WO2012035666A1 - Dérivé d'ester acrylique, dérivé d'alcool, et procédé de production correspondant - Google Patents

Dérivé d'ester acrylique, dérivé d'alcool, et procédé de production correspondant Download PDF

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Publication number
WO2012035666A1
WO2012035666A1 PCT/JP2010/066254 JP2010066254W WO2012035666A1 WO 2012035666 A1 WO2012035666 A1 WO 2012035666A1 JP 2010066254 W JP2010066254 W JP 2010066254W WO 2012035666 A1 WO2012035666 A1 WO 2012035666A1
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group
carbon atoms
derivative
reaction
acrylic ester
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PCT/JP2010/066254
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English (en)
Japanese (ja)
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和哉 清水
山中　雅義
太津彦 林原
岩崎　秀治
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株式会社クラレ
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Priority to KR1020127018876A priority Critical patent/KR20130103649A/ko
Priority to PCT/JP2010/066254 priority patent/WO2012035666A1/fr
Publication of WO2012035666A1 publication Critical patent/WO2012035666A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/46—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by amide or nitrile radicals
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (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
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Definitions

  • the present invention relates to an acrylate derivative and an alcohol derivative and a method for producing them.
  • a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to radiation such as light and electron beams through a mask on which a predetermined pattern is formed. And performing a developing process to form a resist pattern having a predetermined shape on the resist film.
  • a resist material in which the exposed portion changes to a property that dissolves in the developer is referred to as a positive type, and a resist material that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative type.
  • pattern miniaturization has been rapidly progressing due to advances in lithography technology.
  • the exposure light source is generally shortened in wavelength (increased energy).
  • ultraviolet rays typified by g-line and i-line have been used, but at present, mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has started.
  • Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern with fine dimensions.
  • a chemically amplified resist composition containing a base material component whose solubility in an alkaline developer is changed by the action of an acid and an acid generator component that generates an acid upon exposure is used. It has been.
  • a positive chemically amplified resist composition a composition containing a resin component (base resin) whose solubility in an alkaline developer is increased by the action of an acid and an acid generator component is generally used. Yes.
  • a resin having a constitutional unit derived from (meth) acrylic acid ester (acrylic resin) because of its excellent transparency near 193 nm Etc.) are generally used (see, for example, Patent Document 1).
  • a nitrogen-containing organic compound such as an alkylamine or an alkyl alcoholamine is blended in the chemically amplified resist composition.
  • the nitrogen-containing organic compound acts as a quencher that traps the acid generated from the acid generator, and contributes to the improvement of lithography properties such as the resist pattern shape.
  • tertiary amines are generally widely used as the nitrogen-containing organic compounds.
  • various nitrogen-containing organic compounds are used in order to improve process margins and the like when forming isolated patterns (see, for example, Patent Documents 2 and 3).
  • the resist compositions containing nitrogen-containing organic compounds described in Patent Documents 2 and 3 have not yet been able to satisfy the required lithography characteristics and pattern shapes as the pattern becomes finer.
  • the present invention has been made in view of the above circumstances, and is an acrylic ester derivative useful as a raw material for a polymer compound for a resist composition that is excellent in lithography properties and can form a resist pattern having a good shape, and its An object is to provide an intermediate (alcohol derivative) and a method for producing the same.
  • the present inventors use, as a base resin, a polymer compound obtained by polymerizing an acrylate derivative containing a specific nitrogen atom-containing group as a quencher for trapping an acid generated from an acid generator.
  • a base resin a polymer compound obtained by polymerizing an acrylate derivative containing a specific nitrogen atom-containing group as a quencher for trapping an acid generated from an acid generator.
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group
  • R 2 , R 3 , R 5 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom.
  • a method for producing an acrylate derivative (1) which comprises esterifying an alcohol derivative (hereinafter referred to as alcohol derivative (2)).
  • alcohol derivative (2) [3] Alcohol derivative (2).
  • Alcohol derivative (2) [4] In the presence of a base, the following general formula (3)
  • cyclohexene derivative (3) A cyclohexene derivative represented by the following formula (hereinafter referred to as cyclohexene derivative (3)) is oxidized to give the following general formula (4):
  • a method for producing an alcohol derivative (2) comprising: obtaining an epoxy derivative represented by formula (hereinafter referred to as an epoxy derivative (4)), and subjecting the obtained epoxy derivative (4) to a base treatment.
  • an epoxy derivative (4) represented by formula (hereinafter referred to as an epoxy derivative (4))
  • a method for producing an epoxy derivative (4) wherein the cyclohexene derivative (3) is oxidized in the presence of a base.
  • an acrylate derivative and an intermediate thereof (alcohol derivative) useful as a raw material for a polymer compound for a resist composition that has excellent lithography properties and forms a resist pattern with a good shape, and a method for producing them can be provided.
  • acrylic ester derivative (1) The following acrylic ester derivative (1) of the present invention is useful for obtaining a resist composition that is excellent in lithography properties and forms a resist pattern having a good shape.
  • R 1 in the acrylate derivative (1) represents a hydrogen atom, a methyl group or a trifluoromethyl group. Among these, R 1 is preferably a hydrogen atom or a methyl group.
