WO2009107327A1 - 電子吸引性置換基及びラクトン骨格を含む単量体、高分子化合物及びフォトレジスト組成物 - Google Patents
電子吸引性置換基及びラクトン骨格を含む単量体、高分子化合物及びフォトレジスト組成物 Download PDFInfo
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- WO2009107327A1 WO2009107327A1 PCT/JP2009/000402 JP2009000402W WO2009107327A1 WO 2009107327 A1 WO2009107327 A1 WO 2009107327A1 JP 2009000402 W JP2009000402 W JP 2009000402W WO 2009107327 A1 WO2009107327 A1 WO 2009107327A1
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- 0 NC1*CC*C1 Chemical compound NC1*CC*C1 0.000 description 7
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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
- 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
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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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
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0275—Photolithographic processes using lasers
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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
- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
Definitions
- the present invention relates to a photoresist monomer, a polymer compound, a photoresist composition, and a semiconductor manufacturing method using the photoresist composition, which are used when fine processing of a semiconductor is performed.
- a conventional novolac or styrene resin was used, but the wavelength of the ArF excimer laser is 193 nm, which is even shorter, and aromatic such as a novolac or styrene resin.
- aromatic such as a novolac or styrene resin.
- the structure of the resin was replaced with an alicyclic one that does not contain aromatics.
- the resin used is mainly acrylic, and applies a mechanism in which acrylic acid is protected with a protecting group, and the protecting group is eliminated by an acid generated by exposure to form a carboxylic acid, which becomes alkali-soluble.
- the object of the present invention is to maintain stability such as chemical resistance when applied to a resist resin and the like, while having excellent solubility in an organic solvent, hydrolyzability and / or solubility in water after hydrolysis.
- An object of the present invention is to provide a monomer containing a novel lactone skeleton useful as a monomer component such as a high-functional polymer that can be improved, a resin thereof, a composition for photoresist, and a method for producing a semiconductor.
- a further object of the present invention is to provide a resin exhibiting high etching resistance when used as a resin for a photoresist, and to provide a photoresist resin and its composition, particularly used in immersion exposure. is there.
- R a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms
- R 1 represents a substituent bonded to the ring
- An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms which may have a hydroxyl group part protected with a protecting group and may have a halogen atom
- A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a non-bond
- m represents the number of R 1 .
- X represents an electron-withdrawing substituent
- n represents the number of X bonded to the ring
- Y represents a carbon number of 1 to 6.
- the present invention also provides the following formula (I) (Wherein, R a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, R 1 represents a substituent bonded to the ring, An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms which may have a hydroxyl group part protected with a protecting group and may have a halogen atom An alkyl group, a carboxyl group that may form a salt, or a substituted oxycarbonyl group, A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a non-bond, and m represents the number of R 1 .
- R a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms
- R 1 represents
- X represents an electron-withdrawing substituent
- n represents the number of X bonded to the ring
- Y represents a carbon number of 1 to 6.
- a divalent organic group of —COO—Y—C bonded to a polymer chain Three-dimensional position of O- group may be either end, exo)
- the polymer compound which has at least the monomer unit represented by these is provided.
- the polymer compound may further have at least a monomer unit that is eliminated by the action of an acid and becomes alkali-soluble.
- Monomer units that are eliminated by the action of an acid and become alkali-soluble include the following formulas (IIa) to (IId):
- ring Z 1 represents an optionally substituted alicyclic hydrocarbon ring having 5 to 20 carbon atoms.
- Ra represents a hydrogen atom, a halogen atom, or a substituent.
- R 6 and R 7 are the same or different and each represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R 8 being A hydrogen atom or an organic group, at least two of R 6 , R 7 and R 8 may be bonded to each other to form a ring with adjacent atoms) A monomer unit selected from is included.
- the polymer compound may further include at least a monomer unit containing an alicyclic skeleton having at least one substituent.
- the monomer unit containing an alicyclic skeleton having at least one substituent has the following formula (III) (In the formula, ring Z 2 represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms. Ra represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms.
- R 9 is a substituent bonded to ring Z 2 and is the same or different and is an oxo group, an alkyl group, a haloalkyl group, a halogen atom, a hydroxyl group optionally protected by a protecting group, a protected group A hydroxyalkyl group optionally protected with a group, a mercapto group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, an amino group optionally protected with a protecting group, or a protection A sulfonic acid group which may be protected by a group, q is the number of R 9 and represents an integer of 1 to 5) A monomer unit selected from is included.
- the polymer compound includes at least one monomer unit represented by the formula (I), a monomer unit that becomes alkali-soluble by the action of an acid, and a substituent selected from a hydroxyl group and a hydroxymethyl group. And at least a monomer unit containing an alicyclic skeleton.
- the polymer compound may further have at least a monomer unit having a lactone skeleton other than the monomer unit represented by the formula (I).
- the present invention further provides a photoresist composition comprising at least the above-described polymer compound and a photoacid generator.
- the present invention further provides a method for producing a semiconductor, characterized in that a pattern is formed using the photoresist composition.
- the present invention further provides the following formula (6): (Wherein R 1 is a substituent bonded to the ring, and a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxyl group moiety is protected with a protecting group. And a hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom, a carboxyl group which may form a salt, or a substituted oxycarbonyl group, A is a group having 1 to 6 carbon atoms. Represents an alkylene group, an oxygen atom, a sulfur atom or a non-bond, m represents the number of R 1 , and represents an integer of 0 to 8.
- X represents an electron-withdrawing substituent
- n represents X bonded to the ring.
- And is an integer of 1 to 9.
- Z is a chlorine atom, bromine atom or iodine atom
- Y is a divalent organic group having 1 to 6 carbon atoms
- Z—Y—COO— The three-dimensional position may be either end or exo
- the halogen-containing lactone compound represented by these is provided.
- the present invention further provides the following formula (6): (Wherein R 1 is a substituent bonded to the ring, and a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxyl group moiety is protected with a protecting group. And a hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom, a carboxyl group which may form a salt, or a substituted oxycarbonyl group, A is a group having 1 to 6 carbon atoms. Represents an alkylene group, an oxygen atom, a sulfur atom or a non-bond, m represents the number of R 1 , and represents an integer of 0 to 8.
- X represents an electron-withdrawing substituent
- n represents X bonded to the ring. And is an integer of 1 to 9.
- Z is a chlorine atom, bromine atom or iodine atom
- Y is a divalent organic group having 1 to 6 carbon atoms
- Z—Y—COO— The three-dimensional position may be either end or exo
- a halogen-containing lactone compound represented by the following formula (7) In the formula, Ra represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms
- M represents a hydrogen atom, an alkali metal, or an alkaline earth metal.
- R a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms
- R 1 represents a substituent bonded to the ring
- An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms which may have a hydroxyl group part protected with a protecting group and may have a halogen atom
- A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a non-bond
- m represents the number of R 1 .
- X represents an electron-withdrawing substituent
- n represents the number of X bonded to the ring
- Y represents a carbon number of 1 to 6.
- a monomer having a polycyclic ester group containing a novel lactone skeleton which is useful as a monomer component of a high-functional polymer compound capable of improving the viscosity, a resin thereof, a photoresist composition, and a method for producing a semiconductor Is done.
- the monomer containing a lactone skeleton of the present invention has a drastic improvement in solubility in an alkali developer by introducing an electron-withdrawing substituent into a polycyclic skeleton containing a lactone skeleton, thereby producing a semiconductor. This makes it possible to draw clearer patterns.
- R a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms
- R 1 represents a ring [6-oxabicyclo [3.2.
- A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a non-bond.
- m is the number of R 1 and represents an integer of 0 to 8.
- X is an electron-withdrawing substituent
- n is a ring [6-oxabicyclo [3.2.1 1,5 ] octane ring (A is Non-bonded)
- the number of X bonded to the 3-oxatricyclo [4.2.1.0 4,8 ] nonane ring when A is a methylene group
- Y represents a divalent organic group having 1 to 6 carbon atoms, and the steric position of the CH 2 ⁇ C (R a ) COO—Y—COO— group may be either endo or exo.
- X represents an electron-withdrawing substituent
- examples of the electron-withdrawing group include a halogen atom such as a fluorine atom, a halogenated hydrocarbon group such as a trifluoromethyl group, an alkoxy such as a carboxyl group and a methoxycarbonyl group.
