diisocyanate
  • it is any one of a burette derivative derived from a salt, naphthalene diisocyanate, lysine diisocyanate, tetramethyl xylene diisocyanate, or trimethylhexamethylene diisocyanate.
  • a burette derivative derived from hexamethylene diisocyanate is particularly preferred.
  • aminophenols or hydroxyalkylphenols the aforementioned compounds can be used.
  • the reaction between the burette derivative derived from diisocyanate and the aminophenols or hydroxyalkylphenols is carried out by reacting the isocyanurate derived from diisocyanate with the aminophenols or hydroxyalkylphenols and the crosslinking reactive group.
  • the reaction can be performed in the same manner as in the reaction with the introduced reagent.
  • Particularly preferred among the compounds represented by the formula (7) are compounds represented by the following formulas (25-1) to (25-4).
  • the resist conjugate (A) in the present invention is preferably one wherein X in the above formulas (1) to (14) is represented by the following formulas (11) to (III).
  • the compound in which X is represented by the formula (II) is produced by reacting a compound having three or more isocyanate groups, an aminophenol and a reagent for introducing a crosslinking reactive group.
  • the compound in which X is represented by the formula (III) is produced by reacting a compound having three or more isocyanate groups with a hydroxyalkylphenol.
  • the above compounds can be used.
  • Aminophenols or hydroxyalkylphenols are not particularly limited as long as they have a higher reactivity with isocyanate than the phenolic hydroxyl group and have a functional group.
  • aminophenols used for producing the compound represented by the formula (II) wherein X is, for example, P-aminophenol, m-aminophenol, o-aminophenol, 4-aminocatechol, 3 -aminocatechol , 2 aminoresorcinol, 4 aminoresorcinol,
  • Examples thereof include 5-aminoresorcinol, 2-aminohydroquinone, 4-aminopyrogallol, 5-aminopyrogallol, and 2-aminophloroglicinol. Particularly, p-aminophenol and m-aminophenol are preferred.
  • the reaction of a compound having three or more isocyanate groups with an aminophenol or a hydroxyalkylphenol can be carried out by the method described above.
  • the nitrogen content of the resist conjugate (A) is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, and still more preferably 5 to 15% by mass. Is particularly preferred. When the content of the nitrogen element is in the above range, the sensitivity and the resolution are excellent, and the heat resistance and the substrate adhesion required for pattern formation can be obtained.
  • the resist compound (A) is a compound obtained by reacting hydroxybenzoic acid, dihydroxybenzoic acid, or trihydroxybenzoic acid with a crosslinking reactive group-introducing agent under a base catalyst, and an amino group Can also be obtained by condensing a compound having three or more of This method is preferable because by-products can be suppressed.
  • the compound having three or more amino groups is not particularly limited, but includes mesitylenetriamine, triaminobenzene, pararoselin, tris (aminophenol-methane), tris (aminophenyl) thiophosphate. , Lysine ester triamine, 1,6,11-pandecanthramine, 1,8-diamino-14-aminomethyloctane, 1,3,6-hexamethylenetriamine, bicycloheptanetriamine, norbornanetriamine, etc. No. Among these compounds, mesitylenetriamine, triaminobenzene and pararoselin are particularly preferred.
  • the resist compound (A) is obtained by reacting a compound obtained by reacting an aminophenol or a hydroxyalkylphenol with a crosslinking reactive group-introducing agent in the presence of a base catalyst, and a carboxyl group. It can also be obtained by condensing a compound having 3 or more. This method is preferable because by-products can be suppressed.
  • Examples of the compound having three or more carboxyl groups include benzenetetracarboxylic acid, cyclohexanetetracarboxylic acid, benzenetricarboxylic acid, and cyclohexanetricarboxylic acid, and particularly, benzenetricarboxylic acid such as trimesic acid and each hydrogenated trimesic acid. And cyclohexanetricarboxylic acid are preferred.
  • the resist composition of the present invention contains one or more resist compounds (A) described above. When one kind of the resistive conjugate (A) is used, a high resolution can be obtained, and when two or more kinds are used, the film formability and the substrate adhesion may be improved. [0075]
  • the resist composition of the present invention can be directly irradiated with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, and ion beam. Alternatively, it is desirable to add a compound (B) which generates a radical or a cation indirectly.
  • the compound (B-1) that generates a radical a compound that generates a radical by interacting with a radical initiator or a photo-excited sensitizer, mainly a compound, mainly Compounds having both the sensitizing action by ultraviolet light and the ability to generate radicals due to the action are mentioned.
