WO2022138670A1 - 化合物、重合体、組成物、膜形成用組成物、パターンの形成方法、絶縁膜の形成方法及び化合物の製造方法 - Google Patents

化合物、重合体、組成物、膜形成用組成物、パターンの形成方法、絶縁膜の形成方法及び化合物の製造方法 Download PDF

Info

Publication number
WO2022138670A1
WO2022138670A1 PCT/JP2021/047416 JP2021047416W WO2022138670A1 WO 2022138670 A1 WO2022138670 A1 WO 2022138670A1 JP 2021047416 W JP2021047416 W JP 2021047416W WO 2022138670 A1 WO2022138670 A1 WO 2022138670A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
iodine
hydroxyl
ester
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2021/047416
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
禎 大松
悠 岡田
威 小熊
正裕 松本
結士 新美
雅敏 越後
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co 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 Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to CN202180086595.5A priority Critical patent/CN116615405A/zh
Priority to US18/268,940 priority patent/US20230348351A1/en
Priority to JP2022571521A priority patent/JP7814674B2/ja
Priority to KR1020237024950A priority patent/KR20230123513A/ko
Publication of WO2022138670A1 publication Critical patent/WO2022138670A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/24—Halogenated derivatives
    • C07C39/373—Halogenated derivatives with all hydroxy groups on non-condensed rings and with unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
    • C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
    • C07C59/70—Ethers of hydroxy-acetic acid, e.g. substitutes on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/63—Halogen-containing esters of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/10—Oxygen atoms
    • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/16—Halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C08F12/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the present invention relates to a compound, a polymer, a composition, a film-forming composition, a pattern forming method, an insulating film forming method, and a compound manufacturing method.
  • the general resist material so far is a polymer-based resist material capable of forming an amorphous film.
  • a polymer-based resist composition such as polymethylmethacrylate, polyhydroxystyrene having an acid dissociative group, or polyalkylmethacrylate can be mentioned (see, for example, Non-Patent Document 1).
  • a resist thin film prepared by applying a solution of these resist compositions on a substrate is irradiated with ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays, etc. to form a line pattern of about 10 to 100 nm. is doing.
  • Non-Patent Document 2 lithography using an electron beam or extreme ultraviolet (EUV) has a different reaction mechanism from ordinary optical lithography
  • EUV extreme ultraviolet
  • the goal is to form fine patterns of several nm to ten and several nm.
  • a resist composition having higher sensitivity to the exposure light source is required.
  • EUV extreme ultraviolet rays
  • it is required to further increase the sensitivity in terms of throughput.
  • the sensitivity of extreme ultraviolet (EUV) does not necessarily correlate with the sensitivity of electron beam (EB), and it is required to exhibit particularly high sensitivity to extreme ultraviolet (EUV).
  • a resist composition containing a metal complex such as titanium, tin, hafnium or zirconium has been proposed (see, for example, Patent Document 1).
  • the conventionally developed film-forming composition has a problem that the sensitivity to an exposure light source is not sufficiently high in the formation of a finer-lined pattern.
  • the present invention relates to a compound, a polymer, a composition, a film-forming composition, a pattern forming method, an insulating film forming method and a compound, which can obtain a resist having better exposure sensitivity.
  • the purpose is to provide a manufacturing method.
  • the present inventors have found that the exposure sensitivity of a resist formed by using a compound having a specific structure or a polymer containing the compound as a constituent unit can be improved.
  • the present invention has been completed. That is, the present invention is as follows.
  • a compound represented by the following formula (1) is a hydrogen atom, a methyl group or a trifluoromethyl group , RX is an OR B or a hydrogen atom, and RB is a substituted or unsubstituted carbon number of 1 to 30.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • [6] A composition containing 1% by mass or more and 10% by mass or less of the compound represented by the following formula (1A) with respect to the entire compound according to any one of [1] to [5].
  • the formula (1A1), and the formula (1A2), RA , RX, RB and P are the same as the definitions in the formula (1), and R sub is the formula ( 1A1 ) or Represents formula (1A2), where * is a binding site with an adjacent building block.
  • [7] A composition containing the compound according to any one of [1] to [5] and the compound represented by the following formula (1B) in an amount of 1% by mass or more and 10% by mass or less based on the whole compound.
  • the compound according to any one of [1] to [5] is included.
  • the content of impurities containing one or more elements selected from the group consisting of Mn, Al, Si, and Li is 1 mass ppm or less with respect to the entire compound in terms of elements, [9] or [10].
  • the composition according to. [12] The composition according to any one of [9] to [11], wherein the content of the phosphorus-containing compound is 10% by mass or less with respect to the entire compound.
  • X is an organic group having 1 to 5 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, Br, or I, F, Cl, and Br, respectively.
  • L 1 is independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphin group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphorus.
  • the L1 ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphon group, urethane group, urea group, amide group, imide group, or phosphoric acid group is an acid group.
  • Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon group.
  • Urethane group, urea group, amide group, imide group, or phosphoric acid group and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group of Y.
  • Urea group, amide group, imide group, and phosphate group may have a substituent.
  • RA is the same as the definition in equation (1).
  • A is an organic group having 1 to 30 carbon atoms.
  • Z is independently an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, or a carbonate ester group, and the alkoxy group, the ester group, the acetal group, the carboxylalkoxy group, or the carbonate ester group of Z is It may have a substituent and may have a substituent.
  • m is an integer of 0 or more
  • n is an integer of 1 or more
  • r is an integer of 0 or more.
  • RC11 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RC12 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • RC13 is a cycloalkyl group or a heterocycloalkyl group having 4 to 20 carbon atoms, which is formed by combining carbon atoms bonded to RC13 .
  • * Is a binding site with an adjacent structural unit.
  • RC21 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RC22 and RC23 are independently alkyl groups having 1 to 4 carbon atoms.
  • RC24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of carbons 1. It is an alkyl group of about 30, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups. However, one of R 7 to R 10 is a hydroxyl group or a methoxy group), and the step of preparing an iodine-containing alcoholic substrate; b) A dehydration step of dehydrating the iodine-containing alcoholic substrate, A method for producing an iodine-containing vinyl monomer represented by the following formula (1), which comprises.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups.
  • R 7 to R 10 is a hydroxyl group or a methoxy group
  • step of preparing an alcoholic substrate f) With the iodine introduction step of introducing an iodine atom into the alcoholic substrate;
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • a method for producing an iodine-containing vinyl monomer represented by the following formula (2) which comprises.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • RC is an substituted or unsubstituted acyl group having 1 to 30 carbon atoms.
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group, an alkoxy group or an ester.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups.
  • R 7 to R 10 is a hydroxyl group or a methoxy group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups.
  • R 7 to R 10 is a hydroxyl group or a methoxy group
  • step of preparing an alcoholic substrate f)
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups.
  • R 7 to R 10 is a hydroxyl group or a methoxy group.
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group, an alkoxy group or an ester.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • An iodine introduction step of introducing an iodine atom into the ketone substrate and A method for producing an iodine-containing ketone compound represented by the following formula (1-2), which comprises.
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group, an alkoxy group or an ester.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups.
  • R 7 to R 10 is a hydroxyl group or a methoxy group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • a compound, a polymer, a composition, a film-forming composition, a pattern forming method, an insulating film forming method, and a compound manufacturing method which can obtain a resist having better exposure sensitivity. be able to.
  • the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
  • (Meta) acrylate means at least one selected from acrylates, haloacrylates and methacrylates.
  • the halo acrylate means an acrylate in which a halogen is substituted at the position of the methyl group of the methacrylate.
  • Other terms that the expression (meth) has are interpreted in the same manner as (meth) acrylate.
  • (Co) polymer means at least one selected from homopolymers and copolymers.
  • Compound (A) The compound according to the first embodiment (hereinafter, also referred to as “compound (A)” in the first embodiment) is represented by the following formula (1).
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • the compound (A) according to the present embodiment it is possible to provide a compound for obtaining a resist having better exposure sensitivity.
  • substitution means that one or more hydrogen atoms in a functional group are substituted with a substituent unless otherwise defined.
  • the "substituent” is not particularly limited, but is, for example, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, an alkyl group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms.
  • Examples thereof include an aryl group, an alkoxyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and an amino group having 0 to 30 carbon atoms. Be done.
  • the alkyl group may be any of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.
  • RA is a hydrogen atom or a methyl group in the formula (1) from the viewpoint of increasing the hydrophilicity.
  • RB is an alkyl group having 1 to 4 carbon atoms.
  • P is preferably a hydroxyl group, an ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, and more preferably an ester group, an acetal group or a carbonate ester group.
  • the above compound (A) is preferably used in combination with the compound represented by the following formula (1A). That is, the composition according to the present embodiment preferably contains the compound (A) and the compound represented by the formula (1A).
  • the composition contains the compound represented by the formula (1A) in a range of 1% by mass or more and 10% by mass or less with respect to the entire compound (A) from the viewpoint of improving the exposure sensitivity and reducing the residual defects. It is preferable that it is prepared so as to be, more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and 1 mass ppm or more and 1 mass. It is particularly preferable that it is in the range of% or less.
  • the above compound (A) is preferably used in combination with the compound represented by the following formula (1B). That is, the composition according to this embodiment preferably contains the compound (A) and the compound represented by the formula (1B).
  • the composition contains the compound represented by the formula (1B) in a range of 1% by mass or more and 10% by mass or less with respect to the entire compound (A) from the viewpoint of improving the exposure sensitivity and reducing the residual defects. It is preferable that it is prepared so as to be, more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and 1 mass ppm or more and 1 mass. It is particularly preferable that it is in the range of% or less.
  • the composition according to this embodiment preferably contains the compound (A) and the compound represented by the formula (1C).
  • the compound represented by the formula (1C) has a mass of 1 mass ppm or more and 10 mass with respect to the compound (A) with respect to the entire compound (A). It is preferably contained in the range of% or less, more preferably in the range of 1 mass ppm or more and 5 mass% or less, further preferably in the range of 1 mass ppm or more and 3 mass% or less, and 1 mass ppm or more and 1 mass. It is particularly preferable that it is in the range of% or less.
  • RA , RX , RB and P are the same as the definitions in equation (1), but neither RB nor P includes I).
  • the composition of this embodiment contains compound (A).
  • K potassium
  • the content of impurities containing K in the composition is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, and further, in terms of elements, with respect to the entire compound (A). It is preferably 0.1 mass ppm or less, and even more preferably 0.005 mass ppm or less.
  • the content of peroxide is preferably 10% by mass or less, more preferably 1 ppm or less, still more preferably 0.1 ppm or less, based on the whole compound (A). be.
  • one or more elemental impurities selected from the group consisting of Mn (manganese), Al (aluminum), Si (silicon), and Li (lithium) (preferably from the group consisting of Mn and Al).
  • the content of one or more selected elemental impurities is preferably 1 ppm or less, more preferably 0.5 ppm or less, still more preferably 0.1 ppm or less with respect to the entire compound (A) in terms of elements. Is.
  • the content of the phosphorus-containing compound is preferably 10 ppm or less, more preferably 8 ppm or less, and further preferably 5 ppm or less with respect to the entire compound (A).
  • the content of maleic acid is preferably 10 ppm or less, more preferably 8 ppm or less, and further preferably 5 ppm or less with respect to the entire compound (A).
  • the polymer (A) of the present embodiment contains a structural unit derived from the above-mentioned compound (A).
  • the polymer (A) can increase the sensitivity to an exposure light source when blended in the resist composition. In particular, even when extreme ultraviolet rays are used as the exposure light source, sufficient sensitivity can be exhibited and a fine line pattern with a narrow line width can be satisfactorily formed.
  • the stability of the resist composition is improved, and the decrease in sensitivity to the exposure light source is suppressed even when the resist composition is stored for a long period of time.
  • the polymer (A) of the present embodiment contains a structural unit derived from the compound (A).
  • the structural unit derived from the compound (A) contained in the polymer (A) includes, for example, a structural unit represented by the following formula (1-A).
  • RA, RX , RB and P are the same as the definitions in formula (1), and * is a binding site with an adjacent structural unit.
  • the other monomer copolymerized with the compound (A) preferably contains a structural unit represented by the following formula (C0). That is, in the polymer (A), in addition to the structural unit represented by the formula (1-A), the structural unit represented by the following formula (C0), the following formula (C1) or the following formula (C2) is further added. It is preferable to include it.
  • X is an organic group having 1 to 5 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, Br, or I, F, Cl, and Br, respectively.
  • L 1 is independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphin group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphorus.
  • the L1 ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphon group, urethane group, urea group, amide group, imide group, or phosphoric acid group is an acid group.
  • Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon group.
  • Urethane group, urea group, amide group, imide group, or phosphoric acid group and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group of Y.
  • Urea group, amide group, imide group, and phosphate group may have a substituent.
  • RA is the same as the definition in equation (1).
  • A is an organic group having 1 to 30 carbon atoms.
  • Z is independently an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, or a carbonate ester group, and the alkoxy group, the ester group, the acetal group, the carboxylalkoxy group, or the carbonate ester group of Z is It may have a substituent and may have a substituent.
  • m is an integer of 0 or more
  • n is an integer of 1 or more
  • r is an integer of 0 or more.
  • RC11 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RC12 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • RC13 is a cycloalkyl group or a heterocycloalkyl group having 4 to 20 carbon atoms, which is formed by combining carbon atoms bonded to RC13 . * Is a binding site with an adjacent structural unit.
  • RC21 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RC22 and RC23 are independently alkyl groups having 1 to 4 carbon atoms.
  • RC24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. Two or three of the RC22 , RC23 , and RC24 were formed together with carbon atoms bonded to two or three of the RC22 , RC23 , and RC24 . An alicyclic structure having 3 to 20 carbon atoms may be formed. * Is a binding site with an adjacent structural unit. )
  • composition for film formation The film-forming composition of the present embodiment can also be used as an optical component-forming composition to which a lithography technique is applied.
  • Optical components are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, microlenses, frennel lenses, viewing angle control lenses, contrast-enhancing lenses, etc.), retardation films, electromagnetic wave shielding films, and prisms.
  • the composition is an embedded film and a flattening film on a photodiode, a flattening film before and after a color filter, a microlens, and a flattening on a microlens, which are members of a solid-state image sensor that are particularly required to have a high refractive index. It can be suitably used as a film and a conformal film.
  • the film-forming composition of the present embodiment may contain the compound (A), the composition of the present embodiment, or the polymer (A).
  • the film-forming composition of the present embodiment may further contain an acid generator (C), a base generator (G), or an acid diffusion control agent (E) (basic compound).
  • the method for forming the resist pattern of the present embodiment is as follows.
  • the method for forming the insulating film of the present embodiment may include the method for forming the resist pattern of the present embodiment. That is, the method for forming the insulating film of the present embodiment is as follows. A step of forming a resist film on a substrate using the film-forming composition of the present embodiment, The step of exposing the pattern to the resist film and The step of developing the resist film after the exposure and May include.
  • the method for producing the iodine-containing vinyl monomer represented by the formula (1) is a) General structure represented by the following formula (1-1): (In formula (1-1), RA is a hydrogen atom, a methyl group or a trifluoromethyl group , RX is an OR B or a hydrogen atom, and RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups.
  • R 7 to R 10 is a hydroxyl group or a methoxy group
  • the step of preparing an iodine-containing alcoholic substrate May include.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups.
  • R 7 to R 10 is a hydroxyl group or a methoxy group
  • the iodine introduction step of introducing an iodine atom into the alcoholic substrate; May include.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • the method for producing an iodine-containing vinyl monomer represented by the following formula (2) is k)
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • RC is an substituted or unsubstituted acyl group having 1 to 30 carbon atoms.
  • the method for producing an iodine-containing alcoholic compound represented by the following formula (1-1) is c) General structure represented by the following formula (1-2):
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group, an alkoxy group or an ester.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of carbons 1. It is an alkyl group of about 30, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups. However, one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • the method for producing an iodine-containing alcoholic compound represented by the following formula (1-1) is e) General structure represented by the following formula (1-3): (In formula (1-3), RA is a hydrogen atom, a methyl group or a trifluoromethyl group , RX is an OR B or a hydrogen atom, and RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is an alkyl group of about 30, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups. However, one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • the method for producing the iodine-containing ketone compound represented by the following formula (1-2) is g) General structure represented by the following formula (1-4):
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group, an alkoxy group or an ester.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group, an alkoxy group or an ester.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group. be.
  • the method for producing an iodine-containing vinyl monomer represented by the following formula (1) is i) General structure represented by the following formula (1-4): (In the formula (1-4), RX is an OR B or a hydrogen atom, RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group, an alkoxy group or an ester.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of carbons 1. It is an alkyl group of about 30, and P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups. However, one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • the method for producing an iodine-containing vinyl monomer represented by the following formula (1) is a) General structure represented by the following formula (1-5): (In formula (1-5), RA is a hydrogen atom, a methyl group or a trifluoromethyl group , RX is an OR B or a hydrogen atom, and RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • the method for producing an iodine-containing vinyl monomer represented by the following formula (1) is a) General structure represented by the following formula (1-5): (In formula (1-5), RA is a hydrogen atom, a methyl group or a trifluoromethyl group , RX is an OR B or a hydrogen atom, and RB is a substituted or unsubstituted carbon number of carbons 1.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RX is an OR B or a hydrogen atom
  • RB is a substituted or unsubstituted carbon number of 1 to 30.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon.
  • the compounds, polymers, compositions, film-forming compositions, pattern-forming methods, insulating film-forming methods, and compound-producing methods described above in this embodiment may be applied to extreme ultraviolet applications.
  • the second embodiment is an embodiment in the case where RX in the compound (A) in the first embodiment is OR B.
  • the second embodiment is an example for explaining the present invention, and the present invention is not limited to the second embodiment.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group or an alkoxy group.
  • Or a phosphate group is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group or an alkoxy group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RA is preferably a hydrogen atom or a methyl group in order to increase the sensitivity.
  • a trifluoromethyl group is preferable as RA from the viewpoint of enhancing absorption to EUV.
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
  • RB is preferably an alkyl group having 1 to 4 carbon atoms, and an alkyl having 1 to 2 carbon atoms. Groups are more preferred.
  • substitution means that one or more hydrogen atoms in a functional group are substituted with a substituent unless otherwise defined.
  • the "substituent” is not particularly limited, but is, for example, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, an alkyl group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms.
  • Examples thereof include an aryl group, an alkoxyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and an amino group having 0 to 30 carbon atoms. Be done.
  • the alkyl group may be any of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.
  • the alkyl group having 1 to 30 carbon atoms is not limited to the following, but for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, and the like. Examples thereof include an n-pentyl group, an n-hexyl group, an n-dodecyl group and a barrel group.
  • Examples of the aryl group having 6 to 30 carbon atoms include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a perylene group and the like.
  • Examples of the alkenyl group having 2 to 30 carbon atoms include, but are not limited to, an ethynyl group, a propenyl group, a butynyl group, a pentynyl group and the like.
  • Examples of the alkynyl group having 2 to 30 carbon atoms include, but are not limited to, an acetylene group and an ethynyl group.
  • the alkoxy group having 1 to 30 carbon atoms is not limited to the following, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
  • P is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group and a thioether group.
  • Phosphin group, phosphon group, urethane group, urea group, amide group, imide group, or phosphoric acid group and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphin group of P.
  • Phosphon group, urethane group, urea group, amide group, imide group, and phosphate group may have a substituent.
  • the ester group is preferably a tertiary ester group from the viewpoint of increasing sensitivity.
  • * 3 is a binding site with A.
  • P is preferably a hydroxyl group, an ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxylalkoxy group, and an acetal group or a carboxyl group.
  • Carboxyalkoxy groups are even more preferred.
  • an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable.
  • a tertiary ester group, an acetal group, a carbonic acid ester group or a carboxylalkoxy group is preferable.
  • P is preferably a group represented by the following formula (P-1) independently of each other.
  • L 2 is a group that is cleaved by the action of an acid or base.
  • * 1 is a binding site with a benzene ring
  • * 2 is a binding site with R 2 .
  • L 2 is preferably a tertiary ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxylalkoxy group, and an acetal group, from the viewpoint of high sensitivity.
  • a carboxylalkoxy group is more preferable.
  • an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable.
  • P is a formula for the purpose of controlling the polymerizable property of the resin and setting the degree of polymerization within a desired range. It is preferably a group represented by (P-1). Since the compound (A) has iodine, it has a large influence on the active species during the polymer formation reaction and it is difficult to control it as desired. Therefore, the hydrophilic group in the compound (A) is represented by the formula (P-1). By having the group as a protective group, it is possible to suppress the variation in the formation of the copolymer derived from the hydrophilic group and the inhibition of the polymerization.
  • R2 is an aliphatic group containing a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a linear, branched or cyclic heteroatom having 1 to 30 carbon atoms.
  • the group group may or may not have a substituent.
  • R 2 is preferably an aliphatic group.
  • the aliphatic group in R2 is preferably a branched or cyclic aliphatic group.
  • the number of carbon atoms of the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and further preferably 4 or more and 8 or less.
  • the aliphatic group is not particularly limited, and examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group and an adamantyl group.
  • a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferable.
  • it when it is cleaved by the action of an acid or a base, it forms a carboxylic acid group and is insoluble in the dissociated part in the development process. Since the difference in solubility and the difference in dissolution rate between the rows are widened, the resolution is improved, and the residue at the bottom of the pattern in the fine line pattern is particularly suppressed, which is preferable.
  • P is, for example, a group independently represented by any of the following equations.
  • alkoxy group that can be used as P examples include an alkoxy group having 1 or more carbon atoms, and an alkoxy group having 2 or more carbon atoms is used from the viewpoint of the solubility of the resin after resinification in combination with another monomer. Alkoxy groups having 3 or more carbon atoms or a cyclic structure are preferable. Specific examples of the alkoxy group that can be used as P include, but are not limited to, the following.
  • amino group and the amide group that can be used as P a primary amino group, a secondary amino group, a tertiary amino group, a group having a quaternary ammonium salt structure, an amide having a substituent and the like can be appropriately used.
  • Specific examples of the amino group or amide group that can be used include, but are not limited to, the following.
  • the compound (A) according to the second embodiment contains an iodine group and OR B in the molecule, so that a polymer using the compound (A) is applied to a resist composition to form a film, expose, and develop.
  • pattern formation is performed by a lithography process consisting of, by improving the solubility in a developing solution with an iodine group and an OR B group, development defects such as development residue, roughness, and bridge, and other sensitivities and resolutions are achieved. It is expected that it is possible to achieve both lithography performance such as, and as a result, it is possible to improve the pattern quality in finer pattern formation. As a result, it is considered to be effective in improving the pattern quality in a pattern in which a defect due to solubility in a developing solution is a problem, such as a line and space pattern.
  • Examples of the compound (A) according to the second embodiment include compounds having the following structures.
  • composition according to the second embodiment preferably contains the compound (A) and the compound represented by the formula (1A).
  • the composition contains the compound represented by the formula (1A) in a range of 1% by mass or more and 10% by mass or less with respect to the entire compound (A) from the viewpoint of improving the exposure sensitivity and reducing the residual defects. It is preferable that it is prepared so as to be, more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and 1 mass ppm or more and 1 mass. It is particularly preferable that it is in the range of% or less.
  • the exposure sensitivity is improved by the high density of the iodine-containing portion and the P-containing portion in the proximity region. It will be the starting point. Further, the local increase in solubility in the resin leads to reduction of post-development residue defects in the lithography process.
  • Examples of the compound (1A) according to the second embodiment include compounds having the following structures.
  • composition according to the second embodiment preferably contains the compound (A) and the compound represented by the formula (1B).
  • Equation (1B) equation (1B1), or equation (1B2), RA , RB, and P are the same as the definitions in equation (1), n 2 is an integer of 0 to 4, and R sub2 represents the formula (1B1) or the formula (1B2), and * is a binding site with an adjacent structural unit.
  • the composition contains the compound represented by the formula (1B) in a range of 1% by mass or more and 10% by mass or less with respect to the entire compound (A) from the viewpoint of improving the exposure sensitivity and reducing the residual defects. It is preferable that it is prepared so as to be, more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and 1 mass ppm or more and 1 mass. It is particularly preferable that it is in the range of% or less.
  • the exposure sensitivity is improved by the high density of the iodine-containing portion and the P-containing portion in the proximity region. It will be the starting point. Further, the local increase in solubility in the resin leads to reduction of post-development residue defects in the lithography process.
  • Examples of the compound (1B) according to the second embodiment include compounds having the following structures.
  • composition according to the second embodiment preferably contains the compound (A) and the compound represented by the formula (1C).
  • RA , RB and P are the same as the definitions in equation (1). However, neither RB nor P includes I.
  • the compound represented by the formula (1C) is 1 mass ppm or more with respect to the compound (A) 10 with respect to the whole compound (A). It is preferably contained in the range of 1 mass% or less, more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and 1 mass ppm or more 1 It is particularly preferable that the content is in the range of mass% or less.
  • the composition thus prepared tends to be more stable. The reason is not clear, but it is presumed that the iodine atom equilibrium reaction occurs and stabilizes between the iodine-containing compound (A) and the iodine-free compound (1C).
  • the compound (1C) in combination with a compound having a structure in which an iodine atom is eliminated from the compound exemplified as the above-mentioned compound (A).
  • the composition thus produced has enhanced stability, it not only enhances storage stability, but also forms a resin having stable properties, imparts stable performance resist performance, and further. Leads to a reduction in post-development residue defects in the lithography process.
  • the method for using the compound represented by the formula (1C) in the range of 1% by mass or more and 10% by mass or less with respect to the entire compound (A) in the composition containing the compound (A) is not particularly limited. , A method of adding the compound (1C) to the compound (A), a method of producing the compound (1C) as a by-product during the production of the compound (A), and the like.
  • Examples of the compound (1C) according to the second embodiment include compounds having the following structures.
  • the compound represented by the formula (1), wherein P is a hydroxyl group is not particularly limited as an example of the synthesis method, but I, F, Cl, with respect to the hydroxy group-containing aromatic aldehyde derivative.
  • it can be synthesized by introducing a halogen group of Br and then converting an aldehyde group into a vinyl group.
  • a method of reacting iodine chloride in an organic solvent by carrying out an iodination reaction with a hydroxybenzaldehyde derivative see, for example, Japanese Patent Application Laid-Open No. 2012-180326), ⁇ under alkaline conditions.
  • a method of dropping iodine into an alkaline aqueous solution of phenol see JP-A-63-101342 and JP-A-2003-64012) can be appropriately selected.
  • an iodine monochloride-mediated iodination reaction in an organic solvent.
  • the compound (A) of the second embodiment can be synthesized.
  • a Wittig reaction for example, the method described in Synthetic Communications; Vol.22; nb4; 1992p513, Synthesis; Vol.49; nb.23; 2017; p5217
  • a Wittig reaction for example, the method described in Synthetic Communications; Vol.22; nb4; 1992p513, Synthesis; Vol.49; nb.23; 2017; p5217
  • the method for producing the compound (A) (iodine-containing vinyl monomer) represented by the formula (1) is a) General structure represented by equation (1-5): (In the formula (1-5), RA is a hydrogen atom, a methyl group or a trifluoromethyl group, RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and P is a hydroxyl group.
  • Examples of the iodine-containing aldehyde-based substrate or iodine-containing ketone substrate having the general structure represented by the formula (1-5) include 4-hydroxy-3-iodo-5-methoxybenzaldehyde and 3-ethoxy4-hydroxy-. Examples include 5-iodo-benzaldehyde.
  • the Wittig reaction step is a step of forming an alkene by a Wittig reaction, and is a step of forming an alkene from a carbonyl moiety having an aldehyde or a ketone using phosphorus irid, without limitation.
  • triphenylalkylphosphine bromide such as triphenylmethylphosphine bromide, which can form a stable phosphorus irid, can be used.
  • a phosphonium salt as phosphorus iris with a base to form phosphoylide in the reaction system and use it in the above-mentioned reaction.
  • the base conventionally known ones can be used, and for example, an alkali metal salt of alkoxide or the like can be appropriately used.
  • a method of reacting malonic acid under a base for example, Tetrahedron; Vol.46; nb.40; 2005; p6893, Tetrahedron; Vol.63; nb.4 (2007; the method described in p900, US2004 / 118673, etc.) and the like can be appropriately used.