  • R 2 , R 3 , R 5 , R 7 , R 8 , R 9 and R 10 in the acrylate derivative (1) are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, carbon A cycloalkyl group having 3 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms is represented.
  • R 4 and R 6 in the acrylate derivative (1) are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.
  • R 11 in the acrylate derivative (1) represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic hydrocarbon group having 3 to 10 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms which R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represents may be linear or branched.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.
  • an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
  • Examples of the cycloalkyl group having 3 to 6 carbon atoms independently represented by R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 include a cyclopropyl group and a cyclobutyl group. , A cyclopentyl group, and a cyclohexyl group.
  • the alkoxy group having 1 to 6 carbon atoms which R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represents may be linear or branched.
  • methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group and the like can be mentioned.
  • an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group is more preferable.
  • R 2 , R 3 , R 5 , R 7 , R 8 , R 9 and R 10 a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferable, and all of them are hydrogen atoms. preferable.
  • Examples of the alkylene group having 1 to 3 carbon atoms formed by combining R 4 and R 6 include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1- Examples include a diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group. Among these, a methylene group and an ethane-1,2-diyl group are preferable, and a methylene group is more preferable from the viewpoint of obtaining a resist composition that forms a resist pattern having a good shape.
  • R 4 and R 6 are each preferably a hydrogen atom, or an alkylene group having 1 to 3 carbon atoms or —O— in which both are bonded, and a methylene group or —O—. More preferably.
  • the alkyl group having 1 to 6 carbon atoms represented by R 11 may be linear or branched.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s- Examples include a butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group.
  • an alkyl group having 1 to 4 carbon atoms is preferable, a branched alkyl group having 3 or 4 carbon atoms is more preferable, and t- A butyl group is more preferable.
  • Examples of the cyclic hydrocarbon group having 3 to 10 carbon atoms each independently represented by R 11 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantane-1-yl group.
  • R 11 is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group from the viewpoint of obtaining a resist composition that forms a resist pattern having a good shape.
  • S-butyl group, t-butyl group, and adamantane-1-yl group are preferable.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are the alcohol derivative (2). , Cyclohexene derivative (3) and epoxy derivative (4), and later diene derivative (5), acrylic acid halide derivative (6) and amine compound (7), respectively.
  • Specific examples of the acrylate derivative (1) of the present invention are shown below, but are not particularly limited thereto.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 , R 3 , R 5 , R 7 , R 8 , R 9 and R 10 are all hydrogen atoms
  • 11 is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group or adamantane-1-yl group
  • R 4 and R It is preferable that 6 is a methylene group in which both are bonded or —O—.
  • the method for producing the acrylic ester derivative (1) of the present invention is not particularly limited, but it can be produced, for example, by the following first to fourth steps.
  • First step After reacting a diene derivative (hereinafter referred to as diene derivative (5)) with an acrylic acid halide derivative (hereinafter referred to as acrylic acid halide derivative (6)), an amine compound R 11 NH 2 ( R 11 is as defined above, and is hereinafter referred to as amine compound (7)) to obtain a cyclohexene derivative (3).
  • Second step A step of obtaining an epoxy derivative (4) by reacting the cyclohexene derivative (3) with an organic peroxide in the presence of a basic compound.
  • Third step a step of obtaining the alcohol derivative (2) by reacting the epoxy derivative (4) with a basic substance.
  • Fourth step A step of producing the acrylic ester derivative (1) by reacting the alcohol derivative (2) with the acrylic acid derivative.
  • the chemical reaction formula for the first to fourth steps is shown below.
  • the said diene derivative (5) and acrylic acid halide derivative (6) are the structures described in the following chemical reaction formulas.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are as defined above.
  • X is a chlorine atom Represents a bromine atom or an iodine atom.
  • the first step is a step of reacting the diene derivative (5) with the acrylic acid halide derivative (6) [hereinafter referred to as first step-1]. ] And the step of reacting the reaction intermediate obtained in the first step-1 with the amine compound (7) [hereinafter referred to as the first step-2. ].
  • first step-1 Specific examples of the diene derivative (5) used in the first step-1 include butadiene, isoprene, 2,3-dimethylbutadiene, cyclopentadiene, furan and the like.
  • acrylic acid halide derivative (6) used in the first step-1 include acrylic acid chloride, methacrylic acid chloride, acrylic acid bromide, methacrylic acid bromide, crotonic acid chloride, crotonic acid bromide, 3-methyl-2. -Butenoic acid chloride and the like.
  • the amount of the diene derivative (5) used is preferably in the range of 1 to 50 times mol, more preferably in the range of 1 to 10 times mol for the acrylic acid halide derivative (6), from the viewpoint of ease of post-treatment. .
  • the reaction of the first step-1 is carried out in the presence or absence of a solvent.
  • the solvent is not particularly limited as long as it does not inhibit the reaction.