  • radical initiator examples include peroxides such as benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl hydroperoxide, and tamen hydroperoxide; azobisisobutymouth-tolyl, azobiscyclohexane Azo conjugates such as -tolyl and phenyl-trifluoromethane; persulfates such as potassium persulfate and ammonium persulfate; and persulfates such as triethylaluminum, trimethylaluminum, ethylaluminum-dimethyldichloride, and getylaluminum chloride.
  • peroxides such as benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl hydroperoxide, and tamen hydroper
  • Organic aluminum compounds such as tetraethyl lead, getyl zinc, getyl cadmium, and tetraethyl tin; titanium tetrachloride, titanium trichloride, aluminum chloride aluminum, aluminum bromide, stannic chloride, salt Zinc oxide, boron trifluoride, boron trifluoride Chloride such as tiletherate and phosphorus pentafluoride are exemplified.
  • Examples of the above-mentioned compounds which generate a radical by interacting with the photoexcited sensitizer in some way include, for example, various titanocenes described in JP-A-59-152396 and JP-A-61-151197.
  • di-cyclopentagel Ti dichloride dicyclopentagel Ti bis-phenyl, dicyclopentagenyl Ti-bis 2,3,4,5,6 Pentafluorophenyl-1-yl, di-cyclopentagenenyl-bis-1,2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenenyl-Ti-bis-1,2 4,6-trifluorophenyl 1-yl, dicyclopentagenenyl-Ti-2,6 di-fluorophenyl-1-yl, di-cyclopentagenenyl Ti-bis-1,2,4-difluorophenyl 1-yl, di-methylcyclo mouth pentagenenyl-ti-bi 1,2-, 4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentagenenyl-Ti-bis-1,2,6-difluorophenyl-1-yl, di-cyclopentageninole
  • Hexariylbiimidazoles specifically, 2,2, -bis (o-chlorophenol) -4,4 ', 5,5, -tetra ( ⁇ -fluorophenyl) biimidazole, 2,2 , —Bis (o-bromophenyl) 4,4,5,5,1-tetra (p-phenyl) biimidazole, 2,2,1-bis (o-chlorophenol) 4,4,5,5 , 1-tetra (p-chloro-naphthyl) biimidazole, 2,2,1-bis (o-chloro-or-phenyl) -1,4,4,5,5,1-tetra (p-chloro-or-phenyl) biimidazole, 2,2, -bis (obromophenyl) -1,4,4,5,5,1-tetra (p-meth
  • Examples of the compound having both the sensitizing action mainly by ultraviolet light and the ability to generate radicals thereby include, for example, 2,2-dimethoxy-1,2-diphenyl-l-etane-1-one, 2-isopropoxy-1,1, 2-Diphenyl-1-ethane, (1'-hydroxycyclohexyl) phenyl ketone, 2-methyl-11 (4'-methylthiophene) 2 morpholinopropane 1-, 2-benzyl-2 (N, N dimethylamino)-1- (4'-morpholinophenyl) butan-1-one, 2-hydroxy-12-methyl-1-phenylpropane-11-one, 2,4,6 trimethylbenzoy Fe-ketone derivatives such as ludiphen-l-phosphinoxide, 1- [4 '-(2-hydroxyethoxy) phenyl]-2-hydroxy-12-methyl-1-propane-1-one, 4- (N , N-dimethylamino) isoamyl benzoate, 4— ( N
  • Compound power represented by 40 At least one selected from the group powers.
  • R may be the same or different and each independently represents a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, or a branched alkyl group having 3 to 12 carbon atoms.
  • a cyclic alkyl group having 3 to 12 carbon atoms, a linear alkoxy group having 1 to 12 carbon atoms, a branched alkoxy group having 3 to 12 carbon atoms, a cyclic alkoxy group having 3 to 12 carbon atoms, a hydroxyl group, or halogen X— is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or a halogen-substituted aryl group having 6 to 12 carbon atoms.
  • the compound represented by the formula (33) includes triphenylsulfo-dimethyltrifluoromethanesulfonate, triphenylsulfo-dimethylnonafluoro-n-butanesulfonate, triphenylsulfo-dimethyltrifluoromethanesulfonate, triphenylsulfo-dimethyltrifluoromethanesulfonate, octanesulfonate, Diphenyl 4-methylphenyl sulfo-dimethyltrifluoromethanesulfonate, diphenyl 2,4,6 trimethylphenyl sulfo-dimethyltrifluoromethanesulfonate, diphenyl 4-t-butoxyphenyl sulfo-dimethyltrifluoro Fluoromethanesulfonate, diphenyl 4-t-butoxyphenylsulfo-dumnonafluoron butanesulfon
  • the compound represented by the formula (34) includes bis (4t-butylphenyl) odonium trifluoromethanesulfonate and bis (4t-butylphenyl) odo-dimethylnonfluoro n Butanesulfonate, bis (4t-butylphenol) ode-dimethylperfluoro n-octanesulfonate, bis (4t-butylphenol) ode-dimethyl p-toluenesulfonate, bis (4-t) Butynolephene 2) odonium benzene snolephonate, bis (4-t-butyl phenol) odonium 2 trifluoromethylbenzenesulfonate, bis (4-t butyl phenol) odonium 4 trifluoromethylbenzene Sulfonate, bis (4t butylphenol) odonium 2,4 difluorobenzene Sulfonate, bis (4t
  • Q is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an alkyleneoxy group having 1 to 12 carbon atoms (—R′—O; R ′ is an alkylene group having 1 to 12 carbon atoms), R 25 is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or a carbon number. 6 to 12 halogen-substituted aryl groups.
