WO2024071131A1 - Resist composition and method for forming resist pattern - Google Patents
Resist composition and method for forming resist pattern Download PDFInfo
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- WO2024071131A1 WO2024071131A1 PCT/JP2023/034972 JP2023034972W WO2024071131A1 WO 2024071131 A1 WO2024071131 A1 WO 2024071131A1 JP 2023034972 W JP2023034972 W JP 2023034972W WO 2024071131 A1 WO2024071131 A1 WO 2024071131A1
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- 125000004043 oxo group Chemical group O=* 0.000 description 1
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- GJSGGHOYGKMUPT-UHFFFAOYSA-N phenoxathiine Chemical group C1=CC=C2OC3=CC=CC=C3SC2=C1 GJSGGHOYGKMUPT-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011827 silicon-based solvent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LPQZERIRKRYGGM-UHFFFAOYSA-N tert-butyl pyrrolidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCC1 LPQZERIRKRYGGM-UHFFFAOYSA-N 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 125000005579 tetracene group Chemical group 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical group C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical group C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- 125000005556 thienylene group Chemical group 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
Definitions
- the present invention relates to a resist composition and a method of forming a resist pattern.
- a common method of miniaturization is to shorten the wavelength (increase the energy) of the exposure light source.
- Resist materials are required to have lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
- lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
- a chemically amplified resist composition that contains a base component whose solubility in a developer changes due to the action of acid, and an acid generator component that generates acid upon exposure, has been used so far.
- Patent Document 1 discloses a resist composition that contains a resin component (A1) that includes a specific structural unit (a0) that has both an acid-dissociable group and a phenolic hydroxyl group.
- the present invention has been made in consideration of the above circumstances, and aims to provide a resist composition that achieves high sensitivity and has good resolution and CDU, as well as a method for forming a resist pattern using the resist composition.
- a first aspect of the present invention is a resist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid, comprising a resin component (A1) whose solubility in a developer changes due to the action of the acid, and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the resin component (A1) has a structural unit (a01) derived from a compound represented by the following general formula (a0-1), and the fluorine additive component (F) includes a fluorine resin component (F1) that has a structural unit represented by the following general formula (f1):
- W 01 represents a polymerizable group-containing group.
- Ya 01 represents a single bond or a divalent linking group.
- Ra 01 represents an acid-dissociable group.
- q represents an integer of 0 to 3.
- n represents an integer of 1 or more, provided that n ⁇ q ⁇ 2+4.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- X0 is a divalent linking group having no acid dissociable site.
- Rf0 is an organic group having a fluorine atom.
- the second aspect of the present invention is a method for forming a resist pattern, comprising the steps of forming a resist film on a support using the resist composition according to the first aspect, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.
- the present invention provides a resist composition that has high sensitivity and good resolution and CDU, as well as a method for forming a resist pattern using the resist composition.
- alkyl group includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group.
- alkylene group includes linear, branched and cyclic divalent saturated hydrocarbon groups.
- halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- structural unit refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer).
- the phrase "may have a substituent” includes both the case where a hydrogen atom (--H) is replaced with a monovalent group and the case where a methylene group (--CH 2 -) is replaced with a divalent group.
- exposure is intended to include any concept including irradiation with radiation.
- acid-decomposable group refers to a group having acid decomposability in which at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid.
- acid-decomposable groups whose polarity increases under the action of an acid include groups that are decomposed by the action of an acid to generate a polar group.
- the polar group include a carboxy group, a hydroxyl group, an amino group, and a sulfo group (-SO 3 H).
- the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
- acid dissociable group refers to both (i) a group having acid dissociability in which the bond between the acid dissociable group and an atom adjacent to the acid dissociable group can be cleaved by the action of an acid, and (ii) a group in which a part of the bond is cleaved by the action of an acid and then a decarboxylation reaction occurs, thereby cleaving the bond between the acid dissociable group and an atom adjacent to the acid dissociable group.
- the acid dissociable group constituting the acid decomposable group must be a group with lower polarity than the polar group generated by dissociation of the acid dissociable group, and thus, when the acid dissociable group is dissociated by the action of acid, a polar group with higher polarity than the acid dissociable group is generated, and the polarity increases.As a result, the polarity of the entire (A1) component increases.By increasing the polarity, the solubility in the developer changes relatively, and when the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases.
- the “base material component” is an organic compound that has film-forming ability.
- Organic compounds used as base material components are broadly divided into non-polymers and polymers.
- Non-polymers usually have a molecular weight of 500 or more and less than 4000 (hereinafter referred to as “low molecular weight compounds”).
- “resin,” “polymeric compound,” or “polymer” refers to a polymer with a molecular weight of 1000 or more. The molecular weight of the polymer is determined by the weight average molecular weight calculated in terms of polystyrene by GPC (gel permeation chromatography).
- derived structural unit refers to a structural unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond.
- the hydrogen atom bonded to the carbon atom at the ⁇ -position may be substituted with a substituent.
- the substituent (R ⁇ x ) substituting the hydrogen atom bonded to the carbon atom at the ⁇ -position is an atom or group other than a hydrogen atom.
- an itaconic acid diester in which the substituent (R ⁇ x ) is substituted with a substituent containing an ester bond
- an ⁇ -hydroxyacrylic ester in which the substituent (R ⁇ x ) is substituted with a hydroxyalkyl group or a group in which the hydroxyl group is modified.
- the carbon atom at the ⁇ -position of an acrylic acid ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded, unless otherwise specified.
- an acrylic ester in which the hydrogen atom bonded to the carbon atom at the ⁇ -position is substituted with a substituent will sometimes be referred to as an ⁇ -substituted acrylic ester.
- derivative refers to a concept that includes compounds in which the hydrogen atom at the ⁇ -position of the target compound is replaced with other substituents such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof.
- examples of such derivatives include compounds in which the hydrogen atom of the hydroxyl group of a target compound, which may have the hydrogen atom at the ⁇ -position replaced with a substituent, is replaced with an organic group; compounds in which the hydrogen atom at the ⁇ -position of the target compound, which may have the hydrogen atom at the ⁇ -position replaced with a substituent, is bonded to a substituent other than a hydroxyl group, and the like.
- the ⁇ -position refers to the first carbon atom adjacent to the functional group, unless otherwise specified.
- Examples of the substituent that substitutes the hydrogen atom at the ⁇ -position of the hydroxystyrene include the same as those for R ⁇ x .
- the resist composition of this embodiment generates an acid upon exposure, and the solubility of the resist composition in a developer changes due to the action of the acid.
- a resist composition contains a base component (A) (hereinafter also referred to as “component (A)”) whose solubility in a developer changes under the action of an acid, and a fluorine additive component (F) (hereinafter also referred to as “component (F)”) that exhibits decomposition in an alkaline developer.
- the component (A) may generate an acid upon exposure, or an additive component that is formulated separately from the component (A) may generate an acid upon exposure.
- the resist composition of this embodiment may be one that further contains (1) an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as “component (B)”); (2) the component (A) may be a component that generates an acid upon exposure; or (3) the component (A) is a component that generates an acid upon exposure, and further contains component (B). That is, in the above cases of (2) and (3), the component (A) is a "base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid".
- the component (A) is a base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid
- the component (A1) described below is preferably a resin that generates an acid upon exposure and changes its solubility in a developer by the action of the acid.
- a resin a polymer compound having a structural unit that generates an acid upon exposure can be used.
- the structural unit that generates an acid upon exposure a known one can be used.
- the resist composition of this embodiment is preferably the above-mentioned case (1).
- the resist composition of this embodiment preferably contains component (A) and component (B).
- a resist film is formed using the resist composition of this embodiment and selective exposure is performed on the resist film, for example, an acid is generated from component (B) in the exposed parts of the resist film, and the solubility of component (A) in the developer changes due to the action of the acid, whereas the solubility of component (A) in the developer does not change in the unexposed parts of the resist film, resulting in a difference in solubility in the developer between the exposed and unexposed parts.
- the resist film when the resist film is developed, if the resist composition is a positive type, the exposed parts of the resist film are dissolved and removed to form a positive type resist pattern, and if the resist composition is a negative type, the unexposed parts of the resist film are dissolved and removed to form a negative type resist pattern.
- the resist composition of this embodiment may be a positive resist composition or a negative resist composition.
- the resist composition of this embodiment may be for an alkaline development process in which an alkaline developer is used in the development treatment during resist pattern formation, or may be for a solvent development process in which a developer containing an organic solvent (organic developer) is used in the development treatment.
- the component (A) contains a resin component (A1) (hereinafter also referred to as “component (A1)”) whose solubility in a developer changes under the action of an acid.
- component (A1) a resin component (hereinafter also referred to as “component (A1)”
- component (A1) whose solubility in a developer changes under the action of an acid.
- the component (A1) the polarity of the base component changes between before and after exposure, making it possible to obtain good development contrast not only in an alkali development process but also in a solvent development process.
- component (A) other polymeric compounds and/or low molecular weight compounds may be used in combination with the component (A1).
- the component (A) may be used alone or in combination of two or more types.
- the component (A1) is a resin component whose solubility in a developer changes due to the action of an acid.
- the component (A1) has a structural unit (a01) derived from a compound represented by general formula (a0-1) shown below.
- W 01 represents a polymerizable group-containing group.
- Ya 01 represents a single bond or a divalent linking group.
- Ra 01 represents an acid-dissociable group.
- q represents an integer of 0 to 3.
- n represents an integer of 1 or more, provided that n ⁇ q ⁇ 2+4.
- W 01 represents a polymerizable group-containing group.
- the "polymerizable group" in W 01 is a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and refers to a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond.
- the multiple bond in the polymerizable group is cleaved to form the main chain.
- Examples of the polymerizable group in W 01 include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a fluorovinyl group, a difluorovinyl group, a trifluorovinyl group, a difluorotrifluoromethylvinyl group, a trifluoroallyl group, a perfluoroallyl group, a trifluoromethylacryloyl group, a nonylfluorobutylacryloyl group, a vinyl ether group, a fluorine-containing vinyl ether group, an allyl ether group, a fluorine-containing allyl ether group, a styryl group, a vinyl naphthyl group, a fluorine-containing styryl group, a fluorine-containing vinyl naphthyl group, a norbornyl group, a fluorine-containing norbornyl group, and a sily
- the "polymerizable group-containing group" in W 01 may be a group consisting of only a polymerizable group, or may be a group consisting of a polymerizable group and a group other than the polymerizable group.
- Examples of the group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- Optionally substituted divalent hydrocarbon group When the group other than the polymerizable group is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.
- the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
- Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing a ring in the structure.
- the straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
- a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
- the branched aliphatic hydrocarbon group preferably contains 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
- the branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alky
- the linear or branched aliphatic hydrocarbon group may or may not have a substituent.
- substituents include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.
- Aliphatic hydrocarbon groups containing a ring in the structure examples include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc.
- Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above.
- the cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantan, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, tetracyclododecane, etc.
- the cyclic aliphatic hydrocarbon group may or may not have a substituent, which may include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, etc.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
- the alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
- the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
- halogenated alkyl group examples include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.
- some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom.
- the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
- the number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
- aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic heterocycle include a pyridine ring and a thiophene ring.
- aromatic hydrocarbon group examples include a group (arylene group or heteroarylene group) in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle; a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group (aryl group or heteroaryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group).
- the number of carbon
- the aromatic hydrocarbon group may have a hydrogen atom substituted with a substituent.
- a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent.
- the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
- the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.
- the H may be substituted with a substituent such as an alkyl group, acyl, etc.
- the substituent alkyl group, acyl group, etc.
- the substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms.
- Y 21 and Y 22 each independently represent a divalent hydrocarbon group which may have a substituent.
- the divalent hydrocarbon group include the same as those (divalent hydrocarbon groups which may have a substituent) listed above in the description of the divalent linking group.
- Y 21 is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or ethylene group.
- Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group.
- the alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
- m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as the group represented by the formula -[Y 21 -C( ⁇ O)-O] m" -Y 22 -, a group represented by the formula -Y 21 -C( ⁇ O)-O-Y 22 - is particularly preferred. Of these, a group represented by the formula -(CH 2 ) a' -C( ⁇ O)-O-(CH 2 ) b' - is preferred.
- a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.
- b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.
- R X11 , R X12 and R X13 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms
- Ya x0 represents a single bond or a divalent linking group.
- the alkyl group having 1 to 5 carbon atoms in R X11 , R X12 and R X13 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc.
- the halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms.
- a fluorine atom is particularly preferable.
- R X11 and R X12 are each preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.
- R X13 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.
- the divalent linking group for Ya x0 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom, each of which is the same as described above.
- Ya 01 is a single bond or a divalent linking group.
- the divalent linking group in Ya 01 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom, each of which is the same as described above.
- Ra 01 represents an acid dissociable group.
- the acid dissociable group include an "acetal type acid dissociable group,” a “tertiary alkyl ester type acid dissociable group,” and a “secondary alkyl ester type acid dissociable group,” which will be described below.
- Acetal-type acid-dissociable group examples of the acid dissociable group for Ra 01 include acid dissociable groups represented by the following general formula (a0-r-1) (hereinafter sometimes referred to as "acetal-type acid dissociable group").
- Ra 01 and Ra 02 each independently represent a hydrogen atom or an alkyl group.
- Ra 03 represents a hydrocarbon group and may be bonded to either Ra 01 or Ra 02 to form a ring. * represents a bond.
- Ra 01 and Ra 02 each independently represent a hydrogen atom or an alkyl group.
- at least one of Ra 01 and Ra 02 is preferably a hydrogen atom, and more preferably both are hydrogen atoms.
- the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. Specific examples of preferred alkyl groups include linear or branched alkyl groups.
- Ra 01 and Ra 02 are each preferably independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
- examples of the hydrocarbon group for Ra 03 include a linear or branched alkyl group, or a cyclic hydrocarbon group.
- the linear alkyl group preferably has 1 to 5 carbon atoms, more preferably has 1 to 4 carbon atoms, and even more preferably has 1 or 2 carbon atoms.
- Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.
- the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
- the monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
- the aromatic hydrocarbon group of Ra 03 is an aromatic hydrocarbon group
- the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
- the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
- aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic heterocycle include a pyridine ring and a thiophene ring.
- aromatic hydrocarbon group in Ra 03 include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group).
- the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably has 1 carbon atom.
- the cyclic hydrocarbon group in Ra 03 may have a substituent.
- substituents include the same groups as those in Ra x5 described above.
- the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring.
- Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.
- acetal-type acid-dissociable groups are shown below. * indicates a bond.
- Tertiary alkyl ester type acid-dissociable group examples include acid dissociable groups represented by general formula (a0-r-2) shown below.
- acid-dissociable groups represented by the following formula (a0-r-2) those constituted by an alkyl group may be referred to as "tertiary alkyl ester-type acid-dissociable groups" hereinafter for convenience.
- Ra 04 to Ra 06 each independently represent a hydrocarbon group, and Ra 05 and Ra 06 may be bonded to each other to form a ring. * represents a bond.
- Examples of the hydrocarbon group for Ra 04 include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group.
- Examples of the linear or branched alkyl group and cyclic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, and aromatic hydrocarbon group) in Ra 04 are the same as those in Ra 03 .
- the chain or cyclic alkenyl group for Ra 04 is preferably an alkenyl group having 2 to 10 carbon atoms.
- Examples of the hydrocarbon group for Ra 05 and Ra 06 include the same as those for Ra 03 .
- Ra 05 and Ra 06 are bonded to each other to form a ring
- suitable examples of such a ring include a group represented by the following general formula (a0-r2-01), a group represented by the following general formula (a0-r2-02), and a group represented by the following general formula (a0-r2-03).
- suitable examples include groups represented by the following general formula (a0-r2-04).
- Ra 001 is a linear or branched alkyl group which may have a substitution.
- Yaa 0 is a carbon atom.
- Xaa 0 is a group which forms a cyclic hydrocarbon group together with Yaa 0.
- Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms.
- * represents a bond.
- Yab 0 is a carbon atom.
- Xab 0 is a group forming a cyclic hydrocarbon group together with Yab 0.
- Ra 002 to Ra 004 are each independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent cyclic aliphatic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in this linear saturated hydrocarbon group and cyclic aliphatic saturated hydrocarbon group may be substituted. Two or more of Ra 002 to Ra 004 may be bonded to each other to form a cyclic structure. * indicates a bond.
- Yac 0 is a carbon atom.
- Xac 0 is a group forming a cyclic hydrocarbon group together with Yac 0.
- Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms.
- Ra 005 is an aromatic hydrocarbon group. Some or all of the hydrogen atoms in this aromatic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms. * indicates a bond.
- Ra 006 and Ra 007 each independently represent a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may be substituted.
- Ra 008 represents a hydrocarbon group which may have a substituent. * represents a bond.
- Ra 001 represents an optionally substituted straight-chain or branched-chain alkyl group.
- the linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms.
- Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Of these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.
- the branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group.
- Examples of the substituent that the linear or branched alkyl group in Ra 001 may have include the above-mentioned Ra x5 .
- Ra 001 is preferably a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, and even more preferably a linear alkyl group having 1 to 3 carbon atoms.
- Yaa 0 is a carbon atom
- Xaa 0 is a group forming a cyclic hydrocarbon group together with Yaa 0 .
- the cyclic hydrocarbon group may be an aliphatic hydrocarbon group or a condensed cyclic hydrocarbon group of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
- the monocyclic aliphatic hydrocarbon group is preferably a group in which two or more hydrogen atoms have been removed from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, more preferably 5 or 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which two or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
- the aromatic hydrocarbon group in the condensed cyclic hydrocarbon group of an aliphatic hydrocarbon group and an aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
- the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
- aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic heterocycle include a pyridine ring and a thiophene ring.
- condensed cyclic hydrocarbon groups consisting of an aliphatic hydrocarbon group and an aromatic hydrocarbon group are shown below.
- Some or all of the hydrogen atoms in the cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms.
- Specific examples of the substituent that replaces a part or all of the hydrogen atoms of the cyclic hydrocarbon group include the above-mentioned Ra x5 .
- examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.
- the cyclic hydrocarbon group formed by Xaa0 and Yaa0 is preferably a monocyclic or polycyclic aliphatic hydrocarbon group, more preferably a monocyclic aliphatic hydrocarbon group, and still more preferably a monocyclic aliphatic hydrocarbon group having 5 or 6 carbon atoms.