  • saturated hydrocarbon solvents such as hexane, heptane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; methylene chloride, dichloroethane, chloroform and benzene chloride
  • Chlorinated hydrocarbon solvents such as: ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, and furan; ester solvents such as methyl acetate, ethyl acetate, and propyl acetate.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the diene derivative (5). From the viewpoint of ease of post-treatment, 0.5 to 20 A range of mass times is more preferable.
  • the reaction temperature in the first step-1 varies depending on the type of diene derivative (5) and acrylic acid halide derivative (6), but is preferably in the range of ⁇ 30 to 100 ° C., more preferably in the range of ⁇ 10 to 50 ° C. preferable. Moreover, although there is no restriction
  • the reaction time in the first step-1 varies depending on the type and amount of the diene derivative (5) and acrylic acid halide derivative (6), the reaction temperature, etc., but is preferably in the range of about 1 hour to 50 hours.
  • the reaction in the first step-1 is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
  • the reaction mixture containing the reaction intermediate obtained in the first step-1 can be used as it is as the raw material of the first step-2 without any particular purification operation, and it is preferable to do so. .
  • the method for carrying out the first step-1 is not particularly limited, but the reactor is charged with an acrylic acid halide derivative (6) and, optionally, a solvent, and this mixture is mixed with a desired reaction temperature and a desired reaction.
  • a method of dropping the diene derivative (5) under pressure is preferred.
  • amine compound (7) used in the first step-2 include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, cyclo Examples include propylamine, cyclohexylamine, 1-adamantylamine and the like.
  • the amount of the amine compound (7) used is preferably in the range of 1 to 10 moles compared to the acrylic acid halide derivative (6) used in the first step-1. From the viewpoint of ease of post-treatment, A range of 5 moles is more preferred.
  • the reaction of the first step-2 is carried out in the presence or absence of a solvent.
  • the solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include the same solvents as exemplified in the explanation of the first step-1. Therefore, when a solvent is used in the first step-1, it is preferable to use the used solvent as it is in the first step-2.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the diene derivative (5) used in the first step-1, which facilitates post-treatment. From the viewpoint, the range of 0.5 to 20 times by mass is more preferable.
  • the amount of the solvent may be left as it is or may be further added.
  • the reaction temperature in the first step-2 varies depending on the types of the amine compound (7) and the acrylic acid halide derivative (6), but is preferably in the range of ⁇ 30 to 100 ° C., more preferably in the range of ⁇ 10 to 50 ° C. preferable. Moreover, although there is no restriction
  • the reaction time in the first step-2 varies depending on the type and amount of the amine compound (7) and the acrylic acid halide derivative (6), the reaction temperature, etc., but is preferably in the range of about 1 to 50 hours.
  • the reaction in the first step-2 is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
  • the method for carrying out the first step-2 is not particularly limited, but the reactor is charged with the amine compound (7) and, optionally, a solvent, and this mixture is added under a desired reaction temperature and a desired reaction pressure.
  • the method of dropping the reaction intermediate obtained in the first step-1 is preferable.
  • Separation and purification of the cyclohexene derivative (3) from the reaction mixture obtained by the above method can be performed by a method generally used for separation and purification of organic compounds.
  • the cyclohexene derivative (3) can be separated by adding the organic solvent and water after the completion of the reaction in the first step-2, allowing to stand, separating the organic layer from the aqueous layer, and concentrating the organic layer.
  • a highly purified cyclohexene derivative (3) can be obtained by recrystallization, silica gel column chromatography, or the like.
  • ⁇ Second step> Next, the 2nd process regarding the manufacturing method of an epoxy derivative (4) is demonstrated.
  • the organic peroxide used in the second step include peracetic acid, m-chloroperbenzoic acid, dimethyldioxirane and the like.
  • the amount of the organic peroxide used is preferably in the range of 1 to 10 moles relative to the cyclohexene derivative (3), and more preferably in the range of 1 to 5 moles from the viewpoint of ease of post-treatment.
  • the basic compound used in the second step include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; calcium hydroxide and barium hydroxide. Alkaline earth metal hydroxides; alkaline earth metal carbonates such as calcium carbonate and barium carbonate. Among these, alkali metal carbonate is preferable.
  • the amount of the basic compound used is preferably in the range of 1 to 20 moles relative to the organic peroxide, and more preferably in the range of 1 to 10 moles from the viewpoint of ease of post-treatment.
  • the reaction in the second step is usually carried out in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not inhibit the reaction.
  • water saturated hydrocarbon solvents such as hexane, heptane, cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene; methylene chloride, dichloroethane, chloride
  • chlorinated hydrocarbon solvents such as benzene
  • ester solvents such as methyl acetate, ethyl acetate, and isopropyl acetate.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the amount of the solvent used is preferably in the range of 0.5 to 100 times by mass relative to the cyclohexene derivative (3), and more preferably in the range of 0.5 to 20 times by mass from the viewpoint of ease of post-treatment.
  • the reaction temperature in the second step varies depending on the kind of the organic peroxide and the cyclohexene derivative (3), but is preferably in the range of ⁇ 80 to 100 ° C., more preferably in the range of ⁇ 30 to 50 ° C. Moreover, although there is no restriction
  • the reaction time in the second step varies depending on the type and amount of the organic peroxide and cyclohexene derivative (3), the reaction temperature, etc., but is preferably in the range of about 1 to 50 hours.