  • the compound represented by the formula (35) includes N (trifluoromethylsulfo-loxy) succinimide, N- (trifluoromethylsulfo-loxy) phthalimide, and N- (trifluoromethylsulfo-loxy) diphen- Lumaleimide, N— (Trifluoromethylsulfo-loxy) bicyclo [2.2.1] Heptot-1-ene 2,3 dicarboximide, N— (Triflurimide O-methylsulfo-roxy) naphthylimide, N- (10-camphorsulfo-roxy) succinimide, N— (10-camphorsulfo-roxy) phthalimide, N— (10-force camphorsulfo-roxy) diphen-maleimide, N— (10— Camphorsulfo-roxy) bicyclo [2.2.1] hept-5-one-1,3-dicarboximide, N- (10-forcer-sulfo-roxy)
  • R 2b may be the same or different and each independently has 1 to 12 carbon atoms Linear alkyl group, branched alkyl group having 3 to 12 carbon atoms, cyclic alkyl group having 3 to 12 carbon atoms, aryl group having 6 to 12 carbon atoms, heteroaryl group having 3 to 12 carbon atoms, or carbon number 7 to 12 aralkyl groups.
  • Each of the substituents may be substituted with an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, halogen, or a haloalkyl group having 1 to 12 carbon atoms.
  • the compound represented by the formula (36) includes diphenyldisulfone, di (4-methylphenyl) disulfone, dinaphthyldisulfone, di (4tert-butylphenyl) disulfone, and di (4-hydroxyphenyl).
  • Disulfone, di (3-hydroxynaphthyl) disulfone, di (4-phenolic phenole) disnorefone, di (2-phenolic phenole) disnorefone, and di (4-trifluoromethylphenyl) Preferably, at least one selected from the group consisting of disulfones.
  • ′ may be the same or different and each is independently a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, A cyclic alkyl group having 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.
  • Each of the substituents may be substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an alkoxyl group having 1 to 12 carbon atoms.
  • the compound represented by the above formula (37) includes ⁇ (methylsulfo-roximino) phenylacetonitrile, at- (methylsulfo- luximino) -4-methoxyphenyl-acetonitrile, and ⁇ - (trifluoromethylsulfo- oximino) ) —Fue-L-acetonitrile, ⁇ - (Trifluoromethylsulfonyloximino) -4-methoxyphenylacetonitrile, ⁇ - (Ethylsulfo-Loximino) -4-Methoxyfure-Lacetonitrile, at- (Propyl Sulfo-Roxyimino) -4 Methylphen -Racetonitrile, and ⁇ (methylsulfo-roxyimino) -4-bromo-phenylacetonitrile group are preferably at least one selected from the group consisting of: [0092] [For
  • the formula (38) may be the same or different and are each independently a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms.
  • the number of carbon atoms of the halogenated alkyl group is preferably 1 to 5.
  • the compound represented by the above formula (38) can be used as a monoisocyanouric acid, monobromoisocyanuric acid, dichloroisocyanuric acid, dibumoisocyanuric acid, trichloroisocyanuric acid, and tribromoisocyanuric acid. It is preferable that at least one kind is selected.
  • R 29 and R 3 ° each independently represent an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group; cyclopentyl A cycloalkyl group having 3 to 12 carbon atoms such as a cyclohexyl group; a alkoxyl group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; a phenyl group, a tolyl group or a naphthyl group And preferably an aryl group having 6 to 10 carbon atoms.
  • L 29 and L 3 ° are each independently an organic group having a 1,2-naphthoquinonediazide group.
  • Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazido-4-sulfol group, a 1,2-naphthoquinonediazide-5-sulfol group, and a 1,2- 1,2-quinonediazide sulfol such as naphthoquinonediazido 6-sulfol group
  • the groups can be mentioned as preferred.