- Yab 0 is a carbon atom
- Xab 0 is a group forming a cyclic hydrocarbon group together with Yab 0.
- this cyclic hydrocarbon group include the same as the cyclic hydrocarbon group formed by Xaa 0 and Yaa 0 described above.
- Ra 002 to Ra 004 each independently represent a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent cyclic aliphatic saturated hydrocarbon group having 3 to 20 carbon atoms.
- Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 002 to Ra 004 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group.
- Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in Ra 002 to Ra 004 include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; and polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.0 2,6 ]decanyl group, a tricyclo[3.3.1.1 3,7 ]decanyl group, a tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodecanyl group, and an adamantyl group.
- Ra 002 to Ra 004 some or all of the hydrogen atoms in the chain saturated hydrocarbon group and the alicyclic saturated hydrocarbon group may be substituted.
- substituent substituting some or all of the hydrogen atoms in the chain saturated hydrocarbon group and the alicyclic saturated hydrocarbon group include the above-mentioned Ra x5 .
- heteroatom include oxygen atoms, sulfur atoms, and nitrogen atoms.
- Examples of groups containing a carbon-carbon double bond formed by two or more of Ra 002 to Ra 004 bonding to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylidene-ethenyl group, a cyclohexylidene-ethenyl group, etc.
- a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylidene-ethenyl group are preferred.
- Ra 002 to Ra 004 are each independently preferably a hydrogen atom or a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and still more preferably a hydrogen atom.
- Yac 0 is a carbon atom
- Xac 0 is a group forming a cyclic hydrocarbon group together with Yac 0.
- Examples of this cyclic hydrocarbon group include the same as the cyclic hydrocarbon group formed by Xaa 0 and Yaa 0 described above.
- Ra 005 is preferably an aromatic hydrocarbon group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene, even more preferably a group obtained by removing one or more hydrogen atoms from benzene or naphthalene, and particularly preferably a group obtained by removing one or more hydrogen atoms from benzene.
- Some or all of the hydrogen atoms in the aromatic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms.
- Specific examples of the substituent that replaces a part or all of the hydrogen atoms of the aromatic hydrocarbon group include the above-mentioned Ra x5 .
- examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.
- Ra 006 and Ra 007 each independently represent a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms.
- Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 006 and Ra 007 include the same monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms in Ra 002 to Ra 004 described above.
- Ra 006 and Ra 007 are preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
- examples of the substituent include the same groups as those for Ra x5 above.
- Ra 008 represents a hydrocarbon group which may have a substituent.
- Examples of the hydrocarbon group for Ra 008 include a linear or branched alkyl group, and a cyclic hydrocarbon group.
- the linear alkyl group in Ra 008 preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms.
- Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and the like.
- a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the branched alkyl group in Ra 008 preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.
- the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
- the monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
- Ra 008 examples include the same as the aromatic hydrocarbon group for Ra 005.
- Ra 008 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from naphthalene or anthracene, and most preferably a group in which one or more hydrogen atoms have been removed from naphthalene.
- substituent which Ra 008 may have include the same substituents as those which Ra 005 may have.
- Ra 008 in formula (a0-r2-04) is a naphthyl group
- the position at which it bonds to the tertiary carbon atom in formula (a1-r2-4) may be either the 1st or 2nd position of the naphthyl group.
- Ra 008 in formula (a0-r2-04) is an anthryl group
- the position at which it is bonded to the tertiary carbon atom in formula (a0-r2-04) may be any one of the 1-position, 2-position or 9-position of the anthryl group.
- Ra 008 is preferably an alkyl group having 1 to 5 carbon atoms among the above, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
- Examples of the acid dissociable group for Ra 01 include acid dissociable groups represented by general formula (a0-r-3) shown below.
- Ra 07 is a hydrocarbon group.
- Ra 08a and Ra 08b each independently represent a hydrogen atom, a halogen atom, or an alkyl group.
- Ra 09 is a hydrogen atom or a hydrocarbon group.
- Ra 07 and Ra 08a or Ra 08b may be bonded to each other to form a ring.
- Ra 08a or Ra 08b and Ra 09 may be bonded to each other to form a ring.
- * represents a bond to the oxygen atom (-O-) in general formula (a0-1).
- examples of the hydrocarbon group in Ra 07 and Ra 09 include the same as those in Ra 01 above.
- examples of the alkyl group in Ra 08a and Ra 08b include the same as the alkyl group in Ra 01 .
- the hydrocarbon groups in Ra 07 and Ra 09 , and the alkyl groups in Ra 08a and Ra 08b may have a substituent. Examples of the substituent include the above-mentioned Ra x5 .
- Ra 07 and Ra 08a or Ra 08b may be bonded to each other to form a ring.
- the ring may be a polycyclic ring or a monocyclic ring, an alicyclic ring, or an aromatic ring.
- the alicyclic and aromatic rings may contain heteroatoms.
- the ring formed by Ra 07 and Ra 08a or Ra 08b bonding to each other is preferably a monocycloalkene, a ring in which a portion of the carbon atoms of a monocycloalkene is substituted with a heteroatom (such as an oxygen atom or a sulfur atom), or a monocycloalkadiene, more preferably a cycloalkene having 3 to 6 carbon atoms, and more preferably cyclopentene or cyclohexene.
- the ring formed by bonding between Ra 07 and Ra 08a or Ra 08b may be a condensed ring.
- Specific examples of the condensed ring include indan.
- the ring formed by bonding Ra 07 and Ra 08a or Ra 08b together may have a substituent.
- the substituent include the above-mentioned Ra x5 .
- Ra 08a or Ra 08b and Ra 09 may be bonded to each other to form a ring, and examples of the ring include the same as the ring formed by Ra 07 and Ra 08a or Ra 08b being bonded to each other.
- Ra 07 and Ra 08a or Ra 08b are preferably bonded to each other to form a ring, more preferably bonded to each other to form a monocyclic ring, and further preferably bonded to each other to form a monocyclic alicyclic ring.
- Ra 09 is preferably a hydrogen atom.
- the ring formed by bonding Ra 07 and Ra 08a or Ra 08b to each other may have a substituent, and as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is further preferable.
- the acid dissociable group for Ra 01 is preferably a tertiary alkyl ester type acid dissociable group, more preferably an acid dissociable group represented by the above formula (a0-r2-01) or (a0-r2-04), and even more preferably an acid dissociable group represented by the above formula (a0-r2-01).
- q is an integer from 0 to 3.
- the structure is a benzene structure
- the structure is a naphthalene structure
- the structure is an anthracene structure
- the structure is a tetracene structure.
- n is an integer of 1 or more, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.
- all hydrogen atoms in the naphthalene other than those substituted with the polymerizable group-containing group (W 01 ) and the -Ya 01 -(C ⁇ O)-O-Ra 01 group may be substituted with hydroxy groups.
- the substitution positions of the polymerizable group-containing group (W 01 ), the -Ya 01 -(C ⁇ O)-O-Ra 01 group, and the hydroxy group are not particularly limited.
- the structural unit (a01) is preferably a structural unit represented by the following general formula (a0-1-1):
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- Ya 001 is a single bond or a divalent linking group.
- Ya 01 is a single bond or a divalent linking group.
- Rax 01 is an acid-dissociable group represented by the above-mentioned general formula (a0-r-1), (a0-r-2), or (a0-r-3).
- q is an integer of 0 to 3.
- n is an integer of 1 or more. However, n ⁇ q ⁇ 2+4.]
- the alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
- the halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms.
- a fluorine atom is particularly preferable.
- R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.
- Ya 001 represents a single bond or a divalent linking group.
- the divalent linking group for Ya 001 is not particularly limited, and preferred examples thereof include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom, which are the same as the divalent hydrocarbon group and the divalent linking group containing a hetero atom for W 01 , respectively.
- Ya 01 is the same as Ya 01 in the above formula (a0-1).
- Rax01 is an acid dissociable group represented by the above-mentioned general formula (a0-r-1), (a0-r-2), or (a0-r-3).
- Rax 01 is preferably an acid dissociable group represented by any one of the above formulas (a0-r2-01) or (a0-r2-04), and more preferably an acid dissociable group represented by the above formula (a0-r2-01).
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the structural unit (a01) in the resist composition of this embodiment is preferably a structural unit represented by any one of the above formulas (a01-1a-2), (a01-1a-8), (a01-1a-28), (a01-1a-31), (a01-1a-34), and (a01-1a-37), and more preferably a structural unit represented by any one of the above formulas (a01-1a-2), (a01-1a-31), (a01-1a-34), and (a01-1a-37).
- the structural unit (a01) contained in the component (A1) may be of one type, or may be of two or more types.
- the proportion of the structural unit (a01) in the component (A1) relative to the total (100 mol%) of all structural units constituting the component (A1) is preferably at least 10 mol%, more preferably at least 20 mol%, and even more preferably at least 30 mol%, or it may even be 100 mol%.
- the amount of the structural unit (a01) in the component (A1) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %, relative to the total amount (100 mol %) of all structural units constituting the component (A1).
- the component (A1) may include other structural units, in addition to the structural unit (a01), as necessary.
- Examples of other structural units include the structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of acid (provided that this does not fall under the category of the structural unit (a01) above); the structural unit (a10) represented by general formula (a10-1) described below; the structural unit (a2) containing a lactone-containing cyclic group; and the structural unit (a8) derived from a compound represented by general formula (a8-1) described below.
- the component (A1) may further contain a structural unit (a1) in addition to the structural unit (a01).
- the structural unit (a1) is a structural unit (excluding those that fall under the category of the aforementioned structural unit (a01)) that contains an acid-decomposable group whose polarity increases when acted upon by an acid.
- Examples of the acid-dissociable group include those that have been proposed as acid-dissociable groups in base resins for chemically amplified resist compositions.
- Specific examples of groups that have been proposed as the acid dissociable group of the base resin for the chemically amplified resist composition include the above-mentioned "acetal type acid dissociable group,””tertiary alkyl ester type acid dissociable group,” and “secondary alkyl ester type acid dissociable group,” as well as the “tertiary alkyloxycarbonyl acid dissociable group” described below.
- Tertiary alkyloxycarbonyl acid dissociating group examples include acid dissociable groups represented by the following general formula (a1-r-3) (hereinafter, for convenience, may be referred to as "tertiary alkyloxycarbonyl acid dissociable group").
- Ra' 7 to Ra' 9 each represent an alkyl group.
- Ra' 7 to Ra' 9 are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
- the total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 or 4.
- the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the ⁇ -position may be substituted with a substituent.
- Preferred specific examples of the structural unit (a1) include structural units represented by general formula (a1-1) or (a1-2) shown below.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- Va 1 is a divalent hydrocarbon group which may have an ether bond.
- n a1 is an integer of 0 to 2.
- Ra 1 is an acid dissociable group represented by the above-mentioned general formula (a0-r-1), (a0-r-2), or (a0-r-3).
- Wa 1 is n a2 +1 valent hydrocarbon group, n a2 is an integer of 1 to 3
- Ra 2 is an acid dissociable group represented by the above-mentioned general formula (a0-r-1) or (a1-r-3).
- the alkyl group having 1 to 5 carbon atoms represented by R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
- the halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms.
- a fluorine atom is particularly preferable.
- R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.
- the divalent hydrocarbon group for Va1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group as the divalent hydrocarbon group in Va1 may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.
- the linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, further preferably has 1 to 4 carbon atoms, and most preferably has 1 to 3 carbon atoms.
- a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
- the branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably has 3 to 6 carbon atoms, even more preferably has 3 or 4 carbon atoms, and most preferably has 3 carbon atoms.
- the branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ;
- Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc.
- Examples of the linear or branched aliphatic hydrocarbon group include the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be polycyclic or monocyclic.
- the monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
- the aromatic hydrocarbon group as the divalent hydrocarbon group in Va1 is a hydrocarbon group having an aromatic ring.
- the aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this carbon number does not include the number of carbon atoms in the substituents.
- Specific examples of the aromatic ring contained in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom, etc.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic hydrocarbon group examples include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring (arylene group); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring (aryl group) has been substituted with an alkylene group (for example, a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group).
- the number of carbon atoms in the alkylene group is preferably 1 to 4, more preferably 1
- Ra 1 is an acid dissociable group represented by the above formula (a0-r-1), (a0-r-2), or (a0-r-3).
- an acid dissociable group represented by the above formula (a0-r-2) is preferable
- an acid dissociable group represented by either of the above formulas (a0-r2-01) or (a0-r2-04) is more preferable
- an acid dissociable group represented by the above formula (a0-r2-01) is even more preferable.
- the n a2 +1 valent hydrocarbon group in Wa 1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, and is usually preferably saturated.
- Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in the structure, and groups that combine linear or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing a ring in the structure.
- the n a2 +1 valency is preferably divalent to tetravalent, and more preferably divalent or trivalent.
- Ra2 is an acid-dissociable group represented by the above general formula (a0-r-1) or (a1-r-3).
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the structural unit (a1) contained in the component (A1) may be of one type, or two or more types.
- a structural unit represented by the above formula (a1-1) is more preferable, since it is easier to further improve the characteristics (sensitivity, shape, etc.) in electron beam or EUV lithography.
- the proportion of the structural unit (a1) in the component (A1) is preferably 1 to 80 mol %, more preferably 5 to 70 mol %, and even more preferably 10 to 60 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
- the component (A1) may further include a structural unit (a10) represented by general formula (a10-1) below (provided that this does not include those corresponding to the structural unit (a01) or the structural unit (a1)).
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- Ya x1 is a single bond or a divalent linking group.
- Wa x1 is an aromatic hydrocarbon group which may have a substituent.
- n ax1 is an integer of 1 or more.
- R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom, a methyl group, or a trifluoromethyl group is more preferable, a hydrogen atom or a methyl group is still more preferable, and a hydrogen atom is particularly preferable.
- Ya x1 represents a single bond or a divalent linking group.
- the divalent linking group for Ya x1 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- Wa x1 represents an aromatic hydrocarbon group which may have a substituent.
- the aromatic hydrocarbon group in Wa x1 may be a group in which (n ax1 +1) hydrogen atoms have been removed from an aromatic ring which may have a substituent.
- the aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons.
- the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
- aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic heterocycle include a pyridine ring and a thiophene ring.
- examples of the aromatic hydrocarbon group in Wa x1 include groups in which (n ax1 +1) hydrogen atoms have been removed from an aromatic compound containing an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.).
- Wa x1 is preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene, naphthalene, anthracene or biphenyl, more preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene or naphthalene, and even more preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene.
- the aromatic hydrocarbon group in Wa x1 may or may not have a substituent.
- substituents include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group.
- alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include the same as those exemplified as the substituent of the cyclic alicyclic hydrocarbon group in Ya x1 .
- the substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, further preferably an ethyl group or a methyl group, and particularly preferably a methyl group. It is preferable that the aromatic hydrocarbon group in Wa x1 does not have a substituent.
- n ax1 represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1, 2 or 3, and particularly preferably 1 or 2.
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the structural unit (a10) the structural unit represented by the above formula (a10-1-1) is preferred.
- the structural unit (a10) contained in the component (A1) may be of one type, or two or more types.
- the proportion of the structural unit (a10) in the component (A1) is preferably 20 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 30 to 60 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
- the component (A1) may further include a structural unit (a2) that contains a lactone-containing cyclic group (provided that this does not correspond to the structural unit (a1)).
- the lactone-containing cyclic group of the structural unit (a2) is effective in improving the adhesion of the resist film to the substrate when the component (A1) is used to form a resist film.
- the structural unit (a2) has the effects of, for example, appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development, thereby improving the lithography properties, etc.
- the lactone ring is counted as the first ring, and when there is only a lactone ring, it is called a monocyclic group, and when there is further contained another ring structure, it is called a polycyclic group regardless of the structure.
- the lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
- the lactone-containing cyclic group in the structural unit (a2) is not particularly limited and any suitable group can be used. Specific examples include the groups represented by the following general formulae (a2-r-1) to (a2-r-7).
- R" is a hydrogen atom, an alkyl group or a lactone-containing cyclic group;
- A" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom or a sulfur atom, n' is an integer of 0 to 2, and m' is 0 or 1.
- * represents a bond (the same applies hereinafter).
- the alkyl group in Ra'21 is preferably an alkyl group having 1 to 6 carbon atoms.
- the alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Of these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.
- the alkoxy group in Ra' 21 is preferably an alkoxy group having 1 to 6 carbon atoms.
- the alkoxy group is preferably linear or branched. Specific examples include groups in which the alkyl groups listed above as the alkyl groups in Ra' 21 are linked to an oxygen atom (-O-).
- the halogen atom in Ra'21 is preferably a fluorine atom.
- the halogenated alkyl group in Ra' 21 may be a group in which some or all of the hydrogen atoms in the alkyl group in Ra' 21 have been substituted with the halogen atoms.
- a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.
- R" is both a hydrogen atom, an alkyl group, or a lactone-containing cyclic group.
- the alkyl group for R′′ may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms.
- R′′ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is particularly preferably a methyl group or an ethyl group.
- R" is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms.
- Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane.
- More specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane.
- Examples of the lactone-containing cyclic group for R′′ include the same groups as those represented by the general formulae (a2-r-1) to (a2-r-7).
- the hydroxyalkyl group in Ra' 21 preferably has 1 to 6 carbon atoms, and specific examples include the alkyl group in Ra' 21 in which at least one hydrogen atom has been substituted with a hydroxyl group.
- Ra'21 each independently represents a hydrogen atom or a cyano group.
- the alkylene group having 1 to 5 carbon atoms in A" is preferably a straight-chain or branched-chain alkylene group, such as a methylene group, an ethylene group, an n-propylene group or an isopropylene group.
- the alkylene group contains an oxygen atom or a sulfur atom
- specific examples thereof include groups in which -O- or -S- is present at the terminal or between the carbon atoms of the alkylene group, such as -O-CH 2 -, -CH 2 -O-CH 2 -, -S-CH 2 - and -CH 2 -S-CH 2 -.
- A" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.
- the structural unit (a2) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the ⁇ -position may be substituted with a substituent.
- the structural unit (a2) is preferably a structural unit represented by general formula (a2-1) shown below.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- Ya 21 is a single bond or a divalent linking group.