- Aryloxycarbonyl groups such as carbonyl group and phenoxycarbonyl group, acyl groups such as acetyl group, acyloxy groups such as acetoxy group, cyano group, aryl group, 1-alkenyl group, nitro group, sulfo group, alkanesulfonyl group, alkanesulfinyl Group, alkoxysulfonyl group and the like.
- fluorine atom-containing groups such as fluorine atoms and trifluoromethyl groups
- acyloxy groups such as acetoxy groups, cyano groups, nitro groups, sulfo groups, alkanesulfonyl groups, alkanesulfinyl groups, and alkoxysulfonyl groups are electron withdrawing. Is strong, and high hydrolyzability of the lactone ring and high solubility in water after hydrolysis of the polymer compound containing the lactone ring are preferable.
- the halogen atoms as R a and R 1 described in the formula (1) include, for example, fluorine, chlorine, bromine atoms and the like.
- Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups.
- a C 1-4 alkyl group, particularly a methyl group is preferable.
- alkyl group having 1 to 6 carbon atoms having a halogen atom examples include chloroalkyl groups such as chloromethyl group; fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl groups ( Preferably, a C1-3 fluoroalkyl group) etc. are mentioned.
- alkyl group having 1 to 6 carbon atoms having a substituent in R a include the aforementioned alkyl group having 1 to 6 carbon atoms having a halogen atom.
- Examples of the hydroxyalkyl group having 1 to 6 carbon atoms in R 1 include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, and 6-hydroxyhexyl groups.
- Examples of the C1-C6 hydroxyalkyl group having a halogen atom include difluorohydroxymethyl, 1,1-difluoro-2-hydroxyethyl, 2,2-difluoro-2-hydroxyethyl, 1,1,2, And 2-tetrafluoro-2-hydroxyethyl group.
- hydroxyalkyl groups having 1 to 6 carbon atoms which may have a halogen atom
- a hydroxyalkyl group or hydroxyhaloalkyl group having 1 or 2 carbon atoms (particularly 1 carbon atom) is preferable.
- Examples of the protecting group for the hydroxyl group of a hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom include protecting groups usually used as a protecting group for a hydroxyl group in the field of organic synthesis, such as methyl group, methoxy group
- Examples include groups that form an ether or acetal bond with an oxygen atom that constitutes a hydroxyl group such as a methyl group; groups that form an ester bond with an oxygen atom that constitutes a hydroxyl group such as an acetyl group or a benzoyl group.
- Examples of the carboxyl group salt include alkali metal salts, alkaline earth metal salts, and transition metal salts.
- Examples of the substituted oxycarbonyl group include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, propoxycarbonyl group (C 1-4 alkoxy-carbonyl group, etc.); vinyloxycarbonyl, allyloxycarbonyl group, etc. Examples thereof include alkenyloxycarbonyl groups (C 2-4 alkoxy-carbonyl groups and the like); cycloalkyloxycarbonyl groups such as cyclohexyloxycarbonyl groups; aryloxycarbonyl groups such as phenyloxycarbonyl groups and the like.
- R a is preferably a hydrogen atom, a C 1-3 alkyl group such as a methyl group, or a C 1-3 haloalkyl group such as a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
- R 1 is an alkyl group having 1 to 3 carbon atoms such as a methyl group or a trifluoromethyl group or a haloalkyl group, a hydroxyalkyl group having 1 to 3 carbon atoms in which the hydroxy moiety may be protected with a protecting group, or A hydroxyhaloalkyl group (particularly a hydroxymethyl group which may be protected with a protective group such as a hydroxymethyl group or an acetoxymethyl group), a substituted oxycarbonyl group or the like is preferred.
- n is 1 to 9, preferably 1 to 5, and more preferably 1 or 2.
- X is plural, they may be the same or different.
- the position of the electron-withdrawing group X is not particularly limited, but is preferably directly connected to the lactone ring, and particularly preferably directly connected to the ⁇ -position of the carbonyl group of the lactone ring. Directly connected means that the electron-withdrawing group X is directly bonded to the carbon atom constituting the 5-membered ring of the lactone.
- the electron-withdrawing group X When the electron-withdrawing group X is bonded to the lactone ring via one or more atoms, the effect of the electron-withdrawing group is reduced, and the hydrolytic properties of the lactone ring and the high The solubility in water after hydrolysis of the molecular compound is lowered.
- the substituent X When A is non-bonded, the substituent X is located at the 1-position, 2-position, 3-position, 4-position, 5-position, or 8-position of the 6-oxabicyclo [3.2.1 1,5 ] octane ring. Although they may be bonded, the 1-position ( ⁇ position of the lactone) or the 2-position is preferable, and the 1-position ( ⁇ position of the lactone) is particularly preferable.
- the substituent X is the 1-position of a 3-oxatricyclo [4.2.1.0 4,8 ] nonane ring or the like.
- the 3-oxatricyclo [4.2.1.0 4,8 ] nonane ring may be bonded to any position such as 4-position, 5-position, 6-position, 7-position, 8-position, and 9-position.
- 1-position or 9-position (or a position corresponding thereto) is preferable, and the 1-position (or a position corresponding thereto; ⁇ -position of lactone) is particularly preferable.
- A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond
- examples of the alkylene group having 1 to 6 carbon atoms include a methylene group and an alkyl group which may be substituted with an alkyl group.
- A is preferably an alkylene group having 1 to 6 carbon atoms or a non-bond.
- Y represents a divalent organic group having 1 to 6 carbon atoms.
- the divalent organic group include alkylene groups such as methylene, ethylene, propylene and butylene (particularly C 1-6 alkylene group); alkenylene groups such as vinylene (particularly C 2-6 alkenylene group); cyclopentylene, A cycloalkenylene group such as a cyclohexylene group; two or more of these are bonded via a linking group such as an ether bond (—O—), a thioether bond (—S—), or an ester bond (—COO—; —OCO—) And divalent organic groups.
- methylene, ethylene, propylene, or a group in which a C 1-3 alkylene group and a C 1-2 alkylene group are bonded via an ester bond is preferable.
- a halogen atom particularly a fluorine atom are also useful.
- a in the corresponding formula (1) is an alkylene group other than a methylene group, an oxygen atom or a sulfur atom
- R represents a CH 2 ⁇ C (R a ) COO—Y—CO— group
- Ac represents an acetyl group
- X which is a substituent shows an electron-withdrawing substituent.
- reaction route For the method of synthesizing a monomer having an electron-withdrawing substituent represented by the formula (1) and a lactone skeleton, the reaction route is shown by the following formula.
- a polycyclic alcohol containing a lactone skeleton represented by the formula (5) (6-oxabicyclo [3.2.1 1,5 ] octane-7-one derivative substituted with X, 3-oxa-substituted 3-oxa Tricyclo [4.2.1.0 4,8 ] nonan-2-one derivatives and the like) and a carboxylic acid chloride having a Y group substituted with a chlorine atom represented by the formula (4),
- This reaction is preferably performed using an organic solvent (for example, acetonitrile or the like).
- reaction temperature is, for example, about ⁇ 30 ° C. to 100 ° C.
- amount of the compound represented by formula (4) to be used is, for example, about 0.8 to 10 mol with respect to 1 mol of the compound represented by formula (5).
- the obtained intermediate (6) reacts with the unsaturated carboxylic acid represented by the formula (7), or an alkali metal salt or alkaline earth metal salt thereof [(meth) acrylic acid etc.] to give an electron withdrawing property. It is led to the monomer (1) having a substituent and a lactone skeleton.
- This reaction is preferably performed in a solution or suspension state using an organic solvent (for example, N, N-dimethylformamide and the like).
- the hydrogen chloride produced as a by-product of the reaction is preferably reacted with dehydrochlorination by allowing a base to exist in the reaction system.
- the base include alkali metal carbonates or bicarbonates such as potassium carbonate, sodium carbonate, and sodium bicarbonate.
- halogen exchange agents such as alkali metal halides, such as sodium iodide, potassium iodide, sodium bromide, potassium bromide.
- the reaction temperature is, for example, about ⁇ 10 ° C. to 100 ° C.
- Unsaturated carboxylic acid, its alkali metal salt, or alkaline-earth metal salt may be used independently, and may be used in combination of 2 or more type.
- the total amount of the unsaturated carboxylic acid represented by the formula (7) or the alkali metal salt or alkaline earth metal salt thereof is, for example, 0.8 mol with respect to 1 mol of the compound represented by the formula (6).
