WO2021149432A1 - Procédé de formation d'un motif, composition sensible au rayonnement et composé clathrate - Google Patents

Procédé de formation d'un motif, composition sensible au rayonnement et composé clathrate Download PDF

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WO2021149432A1
WO2021149432A1 PCT/JP2020/047658 JP2020047658W WO2021149432A1 WO 2021149432 A1 WO2021149432 A1 WO 2021149432A1 JP 2020047658 W JP2020047658 W JP 2020047658W WO 2021149432 A1 WO2021149432 A1 WO 2021149432A1
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group
compound
polymer
radiation
carbon atoms
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Japanese (ja)
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下川　努
大吾 一戸
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Jsr株式会社
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Priority to JP2021573017A priority Critical patent/JP7472917B2/ja
Publication of WO2021149432A1 publication Critical patent/WO2021149432A1/fr

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    • 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
    • C08F12/26—Nitrogen
    • C08F12/28—Amines
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to pattern forming methods, radiation sensitive compositions and inclusion compounds.
  • a radiation-sensitive composition containing a polymer having a polymerizable group, a cross-linking agent, and a polymerization initiator is widely known (Patent Documents). See 1-3).
  • a crosslinked polymer having a three-dimensional network structure is formed by cross-linking, and it is said that a pattern excellent in heat resistance, solvent resistance, etching resistance and the like can be obtained.
  • the conventional radiation-sensitive composition as described above also has inconveniences such as the formed crosslinked polymer swells during development and causes pattern defects, and the pattern shrinks after crosslink curing.
  • the pattern-forming material and the pattern to be formed are required to have various characteristics according to the intended use and the like. Therefore, it is desired to develop a new pattern-forming material and a pattern-forming method capable of forming a pattern having physical characteristics and performance different from those of the conventional ones.
  • the present invention has been made based on the above circumstances, and is a pattern forming method using a novel pattern forming material, a radiation-sensitive composition that can be used as a novel pattern forming material, and such a radiation-sensitive composition. It is an object of the present invention to provide a clathrate compound suitable as a component of a radiation-sensitive composition.
  • One aspect of the invention made to solve the above problems is a step of forming a coating film on a substrate by a radiation-sensitive composition containing a polymer having a host group and a first guest compound.
  • a pattern forming method comprising a step of exposing a film and a step of developing the coating film after exposure, wherein the host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from a cyclodextrin derivative. be.
  • Another aspect of the present invention is a monovalent group containing a polymer having a host group and a first guest compound, wherein the host group is a cyclodextrin derivative from which one hydrogen atom or hydroxyl group has been removed. It is a radiation-sensitive composition for forming a pattern.
  • Another aspect of the present invention is an inclusion compound in which at least a part of the first guest compound is included in the host group of the polymer having a host group, wherein the host group is one from the cyclodextrin derivative.
  • the hydrogen atom of at least one hydroxyl group of cyclodextrin is a monovalent hydrocarbon group having 1 to 12 carbon atoms, carbon. It has a structure substituted with at least one group selected from the group consisting of an acyl group of numbers 1 to 12 and -CONHR, the R is a methyl group or an ethyl group, and the first guest compound is crosslinked. It is an inclusive compound having a sex group and a hydrocarbon group having 6 to 30 carbon atoms.
  • a pattern forming method using a novel pattern forming material, a radiation-sensitive composition that can be used as a novel pattern-forming material, and such a radiation-sensitive composition can be provided.
  • the radiation-sensitive composition contains a polymer having a host group ([A] polymer) and a first guest compound ([G1] guest compound).
  • the radiation-sensitive composition is a composition for pattern formation.
  • at least a portion of the [G1] guest compound is subsumed in the host group of the [A] polymer.
  • a free [G1] guest compound that is not subsumed in the host group of the [A] polymer may be present.
  • the [G1] guest compound has a guest group, and this guest group may be subsumed by the host group of the [A] polymer.
  • the entire [G1] guest compound may be subsumed in the host group of the [A] polymer.
  • the [G1] guest compound is a compound having a crosslinkable group as the first preferred form ([G1-1] crosslinkable compound) or a photoreactive compound as the second preferred form ([G1-2] photoreactive compound). ) Is preferable.
  • the [G1] guest compound is a [G1-1] crosslinkable compound
  • the [A] polymer and the [G1-1] crosslinkable compound are the same as the [G1-1] crosslinkable compound. It is possible to form an inclusive compound in which a part (usually a part other than the crosslinkable group) is included in the host group of the [A] polymer.
  • a clathrate function as a polymer having a crosslinkable group, and exhibits photocurability when used in combination with, for example, a [C] radiation-sensitive polymerization initiator. Therefore, a pattern can be formed by exposure and development.
  • the radiation sensitive composition is a [A] polymer, a [G1] guest compound which is an encapsulated [G1-1] crosslinkable compound, and a [C] radiation sensitive. It preferably contains a polymerization initiator, and more preferably contains a [B] polymerizable compound.
  • An example of the first preferred embodiment is shown in the scheme diagram below. In the following example, the host group ( ⁇ CD) of the [A] polymer is subsumed with the adamantyl group of the [G1-1] crosslinkable compound adamantyl acrylate to form an embracing compound.
  • a crosslinked structure is formed by a chemical reaction between the group and the vinyl group of 1,2-divinylcyclobutane which is a [B] polymerizable compound, and curing occurs.
  • the polymerizable compound does not exist, and the acryloyl groups of adamantyl acrylate, which is the [G1-1] crosslinkable compound constituting the inclusion compound, act on each other to form a crosslinked structure by a chemical reaction, and curing occurs.
  • the composition may be such that.
  • the [G1] guest compound is a [G1-2] photoreactive compound
  • a coating of a radiation-sensitive composition containing the [A] polymer and the [G1-2] photoreactive compound When the film is irradiated with radiation, the [G1-2] photoreactive compound reacts, and the solubility of the irradiated portion in the developing solution changes. Therefore, a pattern can be formed by exposure and development.
  • the [G1-2] photoreactive compound is a photoisomerizing compound
  • [G1-2] light is used in the [A] polymer and the [G1-2] photoreactive compound (photoisomerizing compound).
  • the guest group of the [G2] polymer was included in the host group, and the [A] polymer and the [G2] polymer were formed. Form a cross-linked structure by host-guest interaction.
  • the radiation-sensitive composition containing the [A] polymer, the [G1-2] photoreactive compound and the [G2] polymer exhibits photocurability, and a pattern can be formed by exposure and development. can.
  • the radiation sensitive composition is a [A] polymer, a [G1] guest compound which is a [G1-2] photoreactive compound contained, and an unincluded [G1] guest compound [ It preferably contains a [G2] guest compound which is a G2] polymer.
  • An example of the second preferred embodiment is shown in the scheme diagram below.
  • the host group of the [A] polymer is subsumed with azobenzene (trans form), which is a [G1-2] photoreactive compound, to form an inclusive compound.
  • azobenzene which is a [G1-2] photoreactive compound
  • azobenzene which is a [G1-2] photoreactive compound
  • the [G2] polymer is added to the host group.
  • a guest group adamantyl group
  • the [A] polymer and the [G2] polymer form a crosslinked structure by a host-guest interaction.
  • the radiation-sensitive composition preferably utilizes the host group of the [A] polymer and the [G1] guest compound or the [G2] guest compound, and causes a chemical reaction or a host-guest associated with irradiation. It forms a crosslinked structure by interaction and can be used as a pattern forming material. Further, as will be described later, by selecting the types of the [G1] guest compound and the [G2] guest compound, and the guest groups contained therein, the sensitivity, the exposure margin, the depth of focus, the LWR (Line Widh Roughness), etc. The properties required for the pattern-forming material, such as the amount of film burr and heat resistance, are enhanced.
  • the radiation-sensitive composition is particularly useful as a negative-type pattern-forming material.
  • each component and the like will be described in detail.
  • the polymer [A] preferably contains a structural unit (I) having a host group.
  • the host group has a structure capable of subsuming at least a part of the [G1] guest compound.
  • the host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from the cyclodextrin derivative, and a group obtained by removing one hydroxyl group from the cyclodextrin derivative is preferable.