- La 21 is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, and R' represents a hydrogen atom or a methyl group.
- Ra 21 is a lactone-containing cyclic group.
- R is the same as above.
- R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferred.
- the divalent linking group for Ya 21 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- Ya 21 is preferably a single bond, an ester bond [--C(.dbd.O)--O--], an ether bond (--O--), a linear or branched alkylene group, or a combination thereof.
- Ya 21 is a single bond, and La 21 is --COO-- or --OCO--.
- Ra 21 represents a lactone-containing cyclic group.
- Suitable examples of the lactone-containing cyclic group for Ra 21 include the groups represented by the above-mentioned general formulae (a2-r-1) to (a2-r-7), respectively.
- the structural unit (a2) contained in the component (A1) may be of one type, or two or more types.
- the proportion of the structural unit (a2) is preferably 1 to 20 mol %, more preferably 1 to 15 mol %, and even more preferably 1 to 10 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
- the proportion of the structural unit (a2) is at least as large as the preferable lower limit, the effects achieved by including the structural unit (a2) can be fully obtained due to the effects described above.
- the proportion of the structural unit (a2) is no more than the upper limit, a balance with other structural units can be achieved, and various lithography properties become favorable.
- the structural unit (a8) is a structural unit derived from a compound represented by general formula (a8-1) shown below. However, those corresponding to the structural unit (a01) or the structural unit (a1) are excluded.
- W2 is a polymerizable group-containing group.
- Yax2 is a single bond or a (n ax2 +1)-valent linking group.
- Yax2 and W2 may form a condensed ring.
- R1 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- R2 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom.
- R2 and Yax2 may be bonded to each other to form a ring structure.
- n ax2 is an integer of 1 to 3.
- the "polymerizable group" in the polymerizable group-containing group of W2 is a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and is, for example, a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond.
- the polymerizable group-containing group may be a group composed only of a polymerizable group, or may be a group composed of a polymerizable group and a group other than the polymerizable group.
- the group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- R X11 , R X12 and R X13 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 represents a single bond or a divalent linking group.
- Examples of the fused ring formed by Ya x2 and W2 include a fused ring formed by the polymerizable group at the W2 site and Ya x2 , and a fused ring formed by Ya x2 and a group other than the polymerizable group at the W2 site.
- the fused ring formed by Ya x2 and W 2 may have a substituent.
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the structural unit (a8) is preferably at least one selected from the group consisting of structural units represented by the chemical formulas (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1-09), and (a8-1-10), and more preferably at least one selected from the group consisting of structural units represented by the chemical formulas (a8-1-01) to (a8-1-04), and (a8-1-09).
- the structural unit (a8) contained in the component (A1) may be of one type, or two or more types.
- the amount of the structural unit (a8) in the component (A1) relative to the total amount (100 mol %) of all structural units constituting the component (A1), is preferably no more than 50 mol %, and more preferably from 0 to 30 mol %.
- the resist composition may contain one type of component (A1) alone or two or more types in combination.
- a polymeric compound having a repeating structure of the structural unit (a01) is preferable, and a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a10) is more preferable; and a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a1).
- the component (A1) is preferably a polymeric compound having a repeating structure of the structural unit (a01); a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a1); a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a10); or a polymeric compound having a repeating structure of the structural unit (a01), a repeating structure of the structural unit (a1), and a repeating structure of the structural unit (a10).
- the proportion of the structural unit (a01) is preferably from 10 to 90 mol %, more preferably from 20 to 80 mol %, even more preferably from 30 to 70 mol %, and particularly preferably from 40 to 60 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
- the proportion of the structural unit (a1) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, even more preferably from 30 to 70 mol%, and particularly preferably from 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
- the proportion of the structural unit (a01) is preferably from 10 to 90 mol %, more preferably from 20 to 80 mol %, even more preferably from 30 to 70 mol %, and particularly preferably from 40 to 60 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
- the proportion of the structural unit (a10) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, even more preferably from 30 to 70 mol%, and particularly preferably from 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
- the proportion of the structural unit (a01) is preferably from 10 to 90 mol %, more preferably from 5 to 60 mol %, even more preferably from 10 to 50 mol %, and particularly preferably from 20 to 40 mol %, based on the total (100 mol %) of all structural units constituting the polymeric compound.
- the proportion of the structural unit (a1) in the polymer compound is preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%, even more preferably from 30 to 50 mol%, and particularly preferably from 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
- the proportion of the structural unit (a10) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, even more preferably from 30 to 70 mol%, and particularly preferably from 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
- the component (A1) can be produced by dissolving monomers from which each structural unit is derived in a polymerization solvent, and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601), and polymerizing the resulting mixture.
- a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601)
- the component (A1) can be produced by dissolving a monomer that derives the structural unit (a01) and, if necessary, a monomer that derives other structural units (for example, a compound in which the hydroxyl group of the monomer that derives the structural unit (a10) is protected) in a polymerization solvent, adding the above-mentioned radical polymerization initiator to the mixture to polymerize, and then, if necessary, carrying out a deprotection reaction.
- a chain transfer agent such as HS-CH 2 -CH 2 -CH 2 -C(CF 3 ) 2 -OH may be used in combination to introduce a -C(CF 3 ) 2 -OH group to the end.
- a copolymer having a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms in this way is effective in reducing development defects and LER (line edge roughness: non-uniform unevenness of the line sidewalls).
- the weight average molecular weight (Mw) of the component (A1) (based on polystyrene equivalent by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000.
- Mw of the component (A1) is no more than the preferred upper limit of this range, the compound has sufficient solubility in a resist solvent for use as a resist, and when it is no less than the preferred lower limit of this range, the compound has good dry etching resistance and good cross-sectional shape of the resist pattern.
- the dispersity (Mw/Mn) of the component (A1) is not particularly limited, but is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and particularly preferably from 1.0 to 2.0, where Mn represents the number average molecular weight.
- the resist composition of this embodiment may also use, as the component (A), a base component (A2) (hereafter referred to as the component (A2)) that does not fall under the category of the component (A1) above and whose solubility in a developer changes under the action of an acid.
- a base component (A2) hereafter referred to as the component (A2)
- the component (A2) may be any compound selected from the many compounds conventionally known as base components for chemically amplified resist compositions.
- the component (A2) may be a polymeric compound or a low molecular weight compound, and may be a combination of two or more of these.
- the proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of component (A).
- the proportion is 25% by mass or more, a resist pattern that is excellent in various lithography properties such as high sensitivity, CDU, resolution, and improved roughness is easily formed.
- the content of component (A) in the resist composition of this embodiment may be adjusted according to the thickness of the resist film to be formed, etc.
- the component (F) includes a fluororesin component (F1) (hereinafter also referred to as “component (F1)”) that has a structural unit represented by general formula (f1) below.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- X0 is a divalent linking group having no acid dissociable site.
- Rf0 is an organic group having a fluorine atom.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- the alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
- the halogenated alkyl group having 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred.
- R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, is more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, is further preferably a hydrogen atom or a methyl group, and is particularly preferably a methyl group.
- X 0 is a divalent linking group that does not have an acid dissociable site.
- the "acid dissociable site” refers to a site in the organic group that dissociates due to the action of an acid generated by exposure, like the above-mentioned "acid dissociable group.”
- Examples of the divalent linking group not having an acid dissociable site for X 0 include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- the term "having a substituent" in the hydrocarbon group means that some or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms.
- the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Such an aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
- aliphatic hydrocarbon groups include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups that contain a ring in the structure.
- the linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms, and most preferably 2 carbon atoms.
- a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group, an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
- a branched alkylene group is preferable, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C ( CH3 ) ( CH2CH3 )-, -C( CH3 )( CH2CH2CH3 ) - , -C( CH2CH3 ) 2- , and the like; alkylethylene groups such as -CH( CH3 ) CH2- , -CH ( CH3 ) CH( CH3 )-, -C ( CH3 )2CH2- , -CH ( CH2CH3 ) CH2- , and the like ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc.
- alkyl group in the alkyl alkylene group a linear alkyl group having 1 to 5 carbon atoms is preferred.
- the chain (straight-chain or branched-chain) aliphatic hydrocarbon group may or may not have a substituent.
- substituents include a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom ( ⁇ O).
- Examples of the aliphatic hydrocarbon group containing a ring include a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring) and a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of the aforementioned chain-like aliphatic hydrocarbon group or is present in the middle of the chain-like aliphatic hydrocarbon group.
- the cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic group a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane.
- the polycyclic group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of such polycycloalkanes include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
- the cyclic aliphatic hydrocarbon group may or may not have a substituent.
- substituents examples include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom ( ⁇ O).
- the aromatic hydrocarbon group examples include divalent aromatic hydrocarbon groups in which one hydrogen atom has been further removed from the aromatic hydrocarbon nucleus of a monovalent aromatic hydrocarbon group, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group; an aromatic hydrocarbon group in which a part of the carbon atoms constituting the ring of the divalent aromatic hydrocarbon group is substituted with a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom;
- the arylalkyl group include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl groups, and aromatic hydrocarbon groups in which one hydrogen atom has been further removed from the aromatic hydrocarbon nucleus.
- aromatic hydrocarbon groups in which a further hydrogen atom has been removed from a phenyl group and aromatic hydrocarbon groups in which a further hydrogen atom has been removed from a naphthyl group are particularly preferred.
- the alkyl chain in the arylalkyl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.
- the aromatic hydrocarbon group may or may not have a substituent.
- substituents examples include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom ( ⁇ O).
- hydrocarbon group which may have a substituent
- a linear, branched or cyclic aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group are more preferred, and a methylene group, an ethylene group, -CH(CH 3 )-, a group in which one further hydrogen atom has been removed from a tetracyclododecanyl group, and an aromatic hydrocarbon group in which one further hydrogen atom has been removed from a phenyl group are particularly preferred.
- a heteroatom is an atom other than carbon and hydrogen atoms, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
- the divalent hydrocarbon group may be the same as the above-mentioned hydrocarbon group which may have a substituent, and a straight-chain or branched-chain aliphatic hydrocarbon group is preferred.
- a divalent linking group containing a heteroatom a combination of the above-mentioned "these groups” and a divalent hydrocarbon group is more preferable, and specifically, a combination of the above-mentioned "these groups” and the above-mentioned aliphatic hydrocarbon group, and a combination of the above-mentioned aliphatic hydrocarbon group, the above-mentioned "these groups” and the above-mentioned aliphatic hydrocarbon group are particularly preferable.
- Rf 0 is an organic group having a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom.
- the fluorine atom-containing hydrocarbon group may be linear, branched, or cyclic and preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, still more preferably has 1 to 10 carbon atoms, and particularly preferably has 1 to 5 carbon atoms.
- the number of fluorine atoms in the fluorine-containing hydrocarbon group is preferably 1-10, more preferably 1-6, and even more preferably 1-3.
- Rf 0 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and a trifluoromethyl group, -CH 2 -CF 3 , -CH 2 -CH 2 -CF 3 , -CH 2 -CF 2 -CF 3 , or -CH(CF 3 ) 2 is preferred.
- the (F1) component preferably has a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- X 01 is a divalent linking group having no acid dissociable site.
- Rf 01 is an organic group having a fluorine atom.
- R in the above general formula (f1-1) is the same as R in the above formula (f1).
- Examples of the divalent linking group not having an acid dissociable site in X 01 in the above general formula (f1-1) include the same as X 0 in the above formula (f1).
- the divalent linking group having no acid dissociable site in X 01 in general formula (f1-1) is preferably a linear or branched aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent, more preferably a linear or branched aliphatic hydrocarbon group which may have a fluorine atom, or an aromatic hydrocarbon group which may have a substituent, and even more preferably a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group having a fluorine atom, or an aromatic hydrocarbon group which may have a substituent.
- the aliphatic hydrocarbon group preferably contains 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms.
- ArX is preferably a phenylene group.
- RZ is preferably a divalent linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably a divalent linear aliphatic hydrocarbon group having 1 to 3 carbon atoms.
- Rf 01 in the above general formula (f1-1) include the same as Rf 0 in the above formula (f1), and are preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, more preferably a trifluoromethyl group, -CH 2 -CF 3 , -CH 2 -CH 2 -CF 3 , -CH 2 -CF 2 -CF 3 , -CH(CF 3 ) 2 , and even more preferably -CH 2 -CF 3 , -CH 2 -CH 2 -CF 3 , -CH(CF 3 ) 2 .
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the structural unit represented by formula (f1-1-2) is preferred among the above.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- X 021 is a cyclic group. A part or all of the hydrogen atoms of the cyclic group may be substituted with a substituent.
- X 022 is a single bond or a divalent linking group having no acid dissociable site.
- Rf 02 is an organic group having a fluorine atom.
- R in the above general formula (f1-2) is the same as R in the above formula (f1).
- X in the above general formula (f1-2) is a cyclic group, and some or all of the hydrogen atoms of the cyclic group may be substituted with a substituent.
- Specific examples of the cyclic group include an aliphatic cyclic group, an arylene group, and a heteroarylene group.
- the aliphatic cyclic group may be a polycyclic group or a monocyclic group.
- the monocyclic group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms, and examples of the monocycloalkane include cyclopentane and cyclohexane.
- the polycyclic group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of such polycycloalkanes include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
- the arylene group is preferably a phenylene group.
- Examples of the heteroarylene group include a thienylene group and an isoxazolene group.
- X 021 in general formula (f1-2) is preferably an arylene group, and more preferably a phenylene group.
- Examples of the divalent linking group not having an acid dissociable site in X 022 in the above general formula (f1-2) include the same as X 0 in the above formula (f1).
- a linear or branched aliphatic hydrocarbon group which may have a substituent is preferable, and a linear aliphatic hydrocarbon group which may have a substituent is more preferable.
- the aliphatic hydrocarbon group preferably contains 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms.
- RY is preferably a divalent linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably a divalent linear aliphatic hydrocarbon group having 1 to 3 carbon atoms.
- Rf 01 in the above general formula (f1-2) may be the same as Rf 0 in the above formula (f1), and is preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, more preferably a trifluoromethyl group, -CH 2 -CF 3 , -CH 2 -CH 2 -CF 3 , -CH 2 -CF 2 -CF 3 , -CH(CF 3 ) 2 , and even more preferably -CH 2 -CF 2 -CF 3 .
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the component (F1) may have other structural units, as well as the structural unit represented by general formula (f1-1) or the structural unit represented by general formula (f1-2) above, if necessary.
- the other structural units include the above-mentioned structural unit (a1), the above-mentioned structural unit (a2), a structural unit derived from acrylic acid, and a structural unit derived from methacrylic acid.
- the component (F1) is preferably a polymeric compound having a repeating structure of the structural unit (f1), more preferably a polymeric compound having a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1) or (a2), and even more preferably a polymeric compound having a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1) or (a2), and a structural unit derived from acrylic acid or methacrylic acid.
- the component (F1) is preferably a polymeric compound comprising a repeating structure of the structural unit (f1); a polymeric compound comprising a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1); a polymeric compound comprising a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a2); a polymeric compound comprising a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid, more preferably a polymeric compound comprising a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1); a polymeric compound comprising a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid, and even more preferably a polymeric compound comprising
- the structural unit (a1) that is copolymerized with the structural unit (f1) is preferably a structural unit represented by the above general formula (a1-1), in which Ra 1 in the formula is an acid-dissociable group represented by the above-mentioned general formula (a0-r-1).
- the structural unit (f1) is preferably a structural unit represented by the above-mentioned general formula (f1-1) or (f1-2).
- the proportion of the structural unit (f1) is preferably 40 to 95 mol %, more preferably 50 to 90 mol %, and even more preferably 60 to 80 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound. Furthermore, the proportion of the structural unit (a1) in the polymer compound is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, and even more preferably from 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
- the proportion of the structural unit (f1) is preferably 40 to 95 mol %, more preferably 50 to 90 mol %, and even more preferably 60 to 80 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
- the proportion of the structural unit (a2) in the polymer compound is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, and even more preferably from 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
- the proportion of the structural unit (f1) relative to the total (100 mol%) of all structural units constituting the polymeric compound is preferably 40 to 95 mol%, more preferably 50 to 90 mol%, and even more preferably 60 to 80 mol%.
- the proportion of the structural unit (a1) in the polymer compound is preferably from 1 to 50 mol%, more preferably from 5 to 40 mol%, and even more preferably from 10 to 30 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
- the proportion of structural units derived from acrylic acid or methacrylic acid in the polymer compound is preferably 1 to 40 mol %, more preferably 1 to 30 mol %, and even more preferably 5 to 20 mol %, relative to the total (100 mol %) of all structural units constituting the polymer compound.
- the weight average molecular weight (Mw) of component (F1) (based on polystyrene equivalent measured by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. When it is below the upper limit of this range, the compound has sufficient solubility in a resist solvent for use as a resist, and when it is above the lower limit of this range, the resist film has good water repellency.
- the dispersity (Mw/Mn) of the component (F1) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0, and most preferably from 1.0 to 2.5.
- the component (F1) may use either a single type, or a combination of two or more types.
- the amount of the component (F1) relative to 100 parts by mass of the component (A1) is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 3 to 7 parts by mass.
- the content of the component (F1) is at least the above preferable lower limit, the resolution and CDU are further improved.
- the content of the component (F1) is equal to or less than the above preferred upper limit, the sensitivity is further improved.
- a fluororesin component (F2) (hereafter referred to as "component (F2)") that does not fall under the category of the component (F1) may be used in combination as the component (F).
- component (F2) a fluororesin component
- the fluororesin component consist solely of the component (F1).
- the resist composition of one embodiment excludes resist compositions that contain the component (F2).
- the proportion of component (F1) in component (F) is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of component (F). If the proportion is 25% by mass or more, a resist pattern that is excellent in various lithography properties such as high sensitivity, resolution, and improved roughness is easily formed.
- the resist composition of this embodiment may further contain other components in addition to the above-mentioned components (A) and (F).
- other components include the following components (B), (D), (E), and (S).
- the resist composition of this embodiment preferably further contains an acid generator component (B) that generates an acid upon exposure.
- an acid generator component (B) that generates an acid upon exposure.
- Such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl- or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.