  • the reaction in the second step is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
  • the reaction in the second step can be stopped by adding a reducing agent.
  • the reducing agent include sodium sulfite, sodium thiosulfate, and sodium hydrogen sulfite.
  • the amount of the reducing agent added is preferably in the range of 1 to 5 times mol with respect to the unreacted organic peroxide, which facilitates post-treatment. From the viewpoint of the above, a range of 1 to 3 moles is more preferable.
  • the method for carrying out the second step is not particularly limited, but the reactor is charged with the cyclohexene derivative (3), the basic compound and the solvent, and this mixture is subjected to a desired reaction temperature and a desired reaction pressure. Then, a method of dropping a mixed solution of an organic peroxide and a solvent is preferable.
  • Separation and purification of the epoxy derivative (4) from the reaction mixture obtained by the above method can be carried out by methods generally used for separation of organic compounds such as solvent extraction and distillation, and further recrystallization and distillation.
  • the purity can be improved by a method generally used for purification of organic compounds such as sublimation.
  • ⁇ Third step> Next, the 3rd process regarding the manufacturing method of alcohol derivative (2) is demonstrated.
  • Specific examples of basic substances used in the third step include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium-t-butoxide, potassium-t-butoxide; hydrogen And alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride.
  • sodium-t-butoxide, potassium-t-butoxide, and sodium hydride are preferable.
  • the amount of the basic substance used is preferably in the range of 1 to 5 moles relative to the epoxy derivative (4), and more preferably in the range of 1 to 3 moles from the viewpoint of ease of post-treatment.
  • the reaction in the third step is usually carried out in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not inhibit the reaction.
  • saturated hydrocarbon solvents such as hexane, heptane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; diethyl ether, diisopropyl ether, tetrahydrofuran and the like Ether solvents; alcohol solvents such as methanol, ethanol, t-butanol and the like.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the epoxy derivative (4), and more preferably in the range of 0.5 to 20 times by mass from the viewpoint of ease of post-treatment.
  • the reaction temperature in the third step varies depending on the basic substance and the type of the epoxy derivative (4), but is preferably in the range of ⁇ 80 to 100 ° C., more preferably in the range of ⁇ 30 to 50 ° C. Moreover, although there is no restriction
  • the reaction time in the third step varies depending on the kind and amount of the basic substance and the epoxy derivative (4), the reaction temperature, etc., but is preferably in the range of about 1 to 50 hours.
  • the reaction in the third step is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
  • the reaction of the third step can be stopped by adding water.
  • the amount of water added is preferably in the range of 1 to 100-fold mol with respect to the basic substance to be used. From the viewpoint of ease of post-treatment, A range of ⁇ 50 times mol is more preferable.
  • the method for carrying out the third step is not particularly limited, but a basic substance and a solvent are charged into the reactor, and this mixture is mixed with an epoxy derivative (4) under a desired reaction temperature and a desired reaction pressure. ) Is preferably added slowly.
  • Separation and purification of the alcohol derivative (2) from the reaction mixture obtained by the above method can be performed by methods generally used for separation of organic compounds such as solvent extraction and distillation, and further recrystallization and distillation. The purity can be improved by a method generally used for purification of organic compounds such as sublimation.
  • Specific examples of the alcohol derivative (2) of the present invention obtained in the third step are shown below, but are not particularly limited thereto.
  • the acrylic ester derivative (1) can be obtained by esterifying the alcohol derivative (2).
  • Method 1 A method of reacting an acrylic acid halide with an alcohol derivative (2) in the presence of a base.
  • Method 2 A method in which acrylic anhydrides and alcohol derivative (2) are reacted in the presence of a base.
  • Method 3 A method of reacting acrylic acid and alcohol derivative (2).
  • Method 1 Specific examples of the acrylic acid halides used in Method 1 include acrylic acid chloride, methacrylic acid chloride, 2-trifluoromethylacrylic acid chloride, acrylic acid bromide, methacrylic acid bromide, 2-trifluoromethylacrylic acid bromide and the like. Can be mentioned. Among these, acrylic acid chloride, methacrylic acid chloride, and 2-trifluoromethylacrylic acid chloride are preferable from the viewpoint of availability.
  • the amount of acrylic acid halides used is preferably in the range of 1 to 10-fold mol with respect to the alcohol derivative (2), and more preferably in the range of 1 to 5-fold mol from the viewpoint of ease of post-treatment.
  • the base used in Method 1 are not particularly limited as long as they neutralize the by-product acid.
  • pyridine 2-methylpyridine, 2-methyl-5-ethylpyridine, 2,6- Nitrogen-containing heterocyclic aromatic compounds such as dimethylpyridine; amines such as triethylamine, triethylenetetramine, triethanolamine, piperazine, diazabicyclo [2.2.2] octane; bicarbonates of alkali metals such as sodium hydrogencarbonate, etc. Is mentioned.
  • the amount of the base used is preferably in the range of 1 to 10 times by mole relative to the alcohol derivative (2), and more preferably in the range of 1 to 5 times by mole from the viewpoint of ease of post-treatment.