- the halogen atom as R a described in the formula (7) includes, for example, a fluorine, chlorine, bromine atom and the like.
- alkyl group having 1 to 6 carbon atoms having a substituent in R a include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl groups and the like.
- a C 1-4 alkyl group, particularly a methyl group is preferable.
- alkyl group having 1 to 6 carbon atoms having a halogen atom examples include chloroalkyl groups such as chloromethyl group; fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl groups ( Preferably, a C1-3 fluoroalkyl group) etc. are mentioned.
- alkali metal as M described in the formula (7) examples include lithium, sodium, potassium, and the like.
- alkaline earth metals as M include beryllium, magnesium and calcium.
- Typical examples of the alkali metal salt of the unsaturated carboxylic acid represented by the formula (7) include sodium methacrylate and sodium acrylate.
- Typical examples of the alkaline earth metal salt of the unsaturated carboxylic acid represented by the formula (7) magnesium methacrylate, magnesium acrylate, and the like can be given.
- the above Z is chlorine, bromine or iodine. Among these, iodine and bromine are more preferable because of high reactivity.
- the compound represented by the formula (1) (a monomer having an electron-withdrawing substituent and a lactone skeleton) can also be produced via the intermediate (6).
- the halogen-containing lactone compound as an intermediate represented by the formula (6) may be used as it is, or halogen exchange is performed in the reaction system to convert it into a more reactive bromine or iodine-containing lactone. The reaction may be carried out.
- the intermediate represented by formula (6) and the compound represented by formula (1) (monomer having an electron-withdrawing substituent and a lactone skeleton) generated by the reaction are filtered, concentrated, distilled, extracted, for example. Can be separated and purified by separation means such as crystallization, recrystallization, column chromatography, or a combination thereof.
- the compound represented by Formula (5) can be manufactured according to the following reaction process formula, for example.
- R 1a is a substituent bonded to a diene chain or a cyclopentadiene ring, and is a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxyl group portion as a protecting group.
- R 1b is a substituent bonded to a carbon atom constituting a carbon-carbon double bond, and is a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxyl group moiety.
- R b represents a hydrogen atom or an organic group (for example, a C 1-4 alkyl group such as a methyl group).
- i is the number of R 1a and represents an integer of 0-6.
- j is the number of R 1b and represents an integer of 0 to 3.
- At least one of i R 1a and j R 1b is an electron-withdrawing substituent.
- a and X are the same as described above.
- the meanings, specific examples, and preferred examples (ranges) of R 1 , m, and n are the same as described above.
- it is preferable that at least one of j R 1b in the formula (9) is an electron-withdrawing substituent, and in particular, an electron-withdrawing substituent is bonded to the ⁇ -position of the —CO 2 R b group. Is preferred.
- a diene compound such as butadienes represented by formula (8) or a cyclopentadiene derivative and an unsaturated carboxylic acid represented by formula (9) or an ester thereof are subjected to a Diels-Alder reaction.
- a cycloaddition product such as a cyclohexene derivative or a bicyclo [2.2.1] heptan-2-ene derivative represented by the formula (10) is obtained, and this is reacted with a peracid or peroxide to give a formula (10 11)
- R b is a hydrogen atom or the like
- the compound represented by the formula (10) is cyclized immediately after epoxidation by acting a peracid or peroxide on the compound represented by the formula (5). In some cases, the compounds represented are obtained as main products.
- diene compound represented by the formula (8) when A is an oxygen atom or a sulfur atom include furan, 2-methylfuran, 3-methylfuran, 2,3-dimethylfuran, thiophene. , 2-methylthiophene, 3-methylthiophene, 2,3-dimethylthiophene and the like.
- the reaction of the compound represented by formula (8) and the compound represented by formula (9) is performed in the presence or absence of a solvent (for example, toluene and the like).
- a solvent for example, toluene and the like.
- a Lewis acid AlCl 3 etc.
- the reaction temperature is, for example, about -70 ° C to 250 ° C.
- examples of the peracid include peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, and the like.
- the amount of peracid to be used is, for example, about 0.8 to 2 mol, preferably about 0.9 to 1.5 mol, per 1 mol of the compound represented by the formula (10).
- Examples of the peroxide to be reacted with the compound represented by the formula (10) include hydrogen peroxide, peroxide, hydroperoxide, peroxo acid, peroxo acid salt, and the like.
- the amount of peroxide such as hydrogen peroxide to be used is, for example, about 0.9 to 5 mol, preferably about 0.9 to 3 mol, per 1 mol of the compound represented by the formula (10).
- the hydrogen peroxide is often used with a metal compound.
- the metal compound include oxides containing metal elements such as W, Mo, V, Mn, and Re, oxo acids or salts thereof, and peroxides. These metal compounds can be used alone or in combination of two or more.
- the oxide include composite oxides containing metal elements such as tungsten oxide, molybdenum oxide, vanadium oxide, manganese oxide, W, Mo, V, and Mn.
- Oxo acids include isopolyacids and heteropolyacids in addition to tungstic acid, molybdic acid, vanadic acid, manganic acid and the like.
- Examples of the oxo acid salt include alkali metal salts, alkaline earth metal salts, ammonium salts, and transition metal salts of the oxo acid.
- Examples of the peroxide containing a metal element include peroxo acids (for example, peroxotungstic acid, peroxomolybdic acid, peroxovanadate, etc.), salts of peroxo acids (alkali metal salts, alkaline earth metal salts of the peroxo acids, Ammonium salts, transition metal salts, etc.), peracids (permanganic acid, etc.), peracid salts (alkali metal salts, alkaline earth metal salts, ammonium salts, transition metal salts, etc. of the peracids).
- the amount of the metal compound used together with hydrogen peroxide is, for example, about 0.0001 to 2 mol, preferably about 0.0005 to 0.5 mol, relative to 1 mol of the compound represented by the formula (10). is there.
- the reaction of the compound represented by the formula (10) with a peracid or peroxide is carried out in the presence or absence of a solvent (for example, methylene chloride, water, etc.).
- a solvent for example, methylene chloride, water, etc.
- the reaction temperature is generally about ⁇ 10 to 100 ° C., preferably about 0 to 80 ° C.
- epoxidation of the double bond of the compound represented by the formula (10) occurs, and an epoxy compound represented by the formula (11) is generated.
- R b is a hydrogen atom
- an intramolecular cyclization reaction involving the opening of an epoxy ring proceeds, and electron withdrawing represented by the formula (5) is performed.
- a polycyclic alcohol containing a functional substituent and a lactone skeleton can be formed.
- R b is a hydrogen atom
- the cyclization reaction of the compound represented by the formula (11) proceeds, for example, only by dissolving the compound represented by the formula (11) in a solvent.
- R b is an organic group
- the compound represented by formula (11) is subjected to a conventional hydrolysis reaction (alkali hydrolysis reaction, acid hydrolysis reaction, neutral hydrolysis, etc.), and R b is a hydrogen atom.
- the cyclization reaction proceeds immediately to produce the compound represented by the formula (5).
- the compound represented by formula (10), the compound represented by formula (11), and the compound represented by formula (5) generated by the reaction are, for example, filtered, concentrated, distilled, extracted, crystallized, and recrystallized. Separation and purification can be performed by separation means such as column chromatography, or a combination thereof.
- the polymer compound of the present invention is a monomer unit (repeating unit) corresponding to a monomer containing an electron-withdrawing substituent represented by the above formula (1) and a lactone skeleton, that is, a monomer represented by the above formula (I) Includes units.
- the monomer unit may contain one kind or two or more kinds.
- Such a polymer compound can be obtained by subjecting a monomer containing an electron-withdrawing substituent represented by the above formula (1) and a lactone skeleton to polymerization.
- the monomer unit represented by the formula (I) has a 6-oxabicyclo [3.2.1 1,5 ] octane-7-one skeleton to which an electron withdrawing substituent is bonded, or an electron withdrawing substituent.
- units having an octan-7-one skeleton or a 3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one skeleton having no electron-withdrawing substituent Compared with units having an octan-7-one skeleton or a 3-oxatricyclo [4.2
- the polymer compound of the present invention is useful as, for example, a high-functional polymer, particularly a photoresist resin, used in a field that requires a function of changing to water solubility by a predetermined treatment.