  • a 1,2 naphthoquinonediazide 1-4-sulfol group and a 1,2 naphthoquinonediazido 5-sulfol group are preferred.
  • p is an integer of 1-3
  • q is an integer of 0-4, and
  • J 29 is a single bond, a polymethylene group having 2 to 4 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, a phenylene group having 6 to 10 carbon atoms, the following formula (41):
  • a substituent represented by -R a -C ( 0) -R.
  • R a and R b represents an alkylene group having Yogu each independently a single bond or a 1 to 3 carbon atoms which may be the same or different, the sum of the carbon number of R a and R b is an 0 to 3
  • R e and R d is represents Yogu each independently a single bond or an alkylene group having 1 to 4 carbon atoms be the same or different, the total number of carbon atoms of R e and R d is 0-4 der Ru
  • Y 29 is A hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms, wherein X 29 and X 3
  • bis (p-toluenesulfol) diazomethane bis (2,4-dimethylphenylsulfol) diazomethane, bis (tert-butylsulfol-) diazomethane, bis (n- Bissulfo- such as butylsulfol-diazomethane, bis (isobutylsulfol-) diazomethane, bis (isopropylsulfol-) diazomethane, bis (n-propylsulfol-) diazomethane and bis (cyclohexylsulfol-) diazomethane; Ludazomethanes, 2- (4-methoxyphenyl) -1,4,6- (bistrichloromethyl) 1,3,5 triazine, 2- (4-methoxynaphthyl) 4,6— (bistrichloromethyl) 1, 3,5 Triazine
  • the component (B) can be used alone or in combination of two or more.
  • the amount of component (B) used is preferably from 0.1 to 30 parts by weight, more preferably from 0.5 to 20 parts by weight, and even more preferably from 1 to 15 parts by weight, per 100 parts by weight of the resist conjugate. Parts by weight. It is preferable that the ratio is in the above range because the sensitivity, the resolution, and the cross-sectional shape of the resist pattern are good.
  • a crosslinking agent a dissolution promoter, a dissolution controlling agent, a sensitizer, One or more kinds of various additives such as surfactants and the like can be added.
  • compounds having a group or a resin can also be added, and in particular, compounds having a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated polyyl group, and a halogenated methyl group, Or a resin is preferred.
  • crosslinking agents can be used alone or in combination of two or more.
  • the amount of the crosslinking agent is preferably 50 parts by weight or less, more preferably 25 parts by weight or less, per 100 parts by weight of the resist conjugate. It is at most 5 parts by weight, particularly preferably at most 5 parts by weight.
  • the sensitizer absorbs the energy of the irradiated radiation and transfers the energy to the compound (B), thereby increasing the amount of radicals or cations generated. It is a component that improves sensitivity.
  • Such sensitizers include, for example, a triphenylmethane-based leuco dye such as leuco crystal violet, leucomalachite green disclosed in U.S. Pat. No. 3,479,185, and erythrocycin.
  • Photoreducing dyes such as jeosin Y, Michler's ketone and aminostyryl ketone disclosed in U.S. Patent No. 3,549,367, U.S. Patent No. 3,652,275, etc.
  • Aromatic ketones such as benzophenone and biacetyl; ⁇ 8-diketones described in U.S. Pat. No. 3,844,790; indanones found in U.S. Pat. No. 4,162,162; Ketocoumarins disclosed in JP-A-52-112681, aminostyrene derivatives and aminopolybutadiene derivatives disclosed in JP-A-59-56403, and US Pat. No. 4,594,310. amino Polyyl heterocycles, julolidine heterocycles described in U.S. Pat. No. 4,966,830, pyromethene dyes described in JP-A-5-241338, pyrenes, phenothiazines, fluorenes, etc. Can be listed, but is not particularly limited.
  • sensitizers can be used alone or in combination of two or more.
  • the compounding amount of the sensitizer is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of the resist conjugate.
  • the surfactant is a component having an effect of improving the coatability, striation, developability as a resist, and the like of the resist composition of the present invention.
  • a surfactant any of a union type, cationic type, non-one type and amphoteric type can be used.
  • preferred surfactants are nonionic surfactants.
  • Nonionic surfactants have a higher affinity for the solvent used in the radiation-sensitive composition. Examples of nonionic surfactants include higher alkyl ethers of polyoxyethylene, higher alkyl ether ethers of polyoxyethylene, and higher fatty acids of polyethylene glycol.
  • F-Top manufactured by Gemcone Earth
  • Megafac manufactured by Dainippon Ink and Chemicals, Inc.
  • Florard manufactured by Sumitomo 3LEM
  • Asahigard Surflon (above, Asahi Glass )
  • KP manufactured by Toho Chemical Co., Ltd.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
  • the amount of the surfactant is preferably 2 parts by weight or less as an effective component of the surfactant per 100 parts by weight of the resist conjugate.