  • the reaction of Method 1 is carried out in the presence or absence of a solvent.
  • the solvent is not particularly limited as long as it does not inhibit the reaction.
  • saturated hydrocarbon solvents such as hexane, heptane, and cyclohexane
  • aromatic hydrocarbon solvents such as benzene, toluene, and xylene
  • methylene chloride, dichloroethane, and benzene chloride such as methylene chloride, dichloroethane, and benzene chloride.
  • Chlorinated hydrocarbon solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, and furan; nitrile solvents such as acetonitrile and benzonitrile; ester solvents such as methyl acetate, ethyl acetate, and propyl acetate; 2-butanone, 4-methyl- Examples thereof include ketone solvents such as 2-pentanone.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types. When carried out in the presence of a solvent, the amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the alcohol derivative (2). From the viewpoint of ease of post-treatment, 0.5 to 20 A range of mass times is more preferable.
  • a polymerization inhibitor can be used to prevent polymerization.
  • polymerization inhibitors include phenolic polymerization inhibitors such as hydroquinone and p-methoxyphenol; N, N′-diisopropyl-p-phenylenediamine, N, N′-di-2-naphthyl-p-phenylenediamine, N Amine polymerization inhibitors such as -phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine; 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamide And N-oxyl polymerization inhibitors such as -2,2,6,6-tetramethylpiperidine-N-oxyl.
  • a polymerization inhibitor can be used alone or in combination of two or more. When a polymerization inhibitor is used, the amount used is not particularly limited and may be determined as appropriate.
  • Method 1 can also be carried out by adding an activator such as 4-dimethylaminopyridine.
  • the reaction temperature in Method 1 varies depending on the types of the alcohol derivative (2) and acrylic acid halides and the presence or absence of the use of an activator, but is generally preferably in the range of ⁇ 50 to 100 ° C., from the viewpoint of reaction rate and polymerization inhibition. A range of ⁇ 30 to 80 ° C. is more preferable.
  • the reaction pressure is not particularly limited, but it is usually preferable to carry out the reaction under normal pressure.
  • the reaction time in Method 1 varies depending on the type, amount used, reaction temperature, etc. of the base, alcohol derivative (2) and acrylic acid halide, but is preferably in the range of about 1 to 50 hours. Method 1 is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
  • the method for carrying out method 1 is not particularly limited, but the reactor is charged with the alcohol derivative (2), a base, and optionally a solvent, a polymerization inhibitor, and an activator.
  • a method of dropping acrylic acid halides at a temperature and a desired reaction pressure is preferred.
  • Acrylic anhydrides used in Method 2 include acrylic anhydride, methacrylic anhydride, 2-trifluoromethylacrylic anhydride, acrylic pivalic anhydride, pivalic anhydride methacrylic acid, Examples include 2-trifluoromethylacrylic acid pivalic acid anhydride, acrylic acid methanesulfonic acid anhydride, methacrylic acid methanesulfonic acid anhydride, and 2-trifluoromethylacrylic acid methanesulfonic acid anhydride.
  • the amount of acrylic anhydride used is preferably in the range of 1 to 10 times mol, more preferably in the range of 1 to 5 times mol for the alcohol derivative (2), from the viewpoint of ease of post-treatment.
  • Examples of the base used in Method 2 include the same bases as those exemplified in Method 1.
  • a base may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the amount of the base used is preferably in the range of 1 to 10 times by mole relative to the alcohol derivative (2), and more preferably in the range of 1 to 5 times by mole from the viewpoint of ease of post-treatment.
  • Method 2 is carried out in the presence or absence of a solvent.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the diene derivative (5), and from the viewpoint of ease of post-treatment, 0.5 to 20 masses. A range of double is more preferable.
  • a polymerization inhibitor can be used to prevent polymerization.
  • the polymerization inhibitor include the same polymerization inhibitors as those exemplified in Method 1.
  • a polymerization inhibitor can be used alone or in combination of two or more. When a polymerization inhibitor is used, the amount used is not particularly limited and may be determined as appropriate.
  • Method 2 can also be carried out by adding an activating agent such as 4-dimethylaminopyridine.
  • the reaction temperature in Method 2 varies depending on the type of the alcohol derivative (2) and the acrylic anhydride and the presence or absence of an activator, but is generally preferably in the range of ⁇ 50 to 100 ° C. From the reaction rate and polymerization inhibition, A range of 30 to 80 ° C. is more preferable.
  • the reaction pressure is not particularly limited, but it is usually preferable to carry out the reaction under normal pressure.
  • the reaction time in Method 2 varies depending on the type and amount of the base, alcohol derivative (2) and acrylic anhydride, the reaction temperature, etc., but is preferably in the range of about 1 to 50 hours. Method 2 is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
  • the acrylic acid used in Method 3 is acrylic acid, methacrylic acid or 2-trifluoromethyl acrylic acid.
  • the amount of acrylic acid used is preferably in the range of 1 to 50 times mol, more preferably in the range of 1 to 20 times mol for the alcohol derivative (2), from the viewpoint of ease of post-treatment.