  • a cyclodextrin derivative is one in which the hydrogen atom of the hydroxyl group of cyclodextrin is substituted with a substituent.
  • substituent include a monovalent hydrocarbon group having 1 to 12 carbon atoms, an acyl group having 1 to 12 carbon atoms, -CONHR and the like.
  • R is a methyl group or an ethyl group. That is, as the cyclodextrin derivative, the hydrogen atom of the hydroxyl group of the cyclodextrin is at least one group (substituent group) selected from the group consisting of a monovalent hydrocarbon group having 1 to 12 carbon atoms, an acyl group and -CONHR. ) Is preferred.
  • Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 carbon atoms. Examples thereof include to 12 monovalent aromatic hydrocarbon groups.
  • Examples of the monovalent chain hydrocarbon group having 1 to 12 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an alkenyl group such as an ethenyl group, a propenyl group and a butenyl group, and an ethynyl group.
  • Examples thereof include an alkynyl group such as a propynyl group and a butynyl group.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include a monovalent monocyclic alicyclic saturated hydrocarbon group such as a cyclopentyl group and a cyclohexyl group, a cyclopentenyl group, and a cyclohexenyl group.
  • Monovalent monocyclic alicyclic unsaturated hydrocarbon group, norbornyl group, adamantyl group and other monovalent polycyclic alicyclic saturated hydrocarbon groups, norbornenyl group and other monovalent polycyclic alicyclic unsaturated hydrocarbons Examples include hydrocarbon groups.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.
  • acyl group having 1 to 12 carbon atoms examples include a formyl group, an acetyl group, a propionyl group, and a benzoyl group.
  • acyl group an acyl group having 1 to 8 carbon atoms is preferable.
  • a monovalent hydrocarbon group having 1 to 12 carbon atoms is preferable, and a monovalent hydrocarbon group having 1 to 4 carbon atoms is more preferable.
  • the hydrogen atom of the hydroxyl group is the total number of the groups in which the hydrogen atom of the hydroxyl group is substituted with the substituent.
  • the number of groups substituted with substituents is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more.
  • the host group can exhibit excellent affinity (inclusiveness) for particularly hydrophobic [G1] guest compounds or hydrophobic guest groups.
  • the cyclodextrin is not particularly limited as long as it is a cyclic oligosaccharide in which a plurality of D-glucoses are bound by ⁇ -1,4 glycoside bonds to form a cyclic structure.
  • the cyclodextrins at least one selected from the group consisting of ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin is preferable.
  • a cyclodextrin it has good inclusion property for an appropriate [G1] guest compound, and is effective for light irradiation in a state where a [G1-2] photoreactive compound (photoisomerizing compound) is included. It can exhibit release properties and the like.
  • a suitable host group includes a group represented by the following formula (H).
  • the group represented by this formula (H) is an example of a group obtained by removing one hydroxyl group from a cyclodextrin derivative.
  • a plurality of R a are each independently hydrogen atom or a substituent.
  • the substituent is a monovalent hydrocarbon group having 1 to 12 carbon atoms, an acyl group having 1 to 12 carbon atoms, or -CONHR.
  • R is a methyl group or an ethyl group.
  • at least one of the plurality of R a is the substituent.
  • p is 5, 6 or 7. * Represents the binding site.
  • R 1 is a hydrogen atom or a methyl group.
  • R 2 is a divalent linking group.
  • R 3 is -O- or -NR 4 - (R 4 is a monovalent hydrocarbon group having a hydrogen atom or a C 1-10.) Is a group represented by.
  • RH is a host group.
  • the divalent linking group represented by R 2 includes, for example, -O-, -S-, -CO-, -CS-, -SO-, -SO 2- , -NR b- , substituted or unsubstituted. Examples thereof include a divalent hydrocarbon group and a divalent group in which two or more of these are combined.
  • R b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. As R b , a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.
  • Examples of the divalent hydrocarbon group include a divalent hydrocarbon group having 1 to 20 carbon atoms.
  • Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 carbon atoms. Examples thereof include ⁇ 20 divalent aromatic hydrocarbon groups.
  • Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms include an alkandyl group such as a methanediyl group, an ethanediyl group, a propanediyl group and a butanjiyl group, an ethanediyl group, a propendyl group, an alkenyl group such as a buthendiyl group and ethyndiyl. Examples thereof include an alkyndiyl group such as a group, a propindiyl group and a butindiyl group.
  • divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms examples include a divalent monocyclic alicyclic saturated hydrocarbon group such as a cyclopentandyl group and a cyclohexanediyl group, a cyclopentendyl group and a cyclohexendyl group.
  • divalent polycyclic alicyclic unsaturated hydrocarbon group such as a tricyclodecendyl group.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an arenediyl group such as a benzenediyl group, a toluenediyl group, a xylenediyl group, a naphthalenediyl group and an anthracendiyl group, a benzenediylmethanediyl group and a benzenediyl group.
  • Examples thereof include an arenediyl alkandiyl group such as an ethanediyl group, a naphthalenediylmethanediyl group and an anthracendiylmethanediyl group.
  • substituent of the divalent hydrocarbon group examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, amino group and carboxy group.
  • Preferable forms of the divalent linking group represented by R 2 include groups represented by the following formulas (2a) to (2f). -CO- (2a) -COO-R "-(2b) -CONR'-R "- (2c) -COO-R "-NR'-CO- (2d) -CONR'-R "-NR'-CO- (2e) -R "-(2f)
  • R' is an independent hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • R is a divalent hydrocarbon group having 1 to 20 carbon atoms independently of each other.
  • R' a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.
  • the divalent hydrocarbon group having 1 to 20 carbon atoms represented by “R” is the same as the divalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the divalent linking group represented by R 2.
  • Examples of the preferred form of "R” are -Ph n- (CH 2 ) m- (Ph is a phenylene group. N is 0 or 1. m is an integer of 0 to 4. However, any of n and m is an integer of 1 or more), and a divalent hydrocarbon group represented by 1) can be mentioned.
  • Examples of the host group represented by RH include the above-mentioned groups such as the group represented by the above formula (H).
  • the [A] polymer can be obtained by polymerizing a monomer containing the monomer (I) giving the structural unit (I) by a known method.
  • the monomer (I) one kind or two or more kinds can be used.
  • Examples of the monomer (I) that gives the structural unit (I) include a monomer represented by the following formula (3).
  • R 1, R 2, R 3 and R H are each synonymous with R 1, R 2, R 3 and R H in the formula (1).
  • RH in the above formula (3) is a monovalent group obtained by removing one hydroxyl group from the cyclodextrin derivative
  • the monomer represented by the above formula (3) is, for example, the following (i) or It can be synthesized by the method of (ii).
  • (I) A method of dehydrating and condensing a compound represented by the following formula (4) and cyclodextrin and substituting a hydrogen atom of a hydroxyl group in the obtained condensate with a substituent
  • ii A hydrogen atom of a hydroxyl group in cyclodextrin.
  • R 1 and R 2 are the same meanings as R 1 and R 2 in the formula (1).
  • R 5 is a group represented by -OH or -NHR 4 (R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms).
  • dehydration condensation between the above formulas the group R 5 with a compound represented by (4) (-OH or -NHR 4) and hydroxyl groups of cyclodextrin is produced.
  • This dehydration condensation can be carried out in a solvent in the presence of an acid catalyst, if necessary.
  • the acid catalyst is not particularly limited, and known catalysts can be widely used, and examples thereof include p-toluenesulfonic acid, aluminum chloride, and hydrochloric acid.
  • the amount of the acid catalyst used can be, for example, 0.01 mol% or more and 20 mol% or less with respect to cyclodextrin.
  • the solvent in the dehydration condensation reaction is not particularly limited, and examples thereof include dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.
  • the reaction temperature and reaction time of dehydration condensation are not limited, and can be carried out under appropriate conditions. From the viewpoint of proceeding with the reaction more rapidly, the reaction temperature is preferably 25 to 100 ° C., and the reaction time is preferably 1 minute to 3 hours.
  • a known method can be adopted as a method for substituting the hydrogen atom of the hydroxyl group in the obtained condensate with a substituent.