  • the resist composition of the present invention may contain one or more additives other than the above-mentioned crosslinking agents, sensitizers, and surfactants, as needed, as long as the object of the present invention is not impaired. More than one kind can be blended.
  • Other additives include, for example, dissolution promoters, dissolution control agents, dyes, pigments, and adhesion aids. For example, it is preferable to mix a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation at the time of exposure can be reduced. Further, it is preferable to add an adhesion auxiliary agent, since the adhesion to the substrate can be improved.
  • additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improver, and the like, and specifically, 4-hydroxy-4'methylchalcone.
  • it is prepared by dissolving each component in a solvent at the time of use to form a homogeneous solution, and then, if necessary, filtering the solution with a filter having a pore diameter of about 0.2 m or the like.
  • the total solid content concentration in the homogeneous solution is usually 50% by mass or less, preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and more preferably 1 to 10% by mass.
  • ethylene glycol Honoré mono-methylol Honoré ether Honoré acetate ethylene glycol Honoré monomethyl E Chino les ether Bruno rare Seteto, ethylene glycol Honoré mono over n - Ethylene glycolone monoenolequinoleate, such as n-butinooleatenoleacetate and ethylene glycol monoenoate acetate; ethylene glycol monoene etherate, such as ethylene glycolone monomethinoleether and ethylene glycolone monoethyl ether Alkyl ethers; propylene glycol Propylene glycol monoalkyl ether acetates such as olemonomethinoleate enoleacetate, propylene glycol olemonoethino oleate enoate acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol o
  • the resist composition of the present invention may be irradiated with, or induced by, visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray and ion beam within a range that does not inhibit the object of the present invention.
  • a compound having a cross-linking reactive group that causes a cross-linking reaction by a chemical reaction a compound having a butyl group, an aryl group, a cinnamoyl group, a bursilyl group, an epoxy group, a chloromethyl group, a phenyl group, a Z- or a resin, can do.
  • the compound having a cross-linking reactive group and the Z or resin are not particularly limited, and the compound and the Z or resin soluble in the alkaline aqueous solution may be combined with visible light and ultraviolet light.
  • crosslinking-reactive group-introducing agent refers to a compound having a crosslinking-reactive group, such as an acid, an acid chloride, an acid anhydride, a carboxylic acid derivative compound such as dicarbonate, an alkylno, or a ride. Of these, acid salt products are particularly preferred.
  • the crosslinking reactive group is a vinyl group, an aryl group, a cinnamoyl group, a bursilyl group, an epoxy group, a methyl halide group, or a phenyl halide group. These may be used as a mixture of one or more.
  • the resist composition of the present invention is usually compounded at 40 to 99.998% by weight of the resist compound (A), 0.001 to 10% by weight of the compound (B), and other components (C) in the total solid content. 0.001 to 50% by weight, preferably 90 to 99.99% by weight, and the compound (B) O. 001 to: LO weight are more preferable. Within the above range, the performance such as resolution is excellent. In the case where the compound (B) functions as a negative resist without the compound (B) in the total solid content, 100% by weight of the resist conjugate (A) is particularly preferable.
  • the resist substrate is a resist substrate on which a resist film made of the resist composition is formed
  • the pattern-formed substrate is a substrate on which the resist film on the resist substrate is exposed.
  • This is a substrate having a patterned resist film obtained by development.
  • pattern forming material refers to a composition formed on a resist substrate and capable of forming a pattern by irradiation of light, extreme ultraviolet (EUV), electron beam, or radiation, and is synonymous with “resist film”.
  • the “patterned wiring board” is a substrate having patterned wirings obtained by etching a pattern forming substrate.
  • a step of applying the resist composition on a substrate to form a resist film a step of heat-treating the resist film as necessary, Exposing the resist film to visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, or ion beam power. And then subjecting the exposed resist film to development using an alkali developing solution.
  • EUV extreme ultraviolet light
  • the resist composition of the present invention is applied onto a substrate such as a silicon wafer or a wafer coated with aluminum by a coating means such as spin coating, casting coating, or roll coating.
  • a coating means such as spin coating, casting coating, or roll coating.
  • a surface treatment agent such as hexamethylene disilazane may be applied on the substrate in advance.
  • the coated substrate is heated as necessary.
  • the heating conditions are preferably 20 to 250 ° C, more preferably 20 to 150 ° C, depending on the composition of the radiation-sensitive composition. Heating is preferable because the adhesiveness of the resist to the substrate may be improved.