  • an acid catalyst is usually used.
  • the acid catalyst include solid acid catalysts such as sulfuric acid, p-toluenesulfonic acid monohydrate, and acidic ion exchange resins.
  • the amount used is preferably in the range of 0.001 to 2 moles, more preferably in the range of 0.01 to 1 moles, relative to the alcohol derivative (2).
  • the amount used may be appropriately set according to the amount used of the alcohol derivative (2).
  • a polymerization inhibitor can be used to prevent polymerization.
  • the polymerization inhibitor include the same polymerization inhibitors as those exemplified in Method 1.
  • a polymerization inhibitor can be used alone or in combination of two or more. When a polymerization inhibitor is used, the amount used is not particularly limited and may be determined as appropriate.
  • the reaction temperature in Method 3 varies depending on the type of the alcohol derivative (2) and the acrylic acid, but is generally preferably in the range of 30 to 150 ° C, more preferably in the range of 50 to 100 ° C.
  • the reaction pressure is not particularly limited, but it is usually preferable to carry out the reaction under normal pressure.
  • the reaction time in Method 3 varies depending on the type and amount of the base, alcohol derivative (2) and acrylic acid, the reaction temperature, etc., but is preferably in the range of about 1 to 50 hours.
  • Method 3 Since the reaction in Method 3 is an equilibrium reaction, it is preferable to carry out the reaction while removing by-product water from the reaction system in order to sufficiently proceed the reaction.
  • a method of removing water for example, a method of removing water from an apparatus such as a decanter using a solvent that forms an azeotrope with water such as hexane or toluene, or a water adsorbent such as molecular sieves is used. The method etc. are mentioned.
  • Separation and purification of the acrylate derivative (1) from the reaction mixture obtained in the above-mentioned method 1, 2 or 3 can be carried out by methods generally used for separation of organic compounds such as solvent extraction and distillation. Further, it is possible to improve the purity by a method generally used for purification of organic compounds such as recrystallization, distillation, sublimation and the like.
  • Polymer compound A polymer obtained by polymerizing the acrylic ester derivative (1) of the present invention alone or a copolymer obtained by copolymerizing the acrylic ester derivative (1) with another polymerizable compound is used for a photoresist composition. It is useful as a high molecular compound.
  • Specific examples of other polymerizable compounds hereinafter referred to as copolymerization monomers that can be copolymerized with the acrylate derivative (1) include compounds represented by the following chemical formulas. However, it is not particularly limited to these.
  • R 12 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 13 represents a polymerizable group
  • R 14 represents a hydrogen atom or —COOR 15
  • R 15 represents an alkyl group having 1 to 3 carbon atoms
  • R 16 represents an alkyl group.
  • Examples of the alkyl group having 1 to 3 carbon atoms that R 12 and R 15 each independently represent in the comonomer include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • Examples of the alkyl group represented by R 16 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, and a t-butyl group.
  • Examples of the polymerizable group represented by R 13 include an acryloyl group, a methacryloyl group, a vinyl group, and a crotonoyl group.
  • the polymer compound can be produced by radical polymerization according to a conventional method.
  • a method for synthesizing a polymer compound having a small molecular weight distribution includes living radical polymerization.
  • a general radical polymerization method includes a radical polymerization initiator and a solvent, and, if necessary, one or more kinds of acrylic ester derivatives (1) and, if necessary, one or more kinds of the above copolymerization monomers. Accordingly, the polymerization is carried out in the presence of a chain transfer agent.
  • the method for carrying out radical polymerization is not particularly limited, and conventional methods such as those used in the production of acrylic polymer compounds such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization can be used.
  • radical polymerization initiator examples include hydroperoxide compounds such as t-butyl hydroperoxide and cumene hydroperoxide; di-t-butyl peroxide, t-butyl- ⁇ -cumyl peroxide, di- ⁇ -cumyl peroxide and the like.
  • examples thereof include dialkyl peroxide compounds; diacyl peroxide compounds such as benzoyl peroxide and diisobutyryl peroxide; azo compounds such as 2,2′-azobisisobutyronitrile and dimethyl-2,2′-azobisisobutyrate.
  • the amount of radical polymerization initiator used can be appropriately selected according to the polymerization conditions such as the acrylate derivative (1), copolymerization monomer, chain transfer agent, solvent used and the polymerization temperature used in the polymerization reaction. Is the total amount of all polymerizable compounds [acrylic ester derivative (1) and comonomer, and so on. In general, the range is 0.005 to 0.2 mol, and more preferably 0.01 to 0.15 mol, relative to 1 mol.
  • chain transfer agent examples include thiol compounds such as dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, and mercaptopropionic acid.
  • thiol compounds such as dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, and mercaptopropionic acid.
  • its use amount is usually preferably in the range of 0.005 to 0.2 mol, more preferably in the range of 0.01 to 0.15 mol, relative to 1 mol of all polymerizable compounds. preferable.
  • the solvent is not particularly limited as long as it does not inhibit the polymerization reaction.
  • propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene Glycol ethers such as glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether; esters such as ethyl lactate, methyl 3-methoxypropionate, methyl acetate, ethyl acetate, propyl acetate; acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone , Methyl amyl ketone, cyclopentanone, cyclohexa Ketones, such as emissions diethyl ether, diisopropyl ether, dibuty
  • the polymerization temperature is usually from 40 to 150 ° C., and preferably from 60 to 120 ° C. from the viewpoint of the stability of the polymer compound produced.
  • the time for the polymerization reaction varies depending on the polymerization conditions such as the acrylate derivative (1), the comonomer, the polymerization initiator, the type and amount of the solvent used, and the temperature of the polymerization reaction, but usually 30 minutes to 48 hours. The range of 1 hour to 24 hours is more preferable.
  • the polymer compound thus obtained can be isolated by ordinary operations such as reprecipitation.
  • the isolated polymer compound can be dried by vacuum drying or the like.
  • the solvent used in the reprecipitation operation include aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene and xylene; methylene chloride, chloroform, chlorobenzene, dichlorobenzene, and the like.
  • Nitrogenated hydrocarbons such as nitromethane; Nitriles such as acetonitrile and benzonitrile; Ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and 1,4-dioxane; Ketones such as acetone and methyl ethyl ketone; Carboxyls such as acetic acid Acid; Esters such as ethyl acetate and butyl acetate; Carbonates such as dimethyl carbonate, diethyl carbonate, and ethylene carbonate; Methanol, ethanol, propanol, isopropyl alcohol Include water; alcohols such as butanol.
  • a photoresist composition is prepared by blending the polymer compound, an organic solvent and a photoacid generator, and a basic compound and additives as necessary.
  • a photoacid generator a photoacid generator conventionally used for a chemically amplified resist can be used.
  • a surfactant, a sensitizer, an antihalation agent, a shape improver, a storage stabilizer, an antifoaming agent, and the like can be added to the photoresist composition.
  • First step (first step-1) 217.2 g (2.400 mol) of acryloyl chloride and 520 g of toluene were charged into a 3 L flask having an internal volume of 2 L equipped with a thermometer, a stirrer, a nitrogen introducing tube and a dropping funnel, and the internal temperature was cooled to 0 ° C.
  • 190.4 g (2.880 mol) of cyclopentadiene was added dropwise from the dropping funnel over 1 hour. After completion of dropping, the mixture was stirred at 0 ° C. for 1 hour to prepare a reaction intermediate solution.
  • the obtained organic layer was concentrated under reduced pressure to obtain a concentrate.
  • 750 ml of ethyl acetate and 250 ml of hexane were added to the concentrate and heated to 40 ° C. to dissolve the concentrate.
  • the precipitated crystals were collected by filtration.
  • the obtained crystals were dried under reduced pressure, and 124.3 g (0.643 mol; yield 26.8%) of Nt-butylbicyclo [2.2.1] hept-5-ene-2-carboxamide having the following characteristics: Got.
  • Example 2 Second Step An Nt-butylbicyclo [2.2.1] hepta-5 was placed in a 3 L three-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a dropping funnel. En-2-carboxamide 50.0 g (0.259 mol), methylene chloride 250 g, potassium carbonate 121.6 g (0.880 mol) and water 550 g were charged, and the internal temperature was cooled to 0 ° C. To this mixture, 75.9 g (0.440 mol) of m-chloroperbenzoic acid and 1559 g of methylene chloride were added dropwise from a dropping funnel over 20 minutes. After stirring at 0-7 ° C.
  • Example 3 Third Step 61.0 g (0.544 mol) of potassium tert-butoxide and 1045 g of tert-butanol were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet tube. The temperature was raised to 50 ° C. To this mixed solution, 56.9 g (0.272 mol) of Nt-butyl-5,6-epoxybicyclo [2.2.1] hept-2-carboxamide was added over 1 hour. Subsequently, after the internal temperature was cooled to 25 ° C., 620 g of 3.9 mass% hydrochloric acid and 1900 ml of ethyl acetate were added and stirred for 30 minutes.
  • the organic layer was washed twice with 400 ml of water.
  • the obtained organic layer was concentrated under reduced pressure to obtain a concentrate.
  • 30 g of methanol and 820 g of diisopropyl ether were added to the resulting concentrate, and the internal temperature was raised to 50 ° C. to dissolve the concentrate.
  • the precipitated crude crystals were collected by filtration. 200 g of ethyl acetate and 200 g of diisopropyl ether were added to the obtained crude crystals, and the internal temperature was raised to 50 ° C. to dissolve the crude crystals.
  • the monomer (2) was synthesized by the method shown below. (Synthesis of monomer (2)) In a three-necked flask with an internal volume of 500 ml, under a nitrogen atmosphere, 20 g (105.14 mmol) of alcohol, 30.23 g (157.71 mmol) of ethyldiisopropylaminocarbodiimide hydrochloride and 0.6 g of dimethylaminopyridine shown in the following chemical reaction formula 300 ml of a tetrahydrofuran (THF) solution of (5 mmol) was added.