- onium salt-based acid generators such as iodonium salts and sulfonium salts
- oxime sulfonate-based acid generators such as bisalkyl- or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes
- nitrobenzylsulfonate-based acid generators iminosulfonate-based acid generators
- onium salt acid generators examples include a compound represented by the following general formula (b-1) (hereinafter also referred to as “component (b-1)”), a compound represented by general formula (b-2) (hereinafter also referred to as “component (b-2)”), or a compound represented by general formula (b-3) (hereinafter also referred to as “component (b-3)”).
- R 101 and R 104 to R 108 are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.
- R 104 and R 105 may be bonded to each other to form a ring structure.
- R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom.
- Y 101 is a divalent linking group containing an oxygen atom or a single bond.
- V 101 to V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group.
- L 101 to L 102 are each independently a single bond or an oxygen atom.
- L 103 to L 105 are each independently a single bond, -CO-, or -SO 2 -.
- m is an integer of 1 or more, and M' m+ is an m-valent onium cation
- R 101 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.
- the cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
- An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity.
- the aliphatic hydrocarbon group is preferably saturated.
- the aromatic hydrocarbon group for R 101 is a hydrocarbon group having an aromatic ring.
- the number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.
- Specific examples of the aromatic ring contained in the aromatic hydrocarbon group of R 101 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which a part of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, etc.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- Specific examples of the aromatic hydrocarbon group for R 101 include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, etc.), etc.
- the number of carbon atoms in the alkylene group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
- the cyclic aliphatic hydrocarbon group for R 101 includes an aliphatic hydrocarbon group containing a ring in the structure.
- Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms.
- the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
- a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane
- a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
- the cyclic aliphatic hydrocarbon group for R 101 is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, further preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.
- the linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3.
- linear alkylene groups are preferred, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], and the like.
- the branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
- the branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc.
- the cyclic hydrocarbon group in R 101 may contain a heteroatom, such as a heterocycle.
- a heteroatom such as a heterocycle.
- Specific examples include the lactone-containing cyclic groups represented by the above general formulae (a2-r-1) to (a2-r-7), the -SO 2 -containing cyclic groups represented by the following general formulae (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the following chemical formulae (r-hr-1) to (r-hr-16).
- * represents a bond bonded to Y 101 in formula (b-1).
- R is a hydrogen atom, an alkyl group, a lactone-containing cyclic group or an -SO 2 - containing cyclic group;
- B" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n' is an integer of 0 to 2. * represents a bond.
- B" represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom.
- B" is preferably an alkylene group having 1 to 5 carbon atoms or --O--, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.
- Examples of the substituent in the cyclic group of R 101 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms.
- the alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
- halogen atom as a substituent, a fluorine atom, a bromine atom or an iodine atom is preferred.
- halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.
- the carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) that constitutes a cyclic hydrocarbon group.
- the cyclic hydrocarbon group in R 101 may be a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused.
- the fused ring include a polycycloalkane having a polycyclic skeleton of a bridged ring system to which one or more aromatic rings are fused.
- Specific examples of the bridged ring polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane.
- the fused ring group is preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane, and more preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicyclo[2.2.2]octane.
- Specific examples of the fused ring group in R 101 include those represented by the following formulae (r-br-1) to (r-br-2). In the formulae, * represents a bond bonded to Y 101 in formula (b-1).
- Examples of the substituent that the fused cyclic group for R 101 may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.
- Examples of the alkyl group, alkoxy group, halogen atom and halogenated alkyl group as the substituent of the condensed cyclic group include the same as those exemplified as the substituent of the cyclic group in R 101 above.
- aromatic hydrocarbon group as the substituent of the fused ring group
- aryl group for example, a phenyl group, a naphthyl group, etc.
- an alkylene group for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.
- heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6), respectively.
- Examples of the alicyclic hydrocarbon group as a substituent of the fused cyclic group include groups obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane or cyclohexane; groups obtained by removing one hydrogen atom from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane or tetracyclododecane; lactone-containing cyclic groups represented by each of the general formulae (a2-r-1) to (a2-r-7); —SO 2 -containing cyclic groups represented by each of the general formulae (b5-r-1) to (b5-r-4); and heterocyclic groups represented by each of the formulae (r-hr-7) to (r-hr-16).
- a monocycloalkane such as cyclopentane or cyclohexane
- a chain alkyl group which may have a substituent may be either a straight chain or a branched chain.
- the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
- the branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10.
- Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
- a chain alkenyl group which may have a substituent may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3.
- Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups.
- Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.
- Examples of the substituent in the chain alkyl or alkenyl group of R 101 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic groups in R 101 above.
- R 101 is preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent.
- the substituent is preferably an iodine atom.
- the cyclic hydrocarbon group is preferably a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane; a lactone-containing cyclic group represented by each of the general formulas (a2-r-1) to (a2-r-7); or an —SO 2 —-containing cyclic group represented by each of the general formulas (b5-r-1) to (b5-r-4), more preferably a phenyl group or a group in which one or more hydrogen atoms have been removed from a polycycloalkane, and even more preferably a phenyl group or an adamantyl group.
- Y 101 is a single bond or a divalent linking group containing an oxygen atom.
- Y 101 may contain an atom other than an oxygen atom.
- the atom other than an oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.
- the divalent linking group containing an oxygen atom include linking groups represented by the following general formulae (y-al-1) to (y-al-7), respectively.
- general formulae (y-al-1) to (y-al-7) what is bonded to R 101 in the above formula (b-1) is V' 101 in the following general formulae (y-al-1) to (y-al-7).
- V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms
- V' 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.
- the divalent saturated hydrocarbon group for V' 102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.
- the alkylene group in V'101 and V'102 may be a linear alkylene group or a branched alkylene group, with a linear alkylene group being preferred.
- Specific examples of the alkylene group in V' 101 and V' 102 include a methylene group [-CH 2 -]; alkylmethylene groups such as -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, and -C(CH 2 CH 3 ) 2 -; an ethylene group [-CH 2 CH 2 -]; alkylethylene groups such as -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, and -CH(CH 2 CH 3 )CH 2 -; a trim
- some of the methylene groups in the alkylene group in V'101 or V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms.
- the aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra'3 in formula (a1-r-1), and more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.
- Y 101 is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, more preferably a linking group represented by each of the above formulas (y-al-1) to (y-al-5), and still more preferably a linking group represented by the above formula (y-al-1).
- V 101 is a single bond, an alkylene group, or a fluorinated alkylene group.
- the alkylene group or fluorinated alkylene group in V 101 preferably has 1 to 4 carbon atoms.
- V 101 is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.
- R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
- R 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.
- anion moiety represented by formula (b-1) include, for example, when Y 101 is a single bond, fluorinated alkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion; and, when Y 101 is a divalent linking group containing an oxygen atom, anions represented by any of the following formulas (an-1) to (an-3) are included.
- R" 101 is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by each of the above chemical formulas (r-hr-1) to (r-hr-6), a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), a chain-like alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent.
- R" 102 is an aliphatic cyclic group which may have a substituent, a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by each of the above general formulas (a2-r-1), (a2-r-3) to (a2-r-7), or an -SO 2 - containing cyclic group represented by each of the above general formulas (b5-r-1) to (b5-r-4).
- R" 103 is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkenyl group which may have a substituent.
- V" 101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms.
- R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
- Each v" is independently an integer of 0 to 3
- each q" is independently an integer of 0 to 20, and n" is 0 or 1.
- the aliphatic cyclic groups which may have a substituent of R" 101 , R" 102 and R" 103 are preferably the groups exemplified as the cyclic aliphatic hydrocarbon group in R 101 in formula (b-1) above.
- substituents include the same as the substituents which may substitute the cyclic aliphatic hydrocarbon group in R 101 in formula (b-1) above.
- the aromatic cyclic group which may have a substituent in R" 101 and R" 103 is preferably a group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R101 in the above formula (b-1).
- substituents include the same as the substituent which may substitute the aromatic hydrocarbon group in R101 in the above formula (b-1).
- the chain alkyl group which may have a substituent in R′′ 101 is preferably a group exemplified as the chain alkyl group in R 101 in the above formula (b-1).
- the chain alkenyl group which may have a substituent in R′′ 103 is preferably a group exemplified as the chain alkenyl group in R 101 in the above formula (b-1).
- R 104 and R 105 each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples of these include the same as R 101 in formula (b-1). However, R 104 and R 105 may be bonded to each other to form a ring. R 104 and R 105 are preferably a chain alkyl group which may have a substituent, and more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group.
- the number of carbon atoms in the chain-like alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3.
- the number of carbon atoms in the chain-like alkyl group of R 104 and R 105 is preferably as small as possible within the above range of the number of carbon atoms, for reasons such as good solubility in a resist solvent.
- the more hydrogen atoms substituted with fluorine atoms the stronger the acid strength becomes, and the more the transparency to high-energy light and electron beams of 250 nm or less is improved, which is preferable.
- the ratio of fluorine atoms in the chain-like alkyl group i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
- V 102 and V 103 each independently represent a single bond, an alkylene group, or a fluorinated alkylene group, and examples of V 101 in formula (b-1) include the same as those described above.
- L 101 and L 102 each independently represent a single bond or an oxygen atom.
- R to R each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples of these include the same as R 101 in formula (b-1).
- L 103 to L 105 each independently represent a single bond, —CO— or —SO 2 —.
- the anion in component (b-1) is preferred as the anion portion of component (B).
- M'm+ represents an m-valent onium cation, of which sulfonium cation and iodonium cation are preferred.
- m is an integer of 1 or more.
- Preferred cationic moieties include organic cations represented by the following general formulas (ca-1) to (ca-3).
- R 201 to R 207 each independently represent an aryl group, an alkyl group or an alkenyl group which may have a substituent.
- R 201 to R 203 and R 206 to R 207 may be bonded to each other to form a ring together with the sulfur atom in the formula.
- R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an -SO 2 - containing cyclic group which may have a substituent.
- the aryl group for R 201 to R 207 can be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferable.
- the alkyl group for R 201 to R 207 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
- the alkenyl group for R 201 to R 207 preferably has 2 to 10 carbon atoms.
- R 201 to R 207 and R 210 may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulas (ca-r-1) to (ca-r-7), respectively.
- R'201 each independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.
- the cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity.
- the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
- the aromatic hydrocarbon group in R'201 is a hydrocarbon group having an aromatic ring.
- the aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, even more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.
- Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in R'201 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- Specific examples of the aromatic hydrocarbon group for R'201 include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.).
- the alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon
- the cyclic aliphatic hydrocarbon group for R'201 includes an aliphatic hydrocarbon group containing a ring in the structure.
- Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms.
- the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
- a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane
- a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
- the cyclic aliphatic hydrocarbon group for R'201 is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.
- the linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
- a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
- the branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc.
- the cyclic hydrocarbon group in R'201 may contain a heteroatom, such as a heterocycle.
- a heteroatom such as a heterocycle.
- Specific examples include the lactone-containing cyclic groups represented by the general formulae (a2-r-1) to (a2-r-7) above, the -SO 2 -containing cyclic groups represented by the general formulae (b5-r-1) to (b5-r-4) above, and the heterocyclic groups represented by the chemical formulae (r-hr-1) to (r-hr-16) above.
- Examples of the substituent in the cyclic group of R'201 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
- the alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
- a fluorine atom is preferred.
- halogenated alkyl group as a substituent examples include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.
- the carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) that constitutes a cyclic hydrocarbon group.
- a chain alkyl group which may have a substituent may be either linear or branched.
- the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and most preferably has 1 to 10 carbon atoms.
- the branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 15 carbon atoms, and most preferably has 3 to 10 carbon atoms.
- Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
- a chain alkenyl group which may have a substituent may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms.
- Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups.
- Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.
- Examples of the substituent in the chain alkyl or alkenyl group of R'201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic groups in R'201 described above.
- the optionally substituted cyclic group, optionally substituted chain alkyl group, or optionally substituted chain alkenyl group for R'201 is as described above, and examples of the optionally substituted cyclic group or optionally substituted chain alkyl group include the same as the acid dissociable group represented by formula (a1-r-2) above.
- R'201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane, a lactone-containing cyclic group represented by each of the general formulae (a2-r-1) to (a2-r-7), an -SO 2 --containing cyclic group represented by each of the general formulae (b5-r-1) to (b5-r-4), etc. are preferred.
- R 201 to R 203 and R 206 to R 207 when bonded to each other to form a ring together with the sulfur atom in the formula, they may be bonded via a heteroatom such as a sulfur atom, an oxygen atom or a nitrogen atom, or a functional group such as a carbonyl group, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )- (wherein R N is an alkyl group having 1 to 5 carbon atoms).
- a heteroatom such as a sulfur atom, an oxygen atom or a nitrogen atom
- a functional group such as a carbonyl group, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )- (wherein R N is an alkyl group having 1 to 5 carbon atoms).
- one ring containing the sulfur atom in the ring skeleton in the formula is preferably a 3- to 10-membered ring including the sulfur atom, and particularly preferably a 5- to 7-membered ring.
- the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.
- R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they represent an alkyl group, they may be bonded to each other to form a ring.
- R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an --SO 2 -- containing cyclic group which may have a substituent.
- the aryl group for R 210 includes unsubstituted aryl groups having 6 to 20 carbon atoms, and is preferably a phenyl group or a naphthyl group.
- the alkyl group for R 210 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
- the alkenyl group for R 210 preferably has 2 to 10 carbon atoms.
- a "-SO 2 -containing polycyclic group” is preferable, and a group represented by the above general formula (b5-r-1) is more preferable.
- Suitable cations represented by the formula (ca-1) include the cations represented by the following chemical formulas (ca-1-1) to (ca-1-70).
- g1, g2, and g3 each represent a repeating number, where g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20.
- R′′ 201 is a hydrogen atom or a substituent, and the substituent is the same as those exemplified as the substituent that R 201 to R 207 and R 210 to R 212 may have.
- Suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, etc.
- Suitable cations represented by the formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).
- the component (B) may use either a single type, or a combination of two or more types.
- the amount of the component (B) in the resist composition is preferably 5 to 40 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the component (A1).
- the content of component (B) is at least the lower limit of the aforementioned preferred range, lithography properties such as sensitivity, CDU, resolution performance, and LWR (line width roughness) reduction are further improved during resist pattern formation.
- the content is no more than the upper limit of the preferred range, a homogeneous solution is more easily obtained when the components of the resist composition are dissolved in an organic solvent, and the storage stability of the resist composition is further improved.
- the resist composition of this embodiment preferably further contains a base component (hereinafter also referred to as “component (D)”) that traps acid generated upon exposure (i.e., controls the diffusion of acid).
- the component (D) acts as a quencher (acid diffusion controller) that traps acid generated in the resist composition upon exposure.
- Examples of the component (D) include a photodegradable base (D1) (hereinafter referred to as “component (D1)”) that decomposes upon exposure to light and loses its acid diffusion controllability, and a nitrogen-containing organic compound (D2) (hereinafter referred to as “component (D2)”) that does not fall under the category of component (D1).
- the photodegradable base (component (D1)) is preferred because it is likely to enhance the roughness reduction properties.
- component (D1) it is possible to easily enhance both the properties of increasing sensitivity and suppressing the occurrence of coating defects.
- the component (D1) is not particularly limited as long as it decomposes upon exposure to light and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "component (d1-1)”), a compound represented by the following general formula (d1-2) (hereinafter referred to as “component (d1-2)”), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "component (d1-3)”):
- component (d1-1) to (d1-3) do not act as quenchers in the exposed areas of the resist film because they decompose and lose their acid diffusion control ability (basicity), but act as quenchers in the unexposed areas of the resist film.
- Rd 1 to Rd 4 are a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.
- Rd 2 in formula (d1-2) a fluorine atom is not bonded to the carbon atom adjacent to the S atom.
- Yd 1 is a single bond or a divalent linking group.
- m is an integer of 1 or more, and each M m+ is independently an m-valent organic cation.
- Rd 1 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples of these groups include the same as those for R' 201 described above.
- Rd 1 is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent.
- substituents which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, a lactone-containing cyclic group represented by each of the above general formulas (a2-r-1) to (a2-r-7), an ether bond, an ester bond, or a combination thereof.
- an ether bond or an ester bond is contained as a substituent, it may be via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the above formulas (y-al-1) to (y-al-5).
- V' 101 in the general formulae (y-al-1) to (y-al-7) is bonded to a carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 1 in formula (d3-1).
- Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and another ring structure).
- the aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane.
- the chain alkyl group preferably has 1 to 10 carbon atoms.
- chain alkyl group examples include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched alkyl groups such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
- linear alkyl groups such as a methyl group, an ethyl group, a propyl group,
- the chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent
- the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4.
- the fluorinated alkyl group may contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.
- M m+ represents an m-valent organic cation.
- Suitable examples of the organic cation of M m+ include the same cations as those represented by the general formulas (ca-1) to (ca-3), respectively, more preferably the cation represented by the general formula (ca-1), and even more preferably the cations represented by the general formulas (ca-1-1) to (ca-1-70), respectively.
- the (d1-1) component may be used alone or in combination of two or more types.
- Rd2 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent
- examples of R'201 include the same as those described above for R'201 .
- the carbon atom adjacent to the S atom does not have a fluorine atom bonded thereto (is not substituted with fluorine), whereby the anion of the component (d1-2) becomes an appropriately weak acid anion, and the quenching ability of the component (D) is improved.
- Rd2 is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent, and more preferably an aliphatic cyclic group which may have a substituent.
- the chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 3 to 10 carbon atoms.
- the aliphatic cyclic group is preferably a group (which may have a substituent) in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, tetracyclododecane, or the like; or a group in which one or more hydrogen atoms have been removed from camphor.
- the hydrocarbon group of Rd2 may have a substituent, and examples of the substituent include the same as the substituents that may be possessed by the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in Rd1 of the above formula (d1-1).
- M m+ represents an m-valent organic cation and is the same as M m+ in formula (d1-1).
- the component (d1-2) may be used alone or in combination of two or more.
- Rd 3 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof include the same as those of R' 201 , and is preferably a cyclic group, chain alkyl group, or chain alkenyl group containing a fluorine atom.
- a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group of Rd 1 is more preferable.
- Rd4 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent
- examples of R'201 include the same as those described above.
- an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group, which may have a substituent is preferable.
- the alkyl group in Rd 4 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc.
- a portion of the hydrogen atoms of the alkyl group in Rd 4 may be substituted with a hydroxyl group, a cyano group, etc.