  • a known alkylation reaction can be widely adopted.
  • the substitution with a hydrocarbon group can be carried out by a method of reacting an alkyl halide with the above condensate in the presence of sodium hydride or the like.
  • the alkyl halide include methyl iodide, ethyl iodide, and propyl iodide.
  • an acyl group such as an acetyl group for a hydrogen atom of a hydroxyl group existing in a condensate (cyclodextrin)
  • a known acylation reaction can be widely adopted.
  • the substitution with an acetyl group can be carried out by a method of reacting acetyl halide with the above condensate in the presence of sodium hydride or the like.
  • acetyl halides include acetyl bromide and acetyl iodide.
  • alkyl carbamate reaction As a method of substituting the hydrogen atom of the hydroxyl group existing in the condensate (cyclodextrin) with -CONHR (R is a methyl group or an ethyl group), for example, a known alkyl carbamate reaction can be widely adopted. ..
  • alkyl carbamate agent used in the alkyl carbamate reaction include alkyl isocyanates such as methyl isocyanate and ethyl isocyanate.
  • the method of substituting the hydrogen atom of the hydroxyl group in cyclodextrin in the above method (ii) with a substituent is a known alkylation reaction, acylation reaction, or alkyl carbamate according to each substitution reaction in the above method (i). It can be carried out by a reaction or the like. Further, the dehydration condensation in the above method (ii) can also be performed by a known method such as the dehydration condensation in the above method (i).
  • the monomer (I) can be synthesized according to the methods described in WO2018 / 159791 and WO2017 / 159346.
  • the lower limit of the content ratio of the structural unit (I) in the [A] polymer 1% by mass is preferable, 2% by mass is more preferable, 3% by mass is further preferable, and 5% by mass is further preferable.
  • the upper limit of the content ratio of the structural unit (I) is preferably 80% by mass, more preferably 50% by mass, further preferably 30% by mass, and even more preferably 20% by mass.
  • the polymer [A] preferably further contains a structural unit (II) having a carboxy group or a phenolic hydroxyl group.
  • a structural unit having a carboxy group is more preferable.
  • Examples of the monomer giving the structural unit (II) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and 4-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; Anhydride of the unsaturated dicarboxylic acid; Examples thereof include (meth) acrylic acid esters having a phenolic hydroxyl group such as 4-hydroxyphenyl (meth) acrylate. As these monomers, one kind or two or more kinds can be used.
  • unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and 4-vinylbenzoic acid
  • Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid
  • Anhydride of the unsaturated dicarboxylic acid examples thereof include (me
  • the lower limit of the content ratio of the structural unit (II) in the [A] polymer 1% by mass is preferable, 3% by mass is more preferable, and 5% by mass is further preferable.
  • the upper limit of the content ratio of the structural unit (II) 50% by mass is preferable, 40% by mass is more preferable, and 30% by mass is further preferable.
  • the polymer [A] preferably contains a structural unit (III) having a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • a structural unit (III) having a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • an aliphatic chain hydrocarbon group is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, and the like.
  • Alkenyl groups such as decyl group, dodecyl group, pentadecyl group, octadecyl group, ethenyl group, propenyl group, butenyl group, hexenyl group, octenyl group, decenyl group, octadecenyl group and other alkenyl groups, ethynyl group, propynyl group, butynyl group, Examples thereof include an alkynyl group such as a hexynyl group, an octynyl group, a decynyl group and an octadecynyl group.
  • Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a benzyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthracenyl group and the like.
  • the lower limit of the number of carbon atoms of this monovalent hydrocarbon group 2 is preferable, 3 is more preferable, and 4 is further preferable.
  • the upper limit of the number of carbon atoms 15 is preferable, and 10 is more preferable.
  • Examples of the monomer giving the structural unit (III) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and the like. Examples thereof include hexyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate, styrene, and phenylvinyl ether.
  • the monomer giving the structural unit (III) is preferably a (meth) acrylic acid ester. As these monomers, one kind or two or more kinds can be used.
  • the lower limit of the content ratio of the structural unit (III) in the [A] polymer 10% by mass is preferable, 30% by mass is more preferable, 50% by mass is further preferable, and 70% by mass is further preferable.
  • the upper limit of the content ratio of the structural unit (III) 95% by mass is preferable, 90% by mass is more preferable, 85% by mass is further preferable, and 80% by mass is more preferable.
  • the polymer [A] may further contain a structural unit (IV) other than the structural units (I) to (III).
  • Examples of the monomer giving the structural unit (IV) include 2-hydroxyethyl (meth) acrylate, polyethylene glycol methyl ether (meth) acrylate, polypropylene glycol methyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene.
  • Glycol mono (meth) acrylate and the like can be mentioned. As these monomers, one kind or two or more kinds can be used.
  • the upper limit of the content ratio of the structural unit (IV) in the [A] polymer is preferably 30% by mass, more preferably 10% by mass, further preferably 3% by mass, and particularly preferably 1% by mass.
  • the [A] polymer does not substantially contain a structural unit (V) having an alicyclic hydrocarbon group having 6 to 30 carbon atoms.
  • An alicyclic hydrocarbon group having 6 to 30 carbon atoms is easily included in a host group which is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from a cyclodextrin derivative. Therefore, when the [A] polymer does not substantially contain such a structural unit (V), the host-guest interaction between the [A] polymer is suppressed, and the [A] polymer and the [A] polymer and [A] polymer are suppressed. Host-guest interactions with the G1] guest compound or the [G2] guest compound are likely to occur.
  • the upper limit of the content ratio of the structural unit (V) in the polymer is preferably 10% by mass, more preferably 3% by mass, further preferably 1% by mass, further preferably 0.1% by mass, and 0% by mass. % Is particularly preferable.
  • the [A] polymer containing a structural unit (V) having an alicyclic hydrocarbon group having 6 to 30 carbon atoms can be preferably used. ..
  • the [A] polymer can be obtained, for example, by polymerizing each of the above monomers by a known method such as radical polymerization.
  • the weight average molecular weight (Mw) of the [A] polymer is usually 1,000 to 100,000, preferably 3,000 to 30,000. Mw refers to the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography.
  • the lower limit of the content of the [A] polymer in the solid content of the radiation-sensitive composition is preferably 10% by mass, more preferably 30% by mass, and even more preferably 50% by mass.
  • the upper limit of this content is preferably 90% by mass, more preferably 80% by mass, further preferably 70% by mass, and even more preferably 60% by mass or 50% by mass.
  • the radiation-sensitive composition containing a crosslinkable compound has particularly good properties required for a pattern-forming material such as sensitivity, exposure margin, depth of focus, LWR, film burr amount, and heat resistance. .. [G1-1]
  • the crosslinkable compound preferably has one or more guest groups and one or more crosslinkable groups.
  • the [G1-1] crosslinkable compound may be a compound having 1 guest group and 1 crosslinkable group.
  • the guest group is not particularly limited as long as it is a group that can be subsumed in the host group of the [A] polymer, but a hydrocarbon group having 6 to 30 carbon atoms is preferable.
  • Hydrocarbon groups having 6 to 30 carbon atoms are usually monovalent groups.
  • Examples of the hydrocarbon group having 6 to 30 carbon atoms include a chain hydrocarbon group having 6 to 30 carbon atoms, an alicyclic hydrocarbon group having 6 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and the like. Can be mentioned.
  • Chain hydrocarbon groups having 6 to 30 carbon atoms include alkyl groups such as hexyl group, octyl group, nonyl group, decyl group, dodecyl group, pentadecyl group and octadecyl group, hexenyl group, octenyl group, decenyl group and octadecenyl group.
  • alkenyl group, hexynyl group, octynyl group, decynyl group, alkynyl group such as octadecynyl group and the like can be mentioned.
  • Examples of the alicyclic hydrocarbon group having 6 to 30 carbon atoms include a monovalent monocyclic alicyclic saturated hydrocarbon group such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group and a cyclododecyl group, and cyclohexenyl.
  • a monovalent monocyclic alicyclic unsaturated hydrocarbon group such as a group, a cyclooctenyl group or a cyclodecenyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group or the like.