  • the method for producing the compound (A) (iodine-containing vinyl monomer) represented by the formula (1) is a) A step of preparing an iodine-containing aldehyde-based substrate or an iodine-containing ketone substrate having a general structure represented by the above formula (1-5); b) With the malonic acid addition step of adding malonic acid to the iodine-containing aldehyde-based substrate or the iodine-containing ketone substrate; c) A hydrolysis step of hydrolyzing the iodine-containing aldehyde substrate or the iodine-containing ketone substrate to which the malonic acid is added to produce an iodine-containing carboxylic acid substrate; d) A decarboxylation step of decarboxylating the iodine-containing carboxylic acid substrate that has been hydrolyzed; And include.
  • the malonic acid addition step in the second embodiment is a step of forming a malonic acid derivative, and is a reaction between aldehyde and malonic acid, malonic acid ester or malonic acid anhydride, without limitation.
  • the hydrolysis step in the second embodiment is a step of forming a carboxylic acidic substrate by hydrolysis, and is a reaction of hydrolyzing an ester by the action of an acid or water, without limitation.
  • the decarboxylation step in the second embodiment is a step of decarboxylating from a carboxylic acidic substrate to obtain a vinyl monomer, and is not limited, but is preferably performed at a low temperature of 100 ° C. or lower, and a fluoride-based catalyst is used. Is more preferable.
  • the method for synthesizing the compound (A) of the second embodiment for example, the method described in the above-mentioned reference material can be appropriately used, but the method is not limited thereto.
  • the compound represented by the formula (1) in which P is an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group or a carbonic acid ester group is not particularly limited as an example of the synthesis method, but is not limited to the formula (1).
  • P is a hydroxyl group
  • an active carboxylic acid derivative compound such as acid chloride, acid anhydride or dicarbonate, alkyl halide, vinyl alkyl ether, dihydropyran, etc. It is obtained by reacting with a halocarboxylic acid alkyl ester or the like.
  • a compound represented by the formula (1) in which P is a hydroxyl group, is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran, or propylene glycol monomethyl ether acetate.
  • an aprotic solvent such as acetone, tetrahydrofuran, or propylene glycol monomethyl ether acetate.
  • vinyl alkyl ether such as ethyl vinyl ether or dihydropyran is added, and the reaction is carried out at normal pressure at 20 to 60 ° C. for 6 to 72 hours in the presence of an acid catalyst such as pyridinium p-toluenesulfonate.
  • the reaction solution is neutralized with an alkaline compound, added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain a compound represented by the formula (1).
  • a compound in which P is an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group or a carbonate ester group can be obtained.
  • a compound represented by the formula (1), in which P is a hydroxyl group is dissolved or suspended in an aprotic solvent such as acetone, THF, or propylene glycol monomethyl ether acetate.
  • an alkyl halide such as ethyl chloromethyl ether or a halocarboxylic acid alkyl ester such as methyl adamantyl bromoacetate is added, and the mixture is reacted at normal pressure at 20 to 110 ° C. for 6 to 72 hours in the presence of an alkaline catalyst such as potassium carbonate. ..
  • the reaction solution is neutralized with an acid such as hydrochloric acid, added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain a compound represented by the formula (1). Therefore, a compound in which P is an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group or a carbonate ester group can be obtained.
  • the method for synthesizing the compound (A) of the second embodiment it is more preferable to include the synthesis method shown below from the viewpoint of suppressing the yield and the amount of waste.
  • the iodine-containing alcoholic substrate used in the second embodiment may be, for example, an iodine-containing alcoholic substrate having a general structure represented by the following formula (1-1).
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group or a carbonate ester group.
  • R 7 to R 10 are , Independently, hydrogen, hydroxyl group, methoxy group, halogen or cyano group, except that one of R 7 to R 10 is a hydroxyl group or methoxy group.
  • Suitable iodine-containing alcoholic substrates are, but are not limited to, 1- (4-hydroxy-3-methoxy-5-iodophenyl) ethanol, 1- (3-ethoxy-4-hydroxy-5-iodophenyl). Examples thereof include ethanol, 4- (1-hydroxyethyl) -3-methoxy-5-iodophenol, and 3-ethoxy-4- (1-hydroxyethyl) -5-iodophenol. At least one iodine is introduced, and it is preferable that two or more iodines are introduced.
  • these iodine-containing alcoholic substrates can be obtained by many methods, it is desirable to obtain them by the methods described below from the viewpoint of availability and yield of raw materials.
  • the method for producing the iodine-containing vinyl monomer represented by the formula (1) is a) A step of preparing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1); b) Includes a dehydration step of dehydrating the iodine-containing alcoholic substrate.
  • organic solvent a wide variety of organic solvents including polar aprotic organic solvents and protic polar organic solvents are used.
  • a single protic and aprotic solvent or a single polar aprotic solvent can be used.
  • a polar aprotic solvent or a mixture thereof is preferable.
  • Solvents are effective but not essential components.
  • Suitable polar aprotic solvents include, but are not limited to, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglime and triglime, and ester solvents such as ethyl acetate and ⁇ -butyrolactone.
  • Solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone, N, N-dimethylacetamide, hexamethylphosphoramide, hexamethyl sublin
  • amide-based solvents such as acid triamide and dimethyl sulfoxide. Dimethyl sulfoxide is preferred.
  • Suitable protonic polar solvents include, but are not limited to, di (propylene glycol) methyl ether, di (ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol. , And n-butanol.
  • the amount of the solvent used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0 to 10000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield. From the viewpoint of the above, it is preferably 100 to 2000 parts by mass.
  • the dehydration step is carried out using, for example, a catalyst.
  • a catalyst a wide variety of dehydration catalysts that function under the reaction conditions of the second embodiment are used.
  • the dehydration catalyst is preferably an acid catalyst.
  • suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, sardine acid, adipic acid, sebacic acid, etc.
  • Organics such as citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, etc.
  • acids include acids, Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride, and solid acids such as silicotonic acid, phosphotung acid, silicate molybdic acid and phosphomolybdic acid. These acid catalysts may be used alone or in combination of two or more.
  • organic acids and solid acids are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as easy availability and handling.
  • the amount of the catalyst used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0.0001 to 100 parts by mass is suitable for 100 parts by mass of the reaction raw material. From the viewpoint of yield, it is preferably 0.001 to 10 parts by mass.
  • polymerization inhibitor a wide variety of polymerization inhibitors that function under the reaction conditions of the second embodiment are used.
  • Polymerization inhibitors are effective but not essential ingredients.
  • suitable antioxidants are, but are not limited to, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors such as Prostab® 5415 (Registered Trademark).
  • the amount of the polymerization inhibitor used can be appropriately set according to the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited, but in general, 0.0001 to 100 parts by mass is suitable for 100 parts by mass of the reaction raw material. From the viewpoint of yield, it is preferably 0.001 to 10 parts by mass.
  • polymerization inhibitor a wide variety of polymerization inhibitors that function under the reaction conditions of the second embodiment are used.
  • the polymerization inhibitor is effective but not an essential component. It is also effective to use a polymerization retarder in combination with a polymerization inhibitor.
  • Polymerization retarders are well known in the art and are compounds that slow down the polymerization reaction but cannot prevent all of the polymerization. Common retarders are aromatic nitro compounds such as dinitro-ortho-cresol (DNOC) and dinitrobutylphenol (DNBP). Methods for producing polymerization retarders are common and well known in the art (eg, US Pat. No.
  • the amount of the polymerization inhibitor used can be appropriately set according to the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited, but in general, 0.0001 to 100 parts by mass is suitable for 100 parts by mass of the reaction raw material. From the viewpoint of yield, it is preferably 0.001 to 10 parts by mass.
  • reaction conditions An iodine-containing alcoholic substrate having the formula (1-1), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol as the iodine-containing alcoholic substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • Method (I) for producing an iodine-containing alcoholic substrate represented by the formula (1-1) is, for example, an iodine-containing ketone substrate having a general structure represented by the formula (1-2). be.
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group or a carbonate ester group.
  • R 7 to R 10 are , Each independently is a hydrogen atom, a hydroxyl group, a methoxy group, a halogen or a cyano group, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • Suitable iodine-containing ketone substrates include, but are not limited to, 4-hydroxy-3-iodo-5-methoxyphenylmethylketone and 5-ethoxy-4-hydroxy-3-iodophenylmethylketone.
  • these iodine-containing ketone substrates can be obtained by many methods, it is desirable to obtain them by the methods described below from the viewpoint of availability and yield of raw materials.
  • the method for producing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1) is c) A step of preparing an iodine-containing ketone substrate having a general structure represented by the formula (1-2); d) Includes a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment.
  • the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) may include the method for producing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1). That is, the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) is c) A step of preparing an iodine-containing ketone substrate having a general structure represented by the formula (1-2); d) It may include a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment.
  • organic solvent a wide variety of organic solvents including polar aprotic organic solvents and protic polar organic solvents are used.
  • a single protic and aprotic solvent or a single polar aprotic solvent can be used.
  • a polar aprotic solvent or a mixture thereof is preferable.
  • Solvents are effective but not essential components.
  • Suitable polar aprotic solvents include, but are not limited to, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglime and triglime, and ester solvents such as ethyl acetate and ⁇ -butyrolactone.
  • Solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone, N, N-dimethylacetamide, hexamethylphosphoramide, hexamethyl sublin
  • amide-based solvents such as acid triamide and dimethyl sulfoxide. Dimethyl sulfoxide is preferred.
  • Suitable protonic polar solvents include, but are not limited to, di (propylene glycol) methyl ether, di (ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol. , And n-butanol.
  • the amount of the solvent used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0 to 10000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield. From the viewpoint of the above, it is preferably 100 to 2000 parts by mass.
  • the reduction step is carried out using, for example, a reducing agent.
  • a reducing agent a wide variety of reducing agents that function under the reaction conditions of the second embodiment are used.
  • Suitable reducing agents include, but are not limited to, metal hydrides, metal hydrogen complex compounds and the like, such as borane dimethyl sulfide, diisobutylaluminum hydride, sodium boron hydride, lithium boron hydride, potassium borohydride, etc.
  • Zinc hydride, Tri-s-butyl boron hydride, Tri-s-butyl boron hydride, Potassium hydride, Triethyl boron hydride, Lithium aluminum hydride, Tri-t-butoxyaluminum hydride, Bis hydride ( Methoxyethoxy) Aluminum sodium and the like can be mentioned.
  • the amount of the catalyst used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but generally, 1 to 500 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield is high. From the viewpoint of the above, it is preferably 10 to 200 parts by mass.
  • quenching agent a wide variety of quenching agents that function under the reaction conditions of the second embodiment are used.
  • the quenching agent has a function of inactivating the reducing agent.
  • Quenching agents are effective but not essential ingredients. Suitable quenching agents include, but are not limited to, ethanol, ammonium chloride water, water, hydrochloric acid, sulfuric acid and the like.
  • the amount of the quenching agent to be used can be appropriately set according to the amount of the reducing agent to be used, and is not particularly limited. Therefore, it is preferably 50 to 200 parts by mass.
  • reaction conditions An iodine-containing ketone substrate having the formula (1-2), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the iodine-containing ketonic substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 4'-hydroxy-3'-iodo-5'-methoxyacetophenone as the iodine-containing ketone substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the iodine-containing ketonic substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the iodine-containing ketonic substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 4'-hydroxy-3'-iodo-5'-methoxyacetophenone as the iodine-containing ketone substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • the alcoholic substrate used in the production of the iodine-containing alcoholic substrate represented by the formula (1-1) is, for example, an alcoholic substrate having a general structure represented by the formula (1-3).
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group.
  • R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups, except that one of R 7 to R 10 is. Or a hydroxyl group or a methoxy group.
  • suitable alcoholic substrates are, but are not limited to, 1- (4-hydroxy-3-methoxyphenyl) ethanol, 1- (3-ethoxy-4-hydroxyphenyl) ethanol, 4- (1-hydroxyethyl). Examples thereof include -3-methoxyphenol and 3-ethoxy-4- (1-hydroxyethyl) phenol.
  • these alcoholic substrates can be obtained by many methods, it is desirable to obtain them by the methods described below from the viewpoint of availability and yield of raw materials.
  • the method for producing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1) is e) A step of preparing an alcoholic substrate having a general structure represented by the formula (1-3); f) The iodine introduction step of introducing an iodine atom into the alcoholic substrate is included.
  • the iodine introduction step in the second embodiment is not particularly limited, but for example, a method of reacting an iodine agent in a solvent (for example, Japanese Patent Application Laid-Open No. 2012-180326), under alkaline conditions, in the presence of ⁇ -cyclodextrin.
  • a method of dropping iodine into an alkaline aqueous solution of phenol Japanese Patent Laid-Open No. 63-101342, Japanese Patent Application Laid-Open No. 2003-64012
  • the iodine agent is not particularly limited, and examples thereof include iodine agents such as iodine chloride, iodine, and N-iodosuccinimide. Among these, iodine chloride is preferable.
  • the method for synthesizing the compound (A) of the second embodiment for example, the method described in the above-mentioned reference material can be appropriately used, but the method is not limited thereto.
  • the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) may include the method for producing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1). That is, the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) is e) A step of preparing an alcoholic substrate having a general structure represented by the formula (1-3); f) It may include an iodine introduction step.
  • organic solvent a wide variety of organic solvents including polar aprotic organic solvents and protic polar organic solvents are used.
  • a single protic and aprotic solvent or a single polar aprotic solvent can be used.
  • a polar aprotic solvent or a mixture thereof is preferable.
  • Solvents are effective but not essential components.
  • Suitable polar aprotic solvents include, but are not limited to, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglime and triglime, and ester solvents such as ethyl acetate and ⁇ -butyrolactone.
  • Solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone, N, N-dimethylacetamide, hexamethylphosphoramide, hexamethyl sublin
  • amide-based solvents such as acid triamide and dimethyl sulfoxide. Dimethyl sulfoxide is preferred.
  • Suitable protonic polar solvents include, but are not limited to, di (propylene glycol) methyl ether, di (ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol. , And n-butanol.
  • the amount of the solvent used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0 to 10000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield. From the viewpoint of the above, it is preferably 100 to 2000 parts by mass.
  • a wide variety of dehydration catalysts that function under the reaction conditions of the second embodiment are used.
  • Acid catalysts are preferred.
  • suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, sardine acid, adipic acid, sebacic acid, etc.
  • Organics such as citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, etc.
  • acids include acids, Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride, and solid acids such as silicotonic acid, phosphotung acid, silicate molybdic acid and phosphomolybdic acid. These acid catalysts may be used alone or in combination of two or more.
  • organic acids and solid acids are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as easy availability and handling.
  • the amount of the catalyst used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0.0001 to 100 parts by mass is suitable for 100 parts by mass of the reaction raw material. From the viewpoint of yield, it is preferably 0.001 to 10 parts by mass.
  • Reaction conditions An alcoholic substrate having the formula (1-3), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 1- (4-hydroxy-3-methoxyphenyl) ethanol as the substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 1- (4-hydroxy-3-methoxyphenyl) ethanol as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • the ketone substrate used in the production of the iodine-containing ketone substrate represented by the formula (1-2) is, for example, a ketone substrate having a general structure represented by the formula (1-4).
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group or a carbonate ester group.
  • R 7 to R 10 are , Each independently is a hydrogen atom, a hydroxyl group, a methoxy group, a halogen or a cyano group, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • Suitable ketone substrates include, but are not limited to, 4-hydroxy-5-methoxyphenylmethylketone and 5-ethoxy-4-hydroxyphenylmethylketone.
  • ketone substrates can be obtained by many methods.
  • the method for producing an iodine-containing ketone substrate having a general structure represented by the formula (1-2) is as follows. g) A step of preparing a ketonic substrate having a general structure represented by the formula (1-4); h) It may include an iodine introduction step of introducing an iodine atom into the ketone substrate.
  • the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) may include the method for producing an iodine-containing ketone substrate having a general structure represented by the formula (1-2). That is, the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) is g) A step of preparing a ketonic substrate having a general structure represented by the formula (1-4); h) It may include an iodine introduction step of introducing an iodine atom into the ketone substrate.
  • organic solvent a wide variety of organic solvents including polar aprotic organic solvents and protic polar organic solvents are used.
  • a single protic and aprotic solvent or a single polar aprotic solvent can be used.
  • a polar aprotic solvent or a mixture thereof is preferable.
  • Solvents are effective but not essential components.
  • Suitable polar aprotic solvents include, but are not limited to, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglime and triglime, and ester solvents such as ethyl acetate and ⁇ -butyrolactone.
  • Solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone, N, N-dimethylacetamide, hexamethylphosphoramide, hexamethyl sublin
  • amide-based solvents such as acid triamide and dimethyl sulfoxide. Dimethyl sulfoxide is preferred.
  • Suitable protonic polar solvents include, but are not limited to, di (propylene glycol) methyl ether, di (ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol. , And n-butanol.
  • the amount of the solvent used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0 to 10000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield. From the viewpoint of the above, it is preferably 100 to 2000 parts by mass.
  • a wide variety of dehydration catalysts that function under the reaction conditions of the second embodiment are used.
  • Acid catalysts are preferred.
  • suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, sardine acid, adipic acid, sebacic acid, etc.
  • Organics such as citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, etc.
  • acids include acids, Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride, and solid acids such as silicotonic acid, phosphotung acid, silicate molybdic acid and phosphomolybdic acid. These acid catalysts may be used alone or in combination of two or more.
  • organic acids and solid acids are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as easy availability and handling.
  • the amount of the catalyst used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0.0001 to 100 parts by mass is suitable for 100 parts by mass of the reaction raw material. From the viewpoint of yield, it is preferably 0.001 to 10 parts by mass.
  • a ketone substrate having the formula (1-4), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • the ketone substrate used in the production of the alcoholic substrate having the general structure represented by the formula (1-3) is, for example, the ketone substrate having the general structure represented by the above formula (1-4). ..
  • the method for producing an alcoholic substrate having a general structure represented by the formula (1-3) is i) A step of preparing a ketonic substrate having a general structure represented by the formula (1-4); j) It may include a reduction step of subjecting the ketone substrate to a reduction treatment.
  • the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) may include the method for producing an alcoholic substrate having a general structure represented by the formula (1-3). That is, the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) is i) A step of preparing a ketonic substrate having a general structure represented by the formula (1-4); j) It may include a reduction step of subjecting the ketone substrate to a reduction treatment.
  • organic solvent a wide variety of organic solvents including polar aprotic organic solvents and protic polar organic solvents are used.
  • a single protic and aprotic solvent or a single polar aprotic solvent can be used.
  • a polar aprotic solvent or a mixture thereof is preferable.
  • Solvents are effective but not essential components.
  • Suitable polar aprotic solvents include, but are not limited to, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglime and triglime, and ester solvents such as ethyl acetate and ⁇ -butyrolactone.
  • Solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone, N, N-dimethylacetamide, hexamethylphosphoramide, hexamethyl sublin
  • amide-based solvents such as acid triamide and dimethyl sulfoxide. Dimethyl sulfoxide is preferred.
  • Suitable protonic polar solvents include, but are not limited to, di (propylene glycol) methyl ether, di (ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol. , And n-butanol.
  • the amount of the solvent used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0 to 10000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield. From the viewpoint of the above, it is preferably 100 to 2000 parts by mass.
  • a reducing agent is used to reduce the ketone substrate.
  • a reducing agent a wide variety of reducing agents that function under the reaction conditions of the second embodiment are used.
  • Suitable reducing agents include, but are not limited to, metal hydrides, metal hydrogen complex compounds and the like, such as borane dimethyl sulfide, diisobutylaluminum hydride, sodium boron hydride, lithium boron hydride, potassium borohydride, etc.
  • Zinc hydride, Tri-s-butyl boron hydride, Tri-s-butyl boron hydride, Potassium hydride, Triethyl boron hydride, Lithium aluminum hydride, Tri-t-butoxyaluminum hydride, Bis hydride ( Methoxyethoxy) Aluminum sodium and the like can be mentioned.
  • the amount of the catalyst used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but generally, 1 to 500 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield is high. From the viewpoint of the above, it is preferably 10 to 200 parts by mass.
  • quenching agent a wide variety of quenching agents that function under the reaction conditions of the second embodiment are used.
  • the quenching agent has a function of inactivating the reducing agent.
  • Quenching agents are effective but not essential ingredients. Suitable quenching agents include, but are not limited to, ethanol, ammonium chloride water, water, hydrochloric acid, sulfuric acid and the like.
  • the amount of the quenching agent to be used can be appropriately set according to the amount of the reducing agent to be used, and is not particularly limited. Therefore, it is preferably 50 to 200 parts by mass.
  • a ketone substrate having the formula (1-4), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • the method for producing an iodine-containing vinyl monomer according to the second embodiment may be a method for producing an iodine-containing vinyl monomer represented by the formula (2), and specifically, a method for producing iodine-containing alkoxystyrene. May be.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RB is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • RC is substituted or substituted. It is an unsubstituted acyl group having 1 to 30 carbon atoms
  • acetoxystyrene produced by the method of the second embodiment include, but are not limited to, 4-acetoxy-3-iodo-5-methoxystyrene and 4-acetoxy-5-ethoxy-3-iodostyrene. ..
  • the iodine-containing vinyl monomer used in the second embodiment is, for example, an iodine-containing vinyl monomer having a general structure represented by the above formula (1).
  • the iodine-containing vinyl monomer having a general structure represented by the formula (2) is k) A step of preparing an iodine-containing vinyl monomer having a general structure represented by the formula (1); l) It may include an acylation step of subjecting the iodine-containing vinyl monomer to an acylation treatment.
  • organic solvent a wide variety of organic solvents including polar aprotic organic solvents and protic polar organic solvents are used.
  • a single protic and aprotic solvent or a single polar aprotic solvent can be used.
  • a polar aprotic solvent or a mixture thereof is preferable.
  • Solvents are effective but not essential components.
  • Suitable polar aprotic solvents include, but are not limited to, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglime and triglime, and ester solvents such as ethyl acetate and ⁇ -butyrolactone.
  • Solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone, N, N-dimethylacetamide, hexamethylphosphoramide, hexamethyl sublin
  • amide-based solvents such as acid triamide and dimethyl sulfoxide. Dimethyl sulfoxide is preferred.
  • Suitable protonic polar solvents include, but are not limited to, di (propylene glycol) methyl ether, di (ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol. , And n-butanol.
  • the amount of the solvent used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0 to 10000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield. From the viewpoint of the above, it is preferably 100 to 2000 parts by mass.
  • the acylation step is carried out using, for example, a catalyst.
  • a catalyst a wide variety of acylation catalysts that function under the reaction conditions of the second embodiment are used.
  • Base catalysts are preferred.
  • suitable base catalysts are not limited, but examples of amine-containing catalysts are pyridine and ethylenediamine, and examples of non-amine basic catalysts are preferably metal salts and particularly potassium or acetate.
  • the catalyst include, but are not limited to, potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide and magnesium oxide. All non-amine base catalysts of the second embodiment are commercially available, for example, from EMSscience (Gibbstown) or Aldrich (Milwaukee).
  • the amount of the catalyst used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but generally, 1 to 5000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield is high. From the viewpoint of the above, it is preferably 50 to 3000 parts by mass.
  • polymerization inhibitor a wide variety of polymerization inhibitors that function under the reaction conditions of the second embodiment are used.
  • Polymerization inhibitors are effective but not essential ingredients.
  • suitable antioxidants are, but are not limited to, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors such as Prostab® 5415 (Registered Trademark).
  • the amount of the polymerization inhibitor used can be appropriately set according to the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited, but in general, 0.0001 to 100 parts by mass is suitable for 100 parts by mass of the reaction raw material. From the viewpoint of yield, it is preferably 0.001 to 10 parts by mass.
  • polymerization inhibitor a wide variety of polymerization inhibitors that function under the reaction conditions of the second embodiment are used.
  • the polymerization inhibitor is effective but not an essential component. It is also effective to use a polymerization retarder in combination with a polymerization inhibitor.
  • Polymerization retarders are well known in the art and are compounds that slow down the polymerization reaction but cannot prevent all of the polymerization. Common retarders are aromatic nitro compounds such as dinitro-ortho-cresol (DNOC) and dinitrobutylphenol (DNBP). Methods for producing polymerization retarders are common and well known in the art (eg, US Pat. No.
  • the amount of the polymerization inhibitor used can be appropriately set according to the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited, but in general, 0.0001 to 100 parts by mass is suitable for 100 parts by mass of the reaction raw material. From the viewpoint of yield, it is preferably 0.001 to 10 parts by mass.
  • reaction conditions An iodine-containing vinyl monomer having the formula (1), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 4-hydroxy-3-iodo-5-methoxystyrene as the substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 4-hydroxy-3-iodo-5-methoxystyrene as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • the compound in the second embodiment is obtained as a crude product by the above reaction and then further purified to remove residual metal impurities. That is, in the compound manufacturing process, from the viewpoint of prevention of deterioration of the resin over time and storage stability, and also from the viewpoint of process suitability when resinified and applied to the semiconductor manufacturing process, manufacturing profitability due to defects, etc. It is preferable to avoid residual gold-damaged impurities derived from the mixing of metal components used as reaction aids or mixed from reaction kettles for manufacturing or other manufacturing equipment.
  • the residual amount of the above-mentioned metal impurities is preferably less than 1 ppm, more preferably less than 100 ppb, further preferably less than 50 ppb, still more preferably less than 10 ppb, respectively, with respect to the resin. Most preferably, it is less than 1 ppb.
  • metal species such as Fe, Ni, Sb, W, and Al, which are classified as transition metals
  • the metal residual amount is 1 ppm or more, the material is modified over time due to the interaction with the compound in the second embodiment. There is a concern that it may cause deterioration.
  • the amount is 1 ppm or more, the remaining amount of metal cannot be sufficiently reduced when a resin for a semiconductor process is produced using the produced compound, and defects derived from residual metal in the semiconductor manufacturing process cannot be sufficiently reduced. There is a concern that it may cause a decrease in profitability due to performance deterioration.
  • the purification method is not particularly limited, but the step of dissolving the compound in the second embodiment in a solvent to obtain a solution (S) and the obtained solution (S) and an acidic aqueous solution are brought into contact with each other.
  • the solvent used in the step of obtaining the solution (S) includes an organic solvent which is optionally immiscible with water, including a step of extracting impurities in the compound in the second embodiment (first extraction step). According to the purification method, the content of various metals that may be contained as impurities in the resin can be reduced.
  • the compound in the second embodiment is dissolved in an organic solvent that is not miscible with water to obtain a solution (S), and the solution (S) is further brought into contact with an acidic aqueous solution for extraction treatment. It can be performed.
  • the organic phase and the aqueous phase can be separated to obtain a resin having a reduced metal content.
  • the solvent that is not arbitrarily mixed with the water used in the purification method is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable, and specifically, the solubility in water at room temperature is 30%. It is an organic solvent which is less than, more preferably less than 20%, and particularly preferably less than 10%.
  • the amount of the organic solvent used is preferably 1 to 100 times by mass with respect to the total amount of the resins used.
  • solvent immiscible with water are not limited to the following, but for example, ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, methyl ethyl ketone and methyl isobutyl.
  • ethers such as diethyl ether and diisopropyl ether
  • esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, methyl ethyl ketone and methyl isobutyl.
  • Ketones such as ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone; ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl Glycol ether acetates such as ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and chloroform. ..
  • toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, and methyl isobutyl ketone, ethyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate are more preferable.
  • Methyl isobutyl ketone and ethyl acetate are even more preferable.
  • the acidic aqueous solution used in the purification method is appropriately selected from a generally known organic compound or an aqueous solution obtained by dissolving an inorganic compound in water.
  • aqueous mineral acid solution in which a mineral acid such as hydrochloric acid, sulfuric acid, nitrate, or phosphoric acid is dissolved in water, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, and maleic acid.
  • Tartrate acid citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid and other organic acids dissolved in water.
  • acidic aqueous solutions can be used alone or in combination of two or more.
  • one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid
  • An aqueous solution of a carboxylic acid such as tartaric acid or citric acid is more preferable, an aqueous solution of sulfuric acid, oxalic acid, tartaric acid or citric acid is more preferable, and an aqueous solution of oxalic acid is even more preferable.
  • polyvalent carboxylic acids such as oxalic acid, tartaric acid, and citric acid are coordinated to metal ions and have a chelating effect, so that the metal can be removed more effectively.
  • water used here it is preferable to use water having a low metal content, for example, ion-exchanged water, etc., in line with the purpose of the purification method in the second embodiment.
  • the pH of the acidic aqueous solution used in the purification method is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the compound.
  • the pH range is about 0 to 5, preferably about 0 to 3.
  • the amount of the acidic aqueous solution used in the purification method is not particularly limited, but the amount used may be used from the viewpoint of reducing the number of extractions for removing the metal and ensuring operability in consideration of the total amount of the liquid. It is preferable to adjust. From the above viewpoint, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, based on 100% by mass of the solution (S).
  • the metal component can be extracted from the compound in the solution (S) by contacting the acidic aqueous solution with the solution (S).
  • the solution (S) may further contain an organic solvent that is optionally miscible with water.