- the polymer compound of the present invention may have other monomer units in addition to the monomer unit represented by the formula (I) according to the use and required function.
- Such another monomer unit is a copolymerization of a polymerizable unsaturated monomer corresponding to the other monomer unit with a monomer containing an electron-withdrawing substituent represented by the formula (1) and a lactone skeleton. Can be formed.
- Examples of the other monomer units include monomer units which are eliminated by the action of an acid and become alkali-soluble, for example, monomer units represented by the above formulas (IIa), (IIb), (IIc) and (IId).
- the polymerizable unsaturated monomers corresponding to the monomer units represented by the formulas (IIa), (IIb), (IIc), and (IId) are represented by the following formulas (2a), (2b), (2c), (2d).
- ring Z 1 represents an alicyclic hydrocarbon ring having 5 to 20 carbon atoms which may have a substituent.
- R a is the same as above.
- R 2 to R 4 are the same or different and each represents an alkyl group having 1 to 6 carbon atoms which may have a substituent.
- R 5 is a substituent bonded to ring Z 1 and is the same or different and is an oxo group, an alkyl group, a hydroxyl group which may be protected with a protecting group, or a hydroxy group which is protected with a protecting group.
- An alkyl group or a carboxyl group which may be protected with a protecting group is shown.
- at least one of p R 5 's represents a —COOR c group.
- R c represents a tertiary hydrocarbon group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group which may have a substituent.
- p represents an integer of 1 to 3.
- R 6 and R 7 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
- R 8 represents a hydrogen atom or an organic group. At least two of R 6 , R 7 and R 8 may be bonded to each other to form a ring with adjacent atoms.
- the alicyclic hydrocarbon ring having 5 to 20 carbon atoms in ring Z 1 may be a single ring or a polycyclic ring such as a condensed ring or a bridged ring.
- Typical alicyclic hydrocarbon rings include, for example, cyclohexane ring, cyclooctane ring, cyclodecane ring, adamantane ring, norbornane ring, norbornene ring, bornane ring, isobornane ring, perhydroindene ring, decalin ring, perhydrofluorene ring.
- the alicyclic hydrocarbon ring includes an alkyl group such as a methyl group (eg, a C 1-4 alkyl group), a halogen atom such as a chlorine atom, a hydroxyl group optionally protected by a protecting group, an oxo group, a protected group It may have a substituent such as a carboxyl group which may be protected with a group.
- the ring Z 1 is preferably a polycyclic alicyclic hydrocarbon ring (bridged hydrocarbon ring) such as an adamantane ring.
- alkyl group having 1 to 6 carbon atoms which may have a substituent in R 2 to R 4 , R 6 and R 7 in the formulas (2a), (2b) and (2d) include, for example, methyl, Linear or branched alkyl groups having 1 to 6 carbon atoms such as ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl and hexyl groups; haloalkyl having 1 to 6 carbon atoms such as trifluoromethyl group Groups and the like.
- examples of the alkyl group represented by R 5 include a straight chain such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl, and dodecyl groups. Examples thereof include branched alkyl groups having about 1 to 20 carbon atoms. Examples of the hydroxyl group that may be protected with a protecting group for R 5 include a hydroxyl group and a substituted oxy group (for example, a C 1-4 alkoxy group such as methoxy, ethoxy, propoxy group, etc.).
- Examples of the hydroxyalkyl group which may be protected with a protecting group include a group in which a hydroxyl group which may be protected with the protecting group is bonded via an alkylene group having 1 to 6 carbon atoms.
- Examples of the carboxyl group that may be protected with a protecting group include a —COOR d group.
- R d represents a hydrogen atom or an alkyl group, and examples of the alkyl group include linear or branched carbon such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and hexyl groups. Examples thereof include alkyl groups of 1 to 6.
- the tertiary hydrocarbon group in R c of the —COOR c group includes, for example, t-butyl, t-amyl, 2-methyl-2-adamantyl, (1-methyl-1-adamantyl) ethyl group Etc.
- the tetrahydrofuranyl group includes a 2-tetrahydrofuranyl group
- the tetrahydropyranyl group includes a 2-tetrahydropyranyl group
- the oxepanyl group includes a 2-oxepanyl group.
- Examples of the organic group for R 8 include a group containing a hydrocarbon group and / or a heterocyclic group.
- the hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.
- Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, and octyl groups (C 1- 8 alkyl groups); linear or branched alkenyl groups such as allyl groups (C 2-8 alkenyl groups, etc.); linear or branched alkynyl groups such as propynyl groups (C 2-8 alkynyl) Group, etc.).
- Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl groups (3 to 8 membered cycloalkyl groups); cycloalkenyl groups such as cyclopentenyl and cyclohexenyl groups (3 to 8 members) Cycloalkenyl groups and the like); bridged carbocyclic groups such as adamantyl and norbornyl groups (C 4-20 bridged carbocyclic groups and the like) and the like.
- Examples of the aromatic hydrocarbon group include C 6-14 aromatic hydrocarbon groups such as phenyl and naphthyl groups.
- Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include benzyl and 2-phenylethyl groups. These hydrocarbon groups are protected with alkyl groups (C 1-4 alkyl groups, etc.), haloalkyl groups (C 1-4 haloalkyl groups, etc.), halogen atoms, hydroxyl groups that may be protected with protecting groups, and protecting groups. It may have a substituent such as a hydroxymethyl group which may be protected, a carboxyl group which may be protected with a protecting group, or an oxo group.
- the protecting group a protecting group conventionally used in the field of organic synthesis can be used.
- heterocyclic group examples include heterocyclic groups containing at least one heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
- Preferred organic groups include C 1-8 alkyl groups, organic groups containing a cyclic skeleton, and the like.
- the “ring” constituting the cyclic skeleton includes a monocyclic or polycyclic non-aromatic or aromatic carbocyclic or heterocyclic ring.
- monocyclic or polycyclic non-aromatic carbocycles and lactone rings are particularly preferable.
- the monocyclic non-aromatic carbocycle include a cycloalkane ring having about 3 to 15 members such as a cyclopentane ring and a cyclohexane ring.
- polycyclic non-aromatic carbocyclic ring bridged carbocyclic ring
- examples of the polycyclic non-aromatic carbocyclic ring include, for example, an adamantane ring; a norbornane ring, a norbornene ring, a bornane ring, an isobornane ring, a tricyclo [5.2.1.0 2,6 ] decane ring, Tetracyclo [4.4.0.1 2,5 .
- a bridged carbocyclic ring such as a bicyclic ring system, a tricyclic ring system, and a tetracyclic ring system (for example, a bridging carbocyclic ring having about 6 to 20 carbon atoms).
- the lactone ring include ⁇ -butyrolactone ring, 4-oxatricyclo [4.3.1.1 3,8 ] undecan-5-one ring, and 3-oxatricyclo [4.2.1.0 4. , 8 ] nonan-2-one ring, 4-oxatricyclo [5.2.1.0 2,6 ] decan-5-one ring, and the like.
- the ring constituting the cyclic skeleton includes an alkyl group such as a methyl group (eg, a C 1-4 alkyl group), a haloalkyl group such as a trifluoromethyl group (eg, a C 1-4 haloalkyl group), a chlorine atom Or a halogen atom such as a fluorine atom, a hydroxyl group that may be protected with a protective group, a hydroxyalkyl group that may be protected with a protective group, a mercapto group that may be protected with a protective group, or a protective group.
- an alkyl group such as a methyl group (eg, a C 1-4 alkyl group), a haloalkyl group such as a trifluoromethyl group (eg, a C 1-4 haloalkyl group), a chlorine atom Or a halogen atom such as a fluorine atom, a hydroxyl group that may be protected with
- It may have a substituent such as a carboxyl group which may be protected, an amino group which may be protected with a protecting group, and a sulfonic acid group which may be protected with a protecting group.
- a protecting group a protecting group conventionally used in the field of organic synthesis can be used.
- the ring constituting the cyclic skeleton may be directly bonded to an oxygen atom (oxygen atom adjacent to R 8 ) shown in the formula (2d) or may be bonded via a linking group.
- the linking group include linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene and trimethylene groups; carbonyl groups; oxygen atoms (ether bonds; —O—); oxycarbonyl groups ( An ester bond; —COO—); an aminocarbonyl group (amide bond; —CONH—); and a group in which a plurality of these are bonded.