  • monovalent polycyclic unsaturated hydrocarbon groups such as an alicyclic saturated hydrocarbon group, a norbornenyl group, a tricyclodecenyl group and a tetracyclododecenyl group.
  • Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms include a phenyl group, a benzyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthracenyl group and the like.
  • hydrocarbon groups having 6 to 30 carbon atoms an alicyclic hydrocarbon group having 6 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms are preferable, and an alicyclic hydrocarbon group having 6 to 30 carbon atoms is preferable. Groups are more preferred. Such hydrocarbon groups can be effectively subsumed, especially with groups derived from cyclodextrin derivatives.
  • a polycyclic group is preferable, and a polycyclic saturated hydrocarbon group is more preferable.
  • the lower limit of the number of carbon atoms of the hydrocarbon group is preferably 8. On the other hand, this upper limit is preferably 20 and more preferably 15.
  • a crosslinkable group is a group capable of forming a crosslinked structure by a chemical reaction.
  • the crosslinkable group include an epoxy group, a cyclic carbonate group, a methylol group (hydroxymethyl structure), a (meth) acryloyl group, a vinyl group and the like.
  • the epoxy group refers to a cyclic ether group, and examples thereof include an oxylanyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).
  • a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is more preferable.
  • crosslinkable compound examples include cyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, ethyl adamantyl (meth) acrylate, and cyclohexyl.
  • At least a part of the [G1-1] crosslinkable compound is usually present in a state where the guest group is subsumed by the host group of the [A] polymer. That is, the [A] polymer and at least a part of the [G1-1] crosslinkable compound form a clathrate compound.
  • the weight average molecular weight (Mw) of the inclusion compound (polymer) formed from the [A] polymer and the [G1-1] crosslinkable compound is usually 1,000 to 100,000, preferably 3,000 to 3,000. It is 30,000.
  • the lower limit of the content of the [G1-1] crosslinkable compound is preferably 1 part by mass, more preferably 10 parts by mass, and even more preferably 20 parts by mass with respect to 100 parts by mass of the [A] polymer.
  • the upper limit of this content 200 parts by mass is preferable, 100 parts by mass is more preferable, and 60 parts by mass is further preferable.
  • the content of the crosslinkable compound is in the above range, various properties required for the pattern-forming material are further improved, such that a crosslinked structure by a chemical reaction can be formed particularly sufficiently.
  • the photoreactive compound is a compound whose structure changes in response to light or other radiation.
  • Photoreactions caused by photoreactive compounds include isomerization reaction, bimolecular cyclization reaction, ring closing reaction, ring opening reaction, addition reaction, desorption reaction, condensation reaction, solvent addition reaction, and nucleophilic reaction. , Electroelectron reaction, radical reaction, complexation reaction and the like, isomerization reaction, bimolecular cyclization reaction, ring closing reaction and ring opening reaction are preferable, and isomerization reaction is more preferable.
  • Examples of the compound that undergoes an isomerization reaction include an azobenzene-based compound and a stilbene-based compound.
  • Examples of the compound that undergoes a bimolecular cyclization reaction include a cinnamic acid-based compound, a coumarin-based compound, and a chalcone-based compound.
  • Examples of the compound that undergoes a ring closure reaction include a diarylethene compound, a flugide compound, and a flugimid compound.
  • Examples of the compound that undergoes the ring-opening reaction include a spiropyran-based compound and a spirooxazine-based compound.
  • the photoreactive compound may be a low molecular weight compound or a high molecular weight compound, but in the case of the high molecular weight compound, it is preferable that the high molecular weight compound has a photoreactive site pendant.
  • the photoreactive compound a photoisomerized compound is preferable, and an azobenzene compound and a stilbene compound are more preferable.
  • the azobenzene-based compound refers to azobenzene and a compound in which at least one hydrogen atom of azobenzene is replaced with a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
  • the stilbene-based compound refers to a stilbene compound in which at least one hydrogen atom of the stilbene is replaced with a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
  • the photoisomerized compound as the [G1-2] photoreactive compound contains azobenzene, stilbene, or at least one hydrogen atom contained therein as a monovalent hydrocarbon group having 1 to 12 carbon atoms or having 1 carbon atom. It is preferably a compound substituted with ⁇ 12 alkoxy groups.
  • a photoisomerized compound in the case of a trans form, it is easily included in the cyclodextrin derivative, while when it is photoisomerized to become a cis form, it is easily released from the cyclodextrin derivative.
  • monovalent hydrocarbon group having 1 to 12 carbon atoms are as described above, and a chain hydrocarbon group is preferable, and a chain hydrocarbon group having 1 to 4 carbon atoms is more preferable.
  • An alkoxy group having 1 to 12 carbon atoms is a group in which a monovalent hydrocarbon group having 1 to 12 carbon atoms and an oxygen atom (—O—) are bonded.
  • a group in which a chain hydrocarbon group and an oxygen atom are bonded is preferable, and a chain hydrocarbon group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group and an oxygen atom are present. Bonded groups are more preferred.
  • At least a part of the [G1-2] photoreactive compound is usually present in a state where the whole molecule or a part of the molecule is subsumed by the host group of the [A] polymer. That is, at least a part of the [A] polymer and the [G1-2] photoreactive compound forms a clathrate compound.
  • the [G1-2] photoreactive compound is a cis-trans isomer, it is usually subsumed in the host group of the [A] polymer in the trans form.
  • the weight average molecular weight (Mw) of the inclusion compound (polymer) formed from the [A] polymer and the [G1-2] photoreactive compound is usually 1,000 to 100,000, preferably 3,000. ⁇ 30,000.
  • the lower limit of the content of the [G1-2] photoreactive compound is preferably 50 mol%, more preferably 100 mol%, based on the content of the host group of the [A] polymer. On the other hand, as the upper limit of this content, 200 mol% is preferable, and 150 mol% is more preferable. [G1-2] When the content of the photoreactive compound is in the above range, various properties required for the pattern-forming material are further improved.
  • the lower limit of the content of the inclusion compound (polymer) formed from the [A] polymer and the [G1-2] photoreactive compound in the solid content of the radiation-sensitive composition is preferably 10% by mass. , 30% by mass is more preferable, and 40% by mass is further preferable. On the other hand, as the upper limit of this content, 90% by mass is preferable, 70% by mass is more preferable, and 60% by mass is further preferable.
  • the content of the inclusion compound is in the above range, various properties required for the pattern-forming material are further improved.
  • the radiation-sensitive composition preferably further contains the [G2] guest compound.
  • the [G2] guest compound is a compound having a guest group other than the [G1-2] photoreactive compound.
  • at least a part of the [G1-2] photoreactive compound is usually a host group of the [A] polymer. Is included in.
  • the [G2] guest compound is usually not subsumed by the host group of the [A] polymer and exists in a free state.
  • the guest group contained in the [G2] guest compound is not particularly limited as long as it is a group that can be included in the host group of the [A] polymer, but a hydrocarbon group having 6 to 30 carbon atoms is preferable, and a hydrocarbon group having 6 to 30 carbon atoms is preferable.
  • the alicyclic hydrocarbon group and the aromatic hydrocarbon group having 6 to 30 carbon atoms are more preferable, and the alicyclic hydrocarbon group having 6 to 30 carbon atoms is further preferable.
  • Such a hydrocarbon group can be effectively included in the host group, particularly the group derived from the cyclodextrin derivative, when the [G1-2] photoreactive compound is released from the host group. Therefore, when a [G2] guest compound having such a hydrocarbon group is used, the properties required for the pattern forming material such as sensitivity, exposure margin, depth of focus, LWR, film burr amount, and heat resistance are particularly good. become.
  • the [G2] guest compound is preferably a polymer containing a structural unit (i) having a guest group (hereinafter, also referred to as a [G2] polymer).
  • the guest group of the structural unit (i) is preferably a hydrocarbon group having 6 to 30 carbon atoms.
  • Specific examples and suitable examples of the hydrocarbon group having 6 to 30 carbon atoms as the guest group of the structural unit (i) are the same as those described in the [G1-1] crosslinkable compound. That is, the lower limit of the number of carbon atoms of the hydrocarbon group is preferably 8. On the other hand, this upper limit is preferably 20 and more preferably 15. Further, among the hydrocarbon groups, an alicyclic hydrocarbon group and an aromatic hydrocarbon group are preferable, and an alicyclic hydrocarbon group is more preferable.