  • THF tetrahydrofuran
  • the mixed solution thus obtained was added dropwise over 3 hours to 67.00 g of methyl ethyl ketone [67.1 g (255.73 mmol) of monomer (3) dissolved in advance] heated to 80 ° C. in a nitrogen atmosphere. After completion of dropping, the reaction solution was heated and stirred for 2 hours, and then the reaction solution was cooled to room temperature.
  • the obtained polymerization solution was dropped into a large amount of n-heptane to precipitate a polymer, and the precipitated white powder was filtered off and washed successively with an n-heptane / 2-propanol mixed solvent and methanol, It was dried to obtain 65 g of polymer compound (A) -7.
  • the unit ratio (molar ratio) is shown in Table 1.
  • the obtained polymerization solution is concentrated under reduced pressure and then added dropwise to a large amount of n-heptane to precipitate a polymer.
  • the precipitated polymer is filtered, washed, and dried to obtain a fluorine-containing polymer compound (C ) -1 was obtained.
  • the fluorine-containing polymer compound (C) -1 had a weight average molecular weight (Mw) of 25000 and a molecular weight dispersity (Mw / Mn) of 1.5.
  • D) -1 Tri-n-pentylamine
  • D) -2 Triethanolamine
  • the resist film was selectively irradiated with an ArF excimer laser (193 nm).
  • a post-exposure baking (PEB) treatment is performed at 95 ° C. for 60 seconds
  • an alkali development treatment is further performed at 23 ° C. with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 10 seconds, and then pure water is used.
  • water rinsing was performed for 30 seconds, followed by shaking off and drying.
  • the resist compositions 1 to 10 obtained by using the acrylic ester derivative (1) according to the present invention are better in both DOF and LWR than the resist compositions 11 to 14 that are not. It was confirmed that a resist pattern having excellent lithography characteristics and a good shape can be formed.
  • the resist compositions 16 to 24 obtained by using the acrylate derivative (1) according to the present invention have a good CDU and roundness compared to the resist compositions 25 to 28 which are not. Therefore, it was confirmed that a resist pattern having excellent lithography characteristics and a good shape can be formed.
  • the acrylic ester derivative (1) of the present invention has excellent lithography properties and is useful as a raw material for a polymer compound for a resist composition that forms a resist pattern having a good shape.
  • the alcohol derivative (2) of the present invention is useful as a synthetic intermediate for the acrylate derivative (1).

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Abstract

La présente invention concerne un dérivé d'ester acrylique convenant comme produit de départ d'un composé macromoléculaire destiné à une composition de produit d'épargne servant à former un motif d'épargne présentant une forme favorable et doté de propriétés lithographiques supérieures. L'invention concerne également un intermédiaire du dérivé d'ester acrylique (dérivé d'alcool), et un procédé de production de ce dérivé d'ester acrylique et de l'intermédiaire du dérivé d'ester acrylique. L'invention concerne plus particulièrement le dérivé d'ester acrylique représenté par la formule jointe. Dans cette formule, R1 est atome d'hydrogène, groupe méthyle ou groupe trifluorométhyle. R2, R3, R5, R7, R8, R9, et R10 sont chacun indépendamment atome d'hydrogène, groupe alkyle en C1-C6, groupe cycloalkyle en C3-C6, ou groupe alcoxy en C1-C6. R4, et R6 sont chacun indépendamment atome d'hydrogène, groupe alkyle en C1-C6, groupe cycloalkyle en C3-C6, ou groupe alcoxy en C1-C6, ou autrement, R4, et R6 forment ensemble un groupe alkylène en C1-C3, ou sont -O-, ou -S-. R1 est atome d'hydrogène, groupe alkyle en C1-C6, ou groupe hydrocarbure cyclique en C3-C10.
PCT/JP2010/066254 2010-09-17 2010-09-17 Dérivé d'ester acrylique, dérivé d'alcool, et procédé de production correspondant WO2012035666A1 (fr)

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PCT/JP2010/066254 WO2012035666A1 (fr) 2010-09-17 2010-09-17 Dérivé d'ester acrylique, dérivé d'alcool, et procédé de production correspondant

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012197382A (ja) * 2011-03-22 2012-10-18 Kuraray Co Ltd アクリル酸エステル誘導体、高分子化合物およびフォトレジスト組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0841133A (ja) * 1994-05-31 1996-02-13 Ucb Sa 放射線硬化性組成物
JP2005024646A (ja) * 2003-06-30 2005-01-27 Fuji Photo Film Co Ltd 樹脂組成物、及び平版印刷版原版
JP2009079091A (ja) * 2007-09-25 2009-04-16 Fujifilm Corp 光硬化性コーティング組成物、オーバープリント及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0841133A (ja) * 1994-05-31 1996-02-13 Ucb Sa 放射線硬化性組成物
JP2005024646A (ja) * 2003-06-30 2005-01-27 Fuji Photo Film Co Ltd 樹脂組成物、及び平版印刷版原版
JP2009079091A (ja) * 2007-09-25 2009-04-16 Fujifilm Corp 光硬化性コーティング組成物、オーバープリント及びその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012197382A (ja) * 2011-03-22 2012-10-18 Kuraray Co Ltd アクリル酸エステル誘導体、高分子化合物およびフォトレジスト組成物

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