  • an organic solvent that is arbitrarily miscible with water is contained, the amount of the compound charged can be increased, the liquid separation property is improved, and purification can be performed with high pot efficiency.
  • the method of adding an organic solvent that is arbitrarily miscible with water is not particularly limited. For example, any of a method of adding to a solution containing an organic solvent in advance, a method of adding to water or an acidic aqueous solution in advance, and a method of adding after contacting a solution containing an organic solvent with water or an acidic aqueous solution may be used. Among these, the method of adding to a solution containing an organic solvent in advance is preferable in terms of workability of operation and ease of control of the amount to be charged.
  • the organic solvent that is arbitrarily miscible with the water used in the purification method is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable.
  • the amount of the organic solvent to be arbitrarily mixed with water is not particularly limited as long as the solution phase and the aqueous phase are separated, but is 0.1 to 100 times by mass with respect to the total amount of the compounds used. It is preferably 0.1 to 50 times by mass, more preferably 0.1 to 20 times by mass.
  • ethers such as tetrahydrofuran and 1,3-dioxolane
  • alcohols such as methanol, ethanol and isopropanol
  • acetone ethylpyrrolidone and other ketones
  • examples thereof include aliphatic hydrocarbons such as ethylene glycol monoethyl ether, ethylene glycol
  • N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable.
  • Each of these solvents can be used alone, or two or more of them can be mixed and used.
  • the temperature at which the extraction process is performed is usually 20 to 90 ° C, preferably 30 to 80 ° C.
  • the extraction operation is performed by, for example, stirring well and then allowing the mixture to stand still. As a result, the metal content contained in the solution (S) is transferred to the aqueous phase. Further, by this operation, the acidity of the solution is lowered, and the deterioration of the compound can be suppressed.
  • the solution phase is recovered by decantation or the like.
  • the standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation between the solution phase containing the solvent and the aqueous phase.
  • the standing time is 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more.
  • the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.
  • the purification method it is preferable to include a step (second extraction step) of extracting impurities in the resin by further contacting the solution phase containing the compound with water after the first extraction step.
  • the extraction treatment is performed using an acidic aqueous solution, and then the solution phase containing the resin and the solvent extracted and recovered from the aqueous solution is further subjected to the extraction treatment with water.
  • the above-mentioned extraction treatment with water is not particularly limited, but can be performed, for example, by mixing the solution phase and water well by stirring or the like, and then allowing the obtained mixed solution to stand still.
  • the solution phase can be recovered by decantation or the like.
  • the water used here is preferably water having a low metal content, for example, ion-exchanged water, for the purpose of the second embodiment.
  • the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.
  • the conditions such as the ratio of use of both in the extraction treatment, the temperature, and the time are not particularly limited, but the same as in the case of the contact treatment with the acidic aqueous solution described above may be used.
  • Moisture that can be mixed in the solution containing the compound and the solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. Further, if necessary, a solvent can be added to the solution to adjust the concentration of the compound to an arbitrary concentration.
  • the compound purification method according to the second embodiment can also be purified by passing a solution of the resin in a solvent through a filter.
  • the content of various metals in the resin can be effectively and significantly reduced.
  • the amounts of these metal components can be measured by the method described in Examples described later.
  • the term "passing liquid" in the second embodiment means that the solution passes from the outside of the filter to the inside of the filter and moves to the outside of the filter again. For example, the solution is simply filtered.
  • the mode of contacting on the surface of the ion exchange resin and the mode of moving the solution outside the ion exchange resin while contacting the solution on the surface are excluded.
  • the filter used for removing the metal component in the solution containing the compound and the solvent can usually be a commercially available filter for liquid filtration.
  • the filtration accuracy of the filter is not particularly limited, but the nominal pore size of the filter is preferably 0.2 ⁇ m or less, more preferably less than 0.2 ⁇ m, still more preferably 0.1 ⁇ m or less, still more preferably 0. It is less than .1 ⁇ m, more preferably 0.05 ⁇ m or less.
  • the lower limit of the nominal pore diameter of the filter is not particularly limited, but is usually 0.005 ⁇ m.
  • the nominal pore size referred to here is a nominal pore size indicating the separation performance of the filter, and is determined by a test method determined by the filter manufacturer, such as a bubble point test, a mercury intrusion method test, and a standard particle capture test.
  • the hole diameter When a commercially available product is used, it is a value described in the manufacturer's catalog data.
  • the filter liquid passing step may be performed twice or more in order to further reduce the content of each metal content in the solution.
  • a hollow fiber membrane filter As the form of the filter, a hollow fiber membrane filter, a membrane filter, a pleated membrane filter, and a filter filled with a filter medium such as non-woven fabric, cellulose, and silica soil can be used.
  • the filter is one or more selected from the group consisting of a hollow fiber membrane filter, a membrane filter and a pleated membrane filter.
  • the material of the filter is polyethylene, polyolefin such as polypropylene, polyethylene resin having a functional group capable of ion exchange by graft polymerization, polyamide, polyester, polar group-containing resin such as polyacrylonitrile, polyethylene fluoride (PTFE) and the like. Fluorohydrate-containing resin can be mentioned.
  • the filter medium of the filter is at least one selected from the group consisting of polyamide, poreolefin resin and fluororesin.
  • polyamide is particularly preferable from the viewpoint of reducing heavy metals such as chromium. From the viewpoint of avoiding metal elution from the filter medium, it is preferable to use a filter other than the sintered metal material.
  • Polyamide-based filters are not limited to the following, but are, for example, Polyfix Nylon Series manufactured by KITZ Micro Filter Co., Ltd., Uruchi Pleated P-Nylon 66 manufactured by Nippon Pole Co., Ltd., Ulchipore N66, and 3M. Life Asure PSN series, Life Asure EF series, etc. manufactured by KITZ Corporation can be mentioned.
  • the polyolefin-based filter is not limited to the following, but includes, for example, Uruchi Pleated PE Clean and Ion Clean manufactured by Nippon Pole Co., Ltd., Protego Series manufactured by Nippon Entegris Co., Ltd., Microguard Plus HC10, Optimizer D, and the like. Can be mentioned.
  • polyester filter examples include, but are not limited to, Geraflow DFE manufactured by Central Filter Industry Co., Ltd., Breeze type PMC manufactured by Nippon Filter Co., Ltd., and the like.
  • polyacrylonitrile-based filter examples include, but are not limited to, ultrafilters AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantech Toyo Co., Ltd.
  • fluororesin-based filter include, but are not limited to, Enflon HTPFR manufactured by Nippon Pole Co., Ltd., Lifesure FA series manufactured by 3M Co., Ltd., and the like. Each of these filters may be used alone or in combination of two or more.
  • the filter may contain an ion exchanger such as a cation exchange resin, a cation charge regulator that causes a zeta potential in the organic solvent solution to be filtered, and the like.
  • an ion exchanger such as a cation exchange resin, a cation charge regulator that causes a zeta potential in the organic solvent solution to be filtered, and the like.
  • the filter containing the ion exchanger include, but are not limited to, the Protego series manufactured by Entegris Japan Co., Ltd., the clan graft manufactured by Kurashiki Textile Manufacturing Co., Ltd., and the like.
  • the filter containing a substance having a positive zeta potential such as polyamide polyamine epichlorohydrin cation resin is not limited to the following, but is not limited to, for example, Zeta Plus 40QSH and Zeta Plus 020GN manufactured by 3M Co., Ltd. , Or Life Asure EF series and the like.
  • the method for purifying the compound according to the second embodiment can also be purified by distilling the compound itself.
  • the distillation method is not particularly limited, but known methods such as atmospheric distillation, vacuum distillation, molecular distillation, and steam distillation can be used.
  • the compound (A) according to the second embodiment can be added to the film-forming composition as it is or as a polymer described later to increase the sensitivity to an exposure light source.
  • the compound (A) or a polymer thereof is preferably used for a photoresist.
  • composition of the second embodiment comprises compound (A).
  • the content of the compound (A) in the second embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more.
  • composition of the second embodiment include a compound represented by the formula (1) other than the formula (1C) as the compound (A) and a compound represented by the formula (1C). It is preferable to include at least.
  • the proportion of the monomer represented by the formula (1C) is preferably 1 mass ppm or more and 10 mass% or less, preferably 20 mass ppm or more or 2 mass by mass, based on the entire monomer represented by the formula (1). % Or less, and more preferably 50% by mass or more and 1% by mass or less.
  • the interaction between the resins at the time of resinification can be reduced, and the interaction between the resins after forming a film using the resin can be achieved.
  • the resulting crystallinity By suppressing the resulting crystallinity, the locality of solubility in the developer during development at the molecular level of several nanometers to several tens of nanometers is reduced, and in a series of lithography processes of exposure, post-exposure baking, and development. It is possible to suppress deterioration of pattern quality such as line edge roughness and residue defects of the pattern formed in the pattern forming process, and further improve the resolution.
  • the effects on these styrene performances are such that the compound represented by the formula (1) and the compound represented by the formula (1C) having a mother nucleus A into which a halogen element, particularly iodine or a fluorine compound is introduced, introduces iodine or the like.
  • the composition of the second embodiment contains compound (A).
  • the content of impurities containing K (potassium) in the composition is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, with respect to the entire compound (A) in terms of elements. Yes, more preferably 0.1 mass ppm or less, still more preferably 0.005 mass ppm or less.
  • the composition of the second embodiment is composed of one or more elemental impurities (preferably Mn and Al) selected from the group consisting of Mn (manganese), Al (aluminum), Si (silicon), and Li (lithium).
  • the content of one or more elemental impurities selected from the group) is preferably 1 ppm or less, more preferably 0.5 ppm or less, still more preferably 0. It is 1 ppm or less.
  • the amounts of K, Mn, Al, Si, Li and the like are measured by inorganic elemental analysis (IPC-AES / IPC-MS). Examples of the inorganic element analyzer include "AG8900" manufactured by Agilent Technologies, Inc.
  • the content of the phosphorus-containing compound is preferably 10 ppm or less, more preferably 8 ppm or less, and further preferably 5 ppm or less with respect to the entire compound (A).
  • the content of maleic acid is preferably 10 ppm or less, more preferably 8 ppm or less, still more preferably 5 ppm or less, based on the whole compound (A).
  • the amounts of the phosphorus-containing compound and maleic acid are calculated by gas chromatography-mass spectrometry (GC-MS) from the area fraction of the GC chart and the peak intensity ratio of the target peak to the reference peak.
  • GC-MS gas chromatography-mass spectrometry
  • the content of the peroxide is preferably 10% by mass or less, more preferably 1 ppm or less, still more preferably 0.1 ppm with respect to the whole compound (A). It is as follows.
  • the peroxide content is determined by adding trichloroacetic acid to the sample by the ammonium ferrothiocianate acid method (hereinafter referred to as AFTA method), and then adding ammonium iron (II) sulfate and potassium thiocyanate, which are known as standard substances.
  • AFTA method ammonium ferrothiocianate acid method
  • the water content is preferably 100,000 ppm or less, more preferably 20,000 ppm or less, still more preferably 1,000 ppm or less, based on the whole compound (A). Yes, more preferably 500 ppm or less, still more preferably 100 ppm or less.
  • the water content is measured by the Karl Fischer method (Karl Fischer moisture measuring device).
  • the polymer (A) of the second embodiment contains a structural unit derived from the above-mentioned compound (A).
  • the polymer (A) can increase the sensitivity to an exposure light source when blended in the resist composition. In particular, even when extreme ultraviolet rays are used as the exposure light source, sufficient sensitivity can be exhibited and a fine line pattern with a narrow line width can be satisfactorily formed.
  • the conventional resist composition may have a decrease in sensitivity to an exposure light source over time due to storage or the like, and there is a difficulty in developing it for actual semiconductor manufacturing.
  • the polymer (A) of the second embodiment the stability of the resist composition is improved, and the decrease in sensitivity to the exposure light source is suppressed even when the resist composition is stored for a long period of time.
  • the polymer (A) of the second embodiment contains a structural unit derived from the compound (A).
  • the structural unit derived from the compound (A) contained in the polymer (A) includes, for example, a structural unit represented by the following formula (1-A).
  • RA, RB and P are the same as the definitions in formula (1), and * is a binding site with an adjacent structural unit.
  • RA is a hydrogen atom or a methyl group.
  • RB is an alkyl group having 1 to 4 carbon atoms.
  • P is a hydroxyl group or a tertiary ester group, an acetal group, a carbonic acid ester group or a carboxylalkoxy group.
  • the polymer (A) can be obtained by polymerizing the compound (A) of the second embodiment or by copolymerizing the compound (A) with another monomer.
  • the polymer (A) can be used, for example, as a material for forming a film for lithography.
  • the amount of the structural unit derived from the compound (A) is preferably 5 mol% or more, more preferably 8 mol% or more, still more preferably 10 mol%, based on the total amount of the monomer components of the polymer (A). % Or more.
  • the amount of the structural unit derived from the compound (A) is 100 mol% or less, preferably 80 mol% or less, and more preferably 50 mol% with respect to the total amount of the monomer components of the polymer (A). It is less than or equal to, more preferably 30 mol% or less.
  • One of the preferred embodiments of the polymer of the second embodiment is a compound represented by the formula (1) as a constituent unit of the polymerized body (A), a monomer represented by the compound (A), and a formula represented by the formula (1). It is preferable to contain at least the compound represented by (1C).
  • the content ratio of the monomer represented by the formula (1C) is preferably 10 ppm or more and 10% by mass or less, and preferably 20 ppm or more and 2% by mass or less with respect to the entire monomer represented by the formula (1). More preferably, it is contained in an amount of 50 ppm or more and 1% by mass or less.
  • an aromatic compound having an unsaturated double bond as a substituent is used as a polymerization unit, and alkaline development is carried out by the action of an acid or a base. It preferably contains a polymerization unit having a functional group that improves solubility in a liquid.
  • the other monomer copolymerized with the compound (A) is not particularly limited, but for example, International Publication WO2016 / 125782, International Publication WO2015 / 115613, JP-A-2015 / 117305, International. Examples thereof include those described in WO2014 / 175275, JP2012 / 162298, or compounds represented by the following formula (C1) or the following formula (C2). Among these, the compound represented by the following formula (C1) or the following formula (C2) is preferable.
  • the other monomer copolymerized with the compound (A) preferably contains a structural unit represented by the following formula (C0). That is, in the polymer (A), in addition to the structural unit represented by the formula (1-A), the structural unit represented by the following formula (C0), the following formula (C1) or the following formula (C2) is further added. It is preferable to include it.
  • the dissolution rate R min of the resin that becomes the pattern convex part during alkaline development in the unexposed part during exposure is determined. It is preferable that the difference in dissolution rate R max with respect to the alkaline developer of the resin that becomes the pattern recess during alkaline development in the exposed part during exposure is larger by 3 orders of magnitude or more, the difference in dissolution rate depending on the presence or absence of a protective group is large, and the bake after exposure. (PEB), it is preferable that the desorption rate of the protective group in development is high. From these viewpoints, it is preferable that the other monomer copolymerized with the compound (A) in the polymer (A) has a structural unit represented by the following formula (C1).
  • RC11 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RC12 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • RC13 is a cycloalkyl group or a heterocycloalkyl group having 4 to 20 carbon atoms, which is formed together with a carbon atom bonded to RC13 . * Is a binding site with an adjacent structural unit.
  • RC12 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the RC13 is preferably a cycloalkyl group or a heterocycloalkyl group having 4 to 10 carbon atoms, which is formed together with a carbon atom bonded to RC13 .
  • the cycloalkyl group or heterocycloalkyl group of RC13 may have a substituent (for example, an oxo group).
  • the amount of the structural unit represented by the formula (C1) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 10 mol% or more, based on the total amount of the monomer components of the polymer (A). It is preferably 20 mol% or more.
  • the amount of the structural unit represented by the formula (C1) is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 80 mol% or less, based on the total amount of the monomer components of the polymer (A). It is preferably 70 mol% or less.
  • the other monomer copolymerized with the compound (A) in the polymer (A) is represented by the following formula (C2) from the viewpoint of the quality of the pattern shape after exposure and development in the lithography process, especially from the viewpoint of roughness and suppression of pattern collapse.
  • the structural unit to be formed is preferable.
  • RC21 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RC22 and RC23 are independently alkyl groups having 1 to 4 carbon atoms.
  • RC24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. Two or three of the RC22 , RC23 , and RC24 were formed together with carbon atoms bonded to two or three of the RC22 , RC23 , and RC24 .
  • An alicyclic structure having 3 to 20 carbon atoms may be formed. * Is a binding site with an adjacent structural unit.
  • RC22 is preferably an alkyl group having 1 to 3 carbon atoms
  • RC24 is a cycloalkyl group having 5 to 10 carbon atoms.
  • the alicyclic structure formed by RC22 , RC23 , and RC24 may contain a plurality of rings such as an adamantyl group.
  • the alicyclic structure may have a substituent (for example, a hydroxyl group or an alkyl group).
  • the amount of the structural unit represented by the formula (C2) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 10 mol% or more, based on the total amount of the monomer components of the polymer (A). It is preferably 20 mol% or more.
  • the amount of the structural unit represented by the formula (C2) is preferably 80 mol% or less, more preferably 60 mol% or less, and further preferably 60 mol% or less, based on the total amount of the monomer components of the polymer (A). It is preferably 40 mol% or less.
  • the raw material for the monomer of the structural unit represented by the formula (C2) is not limited, for example, 2-methyl-2- (meth) acrylic loyloxyadamantan, 2-ethyl-2- (meth) acrylic loyloxyadamantan, 2 -Isopropyl-2- (meth) acrylic loyloxyadamantan, 2-n-propyl-2- (meth) acrylic loyloxyadamantan, 2-n-butyl-2- (meth) acrylicloyloxyadamantan, 1-methyl-1 -(Meta) Acrylic Loyloxycyclopentane, 1-Ethyl-1- (Meta) Acrylic Loyloxycyclopentane, 1-Methyl-1- (Meta) Acrylic Loyloxycyclohexane, 1-Ethyl-1- (Meta) Acrylic Loyl Oxycyclohexane, 1-Methyl-1- (meth) acrylic loyloxycycloheptane, 1-ethyl-1- (
  • the other monomer copolymerized with the compound (A) in the polymer (A) has the following formula (C0) from the viewpoint of exposure in the lithography process, quality of the pattern shape after development, sensitization, especially roughness and suppression of pattern collapse. ) Is preferred.
  • X is an organic group having 1 to 5 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, Br, or I, F, Cl, and Br, respectively.
  • L 1 is independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphin group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphorus.
  • the L1 ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphon group, urethane group, urea group, amide group, imide group, or phosphoric acid group is an acid group.
  • Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon group.
  • Urethane group, urea group, amide group, imide group, or phosphoric acid group and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group of Y.
  • Urea group, amide group, imide group, and phosphate group may have a substituent.
  • RA is the same as the definition in equation (1).
  • A is an organic group having 1 to 30 carbon atoms.
  • Z is independently an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, or a carbonate ester group, and the alkoxy group, the ester group, the acetal group, the carboxylalkoxy group, or the carbonate ester group of Z is It may have a substituent and may have a substituent.
  • m is an integer of 0 or more
  • n is an integer of 1 or more
  • r is an integer of 0 or more.
  • the "organic group having 1 to 5 substituents and having 1 to 30 carbon atoms selected from the group consisting of I, F, Cl, and Br" is not particularly limited, but is a monoiodophenyl group or a diiodophenyl group.
  • Triiododihydroxynaphthyl group Triiododihydroxynaphthyl group, monoiododiacetoxynaphthyl group, diiododiacetoxynaphthyl group, triiododiacetoxynaphthyl group, monoiodo-di-t-butoxycarbonylnaphthyl group, diiodo-di-t-butoxycarbonylnaphthyl group, Triiodo-di-t-butoxycarbonylnaphthyl group,
  • Monobromotrihydroxyphenyl group dibromotrihydroxyphenyl group, monobromotriacetoxyphenyl group, dibromotriacetoxyphenyl group, monobromotri-t-butoxycarbonylphenyl group, dibromotri-t-butoxycarbonylphenyl group, monobromoadamantyl group, dibromo Adamanthyl group, tribromoadamantyl group, monobromohydroxyadamantyl group, dibromohydroxynaphthyl group, monobromoacetoxynaphthyl group, dibromoacetoxyadamantyl group, monobromot-butoxycarbonyladamantyl group, dibromot-butoxycarbonyladamantyl group, tribromot-butoxy Carbonyl adamantyl group, monobromodihydroxyadamantyl group, monobromodiacetoxyadamantyl group, monobromo-di-t-
  • Monochlorophenyl group dichlorophenyl group, trichlorophenyl group, tetrachlorophenyl group, pentachlorophenyl group, monochlorohydroxyphenyl group, dichlorohydroxyphenyl group, trichlorohydroxyphenyl group, monochloroacetoxyphenyl group, dichloroacetoxyphenyl group, trichloroacetoxyphenyl group, monochromero t-butoxycarbonylphenyl group, dichloro t-butoxycarbonylphenyl group, trichloro t-butoxycarbonylphenyl group, monolologihydroxyphenyl group, dichlorodihydroxyphenyl group, trichlorodihydroxyphenyl group, monochlorodiacetoxyphenyl group, dichlorodiacetoxyphenyl group, Trichlorodiacetoxyphenyl group, monoclonal t-butoxycarbonylphenyl group, dichlorodi-t
  • Monochlorotrihydroxyphenyl group dichlorotrihydroxyphenyl group, monochlorotriacetoxyphenyl group, dichlorotriacetoxyphenyl group, monochlorotri-t-butoxycarbonylphenyl group, dichlorotri-t-butoxycarbonylphenyl group, monochloroadamantyl group, dichloroadamantyl Group, trichloroadamantyl group, monochlorohydroxyadamantyl group, dichlorohydroxynaphthyl group, monochloroacetoxynaphthyl group, dichloroacetoxyadamantyl group, monochlorot-butoxycarbonyladamantyl group, dichlorot-butoxycarbonyladamantyl group, trichlorot-butoxycarbonyladamantyl group, Examples thereof include a monoclonal hydroxyadamantyl group, a monoclonal acetoxyadamantyl group,
  • X may be an aromatic group in which one or more F, Cl, Br or I is introduced into the aromatic group.
  • aromatic groups include groups having a benzene ring such as a phenyl group having 1 to 5 halogens and groups having heteroaromatics such as furan, thiophene and pyridine having 1 to 5 halogens.
  • a phenyl group having 1 to 5 I a phenyl group having 1 to 5 F, a phenyl group having 1 to 5 Cl, a phenyl group having 1 to 5 Br, and 1 to 5 F.
  • Phenolic group having 1 to 4, phenol group having 1 to 4 Br, phenol group having 1 to 4 I, furan group having 1 to 3 F, furan group having 1 to 3 Cl, 1 to 3 Br A furan group having 1 to 3, a furan group having 1 to 3 I, a thiophenol group having 1 to 3 F, a thiophenol group having 1 to 3 Cl, a thiophenol group having 1 to 3 Br, and 1 to 3 I.
  • a benzoxazole group having 1 to 4 a benzoxazole group having 1 to 4 Br, a benzoxazole group having 1 to 4 I, a benzothiophene group having 1 to 4 F, and a benzo having 1 to 4 Cl. Examples thereof include a thiophene group, a benzothiophenol group having 1 to 4 Br, and a benzothiophenol group having 1 to 4 I.
  • X may be an alicyclic group in which one or more F, Cl, Br or I is introduced into the alicyclic group.
  • an alicyclic group include an adamantyl group having 1 to 3 halogens, an adamantyl group having 1 to 3 Fs, an adamantyl group having 1 to 3 Cls, and Br 1 to 3 Adamantyl group having 1 to 3, Adamantyl group having 1 to 3 I, Cyclopentyl group having 1 to 3 F, Cyclopentyl group having 1 to 3 Cl, Cyclopentyl group having 1 to 3 Br, 1 to 3 of I Cyclopentyl group having 1 to 3, bicycloundecyl group having 1 to 3 F, bicycloundecyl group having 1 to 3 Cl, bicycloundecyl group having 1 to 3 Br, bicycloundecyl group having 1 to 3 I Examples thereof include a decyl group, a norbornyl group having 1 to 3 Fs,
  • L 1 is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.
  • L 1 is preferably a single bond.
  • the ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphin group, phosphon group, urethane group, urea group, amide group, imide group, or phosphate group of L1 has a substituent. Is also good. Examples of such a substituent are as described above.
  • M is an integer of 0 or more, preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 2 or less, still more preferably 0 or 1, and particularly preferably 0.
  • Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon group.
  • Urethane group, urea group, amide group, imide group, or phosphoric acid group and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group of Y.
  • Urea group, amide group, imide group, and phosphate group may have a substituent.
  • Y is preferably a tertiary ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxylalkoxy group, and an acetal group or a carboxyl group.
  • Carboxyalkoxy groups are even more preferred.
  • an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable.
  • Y is preferably a group represented by the following formula (Y-1) independently of each other.
  • L 2 is a group that is cleaved by the action of an acid or base.
  • * 1 is a binding site with A
  • * 2 is a binding site with R 2 .
  • L 2 is preferably a tertiary ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxylalkoxy group, and an acetal group, from the viewpoint of high sensitivity.
  • a carboxylalkoxy group is more preferable.
  • an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable.
  • Y is a formula for the purpose of controlling the polymerizable property of the resin and setting the degree of polymerization within a desired range. It is preferably a group represented by (Y-1). Since the compound (A) has an X group, it has a large influence on the active species during the polymer formation reaction and it is difficult to control it as desired. Therefore, the hydrophilic group in the compound (A) is represented by the formula (Y-1). By having a group as a protective group, it is possible to suppress variations in polymer formation and polymerization inhibition derived from hydrophilic groups.
  • R2 is an aliphatic group containing a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a linear, branched or cyclic heteroatom having 1 to 30 carbon atoms.
  • the group group may further have a substituent.
  • R 2 is preferably an aliphatic group.
  • the aliphatic group in R2 is preferably a branched or cyclic aliphatic group.
  • the number of carbon atoms of the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and further preferably 4 or more and 8 or less.
  • the aliphatic group is not particularly limited, and examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group and an adamantyl group.
  • a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferable.
  • it when it is cleaved by the action of an acid or a base, it forms a carboxylic acid group and is insoluble in the dissociated part in the development process. Since the difference in solubility and the difference in dissolution rate between the rows are widened, the resolution is improved, and the residue at the bottom of the pattern in the fine line pattern is particularly suppressed, which is preferable.
  • Y include the following. Each is a group independently represented by any of the following equations.
  • Examples of the alkoxy group that can be used as Y include an alkoxy group having 1 or more carbon atoms, and an alkoxy group having 2 or more carbon atoms can be used from the viewpoint of the solubility of the resin after resinification by combining with other monomers.
  • An alkoxy group having 3 or more carbon atoms or a cyclic structure is preferable.
  • Specific examples of the alkoxy group that can be used as Y include, but are not limited to, the following.
  • amino group and the amide group that can be used as Y a primary amino group, a secondary amino group, a tertiary amino group, a group having a quaternary ammonium salt structure, an amide having a substituent and the like can be appropriately used.
  • Specific examples of the amino group or amide group that can be used include, but are not limited to, the following.
  • n is an integer of 1 or more, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 4 or less, still more preferably an integer of 1 or more and 3 or less, and even more preferably 1. Or 2, it is particularly preferably 1.
  • RA is an organic group having 1 to 60 carbon atoms, which may independently have H, I, F, Cl, Br, or a substituent.
  • the substituent of the organic group having 1 to 60 carbon atoms is not particularly limited, and examples thereof include I, F, Cl, Br, and other substituents.
  • the other substituent is not particularly limited, but for example, a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, and the like.
  • Examples thereof include a phosphon group, a urethane group, a urea group, an amide group, an imide group and a phosphoric acid group.
  • the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphin group, phosphon group, urethane group, urea group, amide group, imide group, and phosphoric acid group further have a substituent. You may be doing it.
  • the substituent here include a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
  • the number of carbon atoms of the organic group which may have a substituent in RA is preferably 1 to 30.
  • the organic group having 1 to 60 carbon atoms which may have a substituent is not particularly limited, but is a linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms and having 4 to 60 carbon atoms. Examples thereof include an alicyclic hydrocarbon group and an aromatic group which may contain a heteroatom having 6 to 60 carbon atoms.
  • the linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms is not particularly limited, and for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and the like.
  • Examples thereof include a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, a barrel group and a 2-ethylhexyl group.
  • the alicyclic hydrocarbon group is not particularly limited, and examples thereof include a cyclohexyl group, a cyclododecyl group, a dicyclopentyl group, a tricyclodecyl group, and an adamantyl group.
  • an aromatic group that may contain a heteroatom such as a benzodiazole group, a benzotriazole group, and a benzothiadiazole group can also be appropriately selected.
  • a combination of these organic groups can be selected.
  • the aromatic group that may contain a heteroatom having 6 to 60 carbon atoms is not particularly limited, and is, for example, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a benzodiazole group, and a benzotriazole group. , Benzotriazole group.
  • the methyl group is preferable from the viewpoint of producing a polymer having stable quality.
  • A is an organic group having 1 to 30 carbon atoms.
  • A may be a monocyclic organic group, a double ring organic group, or may have a substituent.
  • A is an aromatic ring which may preferably have a substituent.
  • the carbon number of A is preferably 6 to 14, and more preferably 6 to 10.
  • A is preferably a group represented by any of the following formulas, more preferably a group represented by the following formulas (A-1) to (A-2), and more preferably a group represented by the following formula (A-1). ) Is more preferable.
  • A may have an alicyclic structure which may have a substituent.
  • the "alicyclic structure” is a saturated or unsaturated carbon ring having no aromaticity. Examples of the alicyclic structure include saturated or unsaturated carbon rings having 3 to 30 carbon atoms, and saturated or unsaturated carbon rings having 3 to 20 carbon atoms are preferable.
  • Examples of the alicyclic structure include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloicocil, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and cyclopentadienyl.
  • A may have a heterocyclic structure which may have a substituent.
  • the heterocyclic structure is not particularly limited, and for example, a cyclic nitrogen-containing structure such as pyridine, piperidine, piperidone, benzodiazole, benzotriazole, etc., triazine, cyclic urethane structure, cyclic urea, cyclic amide, cyclic imide, furan, etc.
  • Examples thereof include cyclic ethers such as pyrane and dioxolan, alicyclic groups having a lactone structure such as caprolactone, butyrolactone, nonalactone, decalactone, undecalactone, bicycloundecalactone and phthalide.
  • cyclic ethers such as pyrane and dioxolan
  • alicyclic groups having a lactone structure such as caprolactone, butyrolactone, nonalactone, decalactone, undecalactone, bicycloundecalactone and phthalide.
  • Z is an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, or a carbonic acid ester group, respectively. These groups may have a substituent, and as the substituent, a hydrocarbon group having 1 to 60 carbon atoms which may further have a substituent can be raised.
  • r is an integer of 0 or more, preferably an integer of 0 or more and 2 or less, more preferably an integer of 0 or more and 1 or less, and further preferably 0.
  • [* 3 -OR 22- (C O) -OR 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms)]
  • the ester group is preferably a tertiary ester group from the viewpoint of increasing sensitivity.
  • * 3 is a binding site with A.
  • Z is preferably a tertiary ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxylalkoxy group, and an acetal group or a carboxyl group, from the viewpoint of high sensitivity.
  • Carboxyalkoxy groups are even more preferred.
  • an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable.
  • the other monomer copolymerized with the compound (A) in the polymer (A) preferably has a structural unit represented by the following formula (C3).
  • RC31 is a hydrogen atom, a methyl group or a trifluoromethyl group, and m, A and * are as defined by the above formula (C0).
  • the polymerization reaction is carried out by dissolving the monomer as a constituent unit in a solvent, adding a polymerization initiator, and heating or cooling.
  • the reaction conditions can be arbitrarily set depending on the type of the polymerization initiator, the starting method such as heat and light, the temperature, pressure, concentration, solvent, additives and the like.