  • the structural unit (i) may include a structural unit having an alicyclic hydrocarbon group having 6 to 30 carbon atoms and a structural unit having an aromatic hydrocarbon group having 6 to 30 carbon atoms. good.
  • Examples of the monomer giving the structural unit (i) include cyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and ethyl adamantyl (meth) acrylate.
  • the upper limit of the content ratio of the structural unit (i) is preferably 95% by mass, more preferably 90% by mass, further preferably 80% by mass, and even more preferably 70% by mass or 60% by mass.
  • the content ratio of the structural unit having an alicyclic hydrocarbon group having 6 to 30 carbon atoms in the structural unit (i) is 50 from the viewpoint that a crosslinked structure can be further sufficiently formed by the host-guest interaction. It is preferably mass% or more, and more preferably 60 mass% or more.
  • the [G2] polymer preferably further contains a structural unit (ii) having a crosslinkable group.
  • the crosslinkable group of the structural unit (ii) is a group capable of forming a crosslinked structure by a chemical reaction.
  • crosslinkable group of the structural unit (ii) examples include those similar to those exemplified as the crosslinkable group of the [G1-1] crosslinkable compound, but the (meth) acryloyl group and the epoxy group are used. preferable.
  • the structural unit having a (meth) acryloyl group can be formed, for example, by reacting a (meth) acrylic acid ester having an epoxy group with a carboxy group in a polymer containing a structural unit having a carboxy group.
  • the monomer giving the structural unit having a carboxy group is the same as the example of the monomer giving the structural unit (II) of the polymer [A], and among them, acrylic acid, methacrylic acid and maleic anhydride are preferable. .. These monomers can be used alone or in admixture of two or more.
  • Examples of the (meth) acrylic acid ester having an epoxy group include glycidyl (meth) acrylate, 3- (meth) acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-. epoxytricyclo [5.2.1.0 2.6] decyl (meth) acrylate, tris (4-hydroxyphenyl) ethane triglycidyl ether, and the like.
  • the structural unit having a (meth) acryloyl group obtained by reacting the carboxy group of the structural unit having a carboxy group with the (meth) acrylic acid ester having an epoxy group is represented by the following formula (5). It may be there.
  • R 30 and R 31 are independent hydrogen atoms or methyl groups, respectively.
  • a is an integer from 1 to 6.
  • R 32 is a divalent group represented by the following formula (5-1) or formula (5-2).
  • R 33 is a hydrogen atom or a methyl group.
  • * indicates a site that binds to an oxygen atom.
  • R 32 is a group represented by the formula (5-1).
  • R 32 in the formula (5) becomes a group represented by the formula (5-2).
  • the structural unit having a (meth) acryloyl group is a method of reacting an epoxy group in a polymer containing a structural unit having an epoxy group with (meth) acrylic acid, and a hydroxyl group in a polymer containing a structural unit having a hydroxyl group. It can be formed by a method of reacting a (meth) acrylic acid ester having an isocyanate group with or the like.
  • Examples of the monomer giving a structural unit having an epoxy group include unsaturated compounds containing an oxylanyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).
  • Examples of unsaturated compounds having an oxylanyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7-acrylic acid.
  • Examples of unsaturated compounds having an oxetanyl group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, and 3- (methacryloyl).
  • the lower limit of the content ratio of the structural unit (ii) in the [G2] polymer is preferably 5% by mass, more preferably 20% by mass.
  • the upper limit of the content ratio of the structural unit (ii) 60% by mass is preferable, and 50% by mass is more preferable.
  • the [G2] polymer preferably contains a structural unit having a monovalent hydrocarbon group having 1 to 5 carbon atoms.
  • the solubility of the [G2] polymer is optimized, and the characteristics such as LWR become better.
  • the monomer giving the structural unit (iii) among the monomers giving the structural unit (III) of the above-mentioned [A] polymer, those having a monovalent hydrocarbon group having 1 to 5 carbon atoms. Etc. are exemplified.
  • (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate are preferable.
  • the lower limit of the content ratio of the structural unit (iii) in the [G2] polymer is preferably 5% by mass, more preferably 10% by mass.
  • the upper limit of the content ratio of the structural unit (iii) 60% by mass is preferable, and 40% by mass is more preferable.
  • the [G2] polymer preferably further contains a structural unit (iv) having a carboxy group or a phenolic hydroxyl group.
  • a structural unit having a carboxy group is more preferable. Examples of the monomer giving the structural unit (iv) include the same monomers giving the structural unit (II) described above.
  • the lower limit of the content ratio of the structural unit (iv) in the [G2] polymer is preferably 5% by mass, more preferably 10% by mass.
  • the upper limit of the content ratio of the structural unit (iv) is preferably 40% by mass, more preferably 30% by mass.
  • the [G2] polymer may further contain a structural unit (v) other than the structural units (i) to (iv).
  • Examples of the monomer giving the structural unit (v) include the same monomers giving the structural unit (IV) described above.
  • the upper limit of the content ratio of the structural unit (v) in the [G2] polymer is preferably 30% by mass, more preferably 10% by mass, further preferably 3% by mass, and even more preferably 1% by mass.
  • the [G2] polymer can be obtained, for example, by polymerizing each of the above monomers by a known method such as radical polymerization.
  • the weight average molecular weight (Mw) of the [G2] polymer is usually 1,000 to 100,000, preferably 3,000 to 50,000.
  • the lower limit of the content of the [G2] guest compound ([G2] polymer) in the radiation-sensitive composition is 100 parts by mass in total of the [A] polymer and the [G1-2] photoreactive compound. , 40 parts by mass is preferable, and 60 parts by mass is more preferable. On the other hand, as the upper limit of this content, 200 parts by mass is preferable, and 150 parts by mass is more preferable.
  • the content of the [G2] guest compound ([G2] polymer) is in the above range, various properties required for the pattern-forming material are further improved.
  • the radiation-sensitive composition further contains a [G1-1] crosslinkable compound and a polymerizable compound ([B] polymerizable compound) other than the [G2] polymer containing the structural unit (ii). Is preferable.
  • the polymerizable compound further enhances various properties such as sensitivity, film burr amount, and heat resistance.
  • the polymerizable compound is a compound having a crosslinkable group (polymerizable group) as described above.
  • the polymerizable compound may be used alone or in combination of two or more.
  • polymerizable compound a polymerizable compound having an ethylenically unsaturated bond is preferably used.
  • examples of the polymerizable compound include monofunctional (meth) acrylate compounds such as ⁇ -carboxypolycaprolactone mono (meth) acrylate and 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate; ethylene glycol di ( Meta) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate ) Acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethyloltricyclodecandi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxyprop
  • a polyfunctional (meth) acrylate compound such as a urethane (meth) acrylate compound obtained by reacting with a compound having 3 to 5 (meth) acryloyloxy groups; vinyl such as 1,2-divinylcyclobutane and divinylbenzene. Examples include compounds.
  • the lower limit of the content of the [B] polymerizable compound in the solid content of the radiation-sensitive composition is preferably 0.1% by mass, more preferably 5% by mass.
  • the upper limit of this content is preferably 50% by mass, more preferably 30% by mass.
  • the lower limit of the content of the [B] polymerizable compound is preferably 1 part by mass and more preferably 5 parts by mass with respect to 100 parts by mass of the [A] polymer.
  • the upper limit of this content 100 parts by mass is preferable, and 50 parts by mass is more preferable.
  • the radiation-sensitive composition may preferably contain the [C] radiation-sensitive polymerization initiator.
  • the radiation-sensitive polymerization initiator is a component that produces an active species capable of initiating polymerization (crosslinking reaction) of a component having a crosslinkable group in response to radiation. Examples of the component having a crosslinkable group include a [G1-1] crosslinkable compound, a [G2] polymer containing a structural unit (ii), and a [B] polymerizable compound.
  • Examples of the radiation-sensitive polymerization initiator include radical polymerization initiators.