- At least two of R 6 , R 7 and R 8 may be bonded to each other to form a ring with adjacent atoms.
- the ring include cycloalkane rings such as cyclopropane ring, cyclopentane ring and cyclohexane ring; oxygen-containing rings such as tetrahydrofuran ring, tetrahydropyran ring and oxepane ring; bridged ring and the like.
- stereoisomers may exist, but these can be used alone or as a mixture of two or more.
- the following compounds may be mentioned, but the invention is not limited thereto.
- the following compounds may be mentioned, but the invention is not limited thereto.
- the compound represented by the above formula (2d) can be obtained, for example, by reacting the corresponding vinyl ether compound and (meth) acrylic acid by a conventional method using an acid catalyst.
- 1-adamantyloxy-1-ethyl (meth) acrylate can be produced by reacting 1-adamantyl-vinyl-ether with (meth) acrylic acid in the presence of an acid catalyst.
- the other monomer unit in addition to the above, there may be mentioned a monomer unit that can impart or improve hydrophilicity, water solubility, or other characteristics.
- the monomer corresponding to such a monomer unit include, for example, a hydroxyl group-containing monomer (including a compound in which the hydroxyl group is protected), a mercapto group-containing monomer (a compound in which the mercapto group is protected).
- Carboxyl group-containing monomers including compounds in which carboxyl groups are protected
- amino group-containing monomers including compounds in which amino groups are protected
- sulfonic acid group-containing monomers including Sulfonate skeleton-containing monomers, cyclic ketone skeleton-containing monomers, acid anhydride group-containing monomers, imide group-containing monomers, etc. Examples include polar group-containing monomers.
- Examples of such other monomer units include monomer units containing an alicyclic skeleton having at least one substituent, for example, monomer units represented by the formula (III).
- the polymerizable unsaturated monomer corresponding to the monomer unit represented by the formula (III) is represented by the following formula (3).
- ring Z 2 represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms.
- R a is the same as above.
- R 9 is a substituent bonded to ring Z 2 and is the same or different and protected with an oxo group, an alkyl group, a haloalkyl group, a halogen atom, a hydroxyl group which may be protected with a protecting group, or a protecting group Protected with a hydroxyalkyl group which may be protected, a mercapto group which may be protected with a protecting group, a carboxyl group which may be protected with a protecting group, an amino group which may be protected with a protecting group, or a protecting group The sulfonic acid group which may be made is shown.
- q is the number of R 9 and represents an integer of 1 to 5.
- At least one of q R 9 is an oxo group, a hydroxyl group which may be protected with a protecting group, or a hydroxy group which may be protected with a protecting group.
- the monomer that is an acid group corresponds to a polar group-containing monomer that can impart or improve hydrophilicity or water solubility to a polymer.
- the alicyclic hydrocarbon ring having 6 to 20 carbon atoms in the ring Z 2 may be monocyclic or polycyclic such as a bridged ring.
- Typical alicyclic hydrocarbon rings include, for example, cyclohexane ring, cyclooctane ring, cyclodecane ring, adamantane ring, norbornane ring, norbornene ring, bornane ring, isobornane ring, perhydroindene ring, decalin ring, perhydrofluorene ring.
- Tricyclo [7.4.0.0 3,8 ] tridecane ring trihydroanthracene ring, tricyclo [5.2.1.0 2,6 ] decane ring, tricyclo [4.2.2.1 2, 5 ] Undecane ring, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodecane ring and the like.
- alicyclic hydrocarbon rings a bridged alicyclic hydrocarbon ring such as an adamantane ring is particularly preferable.
- the alkyl group for R 9 is a linear or branched chain such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl, dodecyl groups, etc.
- an alkyl group having about 1 to 20 carbon atoms particularly a C 1-4 alkyl group.
- the haloalkyl group include a haloalkyl group having about 1 to 20 carbon atoms such as a trifluoromethyl group (particularly a C 1-4 haloalkyl group).
- Examples of the halogen atom include a fluorine atom and a chlorine atom.
- Examples of the amino group that may be protected with a protecting group include an amino group and a substituted amino group (for example, C 1-4 alkylamino groups such as methylamino, ethylamino, propylamino group, etc.).
- Examples of the sulfonic acid group that may be protected with a protecting group include —SO 3 Re group.
- R e represents a hydrogen atom or an alkyl group, and examples of the alkyl group include linear or branched carbon such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and hexyl groups. Examples thereof include alkyl groups of 1 to 6.
- R 9 may be protected with a protecting group, a hydroxyl group which may be protected with a protecting group, a hydroxyalkyl group which may be protected with a protecting group, a mercapto group which may be protected with a protecting group, or a carboxyl which may be protected with a protecting group
- the groups are the same as described above.
- the monomer corresponding to the monomer unit containing an alicyclic skeleton having at least one substituent includes an alicyclic skeleton having at least one substituent selected from a hydroxyl group and a hydroxymethyl group (for example, adamantane). Monomers containing a skeleton etc. are preferred.
- Another example of the other monomer unit includes a monomer unit having a lactone skeleton [excluding the monomer unit represented by the formula (I)].
- Specific examples of the compound include the following compounds.
- a polycyclic ester group containing an electron-withdrawing substituent and a lactone skeleton is (meth) acrylic acid. And a monomer directly bonded to.
- the monomer unit is shown in the following formula (V).
- R a is the same as above.
- R 10 is a substituent bonded to the ring, and the halogen atom, the alkyl group having 1 to 6 carbon atoms which may have a halogen atom, the hydroxyl group portion may be protected with a protecting group, and A hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom, a carboxyl group which may form a salt, or a substituted oxycarbonyl group is shown.
- A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a non-bond.
- s is the number of R 10 and represents an integer of 0 to 8.
- X 1 represents an electron-withdrawing substituent
- t represents the number of X 1 bonded to the ring and represents an integer of 1 to 9.
- the steric position of the —COO— group bonded to the polymer chain may be either endo or exo.
- Examples of the halogen atom in R 10 are the same as the halogen atom in R 1 .
- Examples of the electron-withdrawing substituent in X 1 include the same electron-withdrawing substituent in X.
- the monomer corresponding to the monomer unit represented by the formula (IV) includes, for example, an unsaturated carboxylic acid represented by the formula (7) or a reactive derivative thereof in the compound represented by the formula (5). It can manufacture by making it react. More specifically, (a) a compound represented by the formula (5) in a solvent such as tetrahydrofuran, toluene, or methylene chloride, if necessary, in the presence of a base such as triethylamine, pyridine, 4-dimethylaminopyridine or the like.
- a solvent such as tetrahydrofuran, toluene, or methylene chloride
- the ratio of the monomer unit represented by the formula (I) is not particularly limited, but is generally 1 to 90 mol%, preferably 5 to 80%, based on all monomer units constituting the polymer. It is about mol%, more preferably about 10 to 60 mol%. Further, the ratio of the monomer units that are eliminated by the action of an acid and become alkali-soluble is, for example, about 10 to 95 mol%, preferably about 15 to 90 mol%, and more preferably about 20 to 60 mol%.
- a monomer unit corresponding to at least one monomer selected from a hydroxyl group-containing monomer, a mercapto group-containing monomer, and a carboxyl group-containing monomer [for example, in the monomer unit represented by the formula (III) , At least one of q R 9 is a hydroxyl group which may be protected with a protecting group, a hydroxyalkyl group which may be protected with a protecting group, a mercapto group which may be protected with a protecting group, or
- the ratio of the monomer unit which is a carboxyl group which may be protected with a protecting group] is, for example, about 0 to 60 mol%, preferably about 5 to 50 mol%, more preferably about 10 to 40 mol%.
- the monomer mixture is polymerized by a conventional method used for producing acrylic polymers such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization.
- solution polymerization is particularly preferred.
- drop polymerization is preferable among solution polymerization. Specifically, for example, (i) a monomer solution previously dissolved in an organic solvent and a polymerization initiator solution dissolved in an organic solvent are prepared in an organic solvent kept at a constant temperature.
- a monomer solution previously dissolved in an organic solvent and a polymerization initiator solution dissolved in the organic solvent are respectively prepared, and the polymerization initiator solution is dropped into the monomer solution maintained at a constant temperature. It is performed by a method or the like.
- a known solvent can be used.
- ether chain ether such as diethyl ether, propylene glycol monomethyl ether, etc., chain ether such as tetrahydrofuran, dioxane, etc.