  • the polymerization initiator include radical polymerization initiators such as azoisobutyronitrile and peroxides, and anionic polymerization initiators such as alkyllithium and Grignard reagents.
  • the solvent used for the polymerization reaction a commercially available product that is generally available can be used.
  • various solvents such as alcohol, ether, hydrocarbon, and halogen-based solvent can be appropriately used as long as the reaction is not inhibited.
  • a plurality of solvents may be mixed and used as long as the reaction is not inhibited.
  • the polymer (A) obtained by the polymerization reaction can be purified by a known method. Specifically, ultrafiltration, crystallization, microfiltration, pickling, water washing with an electric conductivity of 10 mS / m or less, and extraction can be performed in combination.
  • composition or the film-forming composition of the second embodiment contains the compound (A) or the polymer (A), and is particularly suitable for lithography techniques.
  • the composition or the film-forming composition can be used for lithography film-forming applications, for example, resist film-forming applications (that is, “resist compositions”).
  • the composition or the film-forming composition is used for upper film forming (that is, "upper film forming composition”), intermediate layer forming use (that is, “intermediate layer forming composition”), and lower layer. It can be used for film forming applications (that is, "lower layer film forming composition”) and the like.
  • the composition of the second embodiment it is possible to form a film having high sensitivity and to impart a good resist pattern shape.
  • the film-forming composition of the second embodiment can also be used as an optical component-forming composition to which a lithography technique is applied.
  • Optical components are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, microlenses, frennel lenses, viewing angle control lenses, contrast-enhancing lenses, etc.), retardation films, electromagnetic wave shielding films, and prisms.
  • the composition is an embedded film and a flattening film on a photodiode, a flattening film before and after a color filter, a microlens, and a flattening on a microlens, which are members of a solid-state image sensor that are particularly required to have a high refractive index. It can be suitably used as a film and a conformal film.
  • the film-forming composition of the second embodiment may contain the compound (A), the composition of the second embodiment, or the polymer (A).
  • the film-forming composition of the second embodiment may further contain an acid generator (C), a base generator (G), or an acid diffusion control agent (E) (basic compound).
  • the film-forming composition of the second embodiment may further contain other components such as a base material (B) and a solvent (S), if necessary.
  • each component will be described.
  • the "base material (B)" is a compound (including a resin) other than the compound (A) or the polymer (A), and is a g-ray, i-line, KrF excimer laser (248 nm). ), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), and a substrate applied as a resist for electron beam (EB) (for example, a substrate for lithography or a substrate for resist). .
  • These base materials are not particularly limited and can be used as the base material (B) in the second embodiment.
  • Examples of the base material (B) include phenol novolac resin, cresol novolak resin, hydroxystyrene resin, (meth) acrylic resin, hydroxystyrene- (meth) acrylic copolymer, cycloolefin-maleic acid anhydride copolymer, and the like.
  • Examples thereof include cycloolefins, vinyl ether-maleic acid anhydride copolymers, inorganic resist materials having metal elements such as titanium, tin, hafnium and zirconium, and derivatives thereof.
  • phenol novolac resin cresol novolak resin, hydroxystyrene resin, (meth) acrylic resin, hydroxystyrene- (meth) acrylic copolymer, and titanium, tin, hafnium and zirconium.
  • Inorganic resist materials having metal elements such as, and derivatives thereof are preferable.
  • the derivative is not particularly limited, and examples thereof include those having a dissociative group introduced and those having a crosslinkable group introduced.
  • the derivative into which the dissociative group or the crosslinkable group is introduced can develop a dissociative reaction or a crosslinking reaction by the action of light, an acid or the like.
  • Dissociative group refers to a characteristic group that produces a functional group such as an alkali-soluble group that cleaves and changes its solubility.
  • the alkali-soluble group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group, and a phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable.
  • Crosslinkable group means a group that crosslinks in the presence of a catalyst or in the absence of a catalyst.
  • the crosslinkable group is not particularly limited, and has, for example, an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, a group having a (meth) acryloyl group, a group having an epoxy (meth) acryloyl group, and a hydroxyl group. Examples thereof include a group having a urethane (meth) acryloyl group, a group having a glycidyl group, and a group having a vinyl-containing phenylmethyl group.
  • solvent (S) As the solvent in the second embodiment, a known solvent can be appropriately used as long as the above-mentioned compound (A) or the polymer (A) is at least soluble.
  • the solvent is not particularly limited, but for example, ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate.
  • ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether
  • propylene glycol monomethyl ether acetate (PGMEA) propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono -Propylene glycol monoalkyl ether acetates such as n-butyl ether acetate
  • propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether
  • methyl lactate, ethyl lactate, n-propyl lactate, n lactate -Lactic acid esters such as butyl and n-amyl lactic acid
  • aliphatics such as methyl acetate, ethyl acetate, n-propyl acetate, n-buty
  • Carboxyre esters Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, Other esters such as 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate; toluene , Aromatic hydrocarbons such as xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN); N, N-dimethylformamide , N-Methylacetamide, N, N-dimethylacetamide,
  • the solvent used in the second embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate and ethyl lactate. It is a species, more preferably at least one selected from PGMEA, PGME, CHN, CPN and ethyl lactate.
  • the solid component concentration is not particularly limited, but is preferably 1 to 80% by mass, more preferably 1 to 50, based on the total mass of the film-forming composition. It is by mass, more preferably 2 to 40% by mass, and even more preferably 2 to 10% by mass.
  • the film-forming composition of the second embodiment preferably contains at least one acid generator (C) that directly or indirectly generates an acid by irradiation. Radiation is at least one selected in the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray and ion beam.
  • the acid generator (C) is not particularly limited, but for example, the acid generator (C) described in International Publication No. WO2013 / 024778 can be used.
  • the acid generator (C) may be used alone or in combination of two or more.
  • the blending amount of the acid generator (C) is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, and further preferably 3 to 30% by mass with respect to the total mass of the solid component. It is more preferably 10 to 25% by mass.
  • the method of generating the acid is not particularly limited.
  • Finer processing is possible by using an excimer laser instead of ultraviolet rays such as g-rays and i-rays, and further fine processing is possible by using electron beams, extreme ultraviolet rays, X-rays, and ion beams as high-energy rays. Is possible.
  • Base generator (G) A case where the base generator (G) is a photobase generator will be described.
  • a photobase generator is one that generates a base by exposure and does not show activity under normal conditions of normal temperature and pressure, but when it is irradiated with electromagnetic waves and heated as an external stimulus, it is a base (basic substance). ) Is not particularly limited as long as it occurs.
  • the photobase generator that can be used in the second embodiment is not particularly limited, and known ones can be used, for example, carbamate derivatives, amide derivatives, imide derivatives, ⁇ -cobalt complexes, imidazole derivatives, and cinnamic acid. Examples thereof include amide derivatives and oxime derivatives.
  • the basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
  • a compound having an amino group having a higher basicity is preferable from the viewpoint of sensitivity and resolution.
  • the photobase generator include a base generator having a cinnamon acid amide structure as disclosed in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. 2009/123122, JP-A-2006-189591 and Japanese Patent Laid-Open No.
  • a base having an oxime structure and a base having a carbamoyl oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581 examples thereof include, but are not limited to, generators, compounds described in JP-A-2010-243773, and other known structures of base generators can be used.
  • the photobase generator can be used alone or in combination of two or more.
  • the preferable content of the photobase generator in the sensitive light-sensitive or radiation-sensitive resin composition is the same as the preferable content of the photoacid generator in the sensitive light-sensitive or radiation-sensitive resin composition described above. ..
  • the film-forming composition of the second embodiment may contain an acid diffusion control agent (E) as a basic compound.
  • the acid diffusion control agent (E) controls the diffusion of the acid generated from the acid generator in the resist film by irradiation to prevent an undesired chemical reaction from occurring in the unexposed region.
  • the storage stability of the composition of the second embodiment tends to be improved.
  • the resolution of the film formed by using the composition of the second embodiment can be improved, and the leaving time before irradiation and the leaving time after irradiation can be improved.
  • the acid diffusion control agent (E) is not particularly limited, and examples thereof include radiolytic basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodinenium compounds.
  • the acid diffusion control agent (E) is not particularly limited, but for example, the acid diffusion control agent (E) described in International Publication No. WO2013 / 024778 can be used.
  • the acid diffusion control agent (E) may be used alone or in combination of two or more.
  • the blending amount of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, and further preferably 0. It is 01 to 5% by mass, more preferably 0.01 to 3% by mass.
  • the blending amount of the acid diffusion control agent (E) is within the above range, it tends to be possible to prevent deterioration of resolution, pattern shape, dimensional fidelity and the like. Further, even if the leaving time from the electron beam irradiation to the heating after the irradiation is long, it is possible to suppress the deterioration of the shape of the upper layer portion of the pattern.
  • the blending amount of the acid diffusion control agent (E) is 10% by mass or less, it tends to be possible to prevent deterioration of sensitivity, developability of the unexposed portion, and the like. Further, by using such an acid diffusion control agent, the storage stability of the resist composition is improved, the resolution is improved, and the retention time before irradiation and the retention time after irradiation fluctuate. It is possible to suppress the change in the line width of the resist pattern, and the process stability tends to be excellent.
  • the film-forming composition of the second embodiment contains, as other components (F), a cross-linking agent, a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant and an organic carboxylic acid, as necessary.
  • a cross-linking agent e.g., a cross-linking agent, a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant and an organic carboxylic acid, as necessary.
  • One or two or more kinds of additives such as phosphorus oxoacid or a derivative thereof can be added.
  • the film-forming composition of the second embodiment may contain a cross-linking agent.
  • the cross-linking agent can cross-link at least one of the compound (A), the polymer (A) and the substrate (B).
  • the cross-linking agent is preferably an acid cross-linking agent capable of intramolecularly or intermolecularly cross-linking the substrate (B) in the presence of an acid generated from the acid generator (C).
  • Examples of such an acid cross-linking agent include compounds having one or more groups (hereinafter, referred to as “crosslinkable groups”) capable of cross-linking the substrate (B).
  • crosslinkable group examples include (i) a hydroxy group, a hydroxyalkyl group (alkyl group having 1 to 6 carbon atoms), alkoxy having 1 to 6 carbon atoms (alkyl group having 1 to 6 carbon atoms), and acetoxy (alkyl group having 1 to 6 carbon atoms). Hydroxylalkyl groups such as ( ⁇ 6 alkyl groups) or groups derived from them; (ii) carbonyl groups such as formyl groups, carboxys (alkyl groups having 1 to 6 carbon atoms) or groups derived from them; (iiii).
  • Nitrogen-containing group-containing group such as dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, dietylolaminomethyl group, morpholinomethyl group;
  • glycidyl group-containing group such as glycidyl ether group, glycidyl ester group and glycidyl amino group Group;
  • Allyloxy having 1 to 6 carbon atoms alkyl group having 1 to 6 carbon atoms
  • benzyloxymethyl group and benzoyloxymethyl group such as benzyloxymethyl group and benzoyloxymethyl group, and aralkyloxy having 1 to 6 carbon atoms (1 to 6 carbon atoms).
  • Groups derived from aromatic groups such as (alkyl groups); (vi) polymerizable multiple bond-containing groups such as vinyl groups and isopropenyl groups can be mentioned.
  • a hydroxyalkyl group, an alkoxyalkyl group and the like are preferable, and an alkoxymethyl group is particularly preferable.
  • the cross-linking agent having a cross-linking group is not particularly limited, but for example, the acid cross-linking agent described in International Publication WO2013 / 024778 can be used.
  • the cross-linking agent may be used alone or in combination of two or more.
  • the blending amount of the cross-linking agent is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on the total mass of the solid component. More preferably, it is 20% by mass or less.
  • the dissolution accelerator is a component having an action of increasing the solubility of a solid component in a developing solution and appropriately increasing the dissolution rate of the compound during development.
  • the dissolution accelerator is preferably one having a low molecular weight, and examples thereof include a low molecular weight phenolic compound. Examples of the low molecular weight phenolic compound include bisphenols and tris (hydroxyphenyl) methane. These dissolution accelerators can be used alone or in admixture of two or more.
  • the blending amount of the dissolution accelerator is appropriately adjusted according to the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid component. % Is more preferable, and 0% by mass is particularly preferable.
  • the dissolution control agent is a component having an action of controlling the solubility of a solid component in a developing solution and appropriately reducing the dissolution rate during development.
  • a dissolution control agent one that does not chemically change in steps such as firing of the resist film, irradiation, and development is preferable.
  • the dissolution control agent is not particularly limited, and for example, aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthylketone; Sulfones and the like can be mentioned. These dissolution control agents may be used alone or in combination of two or more.
  • the blending amount of the dissolution control agent is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid components. Is more preferable, and 0% by mass is particularly preferable.
  • the sensitizer has the effect of absorbing the energy of the irradiated radiation and transferring that energy to the acid generator (C), thereby increasing the amount of acid produced, improving the apparent sensitivity of the resist. It is an ingredient that causes.
  • a sensitizer include benzophenones, biacetyls, pyrenes, phenothiazines, fluorenes and the like, but are not particularly limited. These sensitizers can be used alone or in combination of two or more.
  • the blending amount of the sensitizer is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid component. More preferably, 0% by mass is particularly preferable.
  • the surfactant is a component having an action of improving the coatability, striation, developability of the resist, etc. of the composition of the second embodiment.
  • the surfactant may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant or an amphoteric surfactant.
  • Preferred surfactants include nonionic surfactants.
  • the nonionic surfactant has a good affinity with the solvent used for producing the composition of the second embodiment, and can further enhance the effect of the composition of the second embodiment.
  • nonionic surfactant examples include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyethylene glycol higher fatty acid diesters, and the like, but are not particularly limited.
  • Commercially available products of these surfactants are Ftop (manufactured by Gemco), Megafuck (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (manufactured by Sumitomo Three-M), and Asahigard under the following trade names.
  • the blending amount of the surfactant is appropriately adjusted according to the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid component. % Is more preferable, and 0% by mass is particularly preferable.
  • Organic carboxylic acid or phosphorus oxo acid or its derivative For the purpose of preventing deterioration of sensitivity or improving the shape of the resist pattern, retention stability, etc., an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be further contained as an arbitrary component.
  • the organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof can be used in combination with an acid diffusion control agent, or may be used alone.
  • the organic carboxylic acid for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • Examples of the oxo acid of phosphorus or a derivative thereof include phosphoric acid such as phosphoric acid, di-n-butyl ester of phosphoric acid, diphenyl ester of phosphoric acid, or a derivative of such ester, phosphonic acid, dimethyl phosphonic acid ester, and di-phosphonic acid di-.
  • Examples thereof include phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester and phosphonic acid dibenzyl ester or derivatives such as their esters, phosphinic acid such as phosphinic acid and phenylphosphinic acid and derivatives such as their esters. Be done. Of these, phosphonic acid is particularly preferable.
  • the organic carboxylic acid or phosphorus oxoacid or its derivative can be used alone or in combination of two or more.
  • the blending amount of the organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, preferably 0 to 5% by mass, based on the total mass of the solid component. More preferably, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.
  • the composition of the second embodiment may contain one or more additives other than the above-mentioned components, if necessary.
  • additives include dyes, pigments, adhesive aids and the like.
  • a dye or a pigment because the latent image of the exposed portion can be visualized and the influence of halation during exposure can be alleviated.
  • an adhesive aid because the adhesiveness to the substrate can be improved.
  • examples of other additives include anti-halation agents, storage stabilizers, antifoaming agents, shape improvers and the like, specifically 4-hydroxy-4'-methyl chalcone and the like.
  • the total amount of the optional component (F) can be 0 to 99% by mass, preferably 0 to 49% by mass, and 0 to 10% by mass, based on the total mass of the solid components. More preferably, 0 to 5% by mass is further preferable, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.
  • the method for forming the resist pattern of the second embodiment is as follows. A step of forming a resist film on a substrate using the film-forming composition of the second embodiment, The step of exposing the pattern to the resist film and The step of developing the resist film after the exposure and including.
  • the method for forming the insulating film of the second embodiment may include the method of forming the resist pattern of the second embodiment. That is, the method for forming the insulating film of the second embodiment is A step of forming a resist film on a substrate using the film-forming composition of the second embodiment, The step of exposing the pattern to the resist film and The step of developing the resist film after the exposure and May include.
  • the film-forming composition of the second embodiment contains, for example, the compound (A), the composition of the second embodiment, or the polymer (A).
  • the coating method in the step of forming the resist film is not particularly limited, and examples thereof include a spin coater, a dip coater, and a roller coater.
  • the substrate is not particularly limited, and examples thereof include silicon wafers, metals, plastics, glass, and ceramics.
  • heat treatment may be performed at a temperature of about 50 ° C to 200 ° C.
  • the film thickness of the resist film is not particularly limited, but is, for example, 50 nm to 1 ⁇ m.
  • exposure may be performed via a predetermined mask pattern, or maskless shot exposure may be performed.
  • the thickness of the coating film is, for example, about 0.1 to 20 ⁇ m, preferably about 0.3 to 2 ⁇ m.
  • Light rays of various wavelengths such as ultraviolet rays and X-rays, can be used for exposure.
  • an F2 excimer laser (wavelength 157 nm), an ArF excimer laser (wavelength 193 nm), or a KrF excimer laser (wavelength 248 nm) can be used.
  • Far ultraviolet rays such as, extreme ultraviolet rays (wavelength 13n), X-rays, electron beams, etc. are appropriately selected and used. Among these, extreme ultraviolet rays are preferable.
  • the exposure conditions such as the exposure amount are appropriately selected according to the composition of the above-mentioned resin and / or compound, the type of each additive, and the like.
  • a predetermined resist pattern is formed by developing with an alkaline developer at 10 to 50 ° C. for 10 to 200 seconds, preferably 20 to 25 ° C. for 15 to 90 seconds.
  • alkaline developing solution examples include alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, and 1,8-diazabicyclo- [5.
  • Alkaline compounds such as 4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonen are usually concentrated in an amount of 1 to 10% by mass, preferably 1 to 3% by mass.
  • An alkaline aqueous solution dissolved so as to be used is used. Further, a water-soluble organic solvent or a surfactant can be appropriately added to the developer composed of the alkaline aqueous solution.
  • a solvent can also be used as the developer.
  • the solvent used in the developing solution it is preferable to select a solvent having a solubility parameter (SP value) close to that of the compound or resin according to the second embodiment to be used, and it is preferable to select a ketone solvent, an ester solvent, or an alcohol solvent.
  • SP value solubility parameter
  • Amid solvent, polar solvent such as ether solvent, hydrocarbon solvent or alkaline aqueous solution can be used.
  • a positive resist pattern or a negative resist pattern can be prepared depending on the type of the developing solution, but in general, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, or an ether solvent can be produced.
  • a negative resist pattern can be obtained, and in the case of an alkaline aqueous solution, a positive resist pattern can be obtained.
  • the ketone solvent, ester solvent, alcohol solvent, amide solvent, ether solvent, hydrocarbon solvent, and alkaline aqueous solution include those disclosed in International Publication No. 2017/033943.
  • the water content of the developer as a whole is preferably less than 70% by mass, more preferably less than 50% by mass, and less than 30% by mass. More preferably, it is more preferably less than 10% by mass, and particularly preferably it contains substantially no water. That is, the content of the organic solvent in the developing solution is not particularly limited, and is preferably 30% by mass or more and 100% by mass or less, and more preferably 50% by mass or more and 100% by mass or less with respect to the total amount of the developing solution. It is more preferably 70% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.
  • the developing solution contains at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent, and the developing solution contains the resolution and roughness of the resist pattern. It is preferable because it improves the resist performance of the solvent.
  • the vapor pressure of the developer is not particularly limited, and is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less, for example, at 20 ° C.
  • the vapor pressure of the developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less, for example, at 20 ° C.
  • the surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based or silicon-based surfactant can be used.
  • fluorine- or silicon-based surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, and Japanese Patent Application Laid-Open No. 62-170950.
  • the surfactants described in No. 5529881, No. 5296330, No. 5436098, No. 5576143, No. 5294511, and No. 5824451 can be mentioned.
  • it is a nonionic surfactant.
  • the nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.
  • the amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developing solution.
  • a developing method for example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dip method), or a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle).
  • dip method a method of immersing a substrate in a tank filled with a developing solution for a certain period of time
  • paddle a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time
  • a method of spraying the developer on the surface of the substrate spray method
  • a method of continuously spraying the developer on the substrate rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed dynamic discharge method.
  • Etc. can be applied.
  • the time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.
  • a step of stopping the development may be carried out while substituting with another solvent.
  • the rinsing solution used in the rinsing step after development is not particularly limited as long as the resist pattern cured by crosslinking is not dissolved, and a solution containing a general organic solvent or water can be used.
  • a rinsing solution it is preferable to use a rinsing solution containing at least one organic solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent. .. More preferably, after development, a washing step is performed using a rinsing solution containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent.
  • a step of washing with a rinsing solution containing an alcohol-based solvent or an ester-based solvent is performed. Even more preferably, after development, a step of washing with a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after development, a step of washing with a rinsing solution containing a monohydric alcohol having 5 or more carbon atoms is performed.
  • the time for rinsing the pattern is not particularly limited, but is preferably 10 to 90 seconds.
  • the monohydric alcohol used in the rinsing step after development is not particularly limited, and examples thereof include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol and 2 -Butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol , Cyclopentanol, 2-Heptanol, 2-Octanol, 3-Hexanol, 3-Heptanol, 3-Octanol, 4-Octanol and the like can be used, and a particularly preferable monohydric alcohol having 5 or more carbon atoms is 1-. Hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like can be
  • Each of the above components may be mixed in a plurality or mixed with an organic solvent other than the above.
  • the water content in the rinse liquid is not particularly limited, and is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.
  • the vapor pressure of the rinse solution used after development is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and further preferably 0.12 kPa or more and 3 kPa or less at 20 ° C.
  • the vapor pressure of the rinsing liquid By setting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, and the swelling caused by the infiltration of the rinsing liquid is further suppressed, and the dimensions in the wafer surface are further suppressed. The uniformity is improved.
  • An appropriate amount of surfactant can be added to the rinse solution before use.
  • the developed wafer is cleaned with a rinsing solution containing the above-mentioned organic solvent.
  • the method of cleaning treatment is not particularly limited, but for example, a method of continuously applying a rinse solution onto a substrate rotating at a constant speed (rotational coating method), or a method of immersing the substrate in a tank filled with the rinse solution for a certain period of time.
  • a method (dip method), a method of spraying a rinse solution on the surface of the substrate (spray method), etc. can be applied.
  • the cleaning treatment is performed by the rotation coating method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
  • composition of the second embodiment can also be used as an optical component forming composition to which a lithography technique is applied.
  • Optical components are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, microlenses, frennel lenses, viewing angle control lenses, contrast-enhancing lenses, etc.), retardation films, electromagnetic wave shielding films, and prisms.
  • the composition is an embedded film and a flattening film on a photodiode, a flattening film before and after a color filter, a microlens, and a flattening on a microlens, which are members of a solid-state image sensor that are particularly required to have a high refractive index. It can be suitably used as a film and a conformal film.
  • the composition of the second embodiment can be used as a patterning material for lithography applications.
  • the lithography process can be used in various applications such as semiconductors, liquid display panels, display panels using OLEDs, power devices, CCDs and other sensors.
  • the composition of the second embodiment is used on the upper surface side of an insulating layer such as a silicon oxide film or another oxide film in the step of forming a device element on a silicon wafer.
  • a semiconductor element is formed by forming a pattern on the insulating film on the substrate side using etching based on the pattern formed in the above process, and then laminating a metal film or semiconductor material based on the formed insulating film pattern to form a circuit pattern.
  • the composition of the second embodiment can be preferably used for the purpose of constructing the above-mentioned device and other devices.
  • the third embodiment is an embodiment in the case where RX in the compound (A) in the first embodiment is a hydrogen atom .
  • RX in the compound (A) in the first embodiment is a hydrogen atom .
  • the description may be simplified or omitted with respect to the same contents as those of the second embodiment.
  • the third embodiment is an example for explaining the present invention, and the present invention is not limited to the second embodiment.
  • a resist having extremely excellent exposure sensitivity can be obtained. Further, a resist having extremely excellent exposure sensitivity can be obtained by a method for forming a pattern using the compound (A), a method for forming an insulating film, or a method for producing a compound. That is, a compound, a polymer, a composition, a film-forming composition, a pattern forming method, an insulating film forming method and a compound, which can obtain a resist having extremely excellent exposure sensitivity by using the compound (A). Production method can be provided.
  • the iodine atom has a high absorption effect on EUV and the substituent P is immediately adjacent to the iodine atom to absorb the iodine atom.
  • the effect is easily affected and the sensitizing effect is likely to be generated from the substituent P, and further, the opposite side of the iodine atom of the substituent P is unsubstituted, and the sensitizing effect of P is likely to be exhibited. I guess it is because of this.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group and an amino group.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RA is preferably a hydrogen atom or a methyl group in order to increase the sensitivity.
  • a trifluoromethyl group is preferable as RA from the viewpoint of enhancing absorption to EUV.
  • substitution means that one or more hydrogen atoms in a functional group are substituted with a substituent unless otherwise defined.
  • the "substituent” is not particularly limited, but is, for example, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, an alkyl group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms.
  • Examples thereof include an aryl group, an alkoxyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and an amino group having 0 to 30 carbon atoms. Be done.
  • the alkyl group may be any of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.
  • the alkyl group having 1 to 30 carbon atoms is not limited to the following, but for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, and the like. Examples thereof include an n-pentyl group, an n-hexyl group, an n-dodecyl group and a barrel group.
  • Examples of the aryl group having 6 to 30 carbon atoms include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a perylene group and the like.
  • Examples of the alkenyl group having 2 to 30 carbon atoms include, but are not limited to, an ethynyl group, a propenyl group, a butynyl group, a pentynyl group and the like.
  • Examples of the alkynyl group having 2 to 30 carbon atoms include, but are not limited to, an acetylene group and an ethynyl group.
  • the alkoxy group having 1 to 30 carbon atoms is not limited to the following, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
  • P is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group and a thioether group.
  • Phosphin group, phosphon group, urethane group, urea group, amide group, imide group, or phosphoric acid group and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphin group of P.
  • Phosphon group, urethane group, urea group, amide group, imide group, and phosphate group may have a substituent.
  • the ester group is preferably a tertiary ester group from the viewpoint of increasing sensitivity.
  • * 3 is a binding site with A.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, a carboxyl group, a thiol group, an ether group, a thioether group, and a phosphine group from the viewpoint of high sensitivity.
  • Phosphon group, urethane group, urea group, amide group, imide group, or phosphate group is preferable, hydroxyl group, ester group, acetal group, carbonate ester group or carboxylalkoxy group is more preferable, acetal group, carbonate ester group or carboxy.
  • An alkoxy group is more preferable, and an acetal group or a carboxylalkoxy group is particularly preferable. Further, from the viewpoint of producing a stable quality polymer by radical polymerization, an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable. Further, from the viewpoint of increasing the difference in dissolution rate before and after exposure to improve the resolution, a tertiary ester group, an acetal group, a carbonic acid ester group or a carboxylalkoxy group is preferable. From the viewpoint of achieving high sensitivity without adversely affecting other properties, P is preferably an ester group, an acetal group, or a carbonic acid ester group.
  • P is preferably a group represented by the following formula (P-1) independently of each other.
  • L 2 is a group that is cleaved by the action of an acid or base.
  • * 1 is a binding site with a benzene ring
  • * 2 is a binding site with R 2 .
  • L 2 is preferably a tertiary ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxylalkoxy group, and an acetal group, from the viewpoint of high sensitivity.
  • a carboxylalkoxy group is more preferable.
  • an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable.
  • P is a formula for the purpose of controlling the polymerizable property of the resin and setting the degree of polymerization within a desired range. It is preferably a group represented by (P-1). Since the compound (A) has iodine, it has a large influence on the active species during the polymer formation reaction and it is difficult to control it as desired. Therefore, the hydrophilic group in the compound (A) is represented by the formula (P-1). By having the group as a protective group, it is possible to suppress the variation in the formation of the copolymer derived from the hydrophilic group and the inhibition of the polymerization.
  • R2 is an aliphatic group containing a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a linear, branched or cyclic heteroatom having 1 to 30 carbon atoms.
  • the group group may or may not have a substituent.
  • R 2 is preferably an aliphatic group.
  • the aliphatic group in R2 is preferably a branched or cyclic aliphatic group.