  • Examples of the radiation-sensitive polymerization initiator include an oxime ester compound, an acetophenone compound, and a biimidazole compound.
  • the radiation-sensitive polymerization initiator may be used alone or in combination of two or more.
  • oxime ester compound examples include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) and 1,2-octanedione-.
  • acetophenone compound examples include an ⁇ -aminoketone compound and an ⁇ -hydroxyketone compound.
  • Examples of the ⁇ -aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4).
  • -Morphorin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and the like can be mentioned.
  • Examples of the ⁇ -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, and the like. Examples thereof include 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and 1-hydroxycyclohexylphenyl ketone.
  • biimidazole compound examples include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'.
  • a radiation-sensitive acid generator can also be used as the [C] radiation-sensitive polymerization initiator.
  • the radiation-sensitive acid generator include a sulfonimide compound and a tetrahydrothiophenium salt.
  • sulfoneimide compound examples include N- (trifluoromethylsulfonyloxy) -1,8-naphthalenedicarboimide and N- (kanfasulfonyloxy) naphthyldicarboxyimide.
  • tetrahydrothiophenium salt examples include 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethane. Examples thereof include tetrahydrothiophenium salts such as sulfonate.
  • radiation-sensitive acid generator examples include onium salts, oxime sulfonate compounds, thianthrene compounds, and the like. Commercially available products can be used as these radiation-sensitive acid generators.
  • the lower limit of the content of the [C] radiation-sensitive polymerization initiator in the solid content of the radiation-sensitive composition is preferably 0.1% by mass, more preferably 1% by mass.
  • the upper limit of this content 20% by mass is preferable, and 10% by mass is more preferable.
  • the lower limit of the content of the [C] radiation-sensitive polymerization initiator 1 part by mass is preferable and 3 parts by mass is more preferable with respect to 100 parts by mass of the component having a crosslinkable group.
  • the upper limit of this content 50 parts by mass is preferable, and 30 parts by mass is more preferable.
  • the radiation-sensitive composition may contain an antioxidant, a surfactant, an adhesion aid, a solvent and the like, if necessary.
  • antioxidants examples include hindered phenol-based, hindered amine-based, phosphorus-based, thiol-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate ester-based, and triazine-based compounds.
  • a known antioxidant can be used as the antioxidant.
  • the content of the antioxidant in the solid content of the radiation-sensitive composition can be, for example, 0.01% by mass or more and 5% by mass or less.
  • the surfactant examples include a fluorine-based surfactant, a silicone-based surfactant, and the like.
  • the content of the surfactant in the solid content of the radiation-sensitive composition can be, for example, 0.001% by mass or more and 1% by mass or less.
  • a silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxylanyl group is preferably used, and for example, trimethoxysilyl benzoic acid, ⁇ -methacryloxypropyl.
  • the content of the adhesion aid in the solid content of the radiation-sensitive composition can be, for example, 0.01% by mass or more and 5% by mass or less.
  • the solvent examples include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and octanol; Esters such as ethyl acetate, butyl acetate, ethyl lactate, ⁇ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate; Ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether; Amides such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be used.
  • alcohols such as
  • the solvent can be used alone or in combination of two or more.
  • the solid content concentration of the radiation-sensitive composition is, for example, 10% by mass or more and 80% by mass or less.
  • the radiation-sensitive composition can be prepared by mixing the [A] polymer, the [G1] guest compound, and if necessary, other components in a predetermined ratio, and preferably dissolving or dispersing in a suitable solvent.
  • the prepared radiation-sensitive composition is preferably filtered with, for example, a filter having a pore size of about 0.2 ⁇ m.
  • the radiation-sensitive composition is a combination of the [G1] guest compound and the [G2] guest compound
  • it is preferably prepared by the following procedure.
  • the [A] polymer and the [G1] guest compound are mixed to obtain a clathrate compound of the [A] polymer and the [G1] guest compound.
  • This clathrate compound is mixed with the [G2] guest compound and, if necessary, other components to obtain a radiation sensitive composition.
  • the [G1] guest compound can be subsumed in the host group of the [A] polymer, and the [G2] guest compound can be obtained in a non-subsumed state of the radiation-sensitive composition.
  • the [A] polymer and the [G1] guest compound may be mixed in advance to obtain an inclusion compound and then mixed with other components, or the [A] polymer may be mixed. And [G1] guest compounds may be mixed with other components at once.
  • a radiation-sensitive composition in which the [G1] guest compound is subsumed in the host group of the [A] polymer can be obtained.
  • the clathrate compound according to one embodiment of the present invention is A inclusion compound in which at least a part of a first guest compound ([G1] guest compound) is included in the host group of a polymer containing a host group ([A] polymer).
  • the host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from a cyclodextrin derivative.
  • the cyclodextrin derivative is selected from the group in which the hydrogen atom of at least one hydroxyl group of cyclodextrin consists of a monovalent hydrocarbon group having 1 to 12 carbon atoms, an acyl group having 1 to 12 carbon atoms, and -CONHR.
  • the first guest compound ([G1] guest compound) is a clathrate compound having a crosslinkable group and a hydrocarbon group having 6 to 30 carbon atoms.
  • the clathrate compound is the above-mentioned clathrate compound formed from the [A] polymer and the [G1-1] crosslinkable compound in the radiation-sensitive composition according to the embodiment of the present invention. Therefore, the specific embodiment and the preferred embodiment of the clathrate compound are the same as described above.
  • the pattern forming method according to the embodiment of the present invention is (1) A step of forming a coating film on a substrate by a radiation-sensitive composition according to an embodiment of the present invention. It includes (2) a step of exposing the coating film and (3) a step of developing the coating film after exposure.
  • the radiation-sensitive composition is applied onto the substrate and prebaked as necessary to form a coating film.
  • the substrate used in the step (1) include a glass substrate, a silicon wafer, a plastic substrate, and a substrate on which various inorganic films such as silicon nitride are formed on the surface thereof.
  • the plastic substrate include a substrate containing a plastic as a main component, such as polyethylene terephthalate (PET), polybutylene terephthalate, polyether sulfone, polycarbonate, and polyimide.
  • PET polyethylene terephthalate
  • polybutylene terephthalate polybutylene terephthalate
  • polyether sulfone polycarbonate
  • polyimide polyimide
  • a coating method of the radiation-sensitive composition for example, an appropriate method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method, a bar coating method, an inkjet method, etc. may be adopted. can.
  • the prebaking conditions vary depending on the type and content of the components contained in the radiation-sensitive composition, but can be, for example, 60 ° C. or higher and 100 ° C. or lower for 20 seconds or longer and 10 minutes or shorter.
  • the average film thickness of the coating film is preferably 0.1 ⁇ m, more preferably 0.5 ⁇ m, as the lower limit after prebaking.
  • the upper limit is preferably 15 ⁇ m, more preferably 10 ⁇ m, and even more preferably 5 ⁇ m.
  • the coating film formed in the step (1) is irradiated with radiation through a mask having a predetermined pattern.
  • the radiation at this time include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.
  • a radiation-sensitive composition containing an azobenzene-based compound or a stilbene-based compound is used as the [G1-2] photoreactive compound
  • radiation containing at least one wavelength of 246 nm and 365 nm is preferable.
  • the azobenzene compound isomerizes from a trans form to a cis form at a wavelength of 365 nm (i-line or the like).
  • the stilbene compound is isomerized from a trans form to a cis form at a wavelength of 246 nm (KrF excimer laser light or the like).
  • the radiation-sensitive composition contains a [A] polymer, an azobenzene-based compound or a stilbene-based compound as a [G1-2] photoreactive compound, and a [G2] polymer as a [G2] guest compound
  • the [G1-2] reactive compound is released from the host group of the [A] polymer
  • the guest group of the [G2] polymer is released from the [A] polymer.
  • the crosslinked structure of the [A] polymer and the [G2] polymer is effectively formed by being included in the host group of.
  • the radiation is not particularly limited, and radiation of other wavelengths can also be used.
  • the exposure amount of radiation for example, preferably 10J / m 2 or more 100,000J / m 2 or less, 1,000 J / m 2 or more is more preferable.
  • the coating film may be reheated on a hot plate or the like before development.