- ester methyl acetate, ethyl acetate, Glycol ether esters such as butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate
- ketones acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
- amides N, N-dimethylacetamide, N, N-dimethylformamide, etc.
- Sulfoxide such as dimethyl sulfoxide
- alcohol such as methanol, ethanol, propanol
- hydrocarbon aromatic carbonization such as benzene, toluene, xylene
- the polymer obtained by polymerization can be purified by precipitation or reprecipitation.
- the precipitation or reprecipitation solvent may be either an organic solvent or water, or a mixed solvent.
- the organic solvent used as the precipitation or reprecipitation solvent include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatics such as benzene, toluene, and xylene.
- Aromatic hydrocarbons halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.) , Nitrile (acetonitrile, benzonitrile, etc.), ether (chain ether such as diethyl ether, diisopropyl ether, dimethoxyethane; cyclic ether such as tetrahydrofuran, dioxane), ketone (acetone, methyl ethyl ketone) Diisobutyl ketone, etc.), ester (ethyl acetate, butyl acetate, etc.), carbonate (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohol (methanol, ethanol, propanol
- the solvent containing at least hydrocarbon especially aliphatic hydrocarbons, such as hexane
- the mixed solvent of methanol and water are preferable.
- the weight average molecular weight (Mw) of the polymer compound is, for example, about 1,000 to 500,000, preferably about 3000 to 50,000, and the molecular weight distribution (Mw / Mn) is, for example, about 1.5 to 2.5.
- said Mn shows a number average molecular weight
- both Mn and Mw are values of polystyrene conversion.
- the polymer compound of the present invention has high stability such as chemical resistance, is excellent in solubility in organic solvents, and is excellent in hydrolysis and solubility in water after hydrolysis, it has high functionality in various fields. Can be used as a polymer.
- the photoresist composition of the present invention contains at least the polymer compound of the present invention and a photoacid generator, and usually contains a solvent for resist.
- the photoresist composition can be prepared, for example, by adding a photoacid generator to the above-described polymer compound solution of the present invention (resist solvent solution).
- photoacid generator examples include conventional or known compounds that efficiently generate acid upon exposure, such as diazonium salts, iodonium salts (for example, diphenyliodohexafluorophosphate), sulfonium salts (for example, triphenylsulfonium hexafluoroantimony).
- diazonium salts for example, diphenyliodohexafluorophosphate
- sulfonium salts for example, triphenylsulfonium hexafluoroantimony
- sulfonate esters [eg 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, 1,2,3-tri Sulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl) -1-hydroxy-1-ben Irumetan etc.], oxathiazole derivatives, s- triazine derivatives, disulfone derivatives (diphenyl sulfone) imide compound, an oxime sulfonate, a diazonaphthoquinone, and benzoin tosylate.
- photoacid generators can be used alone or in combination of
- the use amount of the photoacid generator can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each repeating unit in the polymer (resin for photoresist), and the like. It can be selected from a range of about 1 to 30 parts by weight, preferably 1 to 25 parts by weight, and more preferably about 2 to 20 parts by weight.
- the resist solvent examples include glycol solvents, ester solvents, ketone solvents, and mixed solvents exemplified as the polymerization solvent.
- propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl isobutyl ketone, methyl amyl ketone, and a mixed solution thereof are preferable, and in particular, propylene glycol monomethyl ether acetate alone solvent, propylene glycol monomethyl ether acetate and A solvent containing at least propylene glycol monomethyl ether acetate such as a mixed solvent of propylene glycol monomethyl ether and a mixed solvent of propylene glycol monomethyl ether acetate and ethyl lactate is preferably used.
- the polymer concentration in the photoresist composition is, for example, about 10 to 40% by weight.
- the photoresist composition may contain an alkali-soluble component such as an alkali-soluble resin (for example, a novolac resin, a phenol resin, an imide resin, a carboxyl group-containing resin), a colorant (for example, a dye), and the like.
- an alkali-soluble component such as an alkali-soluble resin (for example, a novolac resin, a phenol resin, an imide resin, a carboxyl group-containing resin), a colorant (for example, a dye), and the like.
- the photoresist composition thus obtained is applied onto a substrate or a substrate, dried, and then exposed to light on a coating film (resist film) through a predetermined mask (or further subjected to post-exposure baking).
- a coating film resist film
- predetermined mask or further subjected to post-exposure baking
- the base material or the substrate examples include a silicon wafer, metal, plastic, glass, and ceramic.
- the photoresist composition can be applied using a conventional application means such as a spin coater, a dip coater, or a roller coater.
- the thickness of the coating film is, for example, about 0.1 to 20 ⁇ m, preferably about 0.3 to 2 ⁇ m.
- light of various wavelengths for example, ultraviolet rays, X-rays, etc. can be used.
- semiconductor resist g-line, i-line, excimer laser (for example, XeCl, KrF, KrCl, ArF, ArCl, etc.) Etc. are used.
- the exposure energy is, for example, about 1 to 1000 mJ / cm 2 , preferably about 10 to 500 mJ / cm 2 .
- An acid is generated from the photoacid generator by light irradiation, and this acid, for example, a carboxyl group of a repeating unit (a repeating unit having an acid-eliminating group) that becomes alkali-soluble by the action of the acid of the photoresist polymer compound.
- a protecting group such as succinctly desorbs to generate a carboxyl group and the like that contribute to solubilization. Therefore, a predetermined pattern can be accurately formed by development with water or an alkali developer.
- Et in the chemical formula represents an ethyl group.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer indicate standard polystyrene conversion values determined by GPC measurement using a tetrahydrofuran solvent using a refractive index system (RI).
- RI refractive index system
- Example 1 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one was prepared according to the following reaction scheme.
- Example 2 the monomer component was 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one 13.93 g (45 0.7 mmol), 5.39 g (22.8 mmol) of 1-hydroxy-3-methacryloyloxyadamantane, and 10.68 g (45.7 mmol) of 2-methacryloyloxy-2-methyladamantane were used. As a result, 26.2 g of the desired resin was obtained. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 8700, and molecular weight distribution (Mw / Mn) was 1.90.
- Example 2 as a monomer component, 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one 14.45 g (47 .4 mmol), 5.59 g (23.7 mmol) of 1-hydroxy-3-methacryloyloxyadamantane, and 9.95 g (47.4 mmol) of 1- (1-methacryloyloxy-1-methylethyl) cyclohexane were used. When the same operation as in Example 2 was performed, 25.6 g of the desired resin was obtained. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 9100, and molecular weight distribution (Mw / Mn) was 1.85.
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- Example 2 as a monomer component, 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one 13.20 g (43 .3 mmol), 5.45 g (21.6 mmol) of 1,3-dihydroxy-5-methacryloyloxyadamantane, 11.34 g (43.3 mmol) of 1- (1-methacryloyloxy-1-methylethyl) adamantane
- GPC analysis of the recovered polymer revealed that Mw (weight average molecular weight) was 8300 and molecular weight distribution (Mw / Mn) was 1.87.
- Example 2 the monomer component was 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one 13.76 g (45 0.1 mmol), 1,3-dihydroxy-5-methacryloyloxyadamantane 5.68 g (22.6 mmol), and 2-methyl-2-methacryloyloxyadamantane 10.56 g (45.1 mmol). As a result of the same operation, 26.5 g of the desired resin was obtained. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 8500, and molecular weight distribution (Mw / Mn) was 1.89.
- Example 2 the monomer component was 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one 14.27 g (46 .8 mmol), 1.90 g (23.4 mmol) of 1,3-dihydroxy-5-methacryloyloxyadamantane, and 9.83 g (46.8 mmol) of 1- (1-methacryloyloxy-1-methylethyl) cyclohexane were used. Were the same as in Example 2 to obtain 25.4 g of the desired resin. When the recovered polymer was analyzed by GPC, it was found that Mw (weight average molecular weight) was 9000 and molecular weight distribution (Mw / Mn) was 1.88.
- Mw weight average molecular weight
- Example 2 13.36 g (43.8 mmol) of 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one Instead, the same procedure as in Example 2 was used, except that 11.06 g (49.8 mmol) of 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one was used. As a result, 26.6 g of the desired resin was obtained. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 9100, and molecular weight distribution (Mw / Mn) was 1.89.