- the alkoxy group in Rd 4 is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferred.
- the alkenyl group in Rd4 may be the same as the alkenyl group in R'201 , and preferably a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, or a 2-methylpropenyl group. These groups may further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.
- the cyclic group in Rd 4 may be the same as the cyclic group in R' 201 , and is preferably an alicyclic group obtained by removing one or more hydrogen atoms from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane, or an aromatic group such as a phenyl group or naphthyl group.
- a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane
- an aromatic group such as a phenyl group or naphthyl group.
- Yd1 represents a single bond or a divalent linking group.
- the divalent linking group in Yd 1 is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent (an aliphatic hydrocarbon group, an aromatic hydrocarbon group), a divalent linking group containing a hetero atom, etc. These include the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom mentioned in the description of the divalent linking group in Ya 21 in the above formula (a2-1).
- Yd1 is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof.
- the alkylene group is more preferably a linear or branched alkylene group, and further preferably a methylene group or an ethylene group.
- M m+ represents an m-valent organic cation and is the same as M m+ in formula (d1-1).
- the component (d1-3) may be used alone or in combination of two or more.
- the component (D1) may be any one of the above components (d1-1) to (d1-3), or a combination of two or more of them.
- the amount of the component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, relative to 100 parts by mass of the component (A1).
- the amount of the component (D1) is at least as large as the preferred lower limit, particularly good lithography properties and resist pattern shape are likely to be obtained, while when the amount is no more than the upper limit, good sensitivity can be maintained and excellent throughput is also achieved.
- the component (D1) preferably includes the component (d1-1) above.
- the content of the component (d1-1) in the entire component (D) is preferably 50 mass % or more, preferably 70 mass % or more, and more preferably 90 mass % or more.
- the component (D) may consist solely of the compound (d1-1).
- Production method of component (D1) The method for producing the components (d1-1) and (d1-2) is not particularly limited, and they can be produced by known methods.
- the method for producing the component (d1-3) is not particularly limited, and it can be produced, for example, in the same manner as the method described in US 2012-0149916.
- the component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as “component (D2)”) that does not fall under the category of the above-mentioned component (D1).
- component (D2) is not particularly limited as long as it acts as an acid diffusion controller and does not fall under the category of component (D1), and any known component may be used.
- aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred.
- Aliphatic amines are amines that have one or more aliphatic groups, preferably having 1 to 12 carbon atoms.
- aliphatic amines include amines in which at least one of the hydrogen atoms of ammonia NH3 is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms (alkylamines or alkyl alcohol amines), or cyclic amines.
- alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcohol amines such as diethanolamine, triethanolamine, diis
- cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom.
- the heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
- the aliphatic polycyclic amine is preferably one having 6 to 10 carbon atoms, and specific examples thereof include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.
- aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris ⁇ 2-(2-methoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(2-methoxyethoxymethoxy)ethyl ⁇ amine, tris ⁇ 2-(1-methoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(1-ethoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(1-ethoxypropoxy)ethyl ⁇ amine, tris[2- ⁇ 2-(2-hydroxyethoxy)ethoxy ⁇ ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.
- aromatic amine may be used as the component (D2).
- aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and 2,6-di-tert-butylpyridine.
- component (D2) is preferably an alkylamine, more preferably a trialkylamine having 6 to 30 carbon atoms.
- the component (D2) may be used alone or in combination of two or more types.
- the amount of the component (D2) in the resist composition is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the component (A1).
- the amount of the component (D2) is at least as large as the preferred lower limit, particularly good lithography properties and resist pattern shape are likely to be obtained, while when the amount is no more than the upper limit, good sensitivity can be maintained and excellent throughput is also achieved.
- the resist composition of this embodiment may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids, and phosphorus oxoacids and derivatives thereof (hereafter referred to as "component (E)").
- component (E) phosphorus oxoacids and derivatives thereof
- the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, and among these, salicylic acid is preferred.
- phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred.
- the component (E) may use either a single type, or a combination of two or more types.
- the amount of the component (E) per 100 parts by mass of the component (A1) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass.
- the resist composition of this embodiment can be produced by dissolving the resist materials in an organic solvent component (hereafter referred to as “component (S)”).
- component (S) may be used alone or as a mixed solvent of two or more kinds.
- PGMEA propylene glycol monomethyl ether acetate
- EL ethyl lactate
- cyclohexanone a mixed solvent of two or more kinds.
- a mixed solvent of PGMEA and a polar solvent is also preferred.
- the blending ratio (mass ratio) may be appropriately determined taking into consideration the compatibility between PGMEA and the polar solvent, etc.
- a mixed solvent of at least one selected from PGMEA and EL with ⁇ -butyrolactone is also preferred.
- the mixing ratio of the former to the latter is preferably 70:30 to 95:5 by mass.
- the amount of the component (S) used is used so that the solids concentration of the resist composition falls within the range of 0.1 to 20 mass %, and preferably 0.2 to 15 mass %.
- impurities and the like may be removed using a polyimide porous film, a polyamideimide porous film, or the like.
- the resist composition may be filtered using a filter made of a polyimide porous film, a filter made of a polyamideimide porous film, or a filter made of a polyimide porous film and a polyamideimide porous film.
- the polyimide porous film and the polyamideimide porous film include those described in JP 2016-155121 A.
- the resist composition of the present embodiment described above contains a resin component (A1) having the structural unit (a01) described above, and a fluororesin component (F1) having a structural unit represented by general formula (f1). Since the structural unit (a01) has both an acid dissociable group and a phenolic hydroxyl group, the content of the phenolic hydroxyl group can be increased without decreasing the content of the acid dissociable group in the resin component (A1). Therefore, the sensitivity can be improved without decreasing the resolution. On the other hand, since the structural unit (a01) has a relatively highly hydrophobic structure, the developer affinity and hydrophilicity are relatively low.
- the developer affinity and hydrophilicity are improved, and the resist film can be uniformly dissolved in the alkaline development process and the water rinsing process, and the CDU can be improved and the resolution can be further improved. Therefore, according to the resist composition of this embodiment, it is possible to achieve high sensitivity and form a resist pattern with excellent resolution and reduced roughness.
- a method for forming a resist pattern according to the second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition according to the first aspect of the present invention, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.
- One embodiment of the resist pattern forming method is, for example, a resist pattern forming method carried out as follows.
- the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and then baked (post-applied bake (PAB)) at a temperature of, for example, 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film.
- PAB post-applied bake
- the resist film is selectively exposed using an exposure device such as an electron beam lithography device or an ArF lithography device, either through a mask (mask pattern) on which a predetermined pattern has been formed, or by lithography using direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150° C.
- PEB post-exposure bake
- the resist film is developed using an alkaline developer in the case of an alkaline development process, or a developer containing an organic solvent (organic developer) in the case of a solvent development process.
- a rinse process is preferably carried out.
- the rinse process is preferably a water rinse using pure water, and in the case of a solvent development process, a rinse liquid containing an organic solvent is preferably used.
- a treatment may be carried out in which the developer or rinsing liquid adhering to the pattern is removed by using a supercritical fluid. After the development or rinsing treatment, the resist is dried. In some cases, a baking treatment (post-baking) may be performed after the development treatment.
- the support is not particularly limited, and conventionally known materials can be used, such as substrates for electronic components and substrates on which a predetermined wiring pattern is formed. More specifically, examples include silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, and glass substrates. Materials that can be used for the wiring pattern include, for example, copper, aluminum, nickel, and gold.
- the wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays can be used.
- radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays can be used.
- the exposure method for the resist film may be a normal exposure method (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion exposure (liquid immersion lithography).
- Immersion exposure is an exposure method in which the space between the resist film and the lowest lens of the exposure tool is filled with a solvent (immersion medium) that has a refractive index greater than that of air, and exposure (immersion exposure) is then performed in that state.
- the immersion medium is preferably a solvent having a refractive index greater than that of air and less than that of the resist film to be exposed, and examples of such a solvent include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
- water is preferably used as the liquid immersion medium.
- the alkaline developer used in the development treatment in the alkaline development process may be, for example, a 0.1 to 10% by weight aqueous solution of tetramethylammonium hydroxide (TMAH).
- TMAH tetramethylammonium hydroxide
- the organic solvent contained in the organic developer used in the development treatment in the solvent development process may be any organic solvent capable of dissolving the component (A) (the component (A) before exposure), and may be appropriately selected from known organic solvents.
- Specific examples of the organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.
- Ester solvents include, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
- nitrile solvents examples include acetonitrile, propionitrile, valeronitrile, butyronitrile, etc.
- additives can be added to the organic developer as necessary.
- additives include surfactants.
- surfactants There are no particular limitations on the surfactants, but examples of surfactants that can be used include ionic or non-ionic fluorine-based and/or silicon-based surfactants.
- the development process can be carried out by a known development method, such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it still for a certain period of time (paddle method), a method of spraying the developer on the surface of the support (spray method), or a method of continuously applying developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method).
- a known development method such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it still for a certain period of time (paddle method), a method of spraying the developer on the surface of the support (spray method), or a method of continuously applying developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic
- the organic solvent contained in the rinse solution used in the rinsing treatment after the development treatment in the solvent development process can be appropriately selected from the organic solvents listed above as the organic solvents used in the organic developer, which do not easily dissolve the resist pattern.
- at least one solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used alone or in combination of two or more thereof, and may be used in combination with other organic solvents or water.
- the rinse treatment (cleaning treatment) using a rinse solution can be carried out by a known rinse method.
- the rinse treatment method include a method in which the rinse solution is continuously applied onto a support rotating at a constant speed (spin coating method), a method in which the support is immersed in the rinse solution for a certain period of time (dip method), and a method in which the rinse solution is sprayed onto the surface of the support (spray method).
- the resist pattern forming method of this embodiment described above uses the resist composition described above, making it possible to form a resist pattern that is highly sensitive and has good resolution and CDU.
- the resist composition of the above-mentioned embodiment and the various materials used in the pattern formation method of the above-mentioned embodiment preferably do not contain impurities such as metals, metal salts containing halogens, acids, alkalis, and components containing sulfur atoms or phosphorus atoms.
- impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof.
- the content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free (below the detection limit of the measuring device).
- Component (A) The meaning of the abbreviation for component (A), the weight average molecular weight (Mw) and molecular weight dispersity (Mw/Mn) calculated in terms of standard polystyrene determined by GPC measurement, and the copolymerization composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) determined by C -NMR are shown below.
- (A1)-8 A polymer compound represented by the following chemical formula (A1-8).
- the weight average molecular weight (Mw) of the polymer compound (A1-8) is 6,800, and the molecular weight dispersity (Mw/Mn) is 1.58.
- a polymeric compound represented by the following chemical formula (A2-1): The polymeric compound (A2-1) has a weight average molecular weight (Mw) of 6,600, a molecular weight dispersity (Mw/Mn) of 1.66, and a copolymerization composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) of l/m 50/50.
- (B)-1 An acid generator comprising a compound represented by the following chemical formula (B-1).
- (D)-1 An acid diffusion controller consisting of a compound represented by the following chemical formula (D-1).
- (F1)-1 A polymer compound represented by the following chemical formula (F1-1):
- (F1)-2 A polymer compound represented by the following chemical formula (F1-2):
- (F1)-3 A polymer compound represented by the following chemical formula (F1-3):
- (F1)-4 A polymer compound represented by the following chemical formula (F1-4):
- (F1)-6 A polymer compound represented by the following chemical formula (F1-6):
- (F1)-7 A polymer compound represented by the following chemical formula (F1-7):
- (F1)-8 A polymer compound represented by the following chemical formula (F1-8):
- (F2)-1 A polymer compound represented by the following chemical formula (F2-1):
- Each resist composition of the examples was applied using a spinner onto an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and the substrate was pre-baked (PAB) on a hot plate at a temperature of 110° C. for 60 seconds, followed by drying to form a resist film with a thickness of 50 nm.
- HMDS hexamethyldisilazane
- the resist film was exposed to light using an electron beam lithography system JEOL-JBX-9300FS (manufactured by JEOL Ltd.) at an acceleration voltage of 100 kV to form a contact hole pattern (hereinafter referred to as a "CH pattern") in which holes with a diameter of 32 nm were arranged at equal intervals (pitch of 64 nm).
- a post-exposure bake (PEB) treatment was performed at 100° C. for 60 seconds.
- TMAH tetramethylammonium hydroxide
- NMD-3 product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.
Abstract
This resist composition comprises: a resin component (A1) having a constituent unit (a01) derived from a compound represented by general formula (a0-1); and a fluororesin component (F1) having a constituent unit represented by general formula (f1). In the formulas, W01 is a polymerizable group-containing group. Ya01 is a single bond or a divalent linking group. Ra01 is an acid-dissociable group. q is an integer from 0-3. n is an integer equal to or greater than 1. However, n ≤ q × 2 + 4. R is a hydrogen atom, C1-5 alkyl group, or C1-5 halogenated alkyl group. X0 is a divalent linking group that does not have an acid-dissociable site. Rf0 is a fluorine atom-bearing organic group.
Description
本発明は、レジスト組成物及びレジストパターン形成方法に関する。
本願は、２０２２年９月２９日に日本に出願された、特願２０２２－１５５７６６号に基づき優先権主張し、その内容をここに援用する。 The present invention relates to a resist composition and a method of forming a resist pattern.
This application claims priority based on Japanese Patent Application No. 2022-155766, filed in Japan on September 29, 2022, the contents of which are incorporated herein by reference.
本願は、２０２２年９月２９日に日本に出願された、特願２０２２－１５５７６６号に基づき優先権主張し、その内容をここに援用する。 The present invention relates to a resist composition and a method of forming a resist pattern.
This application claims priority based on Japanese Patent Application No. 2022-155766, filed in Japan on September 29, 2022, the contents of which are incorporated herein by reference.
近年、半導体素子や液晶表示素子の製造においては、リソグラフィー技術の進歩により急速にパターンの微細化が進んでいる。微細化の手法としては、一般に、露光光源の短波長化（高エネルギー化）が行われている。
In recent years, advances in lithography technology have led to rapid progress in miniaturizing patterns in the manufacture of semiconductor elements and liquid crystal display elements. A common method of miniaturization is to shorten the wavelength (increase the energy) of the exposure light source.
レジスト材料には、これらの露光光源に対する感度、微細な寸法のパターンを再現できる解像性等のリソグラフィー特性が求められる。
このような要求を満たすレジスト材料として、従来、酸の作用により現像液に対する溶解性が変化する基材成分と、露光により酸を発生する酸発生剤成分と、を含有する化学増幅型レジスト組成物が用いられている。 Resist materials are required to have lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
As a resist material that satisfies such requirements, a chemically amplified resist composition that contains a base component whose solubility in a developer changes due to the action of acid, and an acid generator component that generates acid upon exposure, has been used so far.
このような要求を満たすレジスト材料として、従来、酸の作用により現像液に対する溶解性が変化する基材成分と、露光により酸を発生する酸発生剤成分と、を含有する化学増幅型レジスト組成物が用いられている。 Resist materials are required to have lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
As a resist material that satisfies such requirements, a chemically amplified resist composition that contains a base component whose solubility in a developer changes due to the action of acid, and an acid generator component that generates acid upon exposure, has been used so far.
化学増幅型レジスト組成物においては、一般的に、リソグラフィー特性等の向上のために、特定の構成単位を有する樹脂が用いられている。
例えば、特許文献１には、酸解離性基と、フェノール性水酸基とをいずれも有する特定の構成単位（ａ０）を含む樹脂成分（Ａ１）を含有するレジスト組成物が開示されている。 In chemically amplified resist compositions, generally, resins having specific structural units are used in order to improve lithography properties and the like.
For example, Patent Document 1 discloses a resist composition that contains a resin component (A1) that includes a specific structural unit (a0) that has both an acid-dissociable group and a phenolic hydroxyl group.
例えば、特許文献１には、酸解離性基と、フェノール性水酸基とをいずれも有する特定の構成単位（ａ０）を含む樹脂成分（Ａ１）を含有するレジスト組成物が開示されている。 In chemically amplified resist compositions, generally, resins having specific structural units are used in order to improve lithography properties and the like.
For example, Patent Document 1 discloses a resist composition that contains a resin component (A1) that includes a specific structural unit (a0) that has both an acid-dissociable group and a phenolic hydroxyl group.
リソグラフィー技術のさらなる進歩、レジストパターンの微細化がますます進むなか、例えば、ＥＵＶやＥＢによるリソグラフィーでは、数十ｎｍの微細なパターン形成が目標とされる。このようにレジストパターン寸法が小さくなるほど、感度、解像性、及び、パターン寸法の面内均一性（ＣＤＵ）等のリソグラフィー特性を各々トレードオフすることなく、改善することが求められる。
しかしながら、上述したような従来のレジスト組成物においては、高感度化を図ろうとすると、解像性、及び、ＣＤＵが劣化する傾向があり、これらの特性をいずれも満足させることが困難である。 As lithography technology continues to advance and resist patterns become finer, for example, in EUV and EB lithography, the goal is to form fine patterns of several tens of nanometers. As the resist pattern dimensions become smaller, it is required to improve lithography characteristics such as sensitivity, resolution, and within-wafer uniformity (CDU) of the pattern dimensions without making a trade-off between them.
However, in the conventional resist compositions described above, when an attempt is made to increase the sensitivity, the resolution and CDU tend to deteriorate, making it difficult to satisfy both of these characteristics.
しかしながら、上述したような従来のレジスト組成物においては、高感度化を図ろうとすると、解像性、及び、ＣＤＵが劣化する傾向があり、これらの特性をいずれも満足させることが困難である。 As lithography technology continues to advance and resist patterns become finer, for example, in EUV and EB lithography, the goal is to form fine patterns of several tens of nanometers. As the resist pattern dimensions become smaller, it is required to improve lithography characteristics such as sensitivity, resolution, and within-wafer uniformity (CDU) of the pattern dimensions without making a trade-off between them.
However, in the conventional resist compositions described above, when an attempt is made to increase the sensitivity, the resolution and CDU tend to deteriorate, making it difficult to satisfy both of these characteristics.