  • the heating conditions can be, for example, 60 ° C. or higher and 150 ° C. or lower for 20 seconds or longer and 10 minutes or shorter.
  • step (3) the coating film after exposure in step (2) is developed. Specifically, usually, the coating film irradiated with radiation in the step (2) is developed with a developing solution to remove the non-irradiated portion of the radiation.
  • Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, and methyldiethylamine.
  • TMAH tetramethylammonium hydroxide
  • pyrrole piperidine
  • 1,8-diazabicyclo [5,4,0] -7-undecene 1,5-diazabicyclo
  • Examples thereof include an aqueous solution of an alkali (basic compound) such as 4,3,0] -5-nonane.
  • An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution, or an alkaline aqueous solution containing a small amount of other various organic solvents may be used as the developing solution.
  • a compound having a highly hydrophobic group such as an alkyl group having 6 or more carbon atoms has high solubility in an organic solvent. Therefore, when such a compound is used as the [G1] guest compound or the [G2] guest compound, the dissolution contrast to the organic solvent is increased between the non-exposed part and the exposed part, so that the developability in the organic solvent development is improved. do. For this reason, a developer containing an organic solvent can also be used as the developer.
  • the organic solvent include the solvents listed as optional components of the radiation-sensitive composition.
  • the content of the organic solvent in the developing solution is preferably 50% by mass or more, more preferably 90% by mass or more, still more preferably 99% by mass or more.
  • This organic solvent-based developer may contain an inorganic solvent such as water or other additives.
  • the developing method for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, and a paddle method can be adopted.
  • the development time can be, for example, 20 seconds or more and 120 seconds or less.
  • the patterned coating film may be rinsed by running water washing or the like.
  • the coating film can be heated and fired (post-baked) to promote the curing of the coating film.
  • a good pattern can be formed by exposure and development utilizing the radiation sensitivity of the radiation sensitive composition.
  • the pattern forming method can be used for forming a resist pattern in photolithography. Further, the pattern forming method can also be used for forming various patterns of element members such as interlayer insulating films, spacers, protective films, and colored patterns for color filters.
  • a nuclear magnetic resonance apparatus (“AVANCE 700 type” manufactured by Bruker) was used for 1 H-NMR measurement and 13 C-NMR measurement for structural identification of the compound.
  • the molecular weight of the monomer was measured using a liquid chromatograph mass spectrometer (“LCMS-8045” manufactured by Shimadzu Corporation).
  • the molecular weight of the polymer was measured by gel permeation chromatography (GPC) under the following conditions. Further, Mw / Mn was calculated from the obtained Mw and Mn.
  • reaction solution was heated and stirred at 90 ° C. in an oil bath. After stirring for 1 hour, the reaction solution was allowed to cool at room temperature and poured into 500 mL of acetone. The resulting precipitate was filtered off, washed with acetone, and dried under reduced pressure to give a reaction product.
  • the reaction product was dissolved in 500 mL of distilled water, and separated and purified by preparative high performance liquid chromatography to separate unreacted ⁇ -cyclodextrin and ⁇ CDAAMMe.
  • the target product, ⁇ CDAAMme was obtained by extracting with an organic solvent from an aqueous solution containing ⁇ CDAAMme and removing the organic solvent under reduced pressure (1.8 g of white powder).
  • 1 H-NMR measurement, 13 C-NMR measurement, and LC-MS measurement were performed, and it was confirmed that the target product was ⁇ CDAAMMe.
  • the resulting precipitate was filtered off, washed with acetone, and dried under reduced pressure to give a reaction product.
  • the reaction product was dissolved in 500 mL of distilled water and separated and purified by preparative high performance liquid chromatography to separate unreacted ⁇ -cyclodextrin and ⁇ CDVBA.
  • the target product, ⁇ CDVBA was obtained by extracting with an organic solvent from an aqueous solution containing ⁇ CDVBA and removing the organic solvent under reduced pressure (2.2 g of white powder).
  • the structure of the target product was confirmed to be ⁇ CDVBA of the target product by 1 H-NMR measurement, 13 C-NMR measurement and LC-MS measurement.
  • ⁇ CDVBA was methoxylated in the same manner as in Synthesis Example 2. It was confirmed that methoxylated 4-vinylbenzylamine ⁇ -cyclodextrin (MeO- ⁇ CDVBA) was obtained.
  • This copolymer is referred to as a polymer (A-3a).
  • MeO- ⁇ CDAA mMe / n-butyl acrylate / acrylic acid / styrene 4-MeOAzB MeO- ⁇ CDAA mMe / BA / AA / ST) containing 4-methoxyazobenzene (trans polymer) as a guest molecule.
  • a copolymer was obtained.
  • the obtained copolymer is referred to as a polymer (AG-3a).
  • (2) MeO- ⁇ CDAA mMe / n-butyl acrylate / acrylic acid / styrene (MeO- ⁇ CDAA mMe) was carried out in the same manner as in Synthesis Example 6 except that the MeO- ⁇ CDAA mMe obtained in Synthesis Example 3 was used instead of MeO- ⁇ CDAA mMe.
  • a polymer solution containing a / BA / AA / ST) copolymer was obtained. This copolymer is referred to as a polymer (A-3b).
  • a polymer solution containing an AdA / BzA / MA copolymer was obtained.
  • This copolymer is referred to as a polymer (G-1).
  • the weight average molecular weight (Mw) of the polymer (G-1) was 10,000, and Mw / Mn was 1.8.
  • the temperature of the solution was raised to 80 ° C., maintained at this temperature for 4 hours, then raised to 100 ° C., and the temperature was maintained for 1 hour for polymerization to obtain a solution containing a copolymer. Obtained.
  • 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and the mixture was stirred at 90 ° C. for 30 minutes in an air atmosphere.
  • This copolymer is referred to as a polymer (G-2).
  • the weight average molecular weight (Mw) of the polymer (G-2) was 12,000, and Mw / Mn was 1.9.
  • the temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing an adamantyl methacrylate / glycidyl methacrylate / methacrylic acid copolymer.
  • This copolymer is referred to as a polymer (G-3).
  • the weight average molecular weight (Mw) of the polymer (G-3) was 10,000, and Mw / Mn was 2.3.
  • the weight average molecular weight (Mw) of the polymer (G-4) was 9,000, and Mw / Mn was 2.1.
  • the weight average molecular weight (Mw) of the polymer (G-5) was 8,000, and Mw / Mn was 2.2.
  • a polymer solution containing a benzyl acrylate / methyl acrylate / n-butyl acrylate copolymer was obtained.
  • This copolymer is referred to as a polymer (G-6).
  • the weight average molecular weight (Mw) of the polymer (G-6) was 7,000, and Mw / Mn was 2.0.
  • the temperature was raised to ° C., and this temperature was maintained for 5 hours for polymerization.
  • a polymer solution containing a methyl methacrylate / methacrylic acid / ethyl methacrylate copolymer was obtained.
  • This copolymer is referred to as a polymer (g-1).
  • the weight average molecular weight (Mw) of the polymer (g-1) was 8,000, and Mw / Mn was 1.8.
  • SH 190 manufactured by Toray Dow Corning Silicone
  • Examples 2 to 3, Comparative Example 1 The same as in Example 1 except that the types and amounts of the [A] polymer, the [G1-1] crosslinkable compound, the [B] polymerizable compound and the [C] polymerization initiator were as shown in Table 1.
  • the compositions (T-2) to (T-3) of Examples 2 to 3 and the composition (t-1) of Comparative Example 1 were prepared. In Table 1, "-" indicates that no addition was made.
  • Example 4 50 parts by mass of the polymer (AG-1) as an inclusion compound of the [A] polymer and the [G1-2] photoreactive compound, and 50 parts by mass of the polymer (G-1) as the [G2] polymer.
  • G-1 50 parts by mass of the polymer (G-1) as the [G2] polymer.
  • SH 190 manufactured by Toray Dow Corning Silicone
  • T-4 The composition of Example 4 (T-4) was prepared.