  • the number of carbon atoms of the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and further preferably 4 or more and 8 or less.
  • the aliphatic group is not particularly limited, and examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group and an adamantyl group.
  • a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferable.
  • it when it is cleaved by the action of an acid or a base, it forms a carboxylic acid group and is insoluble in the dissociated part in the development process. Since the difference in solubility and the difference in dissolution rate between the rows are widened, the resolution is improved, and the residue at the bottom of the pattern in the fine line pattern is particularly suppressed, which is preferable.
  • P is, for example, a group independently represented by any of the following equations.
  • alkoxy group that can be used as P examples include an alkoxy group having 1 or more carbon atoms, and an alkoxy group having 2 or more carbon atoms is used from the viewpoint of the solubility of the resin after resinification in combination with another monomer.
  • An alkoxy group having 3 or more carbon atoms or a cyclic structure is preferable.
  • Specific examples of the alkoxy group that can be used as P include, but are not limited to, the following.
  • amino group and the amide group that can be used as P a primary amino group, a secondary amino group, a tertiary amino group, a group having a quaternary ammonium salt structure, an amide having a substituent and the like can be appropriately used.
  • Specific examples of the amino group or amide group that can be used include, but are not limited to, the following.
  • the compound (A) according to the third embodiment has a hydrogen group serving as a proton source at the ortho position of the phenolic hydroxyl group, thereby contributing to the efficiency of the proton generation mechanism after exposure.
  • a polymer using the compound (A) is applied to a resist composition to form a pattern by a lithography process consisting of film formation, exposure, and development, the efficiency of proton generation after exposure is improved, resulting in development residues and development residues. It is possible to make up for the lack of generated protons that are the source of roughness, bridges, etc., and to achieve both development defects and lithography performance such as sensitivity and resolution.
  • the pattern quality in finer pattern formation can be improved.
  • Examples of the compound (A) according to the third embodiment include compounds having the following structures.
  • composition according to the third embodiment preferably contains the compound (A) and the compound represented by the formula (1A).
  • the composition contains the compound represented by the formula (1A) in a range of 1% by mass or more and 10% by mass or less with respect to the entire compound (A) from the viewpoint of improving the exposure sensitivity and reducing the residual defects. It is preferable that it is prepared so as to be, more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and 1 mass ppm or more and 1 mass. It is particularly preferable that it is in the range of% or less.
  • the exposure sensitivity is improved by the high density of the iodine-containing portion and the P-containing portion in the proximity region. It will be the starting point. Further, the local increase in solubility in the resin leads to reduction of post-development residue defects in the lithography process.
  • Examples of the compound (1A) according to the third embodiment include compounds having the following structures.
  • composition according to the third embodiment preferably contains the compound (A) and the compound represented by the formula (1B).
  • RA and P are the same as the definition in the formula (1), n 2 is an integer of 0 to 4, and R sub2 is. It represents the formula (1B1) or the formula (1B2), and * is a binding site with an adjacent structural unit.
  • the composition contains the compound represented by the formula (1B) in a range of 1% by mass or more and 10% by mass or less with respect to the entire compound (A) from the viewpoint of improving the exposure sensitivity and reducing the residual defects. It is preferable that it is prepared so as to be, more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and 1 mass ppm or more and 1 mass. It is particularly preferable that it is in the range of% or less.
  • the exposure sensitivity is improved by the high density of the iodine-containing portion and the P-containing portion in the proximity region. It will be the starting point. Further, the local increase in solubility in the resin leads to reduction of post-development residue defects in the lithography process.
  • Examples of the compound (1B) according to the third embodiment include compounds having the following structures.
  • composition according to the third embodiment preferably contains the compound (A) and the compound represented by the formula (1C).
  • RA and P are the same as the definitions in formula (1). However, P does not include I.
  • the compound represented by the formula (1C) is 1 mass ppm or more with respect to the compound (A) 10 with respect to the whole compound (A). It is preferably contained in the range of 1 mass% or less, more preferably 1 mass ppm or more and 5 mass% or less, further preferably 1 mass ppm or more and 3 mass% or less, and 1 mass ppm or more 1 It is particularly preferable that the content is in the range of mass% or less.
  • the composition thus prepared tends to be more stable. The reason is not clear, but it is presumed that the iodine atom equilibrium reaction occurs and stabilizes between the iodine-containing compound (A) and the iodine-free compound (1C).
  • the compound (1C) in combination with a compound having a structure in which an iodine atom is eliminated from the compound exemplified as the above-mentioned compound (A).
  • the composition thus produced has enhanced stability, it not only enhances storage stability, but also forms a resin having stable properties, imparts stable performance resist performance, and further. Leads to a reduction in post-development residue defects in the lithography process.
  • the method for using the compound represented by the formula (1C) in the range of 1% by mass or more and 10% by mass or less with respect to the entire compound (A) in the composition containing the compound (A) is not particularly limited. , A method of adding the compound (1C) to the compound (A), a method of producing the compound (1C) as a by-product during the production of the compound (A), and the like.
  • Examples of the compound (1C) according to the third embodiment include compounds having the following structures.
  • the compound represented by the formula (1), wherein P is a hydroxyl group is not particularly limited as an example of the synthesis method, but I, F, Cl, with respect to the hydroxy group-containing aromatic aldehyde derivative.
  • it can be synthesized by introducing a halogen group of Br and then converting an aldehyde group into a vinyl group.
  • a method of reacting iodine chloride in an organic solvent by carrying out an iodination reaction with a hydroxybenzaldehyde derivative see, for example, Japanese Patent Application Laid-Open No. 2012-180326), ⁇ under alkaline conditions.
  • a method of dropping iodine into an alkaline aqueous solution of phenol see JP-A-63-101342 and JP-A-2003-64012) can be appropriately selected.
  • an iodine monochloride-mediated iodination reaction in an organic solvent.
  • the compound (A) of the third embodiment can be synthesized.
  • a Wittig reaction for example, the method described in Synthetic Communications; Vol.22; nb4; 1992p513, Synthesis; Vol.49; nb.23; 2017; p5217
  • a Wittig reaction for example, the method described in Synthetic Communications; Vol.22; nb4; 1992p513, Synthesis; Vol.49; nb.23; 2017; p5217
  • the method for producing the compound (A) (iodine-containing vinyl monomer) represented by the formula (1) is a) General structure represented by equation (1-5):
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group and a nitro group.
  • b) includes a Wittig reaction step of forming an alkene from the carbonyl moiety of the iodine-containing aldehyde-based substrate or the iodine-containing ketone substrate by the Wittig reaction.
  • the iodine-containing aldehyde-based substrate or iodine-containing ketone substrate having the general structure represented by the formula (1-5) include 4-hydroxy-3-iodobenzaldehyde and the like.
  • the Wittig reaction step is a step of forming an alkene by the Wittig reaction, and is a step of forming an alkene from a carbonyl moiety having an aldehyde or a ketone using phosphorus irid, without limitation.
  • phosphorus irid triphenylalkylphosphine bromide such as triphenylmethylphosphine bromide, which can form a stable phosphorus irid, can be used.
  • a phosphonium salt as phosphorus iris with a base to form phosphoylide in the reaction system and use it in the above-mentioned reaction.
  • a base conventionally known ones can be used, and for example, an alkali metal salt of alkoxide or the like can be appropriately used.
  • a method of reacting malonic acid under a base for example, Tetrahedron; Vol.46; nb.40; 2005; p6893, Tetrahedron; Vol.63; nb.4 (2007; the method described in p900, US2004 / 118673, etc.) and the like can be appropriately used.
  • the method for producing the compound (A) (iodine-containing vinyl monomer) represented by the formula (1) is a) A step of preparing an iodine-containing aldehyde-based substrate or an iodine-containing ketone substrate having a general structure represented by the above formula (1-5); b) With the malonic acid addition step of adding malonic acid to the iodine-containing aldehyde-based substrate or the iodine-containing ketone substrate; c) A hydrolysis step of hydrolyzing the iodine-containing aldehyde substrate or the iodine-containing ketone substrate to which the malonic acid is added to produce an iodine-containing carboxylic acid substrate; d) A decarboxylation step of decarboxylating the iodine-containing carboxylic acid substrate that has been hydrolyzed; And include.
  • the malonic acid addition step in the third embodiment is a step of forming a malonic acid derivative, and is a reaction between aldehyde and malonic acid, malonic acid ester or malonic acid anhydride, without limitation.
  • the hydrolysis step in the third embodiment is a step of forming a carboxylic acidic substrate by hydrolysis, and is a reaction of hydrolyzing an ester by the action of an acid or water, without limitation.
  • the decarboxylation step in the third embodiment is a step of decarboxylating from a carboxylic acidic substrate to obtain a vinyl monomer, and is not limited, but is preferably performed at a low temperature of 100 ° C. or lower, and a fluoride-based catalyst is used. Is more preferable.
  • the method for synthesizing the compound (A) of the third embodiment for example, the method described in the above-mentioned reference material can be appropriately used, but the method is not limited thereto.
  • the compound represented by the formula (1) in which P is an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group or a carbonic acid ester group is not particularly limited as an example of the synthesis method, but is not limited to the formula (1).
  • P is a hydroxyl group
  • an active carboxylic acid derivative compound such as acid chloride, acid anhydride or dicarbonate, alkyl halide, vinyl alkyl ether, dihydropyran, etc. It is obtained by reacting with a halocarboxylic acid alkyl ester or the like.
  • a compound represented by the formula (1) in which P is a hydroxyl group, is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran, or propylene glycol monomethyl ether acetate.
  • an aprotic solvent such as acetone, tetrahydrofuran, or propylene glycol monomethyl ether acetate.
  • vinyl alkyl ether such as ethyl vinyl ether or dihydropyran is added, and the reaction is carried out at normal pressure at 20 to 60 ° C. for 6 to 72 hours in the presence of an acid catalyst such as pyridinium p-toluenesulfonate.
  • the reaction solution is neutralized with an alkaline compound, added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain a compound represented by the formula (1).
  • a compound in which P is an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group or a carbonate ester group can be obtained.
  • a compound represented by the formula (1), in which P is a hydroxyl group is dissolved or suspended in an aprotic solvent such as acetone, THF, or propylene glycol monomethyl ether acetate.
  • an alkyl halide such as ethyl chloromethyl ether or a halocarboxylic acid alkyl ester such as methyl adamantyl bromoacetate is added, and the mixture is reacted at normal pressure at 20 to 110 ° C. for 6 to 72 hours in the presence of an alkaline catalyst such as potassium carbonate. ..
  • the reaction solution is neutralized with an acid such as hydrochloric acid, added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain a compound represented by the formula (1). Therefore, a compound in which P is an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group or a carbonate ester group can be obtained.
  • the method for synthesizing the compound (A) of the third embodiment it is more preferable to include the synthesis method shown below from the viewpoint of suppressing the yield and the amount of waste.
  • the iodine-containing alcoholic substrate used in the third embodiment may be, for example, an iodine-containing alcoholic substrate having a general structure represented by the following formula (1-1).
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine.
  • a group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 to R 10 are independently hydrogen, hydroxyl group, methoxy group, halogen or cyano group, respectively. However, one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • Suitable iodine-containing alcoholic substrates include, but are not limited to, 1- (4-hydroxy-3-iodophenyl) ethanol and 4- (1-hydroxyethyl) -3-iodophenol. At least one iodine is introduced, and it is preferable that two or more iodines are introduced.
  • these iodine-containing alcoholic substrates can be obtained by many methods, it is desirable to obtain them by the methods described below from the viewpoint of availability and yield of raw materials.
  • the method for producing the iodine-containing vinyl monomer represented by the formula (1) is a) A step of preparing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1); b) Includes a dehydration step of dehydrating the iodine-containing alcoholic substrate.
  • reaction conditions An iodine-containing alcoholic substrate having the formula (1-1), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable.
  • the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 1- (4-hydroxy-3-iodophenyl) ethanol as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • Method (I) for producing an iodine-containing alcoholic substrate represented by the formula (1-1) is, for example, an iodine-containing ketone substrate having a general structure represented by the formula (1-2). be.
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine. It is a group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups. However, one of R 7 to R 10 is a hydroxyl group or a methoxy group.)
  • Suitable iodine-containing ketone substrates include, but are not limited to, 4-hydroxy-3-iodophenylmethyl ketone.
  • these iodine-containing ketone substrates can be obtained by many methods, it is desirable to obtain them by the methods described below from the viewpoint of availability and yield of raw materials.
  • the method for producing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1) is c) A step of preparing an iodine-containing ketone substrate having a general structure represented by the formula (1-2); d) Includes a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment.
  • the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) may include the method for producing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1). That is, the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) is c) A step of preparing an iodine-containing ketone substrate having a general structure represented by the formula (1-2); d) It may include a reduction step of subjecting the iodine-containing ketone substrate to a reduction treatment.
  • reaction conditions An iodine-containing ketone substrate having the formula (1-2), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the iodine-containing ketonic substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 4'-hydroxy-3'-iodoacetophenone as the iodine-containing ketone substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the iodine-containing ketonic substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the iodine-containing ketonic substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 4'-hydroxy-3'-iodoacetophenone as the iodine-containing ketone substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • the alcoholic substrate used in the production of the iodine-containing alcoholic substrate represented by the formula (1-1) is, for example, an alcoholic substrate having a general structure represented by the formula (1-3).
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group and a nitro group.
  • R 7 to R 10 are independent of each other. It is a hydrogen atom, a hydroxyl group, a methoxy group, a halogen or a cyano group, except that one of R 7 to R 10 is a hydroxyl group or a methoxy group.
  • Suitable alcoholic substrates include, but are not limited to, 1- (4-hydroxyphenyl) ethanol, 4- (1-hydroxyethyl) phenol.
  • these alcoholic substrates can be obtained by many methods, it is desirable to obtain them by the methods described below from the viewpoint of availability and yield of raw materials.
  • the method for producing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1) is e) A step of preparing an alcoholic substrate having a general structure represented by the formula (1-3); f) The iodine introduction step of introducing an iodine atom into the alcoholic substrate is included.
  • the iodine introduction step in the third embodiment is not particularly limited, but for example, a method of reacting an iodine agent in a solvent (for example, Japanese Patent Application Laid-Open No. 2012-180326), under alkaline conditions, in the presence of ⁇ -cyclodextrin.
  • a method of dropping iodine into an alkaline aqueous solution of phenol Japanese Patent Laid-Open No. 63-101342, Japanese Patent Application Laid-Open No. 2003-64012
  • the iodine agent is not particularly limited, and examples thereof include iodine agents such as iodine chloride, iodine, and N-iodosuccinimide. Among these, iodine chloride is preferable.
  • the method for synthesizing the compound (A) of the third embodiment for example, the method described in the above-mentioned reference material can be appropriately used, but the method is not limited thereto.
  • the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) may include the method for producing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1). That is, the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) is e) A step of preparing an alcoholic substrate having a general structure represented by the formula (1-3); f) It may include an iodine introduction step.
  • Reaction conditions An alcoholic substrate having the formula (1-3), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 1- (4-hydroxyphenyl) ethanol as the substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 1- (4-hydroxyphenyl) ethanol as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • the ketone substrate used in the production of the iodine-containing ketone substrate represented by the formula (1-2) is, for example, a ketone substrate having a general structure represented by the formula (1-4).
  • P is a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group and a phosphine. It is a group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and R 7 to R 10 are independently hydrogen atoms, hydroxyl groups, methoxy groups, halogens or cyano groups. However, one of R 7 to R 10 is a hydroxyl group or a methoxy group.)
  • Suitable ketone substrates include, but are not limited to, 4-hydroxyphenylmethyl ketone.
  • ketone substrates can be obtained by many methods.
  • the method for producing an iodine-containing ketone substrate having a general structure represented by the formula (1-2) is as follows. g) A step of preparing a ketonic substrate having a general structure represented by the formula (1-4); h) It may include an iodine introduction step of introducing an iodine atom into the ketone substrate.
  • the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) may include the method for producing an iodine-containing ketone substrate having a general structure represented by the formula (1-2). That is, the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) is g) A step of preparing a ketonic substrate having a general structure represented by the formula (1-4); h) It may include an iodine introduction step of introducing an iodine atom into the ketone substrate.
  • a ketone substrate having the formula (1-4), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 4'-hydroxy-3'-methoxyacetophenone as the substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 4'-hydroxyacetophenone as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • the ketone substrate used in the production of the alcoholic substrate having the general structure represented by the formula (1-3) is, for example, the ketone substrate having the general structure represented by the above formula (1-4). ..
  • the method for producing an alcoholic substrate having a general structure represented by the formula (1-3) is i) A step of preparing a ketonic substrate having a general structure represented by the formula (1-4); j) It may include a reduction step of subjecting the ketone substrate to a reduction treatment.
  • the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) may include the method for producing an alcoholic substrate having a general structure represented by the formula (1-3). That is, the method for producing an iodine-containing vinyl monomer having a general structure represented by the formula (1) is i) A step of preparing a ketonic substrate having a general structure represented by the formula (1-4); j) It may include a reduction step of subjecting the ketone substrate to a reduction treatment.
  • organic solvent a wide variety of organic solvents including polar aprotic organic solvents and protic polar organic solvents are used.
  • a single protic and aprotic solvent or a single polar aprotic solvent can be used.
  • a polar aprotic solvent or a mixture thereof is preferable.
  • Solvents are effective but not essential components.
  • Suitable polar aprotic solvents include, but are not limited to, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglime and triglime, and ester solvents such as ethyl acetate and ⁇ -butyrolactone.
  • Solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone, N, N-dimethylacetamide, hexamethylphosphoramide, hexamethyl sublin
  • amide-based solvents such as acid triamide and dimethyl sulfoxide. Dimethyl sulfoxide is preferred.
  • Suitable protonic polar solvents include, but are not limited to, di (propylene glycol) methyl ether, di (ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol. , And n-butanol.
  • the amount of the solvent used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0 to 10000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield. From the viewpoint of the above, it is preferably 100 to 2000 parts by mass.
  • a ketone substrate having the formula (1-4), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 4'-hydroxyacetophenone as the substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 4'-hydroxyacetophenone as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • the method for producing an iodine-containing vinyl monomer according to the third embodiment may be a method for producing an iodine-containing vinyl monomer represented by the formula (2), and specifically, a method for producing iodine-containing alkoxystyrene. May be.
  • RA is a hydrogen atom, a methyl group or a trifluoromethyl group
  • RC is a substituted or unsubstituted acyl group having 1 to 30 carbon atoms.
  • acetoxystyrene produced by the method of the third embodiment include, but are not limited to, 4-acetoxy-3-iodostyrene.
  • the iodine-containing vinyl monomer used in the third embodiment is, for example, an iodine-containing vinyl monomer having a general structure represented by the above formula (1).
  • the iodine-containing vinyl monomer having a general structure represented by the formula (2) is k) A step of preparing an iodine-containing vinyl monomer having a general structure represented by the formula (1); l) It may include an acylation step of subjecting the iodine-containing vinyl monomer to an acylation treatment.
  • organic solvent a wide variety of organic solvents including polar aprotic organic solvents and protic polar organic solvents are used.
  • a single protic and aprotic solvent or a single polar aprotic solvent can be used.
  • a polar aprotic solvent or a mixture thereof is preferable.
  • Solvents are effective but not essential components.
  • Suitable polar aprotic solvents include, but are not limited to, alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglime and triglime, and ester solvents such as ethyl acetate and ⁇ -butyrolactone.
  • Solvents such as acetonitrile, hydrocarbon solvents such as toluene and hexane, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone, N, N-dimethylacetamide, hexamethylphosphoramide, hexamethyl sublin
  • amide-based solvents such as acid triamide and dimethyl sulfoxide. Dimethyl sulfoxide is preferred.
  • Suitable protonic polar solvents include, but are not limited to, di (propylene glycol) methyl ether, di (ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol. , And n-butanol.
  • the amount of the solvent used can be appropriately set according to the substrate to be used, the catalyst, the reaction conditions, etc., and is not particularly limited, but in general, 0 to 10000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and the yield. From the viewpoint of the above, it is preferably 100 to 2000 parts by mass.
  • reaction conditions An iodine-containing vinyl monomer having the formula (1), a catalyst and an organic solvent are added to the reactor to form a reaction mixture.
  • One of the appropriate reactors is used. Further, the reaction can be carried out by appropriately selecting a known method such as a batch type, a semi-batch type or a continuous type.
  • the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. Generally, a temperature of 0 ° C to 200 ° C is suitable, and from the viewpoint of yield, a temperature of 0 ° C to 100 ° C is preferable. For reactions using 4-hydroxy-3-iodostyrene as the substrate, the preferred temperature range is 0 ° C to 100 ° C.
  • the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
  • the pressure can be adjusted using an inert gas such as nitrogen, or by using an intake pump or the like.
  • Reactions at high pressure include, but are not limited to, conventional pressure reactors including shaking vessels, rocker vessel and agitated autoclaves.
  • the preferable reaction pressure is reduced pressure to normal pressure, and reduced pressure is preferable.
  • the reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions take less than 6 hours, with reaction times typically 15-600 minutes. For reactions using 4-hydroxy-3-iodostyrene as the substrate, the preferred reaction time range is 15 ° C to 600 ° C.
  • Isolation and purification can be performed after completion of the reaction using a conventionally known suitable method.
  • the reaction mixture is poured onto ice water and extracted into an organic solvent such as ethyl acetate or diethyl ether.
  • the product is then recovered by removing the solvent using evaporation under reduced pressure.
  • Isolated as a desired high-purity monomer by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification method using activated carbon, etc., which are well known in the art, or a method using a combination thereof. Can be purified.
  • the compound in the third embodiment is obtained as a crude product by the above reaction and then further purified to remove residual metal impurities. That is, in the compound manufacturing process, from the viewpoint of prevention of deterioration of the resin over time and storage stability, and also from the viewpoint of process suitability when resinified and applied to the semiconductor manufacturing process, manufacturing profitability due to defects, etc. It is preferable to avoid residual gold-damaged impurities derived from the mixing of metal components used as reaction aids or mixed from reaction kettles for manufacturing or other manufacturing equipment.
  • the residual amount of the above-mentioned metal impurities is preferably less than 1 ppm, more preferably less than 100 ppb, further preferably less than 50 ppb, still more preferably less than 10 ppb, respectively, with respect to the resin. Most preferably, it is less than 1 ppb.
  • metal species such as Fe, Ni, Sb, W, and Al, which are classified as transition metals
  • the metal residual amount is 1 ppm or more, the material is modified over time due to the interaction with the compound in the third embodiment. There is a concern that it may cause deterioration.
  • the amount is 1 ppm or more, the remaining amount of metal cannot be sufficiently reduced when a resin for a semiconductor process is produced using the produced compound, and defects derived from residual metal in the semiconductor manufacturing process cannot be sufficiently reduced. There is a concern that it may cause a decrease in profitability due to performance deterioration.
  • the purification method is not particularly limited, but the step of dissolving the compound in the third embodiment in a solvent to obtain a solution (S) and the obtained solution (S) and an acidic aqueous solution are brought into contact with each other.
  • the solvent used in the step of obtaining the solution (S) includes an organic solvent which is arbitrarily immiscible with water, including a step of extracting impurities in the compound in the third embodiment (first extraction step). According to the purification method, the content of various metals that may be contained as impurities in the resin can be reduced.
  • the compound in the third embodiment is dissolved in an organic solvent that is not miscible with water to obtain a solution (S), and the solution (S) is further brought into contact with an acidic aqueous solution for extraction treatment. It can be performed.
  • the organic phase and the aqueous phase can be separated to obtain a resin having a reduced metal content.
  • the amount of the acidic aqueous solution used in the purification method is not particularly limited, but the amount used may be used from the viewpoint of reducing the number of extractions for removing the metal and ensuring operability in consideration of the total amount of the liquid. It is preferable to adjust. From the above viewpoint, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, based on 100% by mass of the solution (S).
  • the metal component can be extracted from the compound in the solution (S) by contacting the acidic aqueous solution with the solution (S).
  • the solution (S) may further contain an organic solvent that is optionally miscible with water.
  • an organic solvent that is arbitrarily miscible with water is contained, the amount of the compound charged can be increased, the liquid separation property is improved, and purification can be performed with high pot efficiency.
  • the method of adding an organic solvent that is arbitrarily miscible with water is not particularly limited. For example, any of a method of adding to a solution containing an organic solvent in advance, a method of adding to water or an acidic aqueous solution in advance, and a method of adding after contacting a solution containing an organic solvent with water or an acidic aqueous solution may be used. Among these, the method of adding to a solution containing an organic solvent in advance is preferable in terms of workability of operation and ease of control of the amount to be charged.
  • the purification method it is preferable to include a step (second extraction step) of extracting impurities in the resin by further contacting the solution phase containing the compound with water after the first extraction step.
  • the extraction treatment is performed using an acidic aqueous solution, and then the solution phase containing the resin and the solvent extracted and recovered from the aqueous solution is further subjected to the extraction treatment with water.
  • the above-mentioned extraction treatment with water is not particularly limited, but can be performed, for example, by mixing the solution phase and water well by stirring or the like, and then allowing the obtained mixed solution to stand still.
  • the solution phase can be recovered by decantation or the like.
  • the water used here is preferably water having a low metal content, for example, ion-exchanged water, for the purpose of the third embodiment.
  • the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.
  • the conditions such as the ratio of use of both in the extraction treatment, the temperature, and the time are not particularly limited, but the same as in the case of the contact treatment with the acidic aqueous solution described above may be used.
  • Moisture that can be mixed in the solution containing the compound and the solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. Further, if necessary, a solvent can be added to the solution to adjust the concentration of the compound to an arbitrary concentration.
  • the compound purification method according to the third embodiment can also be purified by passing a solution of the resin in a solvent through a filter.
  • the content of various metals in the resin can be effectively and significantly reduced.
  • the amounts of these metal components can be measured by the method described in Examples described later.
  • the term "passing liquid" in the third embodiment means that the solution passes from the outside of the filter to the inside of the filter and moves to the outside of the filter again. For example, the solution is simply filtered.
  • the mode of contacting on the surface of the ion exchange resin and the mode of moving the solution outside the ion exchange resin while contacting the solution on the surface are excluded.
  • the filter used for removing the metal component in the solution containing the compound and the solvent can usually be a commercially available filter for liquid filtration.
  • the filtration accuracy of the filter is not particularly limited, but the nominal pore size of the filter is preferably 0.2 ⁇ m or less, more preferably less than 0.2 ⁇ m, still more preferably 0.1 ⁇ m or less, still more preferably 0. It is less than .1 ⁇ m, more preferably 0.05 ⁇ m or less.
  • the lower limit of the nominal pore diameter of the filter is not particularly limited, but is usually 0.005 ⁇ m.
  • the nominal pore size referred to here is a nominal pore size indicating the separation performance of the filter, and is determined by a test method determined by the filter manufacturer, such as a bubble point test, a mercury intrusion method test, and a standard particle capture test.
  • the hole diameter When a commercially available product is used, it is a value described in the manufacturer's catalog data.
  • the filter passing step may be performed twice or more in order to further reduce the content of each metal component in the solution.
  • the method for purifying the compound according to the third embodiment can also be purified by distilling the compound itself.
  • the distillation method is not particularly limited, but known methods such as atmospheric distillation, vacuum distillation, molecular distillation, and steam distillation can be used.
  • the compound (A) according to the third embodiment can be added to the film-forming composition as it is or as a polymer described later to increase the sensitivity to an exposure light source.
  • the compound (A) or a polymer thereof is preferably used for a photoresist.
  • composition of the third embodiment comprises compound (A).
  • the content of the compound (A) in the third embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more.
  • composition of the third embodiment include a compound represented by the formula (1) other than the formula (1C) as the compound (A) and a compound represented by the formula (1C). It is preferable to include at least.
  • the proportion of the monomer represented by the formula (1C) is preferably 1 mass ppm or more and 10 mass% or less, preferably 20 mass ppm or more or 2 mass by mass, based on the entire monomer represented by the formula (1). % Or less, and more preferably 50% by mass or more and 1% by mass or less.
  • the interaction between the resins at the time of resinification can be reduced, and the interaction between the resins after forming a film using the resin can be achieved.
  • the resulting crystallinity By suppressing the resulting crystallinity, the locality of solubility in the developer during development at the molecular level of several nanometers to several tens of nanometers is reduced, and in a series of lithography processes of exposure, post-exposure baking, and development. It is possible to suppress deterioration of pattern quality such as line edge roughness and residue defects of the pattern formed in the pattern forming process, and further improve the resolution.
  • the effects on these styrene performances are such that the compound represented by the formula (1) and the compound represented by the formula (1C) having a mother nucleus A into which a halogen element, particularly iodine or a fluorine compound is introduced, introduces iodine or the like.
  • the composition of the third embodiment contains compound (A).