- Mw weight average molecular weight
- Example 3 13.93 g (45.7 mmol) of 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one Instead, the same procedure as in Example 3 was used, except that 11.60 g (52.3 mmol) of 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one was used. As a result, 26.3 g of the desired resin was obtained. GPC analysis of the recovered polymer revealed that Mw (weight average molecular weight) was 9700 and molecular weight distribution (Mw / Mn) was 1.87.
- Example 4 14.45 g (47.4 mmol) of 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one Instead, the same operation as in Example 4 except that 12.11 g (54.5 mmol) of 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one was used. As a result, 25.1 g of the desired resin was obtained. GPC analysis of the recovered polymer revealed that Mw (weight average molecular weight) was 10,000 and molecular weight distribution (Mw / Mn) was 1.90.
- Example 5 13.20 g (43.3 mmol) of 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one Instead, the same procedure as in Example 5 was used, except that 10.92 g (49.2 mmol) of 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one was used. As a result, 27.0 g of the desired resin was obtained. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 9000 and molecular weight distribution (Mw / Mn) was 1.93.
- Example 6 13.76 g (45.1 mmol) of 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one Instead, the same procedure as in Example 6 was used, except that 11.44 g (51.5 mmol) of 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one was used. As a result, 27.1 g of the desired resin was obtained. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 8700, and molecular weight distribution (Mw / Mn) was 1.92.
- Example 7 14.27 g (46.8 mmol) of 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one Instead, the same procedure as in Example 7 was used, except that 11.94 g (53.8 mmol) of 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one was used. As a result, 25.8 g of the desired resin was obtained. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 9500, and molecular weight distribution (Mw / Mn) was 1.88.
- Mw weight average molecular weight
- Example 2 succinic acid 2- (methacryloyloxy) ethyl 1-cyano-2-oxo-3-oxatricyclo [4.2.1.0 4,8 ] nonan-5-yl15. 21 g (38.9 mmol), 1-hydroxy-3-methacryloyloxyadamantane 4.59 g (19.4 mmol), 1- (1-methacryloyloxy-1-methylethyl) adamantane 10.20 g (38.9 mmol) were used. Except for the above, the same operation as in Example 2 was performed to obtain 26.5 g of a desired resin. GPC analysis of the recovered polymer revealed that Mw (weight average molecular weight) was 9400 and molecular weight distribution (Mw / Mn) was 1.90.
- Mw weight average molecular weight
- Example 2 succinic acid 2- (methacryloyloxy) ethyl 1-cyano-2-oxo-3-oxatricyclo [4.2.1.0 4,8 ] nonan-5-yl15. Examples were used except that 79 g (40.3 mmol), 4.77 g (20.2 mmol) of 1-hydroxy-3-methacryloyloxyadamantane, and 9.45 g (40.3 mmol) of 2-methacryloyloxy-2-methyladamantane were used. When the same operation as 2 was performed, 26.5 g of the desired resin was obtained. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 9700, and molecular weight distribution (Mw / Mn) was 1.93.
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- Example 2 succinic acid 2- (methacryloyloxy) ethyl 1-cyano-2-oxo-3-oxatricyclo [4.2.1.0 4,8 ] nonan-5-yl was used as a monomer component. 31 g (41.7 mmol), 1-hydroxy-3-methacryloyloxyadamantane 4.92 g (20.8 mmol), 1- (1-methacryloyloxy-1-methylethyl) cyclohexane 8.77 g (41.7 mmol) were used. Except for the above, the same operation as in Example 2 was performed to obtain 28.0 g of a desired resin. GPC analysis of the recovered polymer revealed that Mw (weight average molecular weight) was 9600 and molecular weight distribution (Mw / Mn) was 1.95.
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- Example 2 succinic acid 2- (methacryloyloxy) ethyl 1-cyano-2-oxo-3-oxatricyclo [4.2.1.0 4,8 ] nonan-5-yl18. 70 g (46.2 mmol), 1,3-dihydroxy-5-methacryloyloxyadamantane 4.66 g (18.5 mmol), 1- (1-methacryloyloxy-1-methylethyl) adamantane 7.27 g (27.7 mmol) Except for the use, the same operation as in the example was performed to obtain 26.0 g of a desired resin. When the collected polymer was analyzed by GPC, it was found that Mw (weight average molecular weight) was 9000 and molecular weight distribution (Mw / Mn) was 1.94.
- Example 2 succinic acid 2- (methacryloyloxy) ethyl 1-cyano-2-oxo-3-oxatricyclo [4.2.1.0 4,8 ] nonan-5-yl18. Except for using 55 g (47.4 mmol), 1,3-dihydroxy-5-methacryloyloxyadamantane 4.78 g (19.0 mmol), 2-methacryloyloxy-2methyladamantane 6.66 g (28.4 mmol) When the same operation as in Example 2 was performed, 26.0 g of the desired resin was obtained. GPC analysis of the recovered polymer revealed that Mw (weight average molecular weight) was 9800 and molecular weight distribution (Mw / Mn) was 1.98.
- Mw weight average molecular weight
- Example 2 succinic acid 2- (methacryloyloxy) ethyl 1-cyano-2-oxo-3-oxatricyclo [4.2.1.0 4,8 ] nonan-5-yl18. 98 g (48.4 mmol), 1,3-dihydroxy-5-methacryloyloxyadamantane 4.90 g (19.4 mmol), 1- (1-methacryloyloxy-1-methylethyl) cyclohexane 6.12 g (29.1 mmol) Except that it was used, the same operation as in Example 2 was performed to obtain 27.5 g of a desired resin. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 8900, and molecular weight distribution (Mw / Mn) was 1.87.
- a photoresist composition was prepared by filtering with a filter.
- the filterability of the filter having a pore diameter of 0.02 ⁇ m was good and it was possible to filter quickly, but in Comparative Examples 1 to 6, it took about 5 times as long as the example. In the latter half of the filtration, it was expected that the filtration rate was particularly slow and the filter medium was frequently replaced.
- This photoresist composition was applied to a silicon wafer by spin coating to form a photosensitive layer having a thickness of 0.7 ⁇ m.
- a photosensitive layer having a thickness of 0.7 ⁇ m.
- the film was exposed through a mask at an irradiation dose of 30 mJ / cm 2 and then post-baked at a temperature of 100 ° C. for 60 seconds.
- it developed for 60 second with the 2.38M tetramethylammonium hydroxide aqueous solution, and rinsed with the ultrapure water.
- a 0.25 ⁇ m line and space pattern was obtained when any of the photoresist polymer solutions of Examples and Comparative Examples was used, but Examples 2 to 7 and 9 to 14 were compared with Comparative Examples. It was clearly clear.