本発明は、上記事情に鑑みてなされたものであって、高感度化が図れ、かつ、解像性、及びＣＤＵが良好なレジスト組成物、並びに当該レジスト組成物を用いたレジストパターン形成方法を提供することを課題とする。
The present invention has been made in consideration of the above circumstances, and aims to provide a resist composition that achieves high sensitivity and has good resolution and CDU, as well as a method for forming a resist pattern using the resist composition.
上記の課題を解決するために、本発明は以下の構成を採用した。
すなわち、本発明の第１の態様は、露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化するレジスト組成物であって、酸の作用により現像液に対する溶解性が変化する樹脂成分（Ａ１）と、アルカリ現像液に対して分解性を示すフッ素添加剤成分（Ｆ）とを含有し、前記樹脂成分（Ａ１）は、下記一般式（ａ０－１）で表される化合物から誘導される構成単位（ａ０１）を有し、前記フッ素添加剤成分（Ｆ）は、下記一般式（ｆ１）で表される構成単位を有するフッ素樹脂成分（Ｆ１）を含む、レジスト組成物である。 In order to solve the above problems, the present invention employs the following configuration.
That is, a first aspect of the present invention is a resist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid, comprising a resin component (A1) whose solubility in a developer changes due to the action of the acid, and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the resin component (A1) has a structural unit (a01) derived from a compound represented by the following general formula (a0-1), and the fluorine additive component (F) includes a fluorine resin component (F1) that has a structural unit represented by the following general formula (f1):
すなわち、本発明の第１の態様は、露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化するレジスト組成物であって、酸の作用により現像液に対する溶解性が変化する樹脂成分（Ａ１）と、アルカリ現像液に対して分解性を示すフッ素添加剤成分（Ｆ）とを含有し、前記樹脂成分（Ａ１）は、下記一般式（ａ０－１）で表される化合物から誘導される構成単位（ａ０１）を有し、前記フッ素添加剤成分（Ｆ）は、下記一般式（ｆ１）で表される構成単位を有するフッ素樹脂成分（Ｆ１）を含む、レジスト組成物である。 In order to solve the above problems, the present invention employs the following configuration.
That is, a first aspect of the present invention is a resist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid, comprising a resin component (A1) whose solubility in a developer changes due to the action of the acid, and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the resin component (A1) has a structural unit (a01) derived from a compound represented by the following general formula (a0-1), and the fluorine additive component (F) includes a fluorine resin component (F1) that has a structural unit represented by the following general formula (f1):
本発明の第２の態様は、支持体上に、前記第１の態様に係るレジスト組成物を用いてレジスト膜を形成する工程、前記レジスト膜を露光する工程、及び前記露光後のレジスト膜を現像してレジストパターンを形成する工程を有するレジストパターン形成方法である。
The second aspect of the present invention is a method for forming a resist pattern, comprising the steps of forming a resist film on a support using the resist composition according to the first aspect, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.
本発明によれば、高感度化が図れ、かつ、解像性、及びＣＤＵが良好なレジスト組成物、並びに当該レジスト組成物を用いたレジストパターン形成方法を提供することができる。
The present invention provides a resist composition that has high sensitivity and good resolution and CDU, as well as a method for forming a resist pattern using the resist composition.
本明細書及び本特許請求の範囲において、「脂肪族」とは、芳香族に対する相対的な概念であって、芳香族性を持たない基、化合物等を意味するものと定義する。
「アルキル基」は、特に断りがない限り、直鎖状、分岐鎖状及び環状の１価の飽和炭化水素基を包含するものとする。アルコキシ基中のアルキル基も同様である。
「アルキレン基」は、特に断りがない限り、直鎖状、分岐鎖状及び環状の２価の飽和炭化水素基を包含するものとする。
「ハロゲン原子」は、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
「構成単位」とは、高分子化合物（樹脂、重合体、共重合体）を構成するモノマー単位（単量体単位）を意味する。
「置換基を有してもよい」と記載する場合、水素原子（－Ｈ）を１価の基で置換する場合と、メチレン基（－ＣＨ２－）を２価の基で置換する場合との両方を含む。
「露光」は、放射線の照射全般を含む概念とする。 In this specification and claims, the term "aliphatic" is a relative concept to aromaticity and is defined as meaning a group, compound, etc. that does not have aromaticity.
Unless otherwise specified, the term "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group.
Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer).
The phrase "may have a substituent" includes both the case where a hydrogen atom (--H) is replaced with a monovalent group and the case where a methylene group (--CH 2 -) is replaced with a divalent group.
The term "exposure" is intended to include any concept including irradiation with radiation.
「アルキル基」は、特に断りがない限り、直鎖状、分岐鎖状及び環状の１価の飽和炭化水素基を包含するものとする。アルコキシ基中のアルキル基も同様である。
「アルキレン基」は、特に断りがない限り、直鎖状、分岐鎖状及び環状の２価の飽和炭化水素基を包含するものとする。
「ハロゲン原子」は、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
「構成単位」とは、高分子化合物（樹脂、重合体、共重合体）を構成するモノマー単位（単量体単位）を意味する。
「置換基を有してもよい」と記載する場合、水素原子（－Ｈ）を１価の基で置換する場合と、メチレン基（－ＣＨ２－）を２価の基で置換する場合との両方を含む。
「露光」は、放射線の照射全般を含む概念とする。 In this specification and claims, the term "aliphatic" is a relative concept to aromaticity and is defined as meaning a group, compound, etc. that does not have aromaticity.
Unless otherwise specified, the term "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group.
Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer).
The phrase "may have a substituent" includes both the case where a hydrogen atom (--H) is replaced with a monovalent group and the case where a methylene group (--CH 2 -) is replaced with a divalent group.
The term "exposure" is intended to include any concept including irradiation with radiation.
「酸分解性基」は、酸の作用により、当該酸分解性基の構造中の少なくとも一部の結合が開裂し得る酸分解性を有する基である。
酸の作用により極性が増大する酸分解性基としては、例えば、酸の作用により分解して極性基を生じる基が挙げられる。
極性基としては、例えばカルボキシ基、水酸基、アミノ基、スルホ基（－ＳＯ３Ｈ）等が挙げられる。
酸分解性基としてより具体的には、前記極性基が酸解離性基で保護された基（例えばＯＨ含有極性基の水素原子を、酸解離性基で保護した基）が挙げられる。 The term "acid-decomposable group" refers to a group having acid decomposability in which at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid.
Examples of acid-decomposable groups whose polarity increases under the action of an acid include groups that are decomposed by the action of an acid to generate a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, and a sulfo group (-SO 3 H).
More specific examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
酸の作用により極性が増大する酸分解性基としては、例えば、酸の作用により分解して極性基を生じる基が挙げられる。
極性基としては、例えばカルボキシ基、水酸基、アミノ基、スルホ基（－ＳＯ３Ｈ）等が挙げられる。
酸分解性基としてより具体的には、前記極性基が酸解離性基で保護された基（例えばＯＨ含有極性基の水素原子を、酸解離性基で保護した基）が挙げられる。 The term "acid-decomposable group" refers to a group having acid decomposability in which at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid.
Examples of acid-decomposable groups whose polarity increases under the action of an acid include groups that are decomposed by the action of an acid to generate a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, and a sulfo group (-SO 3 H).
More specific examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
「酸解離性基」とは、（ｉ）酸の作用により、当該酸解離性基と該酸解離性基に隣接する原子との間の結合が開裂し得る酸解離性を有する基、又は、（ｉｉ）酸の作用により一部の結合が開裂した後、さらに脱炭酸反応が生じることにより、当該酸解離性基と該酸解離性基に隣接する原子との間の結合が開裂し得る基、の双方をいう。
酸分解性基を構成する酸解離性基は、当該酸解離性基の解離により生成する極性基よりも極性の低い基であることが必要で、これにより、酸の作用により該酸解離性基が解離した際に、該酸解離性基よりも極性の高い極性基が生じて極性が増大する。その結果、（Ａ１）成分全体の極性が増大する。極性が増大することにより、相対的に、現像液に対する溶解性が変化し、現像液がアルカリ現像液の場合には溶解性が増大し、現像液が有機系現像液の場合には溶解性が減少する。 The term "acid dissociable group" refers to both (i) a group having acid dissociability in which the bond between the acid dissociable group and an atom adjacent to the acid dissociable group can be cleaved by the action of an acid, and (ii) a group in which a part of the bond is cleaved by the action of an acid and then a decarboxylation reaction occurs, thereby cleaving the bond between the acid dissociable group and an atom adjacent to the acid dissociable group.
The acid dissociable group constituting the acid decomposable group must be a group with lower polarity than the polar group generated by dissociation of the acid dissociable group, and thus, when the acid dissociable group is dissociated by the action of acid, a polar group with higher polarity than the acid dissociable group is generated, and the polarity increases.As a result, the polarity of the entire (A1) component increases.By increasing the polarity, the solubility in the developer changes relatively, and when the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases.
酸分解性基を構成する酸解離性基は、当該酸解離性基の解離により生成する極性基よりも極性の低い基であることが必要で、これにより、酸の作用により該酸解離性基が解離した際に、該酸解離性基よりも極性の高い極性基が生じて極性が増大する。その結果、（Ａ１）成分全体の極性が増大する。極性が増大することにより、相対的に、現像液に対する溶解性が変化し、現像液がアルカリ現像液の場合には溶解性が増大し、現像液が有機系現像液の場合には溶解性が減少する。 The term "acid dissociable group" refers to both (i) a group having acid dissociability in which the bond between the acid dissociable group and an atom adjacent to the acid dissociable group can be cleaved by the action of an acid, and (ii) a group in which a part of the bond is cleaved by the action of an acid and then a decarboxylation reaction occurs, thereby cleaving the bond between the acid dissociable group and an atom adjacent to the acid dissociable group.
The acid dissociable group constituting the acid decomposable group must be a group with lower polarity than the polar group generated by dissociation of the acid dissociable group, and thus, when the acid dissociable group is dissociated by the action of acid, a polar group with higher polarity than the acid dissociable group is generated, and the polarity increases.As a result, the polarity of the entire (A1) component increases.By increasing the polarity, the solubility in the developer changes relatively, and when the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases.
「基材成分」とは、膜形成能を有する有機化合物である。基材成分として用いられる有機化合物は、非重合体と重合体とに大別される。非重合体としては、通常、分子量が５００以上４０００未満のものが用いられる（以下「低分子化合物」という）。以下「樹脂」、「高分子化合物」又は「ポリマー」という場合は、分子量が１０００以上の重合体を示す。重合体の分子量としては、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量を用いるものとする。
The "base material component" is an organic compound that has film-forming ability. Organic compounds used as base material components are broadly divided into non-polymers and polymers. Non-polymers usually have a molecular weight of 500 or more and less than 4000 (hereinafter referred to as "low molecular weight compounds"). Hereinafter, "resin," "polymeric compound," or "polymer" refers to a polymer with a molecular weight of 1000 or more. The molecular weight of the polymer is determined by the weight average molecular weight calculated in terms of polystyrene by GPC (gel permeation chromatography).
「誘導される構成単位」とは、炭素原子間の多重結合、例えば、エチレン性二重結合が開裂して構成される構成単位を意味する。
「アクリル酸エステル」は、α位の炭素原子に結合した水素原子が置換基で置換されていてもよい。該α位の炭素原子に結合した水素原子を置換する置換基（Ｒαｘ）は、水素原子以外の原子又は基である。また、置換基（Ｒαｘ）がエステル結合を含む置換基で置換されたイタコン酸ジエステルや、置換基（Ｒαｘ）がヒドロキシアルキル基やその水酸基を修飾した基で置換されたαヒドロキシアクリルエステルも含むものとする。なお、アクリル酸エステルのα位の炭素原子とは、特に断りがない限り、アクリル酸のカルボニル基が結合している炭素原子のことである。
以下、α位の炭素原子に結合した水素原子が置換基で置換されたアクリル酸エステルを、α置換アクリル酸エステルということがある。 The term "derived structural unit" refers to a structural unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond.
In the "acrylic acid ester", the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R αx ) substituting the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than a hydrogen atom. It also includes an itaconic acid diester in which the substituent (R αx ) is substituted with a substituent containing an ester bond, and an α-hydroxyacrylic ester in which the substituent (R αx ) is substituted with a hydroxyalkyl group or a group in which the hydroxyl group is modified. The carbon atom at the α-position of an acrylic acid ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded, unless otherwise specified.
Hereinafter, an acrylic ester in which the hydrogen atom bonded to the carbon atom at the α-position is substituted with a substituent will sometimes be referred to as an α-substituted acrylic ester.
「アクリル酸エステル」は、α位の炭素原子に結合した水素原子が置換基で置換されていてもよい。該α位の炭素原子に結合した水素原子を置換する置換基（Ｒαｘ）は、水素原子以外の原子又は基である。また、置換基（Ｒαｘ）がエステル結合を含む置換基で置換されたイタコン酸ジエステルや、置換基（Ｒαｘ）がヒドロキシアルキル基やその水酸基を修飾した基で置換されたαヒドロキシアクリルエステルも含むものとする。なお、アクリル酸エステルのα位の炭素原子とは、特に断りがない限り、アクリル酸のカルボニル基が結合している炭素原子のことである。
以下、α位の炭素原子に結合した水素原子が置換基で置換されたアクリル酸エステルを、α置換アクリル酸エステルということがある。 The term "derived structural unit" refers to a structural unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond.
In the "acrylic acid ester", the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R αx ) substituting the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than a hydrogen atom. It also includes an itaconic acid diester in which the substituent (R αx ) is substituted with a substituent containing an ester bond, and an α-hydroxyacrylic ester in which the substituent (R αx ) is substituted with a hydroxyalkyl group or a group in which the hydroxyl group is modified. The carbon atom at the α-position of an acrylic acid ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded, unless otherwise specified.
Hereinafter, an acrylic ester in which the hydrogen atom bonded to the carbon atom at the α-position is substituted with a substituent will sometimes be referred to as an α-substituted acrylic ester.
「誘導体」とは、対象化合物のα位の水素原子がアルキル基、ハロゲン化アルキル基等の他の置換基に置換されたもの、並びにそれらの誘導体を含む概念とする。それらの誘導体としては、α位の水素原子が置換基に置換されていてもよい対象化合物の水酸基の水素原子を有機基で置換したもの；α位の水素原子が置換基に置換されていてもよい対象化合物に、水酸基以外の置換基が結合したもの等が挙げられる。なお、α位とは、特に断りがない限り、官能基と隣接した1番目の炭素原子のことをいう。
ヒドロキシスチレンのα位の水素原子を置換する置換基としては、Ｒαｘと同様のものが挙げられる。 The term "derivative" refers to a concept that includes compounds in which the hydrogen atom at the α-position of the target compound is replaced with other substituents such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof. Examples of such derivatives include compounds in which the hydrogen atom of the hydroxyl group of a target compound, which may have the hydrogen atom at the α-position replaced with a substituent, is replaced with an organic group; compounds in which the hydrogen atom at the α-position of the target compound, which may have the hydrogen atom at the α-position replaced with a substituent, is bonded to a substituent other than a hydroxyl group, and the like. The α-position refers to the first carbon atom adjacent to the functional group, unless otherwise specified.
Examples of the substituent that substitutes the hydrogen atom at the α-position of the hydroxystyrene include the same as those for R αx .
ヒドロキシスチレンのα位の水素原子を置換する置換基としては、Ｒαｘと同様のものが挙げられる。 The term "derivative" refers to a concept that includes compounds in which the hydrogen atom at the α-position of the target compound is replaced with other substituents such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof. Examples of such derivatives include compounds in which the hydrogen atom of the hydroxyl group of a target compound, which may have the hydrogen atom at the α-position replaced with a substituent, is replaced with an organic group; compounds in which the hydrogen atom at the α-position of the target compound, which may have the hydrogen atom at the α-position replaced with a substituent, is bonded to a substituent other than a hydroxyl group, and the like. The α-position refers to the first carbon atom adjacent to the functional group, unless otherwise specified.
Examples of the substituent that substitutes the hydrogen atom at the α-position of the hydroxystyrene include the same as those for R αx .
本明細書及び本特許請求の範囲において、化学式で表される構造によっては、不斉炭素が存在し、エナンチオ異性体（ｅｎａｎｔｉｏｍｅｒ）やジアステレオ異性体（ｄｉａｓｔｅｒｅｏｍｅｒ）が存在し得るものがある。その場合は一つの化学式でそれら異性体を代表して表す。それらの異性体は単独で用いてもよいし、混合物として用いてもよい。
In this specification and claims, some structures represented by chemical formulas may have asymmetric carbons, and enantiomers or diastereoisomers may exist. In such cases, a single chemical formula is used to represent all of the isomers. These isomers may be used alone or as a mixture.
（レジスト組成物）
本実施形態のレジスト組成物は、露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化するものである。
かかるレジスト組成物は、酸の作用により現像液に対する溶解性が変化する基材成分（Ａ）（以下「（Ａ）成分」ともいう）と、アルカリ現像液に対して分解性を示すフッ素添加剤成分（Ｆ）（以下「（Ｆ）成分」ともいう）とを含有する。 (Resist Composition)
The resist composition of this embodiment generates an acid upon exposure, and the solubility of the resist composition in a developer changes due to the action of the acid.
Such a resist composition contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in a developer changes under the action of an acid, and a fluorine additive component (F) (hereinafter also referred to as "component (F)") that exhibits decomposition in an alkaline developer.
本実施形態のレジスト組成物は、露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化するものである。
かかるレジスト組成物は、酸の作用により現像液に対する溶解性が変化する基材成分（Ａ）（以下「（Ａ）成分」ともいう）と、アルカリ現像液に対して分解性を示すフッ素添加剤成分（Ｆ）（以下「（Ｆ）成分」ともいう）とを含有する。 (Resist Composition)
The resist composition of this embodiment generates an acid upon exposure, and the solubility of the resist composition in a developer changes due to the action of the acid.
Such a resist composition contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in a developer changes under the action of an acid, and a fluorine additive component (F) (hereinafter also referred to as "component (F)") that exhibits decomposition in an alkaline developer.