  • the resist film is exposed to a desired pattern by any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray, and ion beam. Exposure conditions and the like are appropriately selected according to the composition of the radiation-sensitive composition and the like. In the present invention, in order to stably form a high-precision fine pattern in exposure, it is preferable to perform heating after radiation irradiation.
  • the heating conditions are preferably 20 to 250 ° C, more preferably 20 to 150 ° C, depending on the composition of the radiation-sensitive composition.
  • a predetermined resist pattern is formed by developing the exposed resist film with a resist soluble developer.
  • the resist friendly ⁇ image solution the resist solution same as can be used as the solvent was adjusted, for example, ethylene glycol monomethyl ether ⁇ cetearyl over preparative, ethylene glycol Honoré monomethyl E Chino les ether Honoré acetate, ethylene glycol Honoré monomethyl over n propyl Ethylene glycolone monoethylene ether acetates (PGMEA), propylene glycol monoethyl ether, such as ethylene glycolone monooleate acetate and ethylene glycolone monooleate acetate, etc.
  • PGMEA propyl Ethylene glycolone monoethylene ether acetates
  • acetate propylene glycol monomethyl over n-propyl ether acetate, propylene glycol monomethyl over n - propylene glycol monoalkylene ether acetates such as butyl acetate; methyl lactate E Lactate esters such as (EL), n-propyl lactate, n-butyl lactate, n-amyl lactate; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, Aliphatic carboxylic acid esters such as methyl propionate and ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxyethyl ethyl pionate, 3-methoxy-2 Methyl methyl propionate, 3-methoxybutyl
  • an appropriate amount of the surfactant can be added to the resist-soluble developer.
  • etching is performed to obtain a patterned wiring board.
  • the etching can be performed by a known method such as dry etching using a plasma gas.
  • plating After forming the resist pattern, plating can be performed.
  • the plating method include copper plating, solder plating, nickel plating, and gold plating.
  • the resist pattern can be stripped with an organic solvent having higher solubility than the resist soluble developer.
  • organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like.
  • peeling method include a dipping method and a spray method.
  • the wiring board on which the resist pattern is formed may have a small-diameter through hole, which is suitable for a multilayer wiring board.
  • the wiring substrate obtained by using the resist composition of the present invention can also be formed by a method of forming a resist pattern, depositing a metal in a vacuum, and then dissolving the resist pattern with a solution, that is, a lift-off method.
  • Tables 1 and 2 show the results of these analyses.
  • the number of atoms of each compound is defined as the value of the descriptive formula.
  • Table 2 shows the NMR measurement results.
  • DMAc dimethimecetamide
  • a solution of example mosquitoes ⁇ the DMAc3ml to 2 lg, APO. 55g / 5mmol (l. 0 equivalents ) was slowly added dropwise to a 5 ml solution of DMAc, and the mixture was stirred at room temperature for 1 hour.
  • the reaction solution was added to a large amount of water for crystallization, and the crystals separated by filtration were dissolved in acetone, and then added again to a large amount of water for crystallization to obtain 0.5 g of a white powder.
  • 0.5 g of the main component 3.02 g (25 mmol) of 3-bromopropene (ACROS reagent), 3.5 g (25 mmol) of potassium carbonate (reagent manufactured by Kanto Idani Gaku Co., Ltd.), sodium iodide (Reagent manufactured by Kanto-Danigaku Co., Ltd.) 0.036 g (0.25 mmol) and 30 ml of acetone were added, and the mixture was stirred at 55 ° C.
  • a solution of example mosquitoes ⁇ the DMAc3ml to 2 lg, APO. 55g / 5mmol (l. 0 equivalents ) was slowly added dropwise to a 5 ml solution of DMAc, and the mixture was stirred at room temperature for 1 hour.
  • the reaction solution was added to a large amount of water for crystallization, and the crystals separated by filtration were dissolved in acetone, and then added again to a large amount of water for crystallization to obtain 0.5 g of a white powder.
  • 0.5 g of the main component, 1.8 g (92.5 mmol) of epichlorohydrin and 0.73 g of 2-propanol were charged, and the mixture was heated to 40 ° C and uniformly dissolved.
  • 0.32 g of an aqueous solution of sodium hydroxide was added dropwise over 90 minutes. During this period, the temperature was gradually raised, and after the completion of the dropwise addition, the temperature in the system was adjusted to 65 ° C., followed by stirring for 30 minutes.
  • a solution of example mosquitoes ⁇ the DMAc3ml to 2 lg, APO. 55g / 5mmol (l. 0 equivalents ) was slowly added dropwise to a 5 ml solution of DMAc, and the mixture was stirred at room temperature for 1 hour.