  • the content of impurities containing K (potassium) in the composition is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, with respect to the entire compound (A) in terms of elements. Yes, more preferably 0.1 mass ppm or less, still more preferably 0.005 mass ppm or less.
  • the content of one or more elemental impurities selected from the group) is preferably 1 ppm or less, more preferably 0.5 ppm or less, still more preferably 0. It is 1 ppm or less.
  • the amounts of K, Mn, Al, Si, Li and the like are measured by inorganic elemental analysis (IPC-AES / IPC-MS). Examples of the inorganic element analyzer include "AG8900" manufactured by Agilent Technologies, Inc.
  • the content of the phosphorus-containing compound is preferably 10 ppm or less, more preferably 8 ppm or less, and further preferably 5 ppm or less with respect to the entire compound (A).
  • the content of maleic acid is preferably 10 ppm or less, more preferably 8 ppm or less, still more preferably 5 ppm or less, based on the whole compound (A).
  • the amounts of the phosphorus-containing compound and maleic acid are calculated by gas chromatography-mass spectrometry (GC-MS) from the area fraction of the GC chart and the peak intensity ratio of the target peak to the reference peak.
  • GC-MS gas chromatography-mass spectrometry
  • the content of the peroxide is preferably 10% by mass or less, more preferably 1 ppm or less, still more preferably 0.1 ppm with respect to the whole compound (A). It is as follows.
  • the peroxide content is determined by adding trichloroacetic acid to the sample by the ammonium ferrothiocianate acid method (hereinafter referred to as AFTA method), and then adding ammonium iron (II) sulfate and potassium thiocyanate, which are known as standard substances.
  • AFTA method ammonium ferrothiocianate acid method
  • the water content is preferably 100,000 ppm or less, more preferably 20,000 ppm or less, still more preferably 1,000 ppm or less, based on the whole compound (A). Yes, more preferably 500 ppm or less, still more preferably 100 ppm or less.
  • the water content is measured by the Karl Fischer method (Karl Fischer moisture measuring device).
  • the polymer (A) of the third embodiment contains a structural unit derived from the above-mentioned compound (A).
  • the polymer (A) can increase the sensitivity to an exposure light source when blended in the resist composition. In particular, even when extreme ultraviolet rays are used as the exposure light source, sufficient sensitivity can be exhibited and a fine line pattern with a narrow line width can be satisfactorily formed.
  • the conventional resist composition may have a decrease in sensitivity to an exposure light source over time due to storage or the like, and there is a difficulty in developing it for actual semiconductor manufacturing.
  • the stability of the resist composition is improved, and the decrease in sensitivity to the exposure light source is suppressed even when the resist composition is stored for a long period of time.
  • the polymer (A) of the third embodiment contains a structural unit derived from the compound (A).
  • the structural unit derived from the compound (A) contained in the polymer (A) includes, for example, a structural unit represented by the following formula (1-A).
  • RA and P are the same as the definitions in formula (1), and * is a binding site with an adjacent structural unit. It is preferable that RA is a hydrogen atom or a methyl group. Further, it is preferable that P is a hydroxyl group or a tertiary ester group, an acetal group, a carbonic acid ester group or a carboxylalkoxy group.
  • the polymer (A) can be obtained by polymerizing the compound (A) of the third embodiment or by copolymerizing the compound (A) with another monomer.
  • the polymer (A) can be used, for example, as a material for forming a film for lithography.
  • the amount of the structural unit derived from the compound (A) is preferably 5 mol% or more, more preferably 8 mol% or more, still more preferably 10 mol%, based on the total amount of the monomer components of the polymer (A). % Or more.
  • the amount of the structural unit derived from the compound (A) is 100 mol% or less, preferably 80 mol% or less, and more preferably 50 mol% with respect to the total amount of the monomer components of the polymer (A). It is less than or equal to, more preferably 30 mol% or less.
  • One of the preferred embodiments of the polymer of the third embodiment is a compound represented by the formula (1) as a constituent unit of the polymerized body (A), a monomer represented by the compound (A), and a formula represented by the formula (1). It is preferable to contain at least the compound represented by (1C).
  • the content ratio of the monomer represented by the formula (1C) is preferably 10 ppm or more and 10% by mass or less, and preferably 20 ppm or more and 2% by mass or less with respect to the entire monomer represented by the formula (1). More preferably, it is contained in an amount of 50 ppm or more and 1% by mass or less.
  • an aromatic compound having an unsaturated double bond as a substituent is used as a polymerization unit, and alkaline development is carried out by the action of an acid or a base. It preferably contains a polymerization unit having a functional group that improves solubility in a liquid.
  • the other monomer copolymerized with the compound (A) is not particularly limited, but for example, International Publication WO2016 / 125782, International Publication WO2015 / 115613, JP-A-2015 / 117305, International. Examples thereof include those described in WO2014 / 175275, JP2012 / 162298, or compounds represented by the following formula (C1) or the following formula (C2). Among these, the compound represented by the following formula (C1) or the following formula (C2) is preferable.
  • the other monomer copolymerized with the compound (A) preferably contains a structural unit represented by the following formula (C0). That is, in the polymer (A), in addition to the structural unit represented by the formula (1-A), the structural unit represented by the following formula (C0), the following formula (C1) or the following formula (C2) is further added. It is preferable to include it.
  • the dissolution rate R min of the resin that becomes the pattern convex part during alkaline development in the unexposed part during exposure is determined. It is preferable that the difference in dissolution rate R max with respect to the alkaline developer of the resin that becomes the pattern recess during alkaline development in the exposed part during exposure is larger by 3 orders of magnitude or more, the difference in dissolution rate depending on the presence or absence of a protective group is large, and the bake after exposure. (PEB), it is preferable that the desorption rate of the protective group in development is high. From these viewpoints, it is preferable that the other monomer copolymerized with the compound (A) in the polymer (A) has a structural unit represented by the following formula (C1).
  • RC11 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RC12 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • RC13 is a cycloalkyl group or a heterocycloalkyl group having 4 to 20 carbon atoms, which is formed together with a carbon atom bonded to RC13 . * Is a binding site with an adjacent structural unit.
  • RC12 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the RC13 is preferably a cycloalkyl group or a heterocycloalkyl group having 4 to 10 carbon atoms, which is formed together with a carbon atom bonded to RC13 .
  • the cycloalkyl group or heterocycloalkyl group of RC13 may have a substituent (for example, an oxo group).
  • the amount of the structural unit represented by the formula (C1) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 10 mol% or more, based on the total amount of the monomer components of the polymer (A). It is preferably 20 mol% or more.
  • the amount of the structural unit represented by the formula (C1) is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 80 mol% or less, based on the total amount of the monomer components of the polymer (A). It is preferably 70 mol% or less.
  • the other monomer copolymerized with the compound (A) in the polymer (A) is represented by the following formula (C2) from the viewpoint of the quality of the pattern shape after exposure and development in the lithography process, especially from the viewpoint of roughness and suppression of pattern collapse.
  • the structural unit to be formed is preferable.
  • RC21 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • RC22 and RC23 are independently alkyl groups having 1 to 4 carbon atoms.
  • RC24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. Two or three of the RC22 , RC23 , and RC24 were formed together with carbon atoms bonded to two or three of the RC22 , RC23 , and RC24 .
  • An alicyclic structure having 3 to 20 carbon atoms may be formed. * Is a binding site with an adjacent structural unit.
  • RC22 is preferably an alkyl group having 1 to 3 carbon atoms
  • RC24 is a cycloalkyl group having 5 to 10 carbon atoms.
  • the alicyclic structure formed by RC22 , RC23 , and RC24 may contain a plurality of rings such as an adamantyl group.
  • the alicyclic structure may have a substituent (for example, a hydroxyl group or an alkyl group).
  • the amount of the structural unit represented by the formula (C2) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 10 mol% or more, based on the total amount of the monomer components of the polymer (A). It is preferably 20 mol% or more.
  • the amount of the structural unit represented by the formula (C2) is preferably 80 mol% or less, more preferably 60 mol% or less, and further preferably 60 mol% or less, based on the total amount of the monomer components of the polymer (A). It is preferably 40 mol% or less.
  • the raw material for the monomer of the structural unit represented by the formula (C2) is not limited, for example, 2-methyl-2- (meth) acrylic loyloxyadamantan, 2-ethyl-2- (meth) acrylic loyloxyadamantan, 2 -Isopropyl-2- (meth) acrylic loyloxyadamantan, 2-n-propyl-2- (meth) acrylic loyloxyadamantan, 2-n-butyl-2- (meth) acrylicloyloxyadamantan, 1-methyl-1 -(Meta) Acrylic Loyloxycyclopentane, 1-Ethyl-1- (Meta) Acrylic Loyloxycyclopentane, 1-Methyl-1- (Meta) Acrylic Loyloxycyclohexane, 1-Ethyl-1- (Meta) Acrylic Loyl Oxycyclohexane, 1-Methyl-1- (meth) acrylic loyloxycycloheptane, 1-ethyl-1- (
  • the other monomer copolymerized with the compound (A) in the polymer (A) has the following formula (C0) from the viewpoint of exposure in the lithography process, quality of the pattern shape after development, sensitization, especially roughness and suppression of pattern collapse. ) Is preferred.
  • X is an organic group having 1 to 5 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, Br, or I, F, Cl, and Br, respectively.
  • L 1 is independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphin group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphorus.
  • the L1 ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphon group, urethane group, urea group, amide group, imide group, or phosphoric acid group is an acid group.
  • Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon group.
  • Urethane group, urea group, amide group, imide group, or phosphoric acid group and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group of Y.
  • Urea group, amide group, imide group, and phosphate group may have a substituent.
  • RA is the same as the definition in equation (1).
  • A is an organic group having 1 to 30 carbon atoms.
  • Z is independently an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, or a carbonate ester group, and the alkoxy group, the ester group, the acetal group, the carboxylalkoxy group, or the carbonate ester group of Z is It may have a substituent and may have a substituent.
  • m is an integer of 0 or more
  • n is an integer of 1 or more
  • r is an integer of 0 or more.
  • X may be an aromatic group in which one or more F, Cl, Br or I is introduced into the aromatic group.
  • aromatic groups include groups having a benzene ring such as a phenyl group having 1 to 5 halogens and groups having heteroaromatics such as furan, thiophene and pyridine having 1 to 5 halogens.
  • a phenyl group having 1 to 5 I a phenyl group having 1 to 5 F, a phenyl group having 1 to 5 Cl, a phenyl group having 1 to 5 Br, and 1 to 5 F.
  • Phenolic group having 1 to 4, phenol group having 1 to 4 Br, phenol group having 1 to 4 I, furan group having 1 to 3 F, furan group having 1 to 3 Cl, 1 to 3 Br A furan group having 1 to 3, a furan group having 1 to 3 I, a thiophenol group having 1 to 3 F, a thiophenol group having 1 to 3 Cl, a thiophenol group having 1 to 3 Br, and 1 to 3 I.
  • a benzoxazole group having 1 to 4 a benzoxazole group having 1 to 4 Br, a benzoxazole group having 1 to 4 I, a benzothiophene group having 1 to 4 F, and a benzo having 1 to 4 Cl. Examples thereof include a thiophene group, a benzothiophenol group having 1 to 4 Br, and a benzothiophenol group having 1 to 4 I.
  • X may be an alicyclic group in which one or more F, Cl, Br or I is introduced into the alicyclic group.
  • an alicyclic group include an adamantyl group having 1 to 3 halogens, an adamantyl group having 1 to 3 Fs, an adamantyl group having 1 to 3 Cls, and Br 1 to 3 Adamantyl group having 1 to 3, Adamantyl group having 1 to 3 I, Cyclopentyl group having 1 to 3 F, Cyclopentyl group having 1 to 3 Cl, Cyclopentyl group having 1 to 3 Br, 1 to 3 of I Cyclopentyl group having 1 to 3, bicycloundecyl group having 1 to 3 F, bicycloundecyl group having 1 to 3 Cl, bicycloundecyl group having 1 to 3 Br, bicycloundecyl group having 1 to 3 I Examples thereof include a decyl group, a norbornyl group having 1 to 3 Fs,
  • L 1 is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group.
  • L 1 is preferably a single bond.
  • the ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphin group, phosphon group, urethane group, urea group, amide group, imide group, or phosphate group of L1 has a substituent. Is also good. Examples of such a substituent are as described above.
  • M is an integer of 0 or more, preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 2 or less, still more preferably 0 or 1, and particularly preferably 0.
  • Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphin group, and a phosphon group.
  • Urethane group, urea group, amide group, imide group, or phosphoric acid group and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group of Y.
  • Urea group, amide group, imide group, and phosphate group may have a substituent.
  • Y is preferably a tertiary ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxylalkoxy group, and an acetal group or a carboxyl group.
  • Carboxyalkoxy groups are even more preferred.
  • an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable.
  • Y is preferably a group represented by the following formula (Y-1) independently of each other.
  • L 2 is a group that is cleaved by the action of an acid or base.
  • * 1 is a binding site with A
  • * 2 is a binding site with R 2 .
  • L 2 is preferably a tertiary ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxylalkoxy group, and an acetal group, from the viewpoint of high sensitivity.
  • a carboxylalkoxy group is more preferable.
  • an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable.
  • Y is a formula for the purpose of controlling the polymerizable property of the resin and setting the degree of polymerization within a desired range. It is preferably a group represented by (Y-1). Since the compound (A) has an X group, it has a large influence on the active species during the polymer formation reaction and it is difficult to control it as desired. Therefore, the hydrophilic group in the compound (A) is represented by the formula (Y-1). By having a group as a protective group, it is possible to suppress variations in polymer formation and polymerization inhibition derived from hydrophilic groups.
  • R2 is an aliphatic group containing a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a linear, branched or cyclic heteroatom having 1 to 30 carbon atoms.
  • the group group may further have a substituent.
  • R 2 is preferably an aliphatic group.
  • the aliphatic group in R2 is preferably a branched or cyclic aliphatic group.
  • the number of carbon atoms of the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and further preferably 4 or more and 8 or less.
  • the aliphatic group is not particularly limited, and examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group and an adamantyl group.
  • a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferable.
  • it when it is cleaved by the action of an acid or a base, it forms a carboxylic acid group and is insoluble in the dissociated part in the development process. Since the difference in solubility and the difference in dissolution rate between the rows are widened, the resolution is improved, and the residue at the bottom of the pattern in the fine line pattern is particularly suppressed, which is preferable.
  • Y include the following. Each is a group independently represented by any of the following equations.
  • n is an integer of 1 or more, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 4 or less, still more preferably an integer of 1 or more and 3 or less, and even more preferably 1. Or 2, it is particularly preferably 1.
  • RA is an organic group having 1 to 60 carbon atoms, which may independently have H, I, F, Cl, Br, or a substituent.
  • the substituent of the organic group having 1 to 60 carbon atoms is not particularly limited, and examples thereof include I, F, Cl, Br, and other substituents.
  • the other substituent is not particularly limited, but for example, a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, and the like.
  • Examples thereof include a phosphon group, a urethane group, a urea group, an amide group, an imide group and a phosphoric acid group.
  • the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphin group, phosphon group, urethane group, urea group, amide group, imide group, and phosphoric acid group further have a substituent. You may be doing it.
  • the substituent here include a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
  • the number of carbon atoms of the organic group which may have a substituent in RA is preferably 1 to 30.
  • the organic group having 1 to 60 carbon atoms which may have a substituent is not particularly limited, but is a linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms and having 4 to 60 carbon atoms. Examples thereof include an alicyclic hydrocarbon group and an aromatic group which may contain a heteroatom having 6 to 60 carbon atoms.
  • the linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms is not particularly limited, and for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and the like.
  • Examples thereof include a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, a barrel group and a 2-ethylhexyl group.
  • the alicyclic hydrocarbon group is not particularly limited, and examples thereof include a cyclohexyl group, a cyclododecyl group, a dicyclopentyl group, a tricyclodecyl group, and an adamantyl group.
  • an aromatic group that may contain a heteroatom such as a benzodiazole group, a benzotriazole group, and a benzothiadiazole group can also be appropriately selected.
  • a combination of these organic groups can be selected.
  • the aromatic group that may contain a heteroatom having 6 to 60 carbon atoms is not particularly limited, and is, for example, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a benzodiazole group, and a benzotriazole group. , Benzotriazole group.
  • the methyl group is preferable from the viewpoint of producing a polymer having stable quality.
  • A is an organic group having 1 to 30 carbon atoms.
  • A may be a monocyclic organic group, a double ring organic group, or may have a substituent.
  • A is an aromatic ring which may preferably have a substituent.
  • the carbon number of A is preferably 6 to 14, and more preferably 6 to 10.
  • A is preferably a group represented by any of the following formulas, more preferably a group represented by the following formulas (A-1) to (A-2), and more preferably a group represented by the following formula (A-1). ) Is more preferable.
  • A may have an alicyclic structure which may have a substituent.
  • the "alicyclic structure” is a saturated or unsaturated carbon ring having no aromaticity. Examples of the alicyclic structure include saturated or unsaturated carbon rings having 3 to 30 carbon atoms, and saturated or unsaturated carbon rings having 3 to 20 carbon atoms are preferable.
  • Examples of the alicyclic structure include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloicocil, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and cyclopentadienyl.
  • A may have a heterocyclic structure which may have a substituent.
  • the heterocyclic structure is not particularly limited, and for example, a cyclic nitrogen-containing structure such as pyridine, piperidin, piperidone, benzodiazole, benzotriazole, etc., triazine, cyclic urethane structure, cyclic urea, cyclic amide, cyclic imide, furan, etc.
  • Examples thereof include cyclic ethers such as pyrane and dioxolan, alicyclic groups having a lactone structure such as caprolactone, butyrolactone, nonalactone, decalactone, undecalactone, bicycloundecalactone and phthalide.
  • cyclic ethers such as pyrane and dioxolan
  • alicyclic groups having a lactone structure such as caprolactone, butyrolactone, nonalactone, decalactone, undecalactone, bicycloundecalactone and phthalide.
  • Z is an alkoxy group, an ester group, an acetal group, a carboxylalkoxy group, or a carbonic acid ester group, respectively. These groups may have a substituent, and as the substituent, a hydrocarbon group having 1 to 60 carbon atoms which may further have a substituent can be raised.
  • r is an integer of 0 or more, preferably an integer of 0 or more and 2 or less, more preferably an integer of 0 or more and 1 or less, and further preferably 0.
  • [* 3 -OR 22- (C O) -OR 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms)]
  • the ester group is preferably a tertiary ester group from the viewpoint of increasing sensitivity.
  • * 3 is a binding site with A.
  • Z is preferably a tertiary ester group, an acetal group, a carbonate ester group or a carboxylalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxylalkoxy group, and an acetal group or a carboxyl group, from the viewpoint of high sensitivity.
  • Carboxyalkoxy groups are even more preferred.
  • an ester group, a carboxylalkoxy group and a carbonic acid ester group are preferable.
  • the other monomer copolymerized with the compound (A) in the polymer (A) preferably has a structural unit represented by the following formula (C3).
  • RC31 is a hydrogen atom, a methyl group or a trifluoromethyl group, and m, A and * are as defined by the above formula (C0).
  • the polymerization reaction is carried out by dissolving the monomer as a constituent unit in a solvent, adding a polymerization initiator, and heating or cooling.
  • the reaction conditions can be arbitrarily set depending on the type of the polymerization initiator, the starting method such as heat and light, the temperature, pressure, concentration, solvent, additives and the like.
  • the polymerization initiator include radical polymerization initiators such as azoisobutyronitrile and peroxides, and anionic polymerization initiators such as alkyllithium and Grignard reagents.
  • the solvent used for the polymerization reaction a commercially available product that is generally available can be used.
  • various solvents such as alcohol, ether, hydrocarbon, and halogen-based solvent can be appropriately used as long as the reaction is not inhibited.
  • a plurality of solvents may be mixed and used as long as the reaction is not inhibited.
  • the polymer (A) obtained by the polymerization reaction can be purified by a known method. Specifically, ultrafiltration, crystallization, microfiltration, pickling, water washing with an electric conductivity of 10 mS / m or less, and extraction can be performed in combination.
  • composition or the film-forming composition of the third embodiment contains the compound (A) or the polymer (A), and is particularly suitable for lithography techniques.
  • the composition or the film-forming composition can be used for lithography film-forming applications, for example, resist film-forming applications (that is, “resist compositions”).
  • the composition or the film-forming composition is used for upper film forming (that is, "upper film forming composition”), intermediate layer forming use (that is, “intermediate layer forming composition”), and lower layer. It can be used for film forming applications (that is, "lower layer film forming composition”) and the like.
  • the composition of the third embodiment it is possible to form a film having high sensitivity and to impart a good resist pattern shape.
  • the film-forming composition of the third embodiment can also be used as an optical component-forming composition to which a lithography technique is applied.
  • Optical components are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, microlenses, frennel lenses, viewing angle control lenses, contrast-enhancing lenses, etc.), retardation films, electromagnetic wave shielding films, and prisms.
  • the composition is an embedded film and a flattening film on a photodiode, a flattening film before and after a color filter, a microlens, and a flattening on a microlens, which are members of a solid-state image sensor that are particularly required to have a high refractive index. It can be suitably used as a film and a conformal film.
  • the film-forming composition of the third embodiment may contain the compound (A), the composition of the third embodiment, or the polymer (A).
  • the film-forming composition of the third embodiment may further contain an acid generator (C), a base generator (G), or an acid diffusion control agent (E) (basic compound).
  • the film-forming composition of the third embodiment may further contain other components such as a base material (B) and a solvent (S), if necessary.
  • the substrate (B), acid generator (C), base generator (G), acid diffusion control agent (E), and other components that may be contained in the film-forming composition of the third embodiment are , Since it is the same as the second embodiment, the description thereof will be omitted here.
  • the method for forming the resist pattern according to the third embodiment is as follows. A step of forming a resist film on a substrate using the film-forming composition of the third embodiment, The step of exposing the pattern to the resist film and The step of developing the resist film after the exposure and including.
  • the method for forming the insulating film according to the third embodiment may include the method for forming the resist pattern according to the third embodiment. That is, the method for forming the insulating film according to the third embodiment is as follows. A step of forming a resist film on a substrate using the film-forming composition of the third embodiment, The step of exposing the pattern to the resist film and The step of developing the resist film after the exposure and May include.
  • the film-forming composition of the third embodiment contains, for example, the compound (A), the composition of the third embodiment, or the polymer (A).
  • the coating method in the step of forming the resist film is not particularly limited, and examples thereof include a spin coater, a dip coater, and a roller coater.
  • the substrate is not particularly limited, and examples thereof include silicon wafers, metals, plastics, glass, and ceramics.
  • heat treatment may be performed at a temperature of about 50 ° C to 200 ° C.
  • the film thickness of the resist film is not particularly limited, but is, for example, 50 nm to 1 ⁇ m.
  • exposure may be performed via a predetermined mask pattern, or maskless shot exposure may be performed.
  • the thickness of the coating film is, for example, about 0.1 to 20 ⁇ m, preferably about 0.3 to 2 ⁇ m.
  • Light rays of various wavelengths such as ultraviolet rays and X-rays, can be used for exposure.
  • an F2 excimer laser (wavelength 157 nm), an ArF excimer laser (wavelength 193 nm), or a KrF excimer laser (wavelength 248 nm) can be used.
  • Far ultraviolet rays such as, extreme ultraviolet rays (wavelength 13n), X-rays, electron beams, etc. are appropriately selected and used. Among these, extreme ultraviolet rays are preferable.
  • the exposure conditions such as the exposure amount are appropriately selected according to the composition of the above-mentioned resin and / or compound, the type of each additive, and the like.
  • a predetermined resist pattern is formed by developing with an alkaline developer at 10 to 50 ° C. for 10 to 200 seconds, preferably 20 to 25 ° C. for 15 to 90 seconds.
  • the water content of the developer as a whole is preferably less than 70% by mass, more preferably less than 50% by mass, and less than 30% by mass. More preferably, it is more preferably less than 10% by mass, and particularly preferably it contains substantially no water. That is, the content of the organic solvent in the developing solution is not particularly limited, and is preferably 30% by mass or more and 100% by mass or less, and more preferably 50% by mass or more and 100% by mass or less with respect to the total amount of the developing solution. It is more preferably 70% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.
  • the amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developing solution.
  • a developing method for example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dip method), or a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle).
  • dip method a method of immersing a substrate in a tank filled with a developing solution for a certain period of time
  • paddle a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time
  • a method of spraying the developer on the surface of the substrate spray method
  • a method of continuously spraying the developer on the substrate rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed dynamic discharge method.
  • Etc. can be applied.
  • the time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.
  • a step of stopping the development may be carried out while substituting with another solvent.
  • the rinsing solution used in the rinsing step after development is not particularly limited as long as the resist pattern cured by crosslinking is not dissolved, and a solution containing a general organic solvent or water can be used.
  • a rinsing solution it is preferable to use a rinsing solution containing at least one organic solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent. .. More preferably, after development, a washing step is performed using a rinsing solution containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent.
  • a step of washing with a rinsing solution containing an alcohol-based solvent or an ester-based solvent is performed. Even more preferably, after development, a step of washing with a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after development, a step of washing with a rinsing solution containing a monohydric alcohol having 5 or more carbon atoms is performed.
  • the time for rinsing the pattern is not particularly limited, but is preferably 10 to 90 seconds.
  • composition of the third embodiment can also be used as an optical component forming composition to which a lithography technique is applied.
  • Optical components are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, microlenses, frennel lenses, viewing angle control lenses, contrast-enhancing lenses, etc.), retardation films, electromagnetic wave shielding films, and prisms.
  • the composition is an embedded film and a flattening film on a photodiode, a flattening film before and after a color filter, a microlens, and a flattening on a microlens, which are members of a solid-state image sensor that are particularly required to have a high refractive index. It can be suitably used as a film and a conformal film.
  • the composition of the third embodiment can be used as a patterning material for lithography applications.
  • the lithography process can be used in various applications such as semiconductors, liquid display panels, display panels using OLEDs, power devices, CCDs and other sensors.
  • the composition of the third embodiment is used on the upper surface side of an insulating layer such as a silicon oxide film or other oxide film in the step of forming a device element on a silicon wafer.
  • a semiconductor element is formed by forming a pattern on the insulating film on the substrate side using etching based on the pattern formed in the above process, and then laminating a metal film or semiconductor material based on the formed insulating film pattern to form a circuit pattern.
  • the composition of the third embodiment can be preferably used.
  • the compounds, polymers, compositions, film-forming compositions, pattern-forming methods, insulating film-forming methods and compound-producing methods described above in the third embodiment may be applied to extreme ultraviolet applications. ..
  • the compound may be used for a composition irradiated with extreme ultraviolet rays (a composition for extreme ultraviolet rays).
  • the polymer may be used for extreme ultraviolet composition.
  • the composition may be a composition for extreme ultraviolet rays.
  • the film-forming composition may be an extreme ultraviolet composition.
  • the pattern forming method may include a step of exposing the pattern to a resist film formed on a substrate by using the film forming composition with extreme ultraviolet rays.
  • the method for forming the insulating film may include a step of exposing a pattern to a resist film formed on a substrate using the film-forming composition with extreme ultraviolet rays.
  • the method for producing the compound may include a method for producing the compound used in the composition irradiated with extreme ultraviolet rays.
  • the composition or film-forming composition in which the compound is used in the third embodiment can increase the sensitivity to an exposure light source, and is sufficient even when extreme ultraviolet rays are used as the exposure light source. It exhibits a high sensitivity and can satisfactorily form a fine line pattern with a narrow line width. Therefore, the method for forming the pattern or the method for forming the insulating film exhibits sufficient sensitivity even when the step of exposing the pattern to extreme ultraviolet rays is included, and can satisfactorily form a fine line pattern having a narrow line width. ..
  • Example number given to each of the following examples shall be an individual example number for each example group. That is, for example, Example 1 of Example Group 1 is distinguished from Example 1 of Example Group 2.
  • Example group 1 The content of organic impurities contained in the compounds prepared in Examples and Comparative Examples is determined by gas chromatography-mass spectrometry (GC-MS) from the area fraction of the GC chart and the peak intensity ratio of the target peak to the reference peak. Calculated. ⁇ Example group 1 >> (Example group 1: Example A1)
  • a 3 L glass flask was dissolved in a reaction vessel containing 283 g (792 mmol) of triphenylphosphonium methyl bromide, 7 mg of methyl hydroquinone, and 1470 mL of dehydrated THF.
  • 148 g (1320 mmol) of potassium tert-butoxide was added in portions to a THF solution in an ice bath while adjusting the temperature to 15 ° C. or lower, and then the mixture was stirred as it was for 30 minutes.
  • 147 g (529 mmol) of 4-hydroxy-3-iodo-5-methoxybenzenecarboaldehyde was added in portions while adjusting the temperature to 25 ° C.
  • Example group 1 Example A1-A
  • Step 1 Malonic acid addition reaction Using a 200 mL eggplant flask connected to a Dean Stark reflux tube, dimethyl malonate (10.6 g, 10.6 g) was added to 10.8 g (38 mmol) of 4-hydroxy-3-iodo-5-methoxybenzaldehyde. 80 mmol), piperidine (3.4 g, 40 mmol), acetic acid (2.4 g, 40 mmol), and 40 mL of benzene were mixed and reacted under reflux conditions for 3 hours. The obtained reaction solution was washed with 20 mL of a 5% by mass HCl aqueous solution and then with a 5% NaHCO 3 aqueous solution. The obtained organic phase was dried over magnesium sulfate and then concentrated under reduced pressure to obtain 11.8 g of the reaction product (M1-1).
  • Step 2 Hydrolysis reaction Using a 1 L eggplant flask connected to a reflux tube, hydrochloric acid (6N, 131 mL) and acetic acid (131 mL) were added to 38 mmol of the product (M1-1) obtained above. Reflux was performed for 48 hours. Then 6M, 500mL NaOH aq. was then extracted with 250 mL of ethyl acetate to recover the organic phase consisting of ethyl acetate. The obtained organic phase was dehydrated with magnesium sulfate, and the filtrate filtered under reduced pressure was concentrated under reduced pressure to obtain 15.2 g of a cinnamic acid derivative (M1-2).
  • Step 3 Decarbonization reaction Using a 1 L eggplant flask, 0.13 g of tetrabutylammonium fluoride trihydrate was added to a solution prepared by dissolving 40 mmol of the cinnamon acid derivative (M1-2) prepared above in 40 mL of dimethyl sulfoxide. A solution prepared by dissolving (0.4 mmol) in 20 mL of dimethyl sulfoxide was slowly added at 10 ° C. and stirred, then heated to 40 ° C. and stirred for 12 hours. The obtained reaction solution was washed three times with 20 mL of pure water, dried over magnesium sulfate, and the filtrate obtained after filtration was concentrated under reduced pressure to give compound A1 represented by the formula (M1). 14.4 g was obtained.
  • Example group 1 Example A1-B
  • Step 1 Synthesis of 4'-hydroxy-3'-iodo-5'-methoxyacetophenone
  • a reactor 61.27 g of 4'-hydroxy-3'-methoxyacetophenone, 91.38 g of iodine, 1,620 mL of methanol, pure water 180 mL was charged, the reactor was immersed in an ice bath, and stirring was started. Subsequently, 44.06 g of an iodic acid aqueous solution having a concentration of 71.9 mass percent was added dropwise over 30 minutes. Subsequently, the reactor was immersed in a water bath at 35 ° C., and stirring was continued for 3.5 hours.