本実施形態のレジスト組成物においては、（Ａ）成分が露光により酸を発生してもよいし、（Ａ）成分とは別に配合された添加剤成分が露光により酸を発生してもよい。
本実施形態のレジスト組成物は、具体的には、（１）露光により酸を発生する酸発生剤成分（Ｂ）（以下「（Ｂ）成分」という）をさらに含有するものであってもよく；（２）（Ａ）成分が露光により酸を発生する成分であってもよく；（３）（Ａ）成分が露光により酸を発生する成分であり、かつ、さらに（Ｂ）成分を含有するものであってもよい。
すなわち、上記（２）及び（３）の場合、（Ａ）成分は、「露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化する基材成分」となる。（Ａ）成分が露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化する基材成分である場合、後述する（Ａ１）成分が、露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化する樹脂であることが好ましい。このような樹脂としては、露光により酸を発生する構成単位を有する高分子化合物を用いることができる。露光により酸を発生する構成単位としては、公知のものを用いることができる。 In the resist composition of this embodiment, the component (A) may generate an acid upon exposure, or an additive component that is formulated separately from the component (A) may generate an acid upon exposure.
Specifically, the resist composition of this embodiment may be one that further contains (1) an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as “component (B)”); (2) the component (A) may be a component that generates an acid upon exposure; or (3) the component (A) is a component that generates an acid upon exposure, and further contains component (B).
That is, in the above cases of (2) and (3), the component (A) is a "base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid". When the component (A) is a base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid, the component (A1) described below is preferably a resin that generates an acid upon exposure and changes its solubility in a developer by the action of the acid. As such a resin, a polymer compound having a structural unit that generates an acid upon exposure can be used. As the structural unit that generates an acid upon exposure, a known one can be used.
本実施形態のレジスト組成物は、具体的には、（１）露光により酸を発生する酸発生剤成分（Ｂ）（以下「（Ｂ）成分」という）をさらに含有するものであってもよく；（２）（Ａ）成分が露光により酸を発生する成分であってもよく；（３）（Ａ）成分が露光により酸を発生する成分であり、かつ、さらに（Ｂ）成分を含有するものであってもよい。
すなわち、上記（２）及び（３）の場合、（Ａ）成分は、「露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化する基材成分」となる。（Ａ）成分が露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化する基材成分である場合、後述する（Ａ１）成分が、露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化する樹脂であることが好ましい。このような樹脂としては、露光により酸を発生する構成単位を有する高分子化合物を用いることができる。露光により酸を発生する構成単位としては、公知のものを用いることができる。 In the resist composition of this embodiment, the component (A) may generate an acid upon exposure, or an additive component that is formulated separately from the component (A) may generate an acid upon exposure.
Specifically, the resist composition of this embodiment may be one that further contains (1) an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as “component (B)”); (2) the component (A) may be a component that generates an acid upon exposure; or (3) the component (A) is a component that generates an acid upon exposure, and further contains component (B).
That is, in the above cases of (2) and (3), the component (A) is a "base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid". When the component (A) is a base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid, the component (A1) described below is preferably a resin that generates an acid upon exposure and changes its solubility in a developer by the action of the acid. As such a resin, a polymer compound having a structural unit that generates an acid upon exposure can be used. As the structural unit that generates an acid upon exposure, a known one can be used.
本実施形態のレジスト組成物は、上記の中でも、上記（１）の場合であるものが好ましい。すなわち、本実施形態のレジスト組成物は、（Ａ）成分と、（Ｂ）成分とを含有するものであることが好ましい。
The resist composition of this embodiment is preferably the above-mentioned case (1). In other words, the resist composition of this embodiment preferably contains component (A) and component (B).
本実施形態のレジスト組成物を用いてレジスト膜を形成し、該レジスト膜に対して選択的露光を行うと、該レジスト膜の露光部では、例えば、（Ｂ）成分から酸が発生し、該酸の作用により（Ａ）成分の現像液に対する溶解性が変化する一方で、該レジスト膜の未露光部では（Ａ）成分の現像液に対する溶解性が変化しないため、露光部と未露光部との間で現像液に対する溶解性の差が生じる。そのため、該レジスト膜を現像すると、該レジスト組成物がポジ型の場合はレジスト膜露光部が溶解除去されてポジ型のレジストパターンが形成され、該レジスト組成物がネガ型の場合はレジスト膜未露光部が溶解除去されてネガ型のレジストパターンが形成される。
When a resist film is formed using the resist composition of this embodiment and selective exposure is performed on the resist film, for example, an acid is generated from component (B) in the exposed parts of the resist film, and the solubility of component (A) in the developer changes due to the action of the acid, whereas the solubility of component (A) in the developer does not change in the unexposed parts of the resist film, resulting in a difference in solubility in the developer between the exposed and unexposed parts. Therefore, when the resist film is developed, if the resist composition is a positive type, the exposed parts of the resist film are dissolved and removed to form a positive type resist pattern, and if the resist composition is a negative type, the unexposed parts of the resist film are dissolved and removed to form a negative type resist pattern.
本実施形態のレジスト組成物は、ポジ型レジスト組成物であってもよく、ネガ型レジスト組成物であってもよい。また、本実施形態のレジスト組成物は、レジストパターン形成時の現像処理にアルカリ現像液を用いるアルカリ現像プロセス用であってもよく、該現像処理に有機溶剤を含む現像液（有機系現像液）を用いる溶剤現像プロセス用であってもよい。
The resist composition of this embodiment may be a positive resist composition or a negative resist composition. The resist composition of this embodiment may be for an alkaline development process in which an alkaline developer is used in the development treatment during resist pattern formation, or may be for a solvent development process in which a developer containing an organic solvent (organic developer) is used in the development treatment.
＜（Ａ）成分＞
本実施形態のレジスト組成物において、（Ａ）成分は、酸の作用により現像液に対する溶解性が変化する樹脂成分（Ａ１）（以下「（Ａ１）成分」ともいう）を含む。
（Ａ１）成分を用いることにより、露光前後で基材成分の極性が変化するため、アルカリ現像プロセスだけでなく、溶剤現像プロセスにおいても、良好な現像コントラストを得ることができる。
（Ａ）成分としては、該（Ａ１）成分とともに他の高分子化合物及び／又は低分子化合物を併用してもよい。 <Component (A)>
In the resist composition of this embodiment, the component (A) contains a resin component (A1) (hereinafter also referred to as “component (A1)”) whose solubility in a developer changes under the action of an acid.
By using the component (A1), the polarity of the base component changes between before and after exposure, making it possible to obtain good development contrast not only in an alkali development process but also in a solvent development process.
As the component (A), other polymeric compounds and/or low molecular weight compounds may be used in combination with the component (A1).
本実施形態のレジスト組成物において、（Ａ）成分は、酸の作用により現像液に対する溶解性が変化する樹脂成分（Ａ１）（以下「（Ａ１）成分」ともいう）を含む。
（Ａ１）成分を用いることにより、露光前後で基材成分の極性が変化するため、アルカリ現像プロセスだけでなく、溶剤現像プロセスにおいても、良好な現像コントラストを得ることができる。
（Ａ）成分としては、該（Ａ１）成分とともに他の高分子化合物及び／又は低分子化合物を併用してもよい。 <Component (A)>
In the resist composition of this embodiment, the component (A) contains a resin component (A1) (hereinafter also referred to as “component (A1)”) whose solubility in a developer changes under the action of an acid.
By using the component (A1), the polarity of the base component changes between before and after exposure, making it possible to obtain good development contrast not only in an alkali development process but also in a solvent development process.
As the component (A), other polymeric compounds and/or low molecular weight compounds may be used in combination with the component (A1).
本実施形態のレジスト組成物において、（Ａ）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。
In the resist composition of this embodiment, the component (A) may be used alone or in combination of two or more types.
・（Ａ１）成分について
（Ａ１）成分は、酸の作用により現像液に対する溶解性が変化する樹脂成分である。 Regarding the Component (A1) The component (A1) is a resin component whose solubility in a developer changes due to the action of an acid.
（Ａ１）成分は、酸の作用により現像液に対する溶解性が変化する樹脂成分である。 Regarding the Component (A1) The component (A1) is a resin component whose solubility in a developer changes due to the action of an acid.
≪構成単位（ａ０１）≫
（Ａ１）成分は、下記一般式（ａ０－１）で表される化合物から誘導される構成単位（ａ０１）を有する。 <Structural unit (a01)>
The component (A1) has a structural unit (a01) derived from a compound represented by general formula (a0-1) shown below.
（Ａ１）成分は、下記一般式（ａ０－１）で表される化合物から誘導される構成単位（ａ０１）を有する。 <Structural unit (a01)>
The component (A1) has a structural unit (a01) derived from a compound represented by general formula (a0-1) shown below.
式（ａ０－１）中、Ｗ０１は、重合性基含有基である。
Ｗ０１における「重合性基」とは、重合性基を有する化合物がラジカル重合等により重合することを可能とする基であり、例えばエチレン性二重結合などの炭素原子間の多重結合を含む基をいう。
構成単位（ａ０１）おいては、該重合性基における多重結合が開裂して主鎖を形成している。 In formula (a0-1), W 01 represents a polymerizable group-containing group.
The "polymerizable group" in W 01 is a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and refers to a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond.
In the structural unit (a01), the multiple bond in the polymerizable group is cleaved to form the main chain.
Ｗ０１における「重合性基」とは、重合性基を有する化合物がラジカル重合等により重合することを可能とする基であり、例えばエチレン性二重結合などの炭素原子間の多重結合を含む基をいう。
構成単位（ａ０１）おいては、該重合性基における多重結合が開裂して主鎖を形成している。 In formula (a0-1), W 01 represents a polymerizable group-containing group.
The "polymerizable group" in W 01 is a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and refers to a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond.
In the structural unit (a01), the multiple bond in the polymerizable group is cleaved to form the main chain.
Ｗ０１における重合性基としては、例えば、ビニル基、アリル基、アクリロイル基、メタクリロイル基、フルオロビニル基、ジフルオロビニル基、トリフルオロビニル基、ジフルオロトリフルオロメチルビニル基、トリフルオロアリル基、パーフルオロアリル基、トリフルオロメチルアクリロイル基、ノニルフルオロブチルアクリロイル基、ビニルエーテル基、含フッ素ビニルエーテル基、アリルエーテル基、含フッ素アリルエーテル基、スチリル基、ビニルナフチル基、含フッ素スチリル基、含フッ素ビニルナフチル基、ノルボルニル基、含フッ素ノルボルニル基、シリル基等が挙げられる。
Examples of the polymerizable group in W 01 include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a fluorovinyl group, a difluorovinyl group, a trifluorovinyl group, a difluorotrifluoromethylvinyl group, a trifluoroallyl group, a perfluoroallyl group, a trifluoromethylacryloyl group, a nonylfluorobutylacryloyl group, a vinyl ether group, a fluorine-containing vinyl ether group, an allyl ether group, a fluorine-containing allyl ether group, a styryl group, a vinyl naphthyl group, a fluorine-containing styryl group, a fluorine-containing vinyl naphthyl group, a norbornyl group, a fluorine-containing norbornyl group, and a silyl group.
Ｗ０１における「重合性基含有基」としては、重合性基のみから構成される基でもよいし、重合性基と該重合性基以外の他の基とから構成される基でもよい。該重合性基以外の他の基としては、置換基を有してもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基等が挙げられる。
The "polymerizable group-containing group" in W 01 may be a group consisting of only a polymerizable group, or may be a group consisting of a polymerizable group and a group other than the polymerizable group. Examples of the group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
・置換基を有してもよい２価の炭化水素基：
該重合性基以外の他の基が、置換基を有してもよい２価の炭化水素基である場合、該炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。 Optionally substituted divalent hydrocarbon group:
When the group other than the polymerizable group is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
該重合性基以外の他の基が、置換基を有してもよい２価の炭化水素基である場合、該炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。 Optionally substituted divalent hydrocarbon group:
When the group other than the polymerizable group is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
・・該重合性基以外の他の基における脂肪族炭化水素基
該脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。該脂肪族炭化水素基は、飽和であってもよく不飽和であってもよく、通常は飽和であることが好ましい。
前記脂肪族炭化水素基としては、直鎖状若しくは分岐鎖状の脂肪族炭化水素基、又は構造中に環を含む脂肪族炭化水素基等が挙げられる。 Aliphatic Hydrocarbon Group in Group Other Than the Polymerizable Group The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing a ring in the structure.
該脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。該脂肪族炭化水素基は、飽和であってもよく不飽和であってもよく、通常は飽和であることが好ましい。
前記脂肪族炭化水素基としては、直鎖状若しくは分岐鎖状の脂肪族炭化水素基、又は構造中に環を含む脂肪族炭化水素基等が挙げられる。 Aliphatic Hydrocarbon Group in Group Other Than the Polymerizable Group The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing a ring in the structure.
・・・直鎖状若しくは分岐鎖状の脂肪族炭化水素基
該直鎖状の脂肪族炭化水素基は、炭素原子数が１～１０であることが好ましく、炭素原子数１～６がより好ましく、炭素原子数１～４がさらに好ましく、炭素原子数１～３が最も好ましい。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基［－ＣＨ２－］、エチレン基［－（ＣＨ２）２－］、トリメチレン基［－（ＣＨ２）３－］、テトラメチレン基［－（ＣＨ２）４－］、ペンタメチレン基［－（ＣＨ２）５－］等が挙げられる。
該分岐鎖状の脂肪族炭化水素基は、炭素原子数が２～１０であることが好ましく、炭素原子数３～６がより好ましく、炭素原子数３又は４がさらに好ましく、炭素原子数３が最も好ましい。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－Ｃ（ＣＨ２ＣＨ３）２－ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数１～５の直鎖状のアルキル基が好ましい。 ...Straight-chain or branched-chain aliphatic hydrocarbon group The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
The branched aliphatic hydrocarbon group preferably contains 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
該直鎖状の脂肪族炭化水素基は、炭素原子数が１～１０であることが好ましく、炭素原子数１～６がより好ましく、炭素原子数１～４がさらに好ましく、炭素原子数１～３が最も好ましい。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基［－ＣＨ２－］、エチレン基［－（ＣＨ２）２－］、トリメチレン基［－（ＣＨ２）３－］、テトラメチレン基［－（ＣＨ２）４－］、ペンタメチレン基［－（ＣＨ２）５－］等が挙げられる。
該分岐鎖状の脂肪族炭化水素基は、炭素原子数が２～１０であることが好ましく、炭素原子数３～６がより好ましく、炭素原子数３又は４がさらに好ましく、炭素原子数３が最も好ましい。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－Ｃ（ＣＨ２ＣＨ３）２－ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数１～５の直鎖状のアルキル基が好ましい。 ...Straight-chain or branched-chain aliphatic hydrocarbon group The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
The branched aliphatic hydrocarbon group preferably contains 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
前記の直鎖状又は分岐鎖状の脂肪族炭化水素基は、置換基を有してもよく、有していなくてもよい。該置換基としては、フッ素原子、フッ素原子で置換された炭素原子数１～５のフッ素化アルキル基、カルボニル基等が挙げられる。
The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.
・・・構造中に環を含む脂肪族炭化水素基
該構造中に環を含む脂肪族炭化水素基としては、環構造中にヘテロ原子を含む置換基を含んでもよい環状の脂肪族炭化水素基（脂肪族炭化水素環から水素原子２個を除いた基）、前記環状の脂肪族炭化水素基が直鎖状又は分岐鎖状の脂肪族炭化水素基の末端に結合した基、前記環状の脂肪族炭化水素基が直鎖状又は分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。前記の直鎖状又は分岐鎖状の脂肪族炭化水素基としては前記と同様のものが挙げられる。
環状の脂肪族炭化水素基は、炭素原子数が３～２０であることが好ましく、炭素原子数３～１２であることがより好ましい。
環状の脂肪族炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから２個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから２個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 ... Aliphatic hydrocarbon groups containing a ring in the structure Examples of the aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantan, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, tetracyclododecane, etc.
該構造中に環を含む脂肪族炭化水素基としては、環構造中にヘテロ原子を含む置換基を含んでもよい環状の脂肪族炭化水素基（脂肪族炭化水素環から水素原子２個を除いた基）、前記環状の脂肪族炭化水素基が直鎖状又は分岐鎖状の脂肪族炭化水素基の末端に結合した基、前記環状の脂肪族炭化水素基が直鎖状又は分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。前記の直鎖状又は分岐鎖状の脂肪族炭化水素基としては前記と同様のものが挙げられる。
環状の脂肪族炭化水素基は、炭素原子数が３～２０であることが好ましく、炭素原子数３～１２であることがより好ましい。
環状の脂肪族炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから２個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから２個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 ... Aliphatic hydrocarbon groups containing a ring in the structure Examples of the aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantan, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, tetracyclododecane, etc.
環状の脂肪族炭化水素基は、置換基を有してもよいし、有していなくてもよい。該置換基としては、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、カルボニル基等が挙げられる。
前記置換基としてのアルキル基としては、炭素原子数１～５のアルキル基が好ましく、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基であることが最も好ましい。
前記置換基としてのアルコキシ基としては、炭素原子数１～５のアルコキシ基が好ましく、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基がより好ましく、メトキシ基、エトキシ基が最も好ましい。
前記置換基としてのハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。
前記置換基としてのハロゲン化アルキル基としては、前記アルキル基の水素原子の一部又は全部が前記ハロゲン原子で置換された基が挙げられる。
環状の脂肪族炭化水素基は、その環構造を構成する炭素原子の一部がヘテロ原子を含む置換基で置換されてもよい。該ヘテロ原子を含む置換基としては、－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－、－Ｓ－、－Ｓ（＝Ｏ）２－、－Ｓ（＝Ｏ）２－Ｏ－が好ましい。 The cyclic aliphatic hydrocarbon group may or may not have a substituent, which may include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, etc.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.
In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Preferred examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O) 2 - and -S(=O) 2 -O-.
前記置換基としてのアルキル基としては、炭素原子数１～５のアルキル基が好ましく、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基であることが最も好ましい。
前記置換基としてのアルコキシ基としては、炭素原子数１～５のアルコキシ基が好ましく、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基がより好ましく、メトキシ基、エトキシ基が最も好ましい。
前記置換基としてのハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。
前記置換基としてのハロゲン化アルキル基としては、前記アルキル基の水素原子の一部又は全部が前記ハロゲン原子で置換された基が挙げられる。
環状の脂肪族炭化水素基は、その環構造を構成する炭素原子の一部がヘテロ原子を含む置換基で置換されてもよい。該ヘテロ原子を含む置換基としては、－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－、－Ｓ－、－Ｓ（＝Ｏ）２－、－Ｓ（＝Ｏ）２－Ｏ－が好ましい。 The cyclic aliphatic hydrocarbon group may or may not have a substituent, which may include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, etc.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.