  • 3.24 g (25 mmol) of bromoke-containing methane and 2.29 g of triethylamine (a reagent manufactured by Kanto-Danigaku Co., Ltd.) were slowly dropped, and the mixture was stirred at room temperature for 3 hours.
  • Acetic TIPTP Echiru Z black port benzene (70Z3 (weight ratio)) 27 wt% solution (Bayer Desmodur RFE, NCO equivalent: 581, nonvolatile content: 27 weight 0/0). 2. 91g and APO 55 g / 5 mmol (l. 0 equivalents) and 3.02 g (25 mmol) of 3-bromopropene were reacted in the same manner as in Synthesis Example 2 to obtain 0.65 g of compound (28-2).
  • APO. 55 g / 5 mmol (1.0 eq) and 2.12 g (22.5 mmol) of Atari iris mouth were reacted in the same manner as in Synthesis Example 1 to obtain 0.55 g of compound (29-1).
  • MDI polymethylene polyisocyanate
  • Tolylene iso Xia acetate E Chi le 75 weight trimethylolpropane ⁇ duct of sulfonate (TDITMP) 0/0 solution manufactured by Sumika Bayer Urethane Co. Sumidur L75, NCO equivalent: 324, nonvolatile content: 75 weight 0 / 0 ) 1.58 g
  • the reaction of APO. 55 g / 5 mmol (1.0 equivalent) and attarylyl chloride 2.12 g (22.5 mmol) was carried out in the same manner as in Synthesis Example 1 to give 0.58 g of compound (24-1). Obtained.
  • TDITMP acetate Echiru 75 weight 0/0 solution manufactured by Sumika Bayer Urethane Co. Sumidur L75, NCO equivalent: 324, nonvolatile content: 75 weight 0/0
  • APO.55g / 5mmol (l.0 Equivalent) and 3.02 g (25 mmol) of 3-bromopropene were reacted in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (24-2).
  • TDITMP acetate Echiru 75 weight 0/0 solution manufactured by Sumika Bayer Urethane Co. Sumidur L75, NCO equivalent: 324, nonvolatile content: 75 weight 0/0
  • 1.58g, APO.55g / 5mmol (l.0 Equivalent) and 3.24 g (25 mmol) of bromochloromethane were reacted in the same manner as in Synthesis Example 4 to obtain 0.58 g of compound (24-4).
  • HDI biuret of sulfonate
  • Synthesis Example 22 Synthesis of compound (25-2) HDI of methoxypropyl acetate Z xylene 75 weight 0/0 solution (manufactured by Sumika Bayer Urethane Co. Sumidur N75, NCO equivalent: 255, nonvolatile content: 75 weight 0/0). 1. 31 g and, APO 55 g / 5 mmol (l. 0 equivalent) and 3.02 g (25 mmol) of 3-bromopropene were reacted in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (25-2).
  • the resist was spin-coated on a clean silicon wafer, and then subjected to a pre-exposure bake (PB) in an oven to form a 0.2-m-thick resist film.
  • PB pre-exposure bake
  • the resist coating was exposed to i-line at a wavelength of 365 nm in Examples 1 to 32, and exposed to an electron beam in Examples 33 to 36, and Comparative Example 1, and then exposed to an electron beam in an oven and then beta-exposed. 4 tables).
  • Developing was performed at 23 ° C for 5 seconds with DMA c by the stationary method. Thereafter, the resultant was dried to form a negative resist pattern.
  • Table 5 shows the evaluation results.
  • a solubility test of the resist compound (A) in a safe solvent was performed at 23 ° C.
  • the solubility in the solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and ethyl lactate and most soluble was evaluated according to the following criteria.
  • the resist composition was spin-coated on a silicon wafer with a spin coater to form a resist film, which was then heated on a hot plate at 110 ° C for 60 minutes, and the resist coating on a 6-inch silicon wafer was evaluated according to the following criteria.
  • the resist pattern was observed with an electron microscope, and the presence or absence of the formation of line and space of IOOnmL & S was confirmed.
  • Type Amount (g) Type Amount (g) Type Amount (g)
  • R-l Irgacure 907 (2-methyl-1 [(4-methylthio) phenyl] 2 morpholinopropane-1-one, Chinoku, manufactured by Specialty Chemicals)

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Abstract

Il est prévu une composition de résist comprenant un ou plusieurs composés de résist (A) satisfaisant à toutes les exigences, à savoir (a) posséder, dans la molécule de celle-ci, au moins un groupe de réticulation subissant une réaction de réticulation directement ou indirectement, par irradiation avec un rayonnement sélectionné parmi le groupe consistant en une lumière visible, un rayon ultraviolet, un laser excimère, un rayon extrême ultraviolet (REUV), un faisceau électronique, un rayon X et un faisceau ionique, (b) posséder, dans la molécule de celle-ci, un ou plusieurs groupes fonctionnels sélectionnés parmi le groupe consistant en un groupe urée, un groupe uréthane, un groupe aminé et un groupe imidé, (c) d’un poids moléculaire de 500 à 5000, et (d) posséder une structure ramifiée ; et le composé de résist. La composition de résist ci-dessus permet la formation d’un motif de résist d’une définition améliorée, ceci se traduisant par la fabrication d’un élément semi-conducteur au degré d’intégration renforcé.