  • Step 2 Synthesis of 1- (4-hydroxy-3-methoxyphenyl) ethanol 8.77 g of sodium borohydride and 180 mL of tetrahydrofuran were charged in the reactor, and the reactor was immersed in an ice bath to start stirring. Subsequently, a mixed solution consisting of 21.00 g of 4'-hydroxy-3'-methoxyacetophenone, 9.32 g of isopropanol and 180 mL of tetrahydrofuran was added dropwise over 3 hours. Subsequently, stirring was continued for 8 hours while the reactor was immersed in the ice bath. Subsequently, 59.47 g of methanol was added to quench the reaction.
  • the reactor was depressurized to 50 hPa and immersed in a water bath at 20 ° C. to concentrate the reaction solution. Subsequently, the reactor was immersed in an ice bath, and 120 mL of cold methanol was added to dilute the reaction solution. Subsequently, the reactor was depressurized to 50 hPa and immersed in a water bath at 20 ° C. to concentrate the reaction solution. Subsequently, the reactor was immersed in an ice bath, and 600 mL of cold methanol was added to dilute the reaction solution. Subsequently, the reaction solution was gradually added to 1,200 g of dilute sulfuric acid having a concentration of 1% by mass with strong stirring and mixed.
  • Step 3-1 Synthesis of 1- (4-Hydroxy-3-iodo-5-methoxyphenyl) ethanol
  • 1.2000 g of 1- (4-hydroxy-3-methoxyphenyl) ethanol, 1.7630 g of iodine, 17.37 mL of methanol was charged, and the reactor was immersed in an ice bath to start stirring.
  • 0.8736 g of a 70 mass percent iodic acid aqueous solution was added dropwise over 30 minutes.
  • the reactor was immersed in a water bath at 25 ° C., and stirring was continued for 3.5 hours.
  • Step 3-2 Synthesis of 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol
  • 1.1881 g of 1- (4-hydroxy-3-methoxyphenyl) ethanol, 1.7472 g of iodine, 15.48 mL of methanol and 1.72 mL of pure water were charged, and the reactor was immersed in an ice bath to start stirring. Subsequently, 0.8687 g of a 70 mass percent iodic acid aqueous solution was added dropwise over 30 minutes. Subsequently, the reactor was immersed in a water bath at 25 ° C., and stirring was continued for 3.5 hours.
  • Step 3-3 Synthesis of 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol
  • 1.2086 g of 1- (4-hydroxy-3-methoxyphenyl) ethanol, 1.7787 g of iodine, 14.00 mL of methanol and 3.50 mL of pure water were charged, and the reactor was immersed in an ice bath to start stirring. Subsequently, 0.8795 g of a 70 mass percent iodic acid aqueous solution was added dropwise over 30 minutes. Subsequently, the reactor was immersed in a water bath at 25 ° C., and stirring was continued for 3.5 hours.
  • Step 4 Synthesis of 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol
  • a mixed solution consisting of 60.00 g of 4'-hydroxy-3'-iodo-5'-methoxyacetophenone, 9.31 g of isopropanol and 180 mL of tetrahydrofuran was added dropwise over 3 hours. Subsequently, stirring was continued for 9 hours while the reactor was immersed in the ice bath.
  • reaction solution was gradually added to 1,200 g of dilute sulfuric acid having a concentration of 1% by mass with strong stirring and mixed.
  • the precipitate was filtered off with a suction filter, squeezed, and washed with 300 mL of a 33.3 volume percent methanol aqueous solution.
  • the precipitate was vacuum dried at 40 ° C. to obtain 58.64 g of 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol. The yield was 97.2 percent.
  • Step 5-1 Synthesis of 4-hydroxy-3-iodo-5-methoxystyrene
  • a reactor 120.00 g of 1- (4-hydroxy-3-methoxyphenyl) ethanol, 7.94 g of concentrated sulfuric acid, 4-hydroxy- 0.30 g of 2,2,6,6-tetramethylpiperidin 1-oxyl free radical and 1,500 mL of dimethyl sulfoxide were charged, and stirring was started.
  • the reactor was depressurized to 30 hPa, and air at a flow rate of 9 mL / min was started to be blown into the reaction solution.
  • the reactor was immersed in a water bath at 90 ° C., and stirring was continued for 5 hours.
  • the reactor was immersed in a water bath at 25 ° C. to cool the reaction solution.
  • the reaction solution was gradually added to 3,000 g of a sodium bisulfite aqueous solution having a concentration of 0.1% by mass with vigorous stirring and mixed.
  • the precipitate was filtered off with a suction filter, squeezed, and washed with 1,500 mL of a 33.3 volume percent methanol aqueous solution.
  • the precipitate was vacuum dried at 40 ° C. to obtain 109.69 g of 4-hydroxy-3-iodo-5-methoxystyrene. The yield was 95.8 percent.
  • Step 5-2 Synthesis of 4-hydroxy-3-iodo-5-methoxystyrene
  • the reactor was depressurized to 30 hPa, immersed in a water bath at 90 ° C., and stirring was continued for 3 hours. Subsequently, the reactor was immersed in a water bath at 25 ° C. to cool the reaction solution.
  • HPLC analysis using a UV detector with a measurement wavelength of 254 nm, 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol and 2-iodo-6-methoxy-4- (1-) in the reaction solution were obtained.
  • the ratio of methoxyethyl) phenol to 4-hydroxy-3-iodo-5-methoxystyrene was 0.08: 0.01: 98.12.
  • Step 5-3 Synthesis of 4-hydroxy-3-iodo-5-methoxystyrene
  • the reactor was depressurized to 30 hPa, immersed in a water bath at 90 ° C., and stirring was continued for 3 hours. Subsequently, the reactor was immersed in a water bath at 25 ° C. to cool the reaction solution.
  • HPLC analysis using a UV detector with a measurement wavelength of 254 nm, 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol and 2-iodo-6-methoxy-4- (1-) in the reaction solution were obtained.
  • the ratio of methoxyethyl) phenol to 4-hydroxy-3-iodo-5-methoxystyrene was 0.06: 0.01: 98.82.
  • Step 5-4 Synthesis of 4-hydroxy-3-iodo-5-methoxystyrene
  • 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol and 2-iodo-6-methoxy-4 2.0045 g of a mixture having a -(1-methoxyethyl) phenol ratio of 74.40: 24.18, 0.3 g of methanesulfonic acid, 0.0020 g of 4-methoxyquinone, and 20 mL of dimethylsulfoxide were charged, and stirring was started. Subsequently, the reactor was depressurized to 30 hPa, immersed in a water bath at 90 ° C., and stirring was continued for 3 hours.
  • Step 5-5) Synthesis of 4-hydroxy-3-iodo-5-methoxystyrene
  • the reactor was depressurized to 30 hPa, immersed in a water bath at 90 ° C., and stirring was continued for 3 hours. Subsequently, the reactor was immersed in a water bath at 25 ° C. to cool the reaction solution.
  • HPLC analysis using a UV detector with a measurement wavelength of 254 nm, 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol and 2-iodo-6-methoxy-4- (1-) in the reaction solution were obtained.
  • the ratio of methoxyethyl) phenol to 4-hydroxy-3-iodo-5-methoxystyrene was 0.10: 0.01: 98.43.
  • Step 5-6 Synthesis of 4-hydroxy-3-iodo-5-methoxystyrene 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol and 2 in a reactor connected to a reflux tube and Dean Stark. -2.045 g of a mixture having an iodo-6-methoxy-4- (1-methoxyethyl) phenol ratio of 74.40: 24.18, 0.2895 mL of concentrated sulfuric acid, 4-hydroxy-2,2,6,6- 0.0020 g of tetramethylpiperidin 1-oxyl free radical, 20 mL of dimethyl sulfoxide, and 20 mL of toluene were charged, and stirring was started.
  • the reactor was depressurized to 30 hPa, immersed in a water bath at 90 ° C., and stirring was continued for 3 hours while removing the solvent component / water distilled off. Subsequently, the reactor was immersed in a water bath at 25 ° C. to cool the reaction solution.
  • HPLC analysis using a UV detector with a measurement wavelength of 254 nm, 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol and 2-iodo-6-methoxy-4- (1-) in the reaction solution were obtained.
  • the ratio of methoxyethyl) phenol to 4-hydroxy-3-iodo-5-methoxystyrene was 0.03: 0.01: 99.11.
  • LC-MS liquid chromatography-mass spectrometry
  • Step 5-7 Synthesis of 4-hydroxy-3-iodo-5-methoxystyrene
  • the reactor was depressurized to 30 hPa, immersed in a water bath at 90 ° C., and stirring was continued for 3 hours. Subsequently, the reactor was immersed in a water bath at 25 ° C. to cool the reaction solution.
  • HPLC analysis using a UV detector with a measurement wavelength of 254 nm, 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol and 2-iodo-6-methoxy-4- (1-) in the reaction solution were obtained.
  • the ratio of methoxyethyl) phenol to 4-hydroxy-3-iodo-5-methoxystyrene was 0.12: 0.01: 98.51.
  • Step 5-8 Synthesis of 4-hydroxy-3-iodo-5-methoxystyrene
  • Example group 1 Synthesis example 1: Example A1a
  • Synthesis of 4-acetoxy-3-iodo-5-methoxystyrene A 100 mL glass flask was used as a reaction vessel, and dimethyl was used as a solvent for 16.7 g (45 mmol) of 4-hydroxy-3-iodo-5-methoxystyrene. After dissolution with sulfoxide, acetic anhydride 2eq. And sulfuric acid 1eq. was added, the temperature was raised to 80 ° C., and stirring was performed for 3 hours. Then, the stirring liquid was cooled, the precipitate was filtered off, washed and dried to obtain 9.0 g of a white solid.
  • Example group 1 Example A2
  • the 4-hydroxy-3-iodo-5-methoxybenzenecarbaldehyde of Example A1 was changed to 3-ethoxy-4-hydroxy-5-iodobenzenecarbaldehyde, and the other reactions were carried out in the same manner as in Example A1.
  • 132 g of 3-ethoxy-4-hydroxy-5-iodostyrene represented by the formula (M2) was isolated.
  • LC-MS liquid chromatography-mass spectrometry
  • a molecular weight of 290 was confirmed.
  • 1 H-NMR measurement was carried out under the above measurement conditions, the following peaks were found, and it was confirmed that the compound A2 had a chemical structure represented by the formula (M2).
  • Example group 1 Synthesis example 2: Example A2a
  • Synthesis Example 1 4-Hydroxy-3-iodo-5-methoxystyrene of Example A1a is changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the rest is the same as that of Synthesis Example 1: Example A1a.
  • the reaction was carried out and 9.1 g of a white solid was isolated.
  • LC-MS liquid chromatography-mass spectrometry
  • Example group 1 Example A3
  • dichloromethane 400 mL of dichloromethane, 41 g of the obtained compound A1, 16.2 g of triethylamine, and 0.7 g of N- (4-pyridyl) dimethylamine (DMAP) were dissolved in a nitrogen flow.
  • DMAP N- (4-pyridyl) dimethylamine
  • Example group 1 Example A4
  • Example A4 In a container having an internal volume of 200 mL equipped with a stirrer, a cooling tube and a burette, 4.61 g (12.4 mmol) of the compound A1 obtained in Example A1 and 2.42 g (12.4 mmol) of ethyl vinyl ether were added to 100 mL of acetone. After charging, 2.5 g of pyridinium p-toluenesulfonate was added, and the contents were stirred at room temperature for 24 hours to carry out a reaction to obtain a reaction solution. Next, the reaction solution was concentrated and filtered to separate the solid matter.
  • Example group 1 Example A5
  • Example A5 In a container having an internal volume of 200 mL equipped with a stirrer, a cooling tube and a burette, 4.61 g (12.4 mmol) of the compound A1 obtained in Example A1 and 2.42 g (12.4 mmol) of tetrahydropyran were added to 100 mL of acetone. After charging, 2.5 g of pyridinium p-toluenesulfonate was added, and the contents were stirred at room temperature for 24 hours to carry out a reaction to obtain a reaction solution. Next, the reaction solution was concentrated and filtered to separate the solid matter.
  • Example group 1 Example A6 Synthesis of compound A6 represented by formula (M6)
  • 61 g (12.4 mmol) and tert-butyl bromoacetate 2.42 g (12.4 mmol) were charged in 100 mL of acetone, and 1.71 g (12.4 mmol) of potassium carbonate and 18-crown-6 (IUPAC name: 1,4) were charged.
  • 7, 10, 13, 16-hexaoxacyclooctadecane was added, and the contents were stirred under reflux for 3 hours to carry out a reaction to obtain a reaction solution.
  • Example group 1 Example A7 Synthesis of compound A7 represented by formula (M7) Compound A1 obtained in Example A1 in a container having an internal volume of 200 mL equipped with a stirrer, a cooling tube and a burette. 61 g (12.4 mmol) and 2.42 g (12.4 mmol) of 2-methyl-2-adamantyl bromoacetic acid were charged in 100 mL of acetone, and 1.71 g (12.4 mmol) of potassium carbonate and 18-crown-6 (IUPAC name) were charged.
  • Example group 1 Example A8 Synthesis of compound A8 represented by formula (M8) Compound A1 obtained in Example A1 in a container having an internal volume of 200 mL equipped with a stirrer, a cooling tube and a burette. 61 g (12.4 mmol) and 1.70 g (12.4 mmol) of t-butyl bromide were charged in 100 mL of acetone, and 1.71 g (12.4 mmol) of potassium carbonate and 18-crown-6 (IUPAC name: 1,4) were charged. 0.4 g of 7,10,13,16-hexaoxacyclooctadecane) was added, and the contents were stirred under reflux for 3 hours to carry out a reaction to obtain a reaction solution.
  • Example group 1 Example A9
  • the 4-hydroxy-3-iodo-5-methoxystyrene of Example A3 was changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the other reactions were carried out in the same manner as in Example A3.
  • 4.6 g of a BOC group substituted product of the compound A2 represented by (M9) (a compound represented by the following formula (M9), hereinafter also referred to as “compound A9”) was obtained.
  • LC-MS liquid chromatography-mass spectrometry
  • Example group 1 Example A10
  • Example A10 4-Hydroxy-3-iodo-5-methoxystyrene of Example A4 was changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the other reactions were carried out in the same manner as in Example A4.
  • LC-MS liquid chromatography-mass spectrometry
  • Example group 1 Example A11
  • 4-Hydroxy-3-iodo-5-methoxystyrene of Example A5 was changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the other reactions were carried out in the same manner as in Example A5.
  • 3.6 g of the compound represented by (M11), hereinafter also referred to as “compound A11”) was obtained.
  • LC-MS liquid chromatography-mass spectrometry
  • a molecular weight of 374 was confirmed.
  • 1 H-NMR measurement was carried out under the above measurement conditions, the following peaks were found, and it was confirmed that the compound had a chemical structure represented by the formula (M10).
  • Example group 1 Example A12
  • the 4-hydroxy-3-iodo-5-methoxystyrene of Example A6 was changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the other reactions were carried out in the same manner as in Example A6.
  • 3.8 g of the compound represented by (M12), hereinafter also referred to as “compound A12”) was obtained.
  • LC-MS liquid chromatography-mass spectrometry
  • LC-MS liquid chromatography-mass spectrometry
  • Example group 1 Example A13
  • the 4-hydroxy-3-iodo-5-methoxystyrene of Example A7 was changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the other reactions were carried out in the same manner as in Example A7.
  • 4.1 g of the compound represented by (M13), hereinafter also referred to as “compound A13”) was obtained.
  • LC-MS liquid chromatography-mass spectrometry
  • a molecular weight of 496 was confirmed.
  • 1 H-NMR measurement was carried out under the above measurement conditions, the following peaks were found, and it was confirmed that the compound had a chemical structure represented by the formula (M12).
  • Example group 1 Example A14
  • the 4-hydroxy-3-iodo-5-methoxystyrene of Example A8 was changed to 3-ethoxy-4-hydroxy-5-iodostyrene, and the other reactions were carried out in the same manner as in Example A8.
  • 3.5 g of the compound represented by (M14), hereinafter also referred to as “compound A14”) was obtained.
  • LC-MS liquid chromatography-mass spectrometry
  • a molecular weight of 346 was observed.
  • 1 H-NMR measurement was carried out under the above measurement conditions, the following peaks were found, and it was confirmed that the compound had a chemical structure represented by the formula (M14).
  • Example group 1 Synthesis example AD1a
  • Synthesis of compound AD1a represented by formula (AD1a) Compound AD1a represented by formula (AD1a) was synthesized by the method described below.
  • the reactor was immersed in a water bath at 25 ° C. to cool the reaction solution.
  • the reaction solution was gradually added to 400 g of a sodium bisulfite aqueous solution having a concentration of 0.1% by mass with vigorous stirring and mixed.
  • the precipitate was filtered off with a suction filter, squeezed, and washed with 200 mL of a 33.3 volume percent methanol aqueous solution.
  • the solvent was distilled off by evaporation and the obtained solid was vacuum dried at 40 ° C. to obtain 7.0 g of a white solid.
  • Example group 1 Synthesis example AD2a
  • the other compounds were reacted in the same manner as in Synthesis Example AD1a to synthesize the compound AD2a represented by the formula (AD2a).
  • Example group 1 Synthesis example AD1b
  • Synthesis of compound AD1b represented by formula (AD1b) Compound AD1b represented by formula (AD1b) was synthesized by the method described below.
  • the reactor was immersed in a water bath at 25 ° C. to cool the reaction solution.
  • the reaction solution was gradually added to 400 g of a sodium bisulfite aqueous solution having a concentration of 0.1% by mass with vigorous stirring and mixed.
  • the precipitate was filtered off with a suction filter, squeezed, and washed with 200 mL of a 33.3 volume percent methanol aqueous solution.
  • the solvent was distilled off by evaporation and the obtained solid was vacuum dried at 40 ° C. to obtain 2.9 g of a white solid.
  • LC-MS liquid chromatography-mass spectrometry
  • Example group 1 Synthesis example AD2b
  • the other reaction was carried out in the same manner as in Synthesis Example AD1b, and the compound AD2b represented by the formula (AD2b) was synthesized.
  • Example group 1 Comparative example A1
  • 4-Hydroxy-3-iodo-5-methoxybenzenecarbaldehyde is changed to 4-hydroxybenzenecarbaldehyde, and the other compounds are reacted in the same manner as in Example A1 to form the desired compound represented by the formula (MR1).
  • 90 g of AR1 (4-hydroxystyrene) was isolated.
  • Example group 1 Reference example AX1 Synthesis of compound AX1 represented by the formula (MX1)
  • MX1 Reaction vessel
  • a 20 mass% iodine chloride aqueous solution 81.2 g, 100 mmol was added dropwise at 50 ° C. over 60 minutes, and then the mixture was stirred at 50 ° C. for 2 hours to obtain 4-hydroxybenzyl alcohol and chloride. It was reacted with iodine.
  • the obtained organic phase is further washed with a 2 mol / L sodium carbonate aqueous solution, water, and saline solution in this order by a liquid separation operation, then filtered, and the solvent is distilled off from the organic phase to obtain compound AX1 (4-hydroxy-. 8.1 g of 3,5-diiodostyrene (a compound represented by the following formula (MX1)) was obtained.
  • compound AX1 (4-hydroxy-. 8.1 g of 3,5-diiodostyrene (a compound represented by the following formula (MX1)) was obtained.
  • the content of inorganic elements and the content of organic impurities were measured by the above-mentioned method, and the results are shown in Table 1.
  • Example group 1 Comparative example A2
  • 4-Hydroxy-3-iodo-5-methoxybenzenecarbaldehyde was changed to 3,4-dihydroxybenzenecarbaldehyde, and the other reactions were carried out in the same manner as in Example A1.
  • 90 g of 3,4-dihydroxystyrene was isolated.
  • the stability of the composition containing the compound obtained in the above-mentioned Example or Comparative Example was evaluated using an index of the amount of change in purity before and after the time-dependent test in a solution state of a single compound or a combination of a plurality of compounds. ..
  • a solution prepared by mixing the compound of the Example or Comparative Example shown in Tables A and A-2 (the compound shown as the compound a1, the compound a2, or the compound a3) and the solvent was prepared.
  • a brown, inactivated 100 mL glass container was filled to 90 mL to prepare a stoppered sample.
  • the aging treatment was carried out for 30 days in a light-shielded constant temperature tester at 45 ° C.
  • the purity of the prepared sample before and after the treatment over time was measured by HPLC analysis.
  • the amount of change in HPLC purity before and after aging was determined by the following and used as an index for evaluation. The obtained results are shown in Table A and Table A-2.
  • Amount of change in purity over time Area% of target component before time-Area% of target component after time (Evaluation criteria)
  • the compound (A) according to the embodiment contains a small amount of the compound of the formula (1A) or the compound of the formula (1C) to improve the stability of the solution state. ..
  • Example group 1 Example B1
  • 1.5 g of the ester was dissolved in 45 mL of tetrahydrofuran and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain a white powdery polymer B1 represented by the following formula (MA1).
  • MA1 white powdery polymer B1 represented by the following formula (MA1).
  • the polystyrene-based monomer (compound A1) is the carbon at the base of the benzene ring, and the methacrylate-based monomer (2-methyl-2-adamantyl methacrylate, ⁇ -butyrolactone methacrylic acid ester, and hydroxyadamantyl methacrylic acid ester) is the carbonyl of the ester bond.
  • the molar ratio was calculated based on the respective integral ratios.
  • Table 2 shows the types of each monomer in the polymer obtained in Example B1, their ratios, and the composition ratios. Table 2 also shows the types of each monomer in the polymers obtained in the examples described below, their ratios, and composition ratios.
  • Example B2 and Comparative Example BR1 Synthesis of Polymer B2 and Polymer BR1 Same as the method described in Example B1 except that 1.5 g of the compound A1 was replaced with the monomer compound of the type and amount shown in Table 2. The synthesis was carried out according to the above method to obtain polymers B2 and BR1 represented by the formula (MA2) and the formula (MAR1). The content of inorganic elements and the content of organic impurities of the polymer were measured by the above-mentioned methods, and the measurement results obtained are shown in Table 3.
  • Example group 1 Example B1P
  • Example B1P Synthesis of polymer B1P
  • Ethyl acetate (PrimePure manufactured by Kanto Chemical Co., Inc.) was used as a solvent to prepare a 10% by mass ethyl acetate solution of compound A1 in which compound A1 was dissolved.
  • Immerse the ion exchange resin "AMBERLYST MSPS2-1 / DRY" (product name, manufactured by Organo Corporation) in ethyl acetate (PrimePure, manufactured by Kanto Chemical Co., Ltd.) for the purpose of removing metal impurities, and remove the solvent after stirring for 1 hour.
  • the ion exchange resin was washed by repeating the washing by the above method 10 times.
  • the washed ion exchange resin is added to the above-mentioned ethyl acetate solution of compound A1 so as to have the same mass as the resin solid content, and the mixture is stirred at room temperature for one day, and then the ion exchange resin is filtered off.
  • the washing was repeated 3 times to prepare an ion-exchanged ethyl acetate solution of compound A1. Further, the same treatment was performed for other monomers to prepare an ion-exchanged monomer-containing ethyl acetate solution.
  • Polymer B1P (chemical structure is a polymer represented by the formula (MA1)) was obtained.
  • the content of inorganic elements and the content of organic impurities after the purification treatment of each monomer compound used for the synthesis of each obtained polymer were measured by the above-mentioned method, and the obtained measurement results are shown in Table 3. show.
  • Example group 1 Examples B2P to B7P
  • Synthesis of polymers B2P to B7P Polymers B2P to B7P were used in the same manner as in Example B1P except that compounds M2 to M7 and MX1 were used instead of the compounds M1.
  • the chemical structure is a polymer represented by the formulas (MA2-MA7) and BX1.
  • the content of inorganic elements and the content of organic impurities after the purification treatment of each monomer compound used for the synthesis of each obtained polymer were measured by the above-mentioned method, and the obtained measurement results are shown in Table 3. show.
  • MAMA 2-Methyl-2-adamantyl methacrylate
  • BLMA ⁇ -butyrolactone methacrylic acid ester
  • HAMA hydroxyadamantyl Methacrylic acid ester
  • DL Below the detection limit ( ⁇ 0.1ppm)
  • Example group 1 Examples BD1 to BD30
  • Synthesis of polymers PMD1 to PMD30 instead of compound M1, compounds a1, compound a2, and compound a3 shown in Tables 2-2 and 2-3 are used in the ratios shown.
  • Polymers BD1 to BD30 (chemical structures are polymers represented by the formulas (PMD1 to PMD30)) were obtained in the same manner as in Example B1P except that they were used.
  • the inorganic element content and the organic impurity content of each monomer compound used in the synthesis of each of the obtained polymers were measured by the above-mentioned methods, and the obtained measurement results are shown in Tables 3-2 and 3 Shown in -3.
  • EUV extreme ultraviolet
  • EUVES-7000 product name, manufactured by Litho Tech Japan Corporation
  • the exposure amount was increased from 1 mJ / cm 2 to 80 mJ / cm 2 by 1 mJ / cm 2 without a mask.
  • the wafer was baked (PEB) at 110 ° C. for 90 seconds, developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and shot exposure for 80 shots was performed on the wafer. A wafer was obtained.
  • TMAH tetramethylammonium hydroxide
  • the film thickness was measured with an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), profile data of the film thickness with respect to the exposure amount was acquired, and the film thickness with respect to the exposure amount was obtained.
  • the exposure amount at which the gradient of the film thickness fluctuation amount was the largest was calculated as a sensitivity value (mJ / cm 2 ), and used as an index of the EUV sensitivity of the resist.
  • the solution prepared by the above EUV sensitivity evaluation is subjected to forced aging treatment under light-shielding conditions of 40 ° C./240 hours, and the EUV sensitivity evaluation is performed in the same manner for the liquid after the aging treatment, and the evaluation is made according to the amount of change in sensitivity.
  • the sensitivity value at which the slope value is maximized is measured as the standard sensitivity in the film thickness-sensitivity curve after development when the horizontal axis is the sensitivity and the vertical axis is the film thickness. did.
  • EUV extreme ultraviolet
  • EUVES-7000 product name, manufactured by Litho Tech Japan Corporation
  • TMAH tetramethylammonium hydroxide
  • the wafer produced by etching was subjected to defect evaluation with a defect inspection device "Surfscan SP5" (product name, manufactured by KLA), and the number of cone defects of 19 nm or more was determined as an index of etching defects.
  • EB pattern 2-TMAH aqueous solution development 8 parts by mass of the compound or polymer obtained in Examples or Comparative Examples, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 1 part by mass of triphenylsulfonium trifluoromethanesulfonate, 0.2 parts by mass of tributylamine.
  • a solution was prepared by blending parts and 92 parts by mass of PGMEA. The solution was applied onto a silicon wafer and baked at 120 ° C. for 60 seconds to form a resist film having a film thickness of 80 nm.
  • the introduction of the compound of the present invention in the second embodiment is particularly excellent in the resolution of the line and space pattern in thin lines.
  • EUV sensitivity-organic solvent development A solution containing the compound or polymer obtained in the Example or Comparative Example was prepared by the same method as for EUV sensitivity-TMAH aqueous solution development, coated on a silicon wafer, and baked at 110 ° C. for 60 seconds to a thickness of 100 nm. A photoresist layer was formed. Next, with the extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Litho Tech Japan Corporation), the exposure amount was increased from 1 mJ / cm 2 to 80 mJ / cm 2 by 1 mJ / cm 2 without a mask. After the shot exposure, the wafer was baked (PEB) at 110 ° C.
  • EUV extreme ultraviolet
  • the film thickness was measured with an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), profile data of the film thickness with respect to the exposure amount was acquired, and the film thickness with respect to the exposure amount was obtained.
  • the exposure amount at which the gradient of the film thickness fluctuation amount was the largest was calculated as a sensitivity value (mJ / cm 2 ), and used as an index of the EUV sensitivity of the resist.
  • Example or Comparative Example A solution containing the compound or polymer obtained in Example or Comparative Example was prepared by the same method as in EB pattern-TMAH aqueous solution development, applied on a silicon wafer, and baked at 110 to 130 ° C. for 60 seconds to form a film thickness. A 100 nm resist film was formed. Next, it was exposed with an electron beam lithography system "ELS-7500" (product name, manufactured by Elionix Inc., 50 keV), baked (PEB) at 115 ° C. for 90 seconds, developed with butyl acetate for 30 seconds, and a negative pattern was formed. Obtained. The exposure amount was adjusted so that the half pitch was 50 nm line and space.
  • ELS-7500 electron beam lithography system
  • Example group 2 Example A1
  • a 3 L glass flask was dissolved in a reaction vessel containing 283 g (792 mmol) of triphenylphosphonium methyl bromide, 7 mg of methyl hydroquinone, and 1470 mL of dehydrated THF.
  • 148 g (1320 mmol) of potassium tert-butoxide was added in portions to a THF solution in an ice bath while adjusting the temperature to 15 ° C. or lower, and then the mixture was stirred as it was for 30 minutes. Further, while adjusting the temperature to 25 ° C.
  • Example group 2 Examples A1-A
  • Step 1 Malonic acid addition reaction Using a 200 mL eggplant flask connected to a Dean Stark reflux tube, dimethyl malonate (10.6 g, 80 mmol) and piperidine were used against 9.4 g (38 mmol) of 4-hydroxy-3-iodobenzaldehyde. (3.4 g, 40 mmol), acetic acid (2.4 g, 40 mmol) and 40 mL of benzene were mixed and reacted under reflux conditions for 3 hours. The obtained reaction solution was washed with 20 mL of a 5% by mass HCl aqueous solution and then with a 5% NaHCO 3 aqueous solution. The obtained organic phase was dried over magnesium sulfate and then concentrated under reduced pressure to obtain 10.5 g of the reaction product (M1-1).
  • Step 2 Hydrolysis reaction Using a 1 L eggplant flask connected to a reflux tube, hydrochloric acid (6N, 131 mL) and acetic acid (131 mL) were added to 38 mmol of the product (M1-1) obtained above. Reflux was performed for 48 hours. Then 6M, 500mL NaOH aq. was then extracted with 250 mL of ethyl acetate to recover the organic phase consisting of ethyl acetate. The obtained organic phase was dehydrated with magnesium sulfate, and the filtrate filtered under reduced pressure was concentrated under reduced pressure to obtain 10.1 g of a cinnamic acid derivative (M1-2).
  • Step 3 Decarbonization reaction Using a 1 L eggplant flask, 0.13 g of tetrabutylammonium fluoride trihydrate was added to a solution prepared by dissolving 40 mmol of the cinnamon acid derivative (M1-2) prepared above in 40 mL of dimethyl sulfoxide. A solution prepared by dissolving (0.4 mmol) in 20 mL of dimethyl sulfoxide was slowly added at 10 ° C. and stirred, then heated to 40 ° C. and stirred for 12 hours. The obtained reaction solution was washed three times with 20 mL of pure water, dried over magnesium sulfate, and the filtrate obtained after filtration was concentrated under reduced pressure to give compound A1 represented by the formula (M1). 9.2 g was obtained.
  • Example group 2 Example A2
  • 4-Hydroxy-3-iodobenzenecarbaldehyde is changed to 4-methoxy-3-iodobenzenecarbaldehyde, and the other reactions are carried out in the same manner as in Example A1.
  • -129 g of iodo-4-methoxystyrene was isolated.
  • LC-MS liquid chromatography-mass spectrometry
  • Example group 2 Examples A1-B
  • Step 1 Synthesis of 4'-hydroxy-3'-iodoacetophenone 50.20 g of 4'-hydroxy-acetophenone, 91.38 g of iodine, 1,620 mL of methanol and 180 mL of pure water are charged in the reactor, and the reactor is bathed in an ice bath. Soaked in iodine and started stirring. Subsequently, 44.06 g of an iodic acid aqueous solution having a concentration of 71.9 mass percent was added dropwise over 30 minutes. Subsequently, the reactor was immersed in a water bath at 35 ° C., and stirring was continued for 3.5 hours.
  • Step 2 Synthesis of 1- (4-hydroxy-3-methoxyphenyl) ethanol 8.77 g of sodium borohydride and 180 mL of tetrahydrofuran were charged in the reactor, and the reactor was immersed in an ice bath to start stirring. Subsequently, a mixed solution consisting of 17.20 g of 4'-hydroxyacetophenone, 9.32 g of isopropanol and 180 mL of tetrahydrofuran was added dropwise over 3 hours. Subsequently, stirring was continued for 8 hours while the reactor was immersed in the ice bath. Subsequently, 59.47 g of methanol was added to quench the reaction.
  • the reactor was depressurized to 50 hPa and immersed in a water bath at 20 ° C. to concentrate the reaction solution. Subsequently, the reactor was immersed in an ice bath, and 120 mL of cold methanol was added to dilute the reaction solution. Subsequently, the reactor was depressurized to 50 hPa and immersed in a water bath at 20 ° C. to concentrate the reaction solution. Subsequently, the reactor was immersed in an ice bath, and 600 mL of cold methanol was added to dilute the reaction solution. Subsequently, the reaction solution was gradually added to 1,200 g of dilute sulfuric acid having a concentration of 1% by mass with strong stirring and mixed.
  • Step 3-1 Synthesis of 1- (4-Hydroxy-3-iodophenyl) ethanol 0.9800 g of 1- (4-hydroxyphenyl) ethanol, 1.7630 g of iodine and 17.37 mL of methanol are charged in the reactor and reacted.
  • the vessel was immersed in an ice bath and stirring was started. Subsequently, 0.8736 g of a 70 mass percent iodic acid aqueous solution was added dropwise over 30 minutes. Subsequently, the reactor was immersed in a water bath at 25 ° C., and stirring was continued for 3.5 hours.
  • Step 3-2 Synthesis of 1- (4-hydroxy-3-iodo-5-methoxyphenyl) ethanol
  • 0.9759 g of 1- (4-hydroxyphenyl) ethanol, 1.7472 g of iodine, 15.48 mL of methanol , 1.72 mL of pure water was charged, and the reactor was immersed in an ice bath to start stirring.
  • 0.8687 g of a 70 mass percent iodic acid aqueous solution was added dropwise over 30 minutes.
  • the reactor was immersed in a water bath at 25 ° C., and stirring was continued for 3.5 hours.
  • Step 3-3 Synthesis of 1- (4-hydroxy-3-iodophenyl) ethanol
  • 0.9928 g of 1- (4-hydroxyphenyl) ethanol, 1.7787 g of iodine, 14.00 mL of methanol, and pure water 3 .50 mL was charged and the reactor was immersed in an ice bath to start stirring.
  • 0.8795 g of a 70 mass percent iodic acid aqueous solution was added dropwise over 30 minutes.
  • the reactor was immersed in a water bath at 25 ° C., and stirring was continued for 3.5 hours.
  • Step 4 Synthesis of 1- (4-hydroxy-3-iodophenyl) ethanol 8.77 g of sodium borohydride and 180 mL of tetrahydrofuran were charged in the reactor, and the reactor was immersed in an ice bath to start stirring. Subsequently, a mixed solution consisting of 53.84 g of 4'-hydroxy-3'-iodoacetophenone, 9.31 g of isopropanol and 180 mL of tetrahydrofuran was added dropwise over 3 hours. Subsequently, stirring was continued for 9 hours while the reactor was immersed in the ice bath. Subsequently, 59.47 g of methanol was added to quench the reaction.
  • the reactor was depressurized to 50 hPa and immersed in a water bath at 20 ° C. to concentrate the reaction solution. Subsequently, the reactor was immersed in an ice bath, and 120 mL of cold methanol was added to dilute the reaction solution. Subsequently, the reactor was depressurized to 50 hPa and immersed in a water bath at 20 ° C. to concentrate the reaction solution. Subsequently, the reactor was immersed in an ice bath, and 600 mL of cold methanol was added to dilute the reaction solution. Subsequently, the reaction solution was gradually added to 1,200 g of dilute sulfuric acid having a concentration of 1% by mass with strong stirring and mixed.
  • Step 5-1 Synthesis of 4-hydroxy-3-iodostyrene
  • a reactor 98.57 g of 1- (4-hydroxyphenyl) ethanol, 7.94 g of concentrated sulfuric acid, 4-hydroxy-2,2,6,6- 0.30 g of tetramethylpiperidin 1-oxyl free radical and 1,500 mL of dimethyl sulfoxide were charged, and stirring was started.
  • the reactor was depressurized to 30 hPa, and air at a flow rate of 9 mL / min was started to be blown into the reaction solution.
  • the reactor was immersed in a water bath at 90 ° C., and stirring was continued for 5 hours.
  • the reactor was immersed in a water bath at 25 ° C. to cool the reaction solution.
  • the reaction solution was gradually added to 3,000 g of a sodium bisulfite aqueous solution having a concentration of 0.1% by mass with vigorous stirring and mixed.
  • the precipitate was filtered off with a suction filter, squeezed, and washed with 1,500 mL of a 33.3 volume percent methanol aqueous solution.
  • the precipitate was vacuum dried at 40 ° C. to obtain 97.76 g of 4-hydroxy-3-iodostyrene. The yield was 95.7 percent.
  • Step 5-2 Synthesis of 4-hydroxy-3-iodostyrene
  • the ratio of 1- (4-hydroxy-3-iodophenyl) ethanol to 2-iodo-4- (1-methoxyethyl) phenol in the reactor is 73.
  • Example group 2 Synthesis example 1 Synthesis of 4-acetoxy-3-iodostyrene A 100 mL glass flask was used as a reaction vessel and dissolved in 14.9 g (45 mmol) of 4-hydroxy-3-iodostyrene using dimethyl sulfoxide as a solvent. Acetic anhydride 2eq. And sulfuric acid 1eq. was added, the temperature was raised to 80 ° C., and stirring was performed for 3 hours. Then, the stirring liquid was cooled, the precipitate was filtered off, washed and dried to obtain 9.0 g of a white solid.
  • Example group 2 Example A3
  • DMAP N- (4-pyridyl) dimethylamine