Abstract
Description
で表される電子吸引性置換基及びラクトン骨格を含む単量体を提供する。
で表されるモノマー単位を少なくとも有する高分子化合物を提供する。
から選ばれるモノマー単位が含まれる。
から選ばれるモノマー単位が含まれる。
で表されるハロゲン含有ラクトン化合物を提供する。
で表されるハロゲン含有ラクトン化合物と
下記式(7)
で表される不飽和カルボン酸、又はそのアルカリ金属塩、若しくはアルカリ土類金属塩とを反応させて、
下記式(1)
で表される電子吸引性置換基及びラクトン骨格を含む単量体を製造する方法を提供する。
本発明の電子吸引性置換基及びラクトン骨格を含む単量体(6-オキサビシクロ[3.2.11,5]オクタン-7-オン誘導体及び3-オキサトリシクロ[4.2.1.04,8]ノナン-2-オン誘導体等)は前記式(1)で表される。式(1)中、Raは水素原子、ハロゲン原子、又は置換基を有していてもよい炭素数1~6のアルキル基を示し、R1は環[6-オキサビシクロ[3.2.11,5]オクタン環(Aが非結合の場合)、3-オキサトリシクロ[4.2.1.04,8]ノナン環(Aがメチレン基の場合)(=4-オキサトリシクロ[4.2.1.03,7]ノナン環等]に結合している置換基であって、ハロゲン原子、ハロゲン原子を有していてもよい炭素数1~6のアルキル基、ヒドロキシル基部分が保護基で保護されていてもよく且つハロゲン原子を有していてもよい炭素数1~6のヒドロキシアルキル基、塩を形成していてもよいカルボキシル基、又は置換オキシカルボニル基を示す。Aは炭素数1~6のアルキレン基、酸素原子、硫黄原子又は非結合を示す。mはR1の個数であって0~8の整数を示す。Xは電子吸引性置換基を示し、nは環[6-オキサビシクロ[3.2.11,5]オクタン環(Aが非結合の場合)、3-オキサトリシクロ[4.2.1.04,8]ノナン環(Aがメチレン基の場合)に結合しているXの個数であって1~9の整数を示す。Yは炭素数1~6の2価の有機基を示す。CH2=C(Ra)COO-Y-COO-基の立体的な位置はエンド、エキソの何れであってもよい。
本発明の高分子化合物は上記式(1)で表される電子吸引性置換基及びラクトン骨格を含む単量体に対応するモノマー単位(繰り返し単位)、すなわち前記式(I)で表されるモノマー単位を含んでいる。該モノマー単位は1種又は2種以上含んでいてもよい。このような高分子化合物は、上記式(1)で表される電子吸引性置換基及びラクトン骨格を含む単量体を重合に付すことにより得ることができる。
高分子化合物の重量平均分子量(Mw)は、例えば1000~500000程度、好ましくは3000~50000程度であり、分子量分布(Mw/Mn)は、例えば1.5~2.5程度である。なお、前記Mnは数平均分子量を示し、Mn、Mwともにポリスチレン換算の値である。
下記の反応工程式に従って、1-シアノ-5-ヒドロキシ-3-オキサトリシクロ[4.2.1.04,8]ノナン-2-オンを製造した。
[式(5a)で表される1-シアノ-5-ヒドロキシ-3-オキサトリシクロ[4.2.1.04,8]ノナン-2-オンのスペクトルデータ]
1H-NMR(CDCl3) δ:4.52-4.54(1H), 3.69-3.73(2H), 2.54-2.55(1H), 2.29-2.35(2H), 2.13-2.16(1H), 1.85-1.88(1H)
下記の反応工程式に従って、1-シアノ-5-(2-メタクリロイルオキシアセトキシ)-3-オキサトリシクロ[4.2.1.04,8]ノナン-2-オンを製造した。
1H-NMR(DMSO-d6) δ:4.79(1H,m),4.66(1H,m),4.32-4.43(2H,m),3.79(1H,m),2.59(1H,m),2.28-2.39(2H,m),2.00(1H,m),1.85(1H,m)
1H-NMR (CDCl3) δ:6.21(1H,m),5.70(1H,m),4.64-4.72(4H,m),3.65(1H,m),2.74(1H,m),2.39(1H,dd),2.26(1H,dd),2.12-2.19(1H,m),1.94-2.00(4H,m)
下記の反応工程式に従ってコハク酸 2-(メタクリロイルオキシ)エチル 1-シアノ-2-オキソ-3-オキサトリシクロ[4.2.1.04,8]ノナン-5-イルを製造した。
1H-NMR(CDCl3) δ:6.12(s,1H), 5.61(s,1H), 4.67(m,1H), 4.61(s,1H), 4.35(s,1H), 3.61(m,1H)、2.71(m,1H)、2.60-2.69(m,4H)、2.36-2.40(m,1H)、2.19-2.25(m,2H)、1.97(m,1H)、1.94(s,3H)
下記構造の高分子化合物の合成
下記構造の高分子化合物の合成
下記構造の高分子化合物の合成
下記構造の高分子化合物の合成
下記構造の高分子化合物の合成
下記構造の高分子化合物の合成
実施例及び比較例で得られた各フォトレジスト用ポリマー樹脂にプロピレングリコールモノメチルエーテルアセテート(PGMEA)及びプロピレングリコールモノメチルエーテル(PGME)を添加して、ポリマー濃度20重量%のPGMEA/PGME(重量比6/4)溶液となるように、樹脂を溶解した。実施例2~7では速やかに溶解したが、比較例1~6では実施例に比較して2~4倍の時間を要した。得られた各フォトレジスト用ポリマー溶液に、ポリマー100重量部に対して10重量部のトリフェニルスルホニウムヘキサフルオロアンチモネートを加え、さらにPGMEAを加えてポリマー濃度15重量%に調整し、孔径0.02μmのフィルターで濾過することによりフォトレジスト組成物を調製した。実施例2~7及び9~14では孔径0.02μmのフィルターでの濾過性もよく速やかに濾過できたが、比較例1~6では実施例に比較して5倍程度の時間を要した。濾過後半は特に濾過速度が遅くなり濾材の交換も頻繁になることが予想された。
このフォトレジスト組成物をシリコンウエハーにスピンコーティング法により塗布し、厚み0.7μmの感光層を形成した。ホットプレート上で温度100℃で150秒間プリベークした後、波長193nmのArFエキシマレーザーを用い、マスクを介して、照射量30mJ/cm2で露光した後、100℃の温度で60秒間ポストベークした。次いで、2.38Mのテトラメチルアンモニウムヒドロキシド水溶液により60秒間現像し、超純水でリンスした。実施例及び比較例の何れのフォトレジスト用ポリマー溶液を用いた場合にも、0.25μmのライン・アンド・スペースパターンは得られたが、実施例2~7及び9~14は比較例と比べ明らかに鮮明であった。
Claims (12)
- 下記式(1)
で表される電子吸引性置換基及びラクトン骨格を含む単量体。 - 下記式(I)
で表されるモノマー単位を少なくとも有する高分子化合物。 - 式(I)で表されるモノマー単位に加えて、さらに、酸の作用により脱離してアルカリ可溶となるモノマー単位を少なくとも有する請求項2記載の高分子化合物。
- 酸の作用により脱離してアルカリ可溶となるモノマー単位が、下記式(IIa)~(IId)
から選ばれるモノマー単位である請求項3記載の高分子化合物。 - 式(I)で表されるモノマー単位に加えて、さらに、少なくとも1つの置換基を有する脂環式骨格を含有するモノマー単位を少なくとも有する請求項2~4の何れかの項に記載の高分子化合物。
- 少なくとも1つの置換基を有する脂環式骨格を含有するモノマー単位が、下記式(III)
から選ばれるモノマー単位である請求項5記載の高分子化合物。 - 式(I)で表されるモノマー単位と、酸の作用により脱離してアルカリ可溶となるモノマー単位と、ヒドロキシル基及びヒドロキシメチル基から選択された置換基を少なくとも1つ有する脂環式骨格を含有するモノマー単位とを少なくとも有する請求項3記載の高分子化合物。
- 式(I)で表されるモノマー単位に加えて、さらに、式(I)で表されるモノマー単位以外のラクトン骨格を有するモノマー単位を少なくとも有する請求項2~7の何れかの項に記載の高分子化合物。
- 請求項2~8の何れかの項に記載の高分子化合物と光酸発生剤とを少なくとも含むフォトレジスト組成物。
- 請求項9記載のフォトレジスト組成物を使用してパターンを形成することを特徴とする半導体の製造方法。
- 下記式(6)
で表されるハロゲン含有ラクトン化合物。 - 下記式(6)
で表されるハロゲン含有ラクトン化合物と
下記式(7)
で表される不飽和カルボン酸、又はそのアルカリ金属塩、若しくはアルカリ土類金属塩とを反応させて、
下記式(1)
で表される電子吸引性置換基及びラクトン骨格を含む単量体を製造する方法。
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Cited By (12)
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JP2010170067A (ja) * | 2008-03-26 | 2010-08-05 | Fujifilm Corp | 感活性光線性又は感放射線性樹脂組成物及びそれを用いたパターン形成方法 |
JP2010168523A (ja) * | 2008-03-26 | 2010-08-05 | Fujifilm Corp | 重合性化合物及び該重合性化合物を重合させた高分子化合物 |
US7833694B2 (en) | 2008-03-13 | 2010-11-16 | Shin-Etsu Chemical Co., Ltd. | Lactone-containing compound, polymer, resist composition, and patterning process |
US8062831B2 (en) | 2008-05-02 | 2011-11-22 | Shin-Etsu Chemical Co., Ltd. | Carboxyl-containing lactone compound, polymer, resist composition, and patterning process |
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JP5562826B2 (ja) | 2014-07-30 |
US20100297555A1 (en) | 2010-11-25 |
CN101959909A (zh) | 2011-01-26 |
KR101550947B1 (ko) | 2015-09-07 |
KR20100137427A (ko) | 2010-12-30 |
CN101959909B (zh) | 2013-03-13 |
JPWO2009107327A1 (ja) | 2011-06-30 |
US8637623B2 (en) | 2014-01-28 |
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