PCT/JP2005/009249 2004-05-21 2005-05-20 Composé de résist et composition de résist WO2005114331A1 (fr)

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JP2006291188A (ja) * 2005-03-15 2006-10-26 Showa Denko Kk （メタ）アクリロイル基含有芳香族イソシアネート化合物およびその製造方法
WO2006132139A1 (fr) * 2005-06-06 2006-12-14 Mitsubishi Gas Chemical Company, Inc. Composé pour réserve et composition de réserve
JP2009203186A (ja) * 2008-02-28 2009-09-10 Fujifilm Corp フォトレジスト用化合物、フォトレジスト液、およびこれを用いるエッチング方法
JP2009203189A (ja) * 2008-02-28 2009-09-10 Fujifilm Corp フォトレジスト用化合物、フォトレジスト液、およびこれを用いるエッチング方法
WO2011054792A1 (fr) * 2009-11-03 2011-05-12 Bayer Materialscience Ag Acrylates d'uréthane à haut indice de réfraction et densité de double liaison réduite
US8044235B2 (en) 2005-03-15 2011-10-25 Showa Denko K.K. (Meth) acryloyl group-containing aromatic isocyanate compound and production process thereof
JP4806019B2 (ja) * 2005-07-20 2011-11-02 イーストマン コダック カンパニー 平版印刷版に適したフォトポリマー組成物
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US8859174B2 (en) 2011-05-24 2014-10-14 Canon Kabushiki Kaisha Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
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CN108129354A (zh) * 2017-12-28 2018-06-08 湖北航天化学技术研究所 凝胶剂、凝胶组合物及凝胶制备方法
US20210155639A1 (en) * 2019-11-27 2021-05-27 Facebook Technologies, Llc Thiophosphate and phosphine sulfide derivatized monomers and polymers for volume bragg gratings
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JP2006291188A (ja) * 2005-03-15 2006-10-26 Showa Denko Kk （メタ）アクリロイル基含有芳香族イソシアネート化合物およびその製造方法
US8044235B2 (en) 2005-03-15 2011-10-25 Showa Denko K.K. (Meth) acryloyl group-containing aromatic isocyanate compound and production process thereof
WO2006103979A1 (fr) * 2005-03-15 2006-10-05 Showa Denko K.K. Groupe (meth)acryloyl contenant un compose d'isocyanate aromatique et procede de fabrication correspondant
WO2006132139A1 (fr) * 2005-06-06 2006-12-14 Mitsubishi Gas Chemical Company, Inc. Composé pour réserve et composition de réserve
JP4806019B2 (ja) * 2005-07-20 2011-11-02 イーストマン コダック カンパニー 平版印刷版に適したフォトポリマー組成物
JP2009203186A (ja) * 2008-02-28 2009-09-10 Fujifilm Corp フォトレジスト用化合物、フォトレジスト液、およびこれを用いるエッチング方法
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US8808946B2 (en) 2009-11-03 2014-08-19 Bayer Materialscience Ag Urethane acrylate having a high refractive index and reduced double bond density
WO2011054792A1 (fr) * 2009-11-03 2011-05-12 Bayer Materialscience Ag Acrylates d'uréthane à haut indice de réfraction et densité de double liaison réduite
CN102574877A (zh) * 2009-11-03 2012-07-11 拜尔材料科学股份公司 具有高折射率和降低的双键密度的氨基甲酸酯丙烯酸酯
KR101747467B1 (ko) 2009-11-03 2017-06-14 코베스트로 도이칠란드 아게 굴절률이 높고 이중 결합 밀도가 감소된 우레탄 아크릴레이트
US8859174B2 (en) 2011-05-24 2014-10-14 Canon Kabushiki Kaisha Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
JP2013137490A (ja) * 2011-05-24 2013-07-11 Canon Inc 電子写真感光体、電子写真感光体の製造方法、プロセスカートリッジおよび電子写真装置
EP2527922A1 (fr) * 2011-05-24 2012-11-28 Canon Kabushiki Kaisha Élément photosensible électrophotographique, son procédé de production, cartouche de traitement, appareil électrophotographique et composé d'urée
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