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Emergency Medicine (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/JP2021/047416 2020-12-21 2021-12-21 化合物、重合体、組成物、膜形成用組成物、パターンの形成方法、絶縁膜の形成方法及び化合物の製造方法 Ceased WO2022138670A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202180086595.5A CN116615405A (zh) 2020-12-21 2021-12-21 化合物、聚合物、组合物、膜形成用组合物、图案的形成方法、绝缘膜的形成方法及化合物的制造方法
US18/268,940 US20230348351A1 (en) 2020-12-21 2021-12-21 Compound, polymer, composition, composition for film formation, pattern formation method, insulating film formation method, and method for producing compound
JP2022571521A JP7814674B2 (ja) 2020-12-21 2021-12-21 化合物、重合体、組成物、膜形成用組成物、パターンの形成方法、絶縁膜の形成方法及び化合物の製造方法
KR1020237024950A KR20230123513A (ko) 2020-12-21 2021-12-21 화합물, 중합체, 조성물, 막형성용 조성물, 패턴의형성방법, 절연막의 형성방법 및 화합물의 제조방법

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2020211688 2020-12-21
JP2020-211688 2020-12-21
JP2021-017621 2021-02-05
JP2021017621 2021-02-05

Publications (1)

Publication Number Publication Date
WO2022138670A1 true WO2022138670A1 (ja) 2022-06-30

Family

ID=82159406

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/047416 Ceased WO2022138670A1 (ja) 2020-12-21 2021-12-21 化合物、重合体、組成物、膜形成用組成物、パターンの形成方法、絶縁膜の形成方法及び化合物の製造方法

Country Status (5)

Country Link
US (1) US20230348351A1 (https=)
JP (1) JP7814674B2 (https=)
KR (1) KR20230123513A (https=)
TW (1) TW202241836A (https=)
WO (1) WO2022138670A1 (https=)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023051837A (ja) * 2021-09-30 2023-04-11 ローム アンド ハース エレクトロニック マテリアルズ エルエルシー ヨウ素含有酸開裂性化合物、それから誘導されるポリマー、及びフォトレジスト組成物
WO2024005049A1 (ja) * 2022-06-28 2024-01-04 三菱瓦斯化学株式会社 組成物、樹脂組成物、膜形成用組成物、パターン形成方法及び化合物
WO2024135708A1 (ja) * 2022-12-20 2024-06-27 三菱瓦斯化学株式会社 化合物の製造方法、重合体、組成物、パターン形成方法
WO2025079648A1 (ja) * 2023-10-11 2025-04-17 三菱瓦斯化学株式会社 化合物、組成物、樹脂組成物、膜形成用組成物、リソグラフィー用膜形成用組成物、レジスト膜形成用組成物
WO2025253927A1 (ja) * 2024-06-03 2025-12-11 東京応化工業株式会社 レジスト組成物、レジストパターン形成方法、化合物、及び高分子化合物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000122291A (ja) * 1998-10-09 2000-04-28 Mitsubishi Electric Corp 化学増幅レジスト用材料、感光性樹脂組成物および該組成物を半導体装置の製造に使用する方法
JP2019061217A (ja) * 2017-09-25 2019-04-18 信越化学工業株式会社 レジスト材料及びパターン形成方法
WO2020137935A1 (ja) * 2018-12-27 2020-07-02 三菱瓦斯化学株式会社 化合物、（共）重合体、組成物、パターン形成方法、及び化合物の製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6196897B2 (ja) 2013-12-05 2017-09-13 東京応化工業株式会社 ネガ型レジスト組成物、レジストパターン形成方法及び錯体
JP7222674B2 (ja) 2017-12-15 2023-02-15 信越化学工業株式会社 反射防止膜、反射防止膜の製造方法、及び眼鏡型ディスプレイ
WO2019187881A1 (ja) 2018-03-30 2019-10-03 富士フイルム株式会社 Ｅｕｖ光用ネガ型感光性組成物、パターン形成方法、電子デバイスの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000122291A (ja) * 1998-10-09 2000-04-28 Mitsubishi Electric Corp 化学増幅レジスト用材料、感光性樹脂組成物および該組成物を半導体装置の製造に使用する方法
JP2019061217A (ja) * 2017-09-25 2019-04-18 信越化学工業株式会社 レジスト材料及びパターン形成方法
WO2020137935A1 (ja) * 2018-12-27 2020-07-02 三菱瓦斯化学株式会社 化合物、（共）重合体、組成物、パターン形成方法、及び化合物の製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023051837A (ja) * 2021-09-30 2023-04-11 ローム アンド ハース エレクトロニック マテリアルズ エルエルシー ヨウ素含有酸開裂性化合物、それから誘導されるポリマー、及びフォトレジスト組成物
WO2024005049A1 (ja) * 2022-06-28 2024-01-04 三菱瓦斯化学株式会社 組成物、樹脂組成物、膜形成用組成物、パターン形成方法及び化合物
WO2024135708A1 (ja) * 2022-12-20 2024-06-27 三菱瓦斯化学株式会社 化合物の製造方法、重合体、組成物、パターン形成方法
WO2025079648A1 (ja) * 2023-10-11 2025-04-17 三菱瓦斯化学株式会社 化合物、組成物、樹脂組成物、膜形成用組成物、リソグラフィー用膜形成用組成物、レジスト膜形成用組成物
WO2025253927A1 (ja) * 2024-06-03 2025-12-11 東京応化工業株式会社 レジスト組成物、レジストパターン形成方法、化合物、及び高分子化合物

Also Published As

Publication number Publication date
US20230348351A1 (en) 2023-11-02
JPWO2022138670A1 (https=) 2022-06-30
JP7814674B2 (ja) 2026-02-17
TW202241836A (zh) 2022-11-01
KR20230123513A (ko) 2023-08-23

Similar Documents

Publication Publication Date Title
JP7582193B2 (ja) 化合物、重合体、組成物、膜形成用組成物、パターン形成方法、絶縁膜の形成方法及び化合物の製造方法、並びにヨウ素含有ビニルポリマーおよびそのアセチル化誘導体の製造方法
JP7579516B2 (ja) 化合物、（共）重合体、組成物、パターン形成方法、及び化合物の製造方法
JP7814674B2 (ja) 化合物、重合体、組成物、膜形成用組成物、パターンの形成方法、絶縁膜の形成方法及び化合物の製造方法
JP5713011B2 (ja) 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
KR101771723B1 (ko) 감방사선성 수지 조성물 및 이에 의해 형성되는 레지스트 피막
US20230096137A1 (en) Composition for lithography and pattern formation method
JP2018028574A (ja) 感放射線性樹脂組成物、レジストパターン形成方法及び感放射線性酸発生剤
WO2021230300A1 (ja) 化合物、（共）重合体、組成物、レジストパターン形成方法、並びに化合物及び（共）重合体の製造方法
CN103254346A (zh) 光敏共聚物，包含所述共聚物的光致抗蚀剂以及由其形成的制品
WO2017130629A1 (ja) 感放射線性樹脂組成物及びレジストパターン形成方法
JPWO2020040161A1 (ja) 化合物、及びそれを含む組成物、並びに、レジストパターンの形成方法及び絶縁膜の形成方法
WO2021029396A1 (ja) 化合物、（共）重合体、組成物、及びパターン形成方法
JPWO2020040162A1 (ja) 化合物、及びそれを含む組成物、並びに、レジストパターンの形成方法及び絶縁膜の形成方法
WO2024005049A1 (ja) 組成物、樹脂組成物、膜形成用組成物、パターン形成方法及び化合物
WO2015037520A1 (ja) 樹脂組成物、レジストパターン形成方法及び重合体
CN116615405A (zh) 化合物、聚合物、组合物、膜形成用组合物、图案的形成方法、绝缘膜的形成方法及化合物的制造方法
JP6794728B2 (ja) 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
WO2026063516A1 (ja) 化合物、組成物、（共）重合体、膜形成用組成物、及び化合物の製造方法
JP5729079B2 (ja) 液浸露光用感放射線性樹脂組成物
JP2018005064A (ja) 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21910810

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022571521

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 18268940

Country of ref document: US

Ref document number: 202180086595.5

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 20237024950

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21910810

Country of ref document: EP

Kind code of ref document: A1