  • Example 5 50 parts by mass of the polymer (AG-1) as an inclusion compound of the [A] polymer and the [G1-2] photoreactive compound, 50 parts by mass of the polymer (G-2) as the [G2] polymer, And [C] (C-1) etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) 5 as a polymerization initiator. Parts by weight were added and dissolved in propylene glycol monomethyl ether acetate.
  • Example 5 the composition of Example 5 (the composition of Example 5).
  • T-5) was prepared.
  • Examples 6 to 13, Comparative Example 2 The types and amounts of the inclusion compound or the [A] polymer, the [G2] polymer or the comparative polymer, and the [C] polymerization initiator of the [A] polymer and the [G1-2] photoreactive compound are shown.
  • the compositions (T-6) to (T-13) of Examples 6 to 13 and the composition (t-2) of Comparative Example 2 were prepared in the same manner as in Example 5 except as shown in 2. did. In Table 2, "-" indicates that no addition was made.
  • a lower antireflection film (“ARC66” manufactured by Brewer Science Co., Ltd.) is applied onto an 8-inch silicon wafer using a spin coater ("CLEAN TRACK Lithius Pro i” manufactured by Tokyo Electron Limited), and then heated at 205 ° C. for 60 seconds. By doing so, a lower antireflection film having a thickness of 0.15 ⁇ m was formed. Then, using the spin coater, each composition shown in Tables 1 and 2 was applied, and PB was performed at 90 ° C. for 60 seconds. Then, it was cooled at 23 ° C. for 30 seconds to form a coating film having a film thickness of 2.0 ⁇ m.
  • the coating film was exposed using an i-line exposure apparatus (manufactured by Nikon Seiki Company) or a KrF exposure apparatus (manufactured by Nikon Seiki Company). Then, on a hot plate, it was heated at a temperature of 120 ° C. for 60 seconds, and then cooled at 23 ° C. for 30 seconds. Then, the coating film was paddle-developed with a predetermined developer for 30 seconds. After development, the coating film was rinsed with pure water to obtain a pattern. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4000) was used for length measurement. In the exposure step, the i-line exposure apparatus and the KrF exposure apparatus were used for exposure depending on the guest compound used. Specifically, in the composition containing the azobenzene-based compound as the guest compound, an i-ray exposure apparatus was used. For other compositions, a KrF exposure apparatus was used.
  • the optimum exposure amount was defined as the exposure amount such that the line pattern formed by the above pattern forming method had a 1 ⁇ m line / 2 ⁇ m pitch, and this optimum exposure amount was defined as the sensitivity (mJ / cm 2 ).
  • the sensitivity was 160 mJ / cm 2 or less, it was judged that it could be sufficiently used as a radiation-sensitive pattern forming material, and when it was 100 mJ / cm 2 or less, it was judged to be particularly good.
  • Exposure margin (EL) The range of the amount of exposure when the line pattern after reduced projection exposure is exposed through a mask such that the line pattern is 1 ⁇ m line / 2 ⁇ m pitch and the line width of the formed line pattern is within ⁇ 15% of the 1 ⁇ m line.
  • the ratio to the optimum exposure amount was defined as the exposure margin (EL (%)).
  • the EL value is 4% or more, it is judged that it can be sufficiently used as a radiation-sensitive pattern forming material, and when it is 15% or more, the variation in patterning performance with respect to the change in exposure amount is small and particularly good. It was judged.
  • DOF Depth Of Focus
  • a line pattern of 1 ⁇ m line / 2 ⁇ m pitch was formed in the same manner as in the case of the sensitivity evaluation. It was developed with 2.38% TMAH developer at 23 ° C. for 60 seconds and dried. After the series of processes was completed, the film thickness of the remaining resist film was measured, and the value obtained by subtracting the residual film thickness from the initial film thickness was taken as the amount of film loss.
  • An optical interference type film thickness measuring device (Lambda Ace, manufactured by Dainippon Screen Mfg. Co., Ltd.) was used for film thickness measurement. The initial film thickness is the film thickness before exposure after coating on the substrate. When the measured film loss amount was 0.8 ⁇ m or less, the film sag amount was judged to be sufficiently small, and when the film loss amount was 0.3 ⁇ m or less, it was judged to be particularly good.
  • each of the compositions of Examples 1 to 13 can be used as a pattern-forming material having a radiation-sensitive property.
  • each of the compositions of Examples 1 to 12 has good evaluations of sensitivity, exposure margin, depth of focus, LWR, film burr amount, and heat resistance, and it can be seen that they are particularly preferable as a pattern forming material. ..
  • the compositions of Examples 1 to 3 exhibit higher sensitivity, heat resistance, etc. than the compositions of Comparative Example 1, it is said that a crosslinked structure is formed between the [A] polymers. Guessed.
  • the radiation-sensitive composition of the present invention can be suitably used as a pattern-forming material such as a resist pattern.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L'invention concerne : un procédé de formation d'un motif à l'aide d'un nouveau matériau de formation de motifs ; une composition sensible au rayonnement utilisable en tant que nouveau matériau de formation de motifs ; et un composé clathrate approprié pour être utilisé en tant que constituant d'une telle composition sensible au rayonnement. Un aspect de la présente invention concerne un procédé de formation d'un motif qui comprend une étape dans laquelle une composition sensible au rayonnement comprenant à la fois un polymère comprenant un groupe hôte et un premier composé invité est utilisée pour former un film de revêtement sur un substrat, une étape dans laquelle le film de revêtement est exposé à de la lumière et une étape dans laquelle le film de revêtement exposé est développé, le groupe hôte étant un groupe monovalent formé par élimination d'un atome d'hydrogène ou d'un groupe hydroxyle d'un dérivé cyclodextrine.
PCT/JP2020/047658 2020-01-20 2020-12-21 Procédé de formation d'un motif, composition sensible au rayonnement et composé clathrate WO2021149432A1 (fr)

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WO2022049911A1 (fr) * 2020-09-01 2022-03-10 Jsr株式会社 Composition de résine sensible au rayonnement et procédé de formation de motif
WO2023171709A1 (fr) * 2022-03-09 2023-09-14 国立大学法人大阪大学 Composition de résine et procédé de production associé

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JP2005306917A (ja) * 2004-04-16 2005-11-04 Jsr Corp フッ素含有シクロデキストリン誘導体、ポリロタキサンおよび感放射線性樹脂組成物
WO2012036069A1 (fr) * 2010-09-14 2012-03-22 国立大学法人大阪大学 Procédé d'auto-assemblage de matériaux et procédé d'adhérence sélective sur la base de la reconnaissance moléculaire
WO2017159346A1 (fr) * 2016-03-18 2017-09-21 国立大学法人大阪大学 Matériau macromoléculaire, procédé pour le produire et composition de monomère polymérisable
WO2018207934A1 (fr) * 2017-05-11 2018-11-15 国立大学法人大阪大学 Composition pour polymérisation, polymère de celle-ci et procédé de production de polymère
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JP4547558B2 (ja) 2004-03-31 2010-09-22 学校法人 芝浦工業大学 形状記憶素子
JP2019214719A (ja) 2018-06-12 2019-12-19 Ａｇｃ株式会社 粉体塗料及び粉体塗料の製造方法

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JP2005306917A (ja) * 2004-04-16 2005-11-04 Jsr Corp フッ素含有シクロデキストリン誘導体、ポリロタキサンおよび感放射線性樹脂組成物
WO2012036069A1 (fr) * 2010-09-14 2012-03-22 国立大学法人大阪大学 Procédé d'auto-assemblage de matériaux et procédé d'adhérence sélective sur la base de la reconnaissance moléculaire
WO2017159346A1 (fr) * 2016-03-18 2017-09-21 国立大学法人大阪大学 Matériau macromoléculaire, procédé pour le produire et composition de monomère polymérisable
WO2018207934A1 (fr) * 2017-05-11 2018-11-15 国立大学法人大阪大学 Composition pour polymérisation, polymère de celle-ci et procédé de production de polymère
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WO2022049911A1 (fr) * 2020-09-01 2022-03-10 Jsr株式会社 Composition de résine sensible au rayonnement et procédé de formation de motif
WO2023171709A1 (fr) * 2022-03-09 2023-09-14 国立大学法人大阪大学 Composition de résine et procédé de production associé

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