In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Preferred examples of the substituent containing a hetero atom include -O-, -C(=O)-O-, -S-, -S(=O) 2 - and -S(=O) 2 -O-.
・・該重合性基以外の他の基における芳香族炭化水素基
該芳香族炭化水素基は、芳香環を少なくとも１つ有する炭化水素基である。
この芳香環は、４ｎ＋２個のπ電子をもつ環状共役系であれば特に限定されず、単環式でも多環式でもよい。芳香環の炭素原子数は５～３０であることが好ましく、炭素原子数５～２０がより好ましく、炭素原子数６～１５がさらに好ましく、炭素原子数６～１２が特に好ましい。ただし、該炭素原子数には、置換基における炭素原子数を含まないものとする。芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
芳香族炭化水素基として具体的には、前記芳香族炭化水素環又は芳香族複素環から水素原子２つを除いた基（アリーレン基又はヘテロアリーレン基）；２以上の芳香環を含む芳香族化合物（例えばビフェニル、フルオレン等）から水素原子２つを除いた基；前記芳香族炭化水素環又は芳香族複素環から水素原子１つを除いた基（アリール基又はヘテロアリール基）の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基におけるアリール基から水素原子をさらに１つ除いた基）等が挙げられる。前記のアリール基又はヘテロアリール基に結合するアルキレン基の炭素原子数は、１～４であることが好ましく、炭素原子数１～２であることがより好ましく、炭素原子数１であることが特に好ましい。 --Aromatic Hydrocarbon Group in Group Other Than the Polymerizable Group The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group include a group (arylene group or heteroarylene group) in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle; a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group (aryl group or heteroaryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
該芳香族炭化水素基は、芳香環を少なくとも１つ有する炭化水素基である。
この芳香環は、４ｎ＋２個のπ電子をもつ環状共役系であれば特に限定されず、単環式でも多環式でもよい。芳香環の炭素原子数は５～３０であることが好ましく、炭素原子数５～２０がより好ましく、炭素原子数６～１５がさらに好ましく、炭素原子数６～１２が特に好ましい。ただし、該炭素原子数には、置換基における炭素原子数を含まないものとする。芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
芳香族炭化水素基として具体的には、前記芳香族炭化水素環又は芳香族複素環から水素原子２つを除いた基（アリーレン基又はヘテロアリーレン基）；２以上の芳香環を含む芳香族化合物（例えばビフェニル、フルオレン等）から水素原子２つを除いた基；前記芳香族炭化水素環又は芳香族複素環から水素原子１つを除いた基（アリール基又はヘテロアリール基）の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基におけるアリール基から水素原子をさらに１つ除いた基）等が挙げられる。前記のアリール基又はヘテロアリール基に結合するアルキレン基の炭素原子数は、１～４であることが好ましく、炭素原子数１～２であることがより好ましく、炭素原子数１であることが特に好ましい。 --Aromatic Hydrocarbon Group in Group Other Than the Polymerizable Group The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group include a group (arylene group or heteroarylene group) in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle; a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group (aryl group or heteroaryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
前記芳香族炭化水素基は、当該芳香族炭化水素基が有する水素原子が置換基で置換されていてもよい。例えば、当該芳香族炭化水素基中の芳香環に結合した水素原子が置換基で置換されていてもよい。該置換基としては、例えば、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基等が挙げられる。
前記置換基としてのアルキル基としては、炭素原子数１～５のアルキル基が好ましく、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基であることが最も好ましい。
前記置換基としてのアルコキシ基、ハロゲン原子及びハロゲン化アルキル基としては、前記環状の脂肪族炭化水素基が有する水素原子を置換する置換基として例示したものが挙げられる。 The aromatic hydrocarbon group may have a hydrogen atom substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.
前記置換基としてのアルキル基としては、炭素原子数１～５のアルキル基が好ましく、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基であることが最も好ましい。
前記置換基としてのアルコキシ基、ハロゲン原子及びハロゲン化アルキル基としては、前記環状の脂肪族炭化水素基が有する水素原子を置換する置換基として例示したものが挙げられる。 The aromatic hydrocarbon group may have a hydrogen atom substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.
・ヘテロ原子を含む２価の連結基：
該重合性基以外の他の基が、ヘテロ原子を含む２価の連結基である場合、該連結基として好ましいものとして、－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－、－ＮＨ－Ｃ（＝ＮＨ）－（Ｈはアルキル基、アシル基等の置換基で置換されていてもよい。）、－Ｓ－、－Ｓ（＝Ｏ）２－、－Ｓ（＝Ｏ）２－Ｏ－、一般式－Ｙ２１－Ｏ－Ｙ２２－、－Ｙ２１－Ｏ－、－Ｙ２１－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－Ｙ２１－、－［Ｙ２１－Ｃ（＝Ｏ）－Ｏ］ｍ”－Ｙ２２－、－Ｙ２１－Ｏ－Ｃ（＝Ｏ）－Ｙ２２－または－Ｙ２１－Ｓ（＝Ｏ）２－Ｏ－Ｙ２２－で表される基［式中、Ｙ２１およびＹ２２はそれぞれ独立して置換基を有してもよい２価の炭化水素基であり、Ｏは酸素原子であり、ｍ”は０～３の整数である。］等が挙げられる。
前記のへテロ原子を含む２価の連結基が－Ｃ（＝Ｏ）－ＮＨ－、－Ｃ（＝Ｏ）－ＮＨ－Ｃ（＝Ｏ）－、－ＮＨ－、－ＮＨ－Ｃ（＝ＮＨ）－の場合、そのＨはアルキル基、アシル等の置換基で置換されていてもよい。該置換基（アルキル基、アシル基等）は、炭素原子数が１～１０であることが好ましく、１～８であることがさらに好ましく、１～５であることが特に好ましい。
一般式－Ｙ２１－Ｏ－Ｙ２２－、－Ｙ２１－Ｏ－、－Ｙ２１－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－Ｙ２１－、－［Ｙ２１－Ｃ（＝Ｏ）－Ｏ］ｍ”－Ｙ２２－、－Ｙ２１－Ｏ－Ｃ（＝Ｏ）－Ｙ２２－または－Ｙ２１－Ｓ（＝Ｏ）２－Ｏ－Ｙ２２－中、Ｙ２１およびＹ２２は、それぞれ独立して、置換基を有してもよい２価の炭化水素基である。該２価の炭化水素基としては、前記２価の連結基としての説明で挙げた（置換基を有してもよい２価の炭化水素基）と同様のものが挙げられる。
Ｙ２１としては、直鎖状の脂肪族炭化水素基が好ましく、直鎖状のアルキレン基がより好ましく、炭素原子数１～５の直鎖状のアルキレン基がさらに好ましく、メチレン基又はエチレン基が特に好ましい。
Ｙ２２としては、直鎖状又は分岐鎖状の脂肪族炭化水素基が好ましく、メチレン基、エチレン基又はアルキルメチレン基がより好ましい。該アルキルメチレン基におけるアルキル基は、炭素原子数１～５の直鎖状のアルキル基が好ましく、炭素原子数１～３の直鎖状のアルキル基がより好ましく、メチル基が最も好ましい。
式－［Ｙ２１－Ｃ（＝Ｏ）－Ｏ］ｍ”－Ｙ２２－で表される基において、ｍ”は０～３の整数であり、０～２の整数であることが好ましく、０又は１がより好ましく、１が特に好ましい。つまり、式－［Ｙ２１－Ｃ（＝Ｏ）－Ｏ］ｍ”－Ｙ２２－で表される基としては、式－Ｙ２１－Ｃ（＝Ｏ）－Ｏ－Ｙ２２－で表される基が特に好ましい。中でも、式－（ＣＨ２）ａ’－Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｂ’－で表される基が好ましい。該式中、ａ’は、１～１０の整数であり、１～８の整数が好ましく、１～５の整数がより好ましく、１又は２がさらに好ましく、１が最も好ましい。ｂ’は、１～１０の整数であり、１～８の整数が好ましく、１～５の整数がより好ましく、１又は２がさらに好ましく、１が最も好ましい。 Divalent linking groups containing heteroatoms:
When the group other than the polymerizable group is a divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted by a substituent such as an alkyl group or an acyl group), -S-, -S(=O) 2 -, -S(=O) 2 -O-, the general formula -Y 21 -O-Y 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-Y 21 -, -[Y 21 -C(=O)-O] m " -Y 22 -, -Y 21 -O-C(=O)-Y 22 - or -Y 21 Examples of the alkyl group include a group represented by -S(=O) 2 -O-Y 22 - (wherein Y 21 and Y 22 each independently represent a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m" represents an integer of 0 to 3).
When the divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, acyl, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms.
In the general formula -Y 21 -O-Y 22 -, -Y 21 -O-, -Y 21 -C(═O)-O-, -C(═O)-O-Y 21 -, -[Y 21 -C(═O)-O] m" -Y 22 -, -Y 21 -O-C(═O)-Y 22 - or -Y 21 -S(═O) 2 -O-Y 22 -, Y 21 and Y 22 each independently represent a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as those (divalent hydrocarbon groups which may have a substituent) listed above in the description of the divalent linking group.
Y 21 is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or ethylene group.
Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by the formula -[Y 21 -C(═O)-O] m" -Y 22 -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as the group represented by the formula -[Y 21 -C(═O)-O] m" -Y 22 -, a group represented by the formula -Y 21 -C(═O)-O-Y 22 - is particularly preferred. Of these, a group represented by the formula -(CH 2 ) a' -C(═O)-O-(CH 2 ) b' - is preferred. In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.
該重合性基以外の他の基が、ヘテロ原子を含む２価の連結基である場合、該連結基として好ましいものとして、－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－、－ＮＨ－、－ＮＨ－Ｃ（＝ＮＨ）－（Ｈはアルキル基、アシル基等の置換基で置換されていてもよい。）、－Ｓ－、－Ｓ（＝Ｏ）２－、－Ｓ（＝Ｏ）２－Ｏ－、一般式－Ｙ２１－Ｏ－Ｙ２２－、－Ｙ２１－Ｏ－、－Ｙ２１－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－Ｙ２１－、－［Ｙ２１－Ｃ（＝Ｏ）－Ｏ］ｍ”－Ｙ２２－、－Ｙ２１－Ｏ－Ｃ（＝Ｏ）－Ｙ２２－または－Ｙ２１－Ｓ（＝Ｏ）２－Ｏ－Ｙ２２－で表される基［式中、Ｙ２１およびＹ２２はそれぞれ独立して置換基を有してもよい２価の炭化水素基であり、Ｏは酸素原子であり、ｍ”は０～３の整数である。］等が挙げられる。
前記のへテロ原子を含む２価の連結基が－Ｃ（＝Ｏ）－ＮＨ－、－Ｃ（＝Ｏ）－ＮＨ－Ｃ（＝Ｏ）－、－ＮＨ－、－ＮＨ－Ｃ（＝ＮＨ）－の場合、そのＨはアルキル基、アシル等の置換基で置換されていてもよい。該置換基（アルキル基、アシル基等）は、炭素原子数が１～１０であることが好ましく、１～８であることがさらに好ましく、１～５であることが特に好ましい。
一般式－Ｙ２１－Ｏ－Ｙ２２－、－Ｙ２１－Ｏ－、－Ｙ２１－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－Ｙ２１－、－［Ｙ２１－Ｃ（＝Ｏ）－Ｏ］ｍ”－Ｙ２２－、－Ｙ２１－Ｏ－Ｃ（＝Ｏ）－Ｙ２２－または－Ｙ２１－Ｓ（＝Ｏ）２－Ｏ－Ｙ２２－中、Ｙ２１およびＹ２２は、それぞれ独立して、置換基を有してもよい２価の炭化水素基である。該２価の炭化水素基としては、前記２価の連結基としての説明で挙げた（置換基を有してもよい２価の炭化水素基）と同様のものが挙げられる。
Ｙ２１としては、直鎖状の脂肪族炭化水素基が好ましく、直鎖状のアルキレン基がより好ましく、炭素原子数１～５の直鎖状のアルキレン基がさらに好ましく、メチレン基又はエチレン基が特に好ましい。
Ｙ２２としては、直鎖状又は分岐鎖状の脂肪族炭化水素基が好ましく、メチレン基、エチレン基又はアルキルメチレン基がより好ましい。該アルキルメチレン基におけるアルキル基は、炭素原子数１～５の直鎖状のアルキル基が好ましく、炭素原子数１～３の直鎖状のアルキル基がより好ましく、メチル基が最も好ましい。
式－［Ｙ２１－Ｃ（＝Ｏ）－Ｏ］ｍ”－Ｙ２２－で表される基において、ｍ”は０～３の整数であり、０～２の整数であることが好ましく、０又は１がより好ましく、１が特に好ましい。つまり、式－［Ｙ２１－Ｃ（＝Ｏ）－Ｏ］ｍ”－Ｙ２２－で表される基としては、式－Ｙ２１－Ｃ（＝Ｏ）－Ｏ－Ｙ２２－で表される基が特に好ましい。中でも、式－（ＣＨ２）ａ’－Ｃ（＝Ｏ）－Ｏ－（ＣＨ２）ｂ’－で表される基が好ましい。該式中、ａ’は、１～１０の整数であり、１～８の整数が好ましく、１～５の整数がより好ましく、１又は２がさらに好ましく、１が最も好ましい。ｂ’は、１～１０の整数であり、１～８の整数が好ましく、１～５の整数がより好ましく、１又は２がさらに好ましく、１が最も好ましい。 Divalent linking groups containing heteroatoms:
When the group other than the polymerizable group is a divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted by a substituent such as an alkyl group or an acyl group), -S-, -S(=O) 2 -, -S(=O) 2 -O-, the general formula -Y 21 -O-Y 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-Y 21 -, -[Y 21 -C(=O)-O] m " -Y 22 -, -Y 21 -O-C(=O)-Y 22 - or -Y 21 Examples of the alkyl group include a group represented by -S(=O) 2 -O-Y 22 - (wherein Y 21 and Y 22 each independently represent a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m" represents an integer of 0 to 3).
When the divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, acyl, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms.
In the general formula -Y 21 -O-Y 22 -, -Y 21 -O-, -Y 21 -C(═O)-O-, -C(═O)-O-Y 21 -, -[Y 21 -C(═O)-O] m" -Y 22 -, -Y 21 -O-C(═O)-Y 22 - or -Y 21 -S(═O) 2 -O-Y 22 -, Y 21 and Y 22 each independently represent a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as those (divalent hydrocarbon groups which may have a substituent) listed above in the description of the divalent linking group.
Y 21 is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or ethylene group.
Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by the formula -[Y 21 -C(═O)-O] m" -Y 22 -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as the group represented by the formula -[Y 21 -C(═O)-O] m" -Y 22 -, a group represented by the formula -Y 21 -C(═O)-O-Y 22 - is particularly preferred. Of these, a group represented by the formula -(CH 2 ) a' -C(═O)-O-(CH 2 ) b' - is preferred. In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.
Ｗ０１としては、例えば、化学式：Ｃ（ＲＸ１１）（ＲＸ１２）＝Ｃ（ＲＸ１３）－Ｙａｘ０－で表される基、が好適に挙げられる。
この化学式中、ＲＸ１１、ＲＸ１２及びＲＸ１３は、それぞれ、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり、Ｙａｘ０は、単結合または２価の連結基である。 Suitable examples of W 01 include groups represented by the chemical formula: C(R x11 )(R x12 )=C(R x13 )-Ya x0 -.
In this chemical formula, R X11 , R X12 and R X13 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 represents a single bond or a divalent linking group.
この化学式中、ＲＸ１１、ＲＸ１２及びＲＸ１３は、それぞれ、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり、Ｙａｘ０は、単結合または２価の連結基である。 Suitable examples of W 01 include groups represented by the chemical formula: C(R x11 )(R x12 )=C(R x13 )-Ya x0 -.
In this chemical formula, R X11 , R X12 and R X13 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 represents a single bond or a divalent linking group.
ＲＸ１１、ＲＸ１２及びＲＸ１３における炭素原子数１～５のアルキル基は、炭素原子数１～５の直鎖状または分岐鎖状のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。炭素原子数１～５のハロゲン化アルキル基は、前記炭素原子数１～５のアルキル基の水素原子の一部または全部がハロゲン原子で置換された基である。該ハロゲン原子としては、特にフッ素原子が好ましい。
これらの中でも、ＲＸ１１及びＲＸ１２としては、それぞれ、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子、メチル基がさらに好ましく、水素原子が特に好ましい。
また、ＲＸ１３としては、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子、メチル基がさらに好ましく、水素原子が特に好ましい。 The alkyl group having 1 to 5 carbon atoms in R X11 , R X12 and R X13 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.
Among these, R X11 and R X12 are each preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.
Furthermore, R X13 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.
これらの中でも、ＲＸ１１及びＲＸ１２としては、それぞれ、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子、メチル基がさらに好ましく、水素原子が特に好ましい。
また、ＲＸ１３としては、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子、メチル基がさらに好ましく、水素原子が特に好ましい。 The alkyl group having 1 to 5 carbon atoms in R X11 , R X12 and R X13 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.
Among these, R X11 and R X12 are each preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.
Furthermore, R X13 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.
Ｙａｘ０における２価の連結基としては、特に限定されないが、置換基を有してもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基等が好適なものとして挙げられ、それぞれ上記と同様である。
The divalent linking group for Ya x0 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom, each of which is the same as described above.
上記の中でも、Ｙａｘ０としては、エステル結合［－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－］、エーテル結合（－Ｏ－）、直鎖状若しくは分岐鎖状のアルキレン基、芳香族炭化水素基又はこれらの組合せ、あるいは単結合であることが好ましい。これらの中でも、Ｙａｘ０としては、エステル結合［－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－］と直鎖状のアルキレン基との組み合わせ、又は単結合であることがより好ましく、単結合であることがさらに好ましい。
Among the above, Ya x0 is preferably an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group, or a combination thereof, or a single bond. Among these, Ya x0 is more preferably a combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group, or a single bond, and even more preferably a single bond.
式（ａ０－１）中、Ｙａ０１は単結合又は２価の連結基である。Ｙａ０１における２価の連結基としては、特に限定されないが、置換基を有してもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基等が好適なものとして挙げられ、それぞれ上記と同様である。
In formula (a0-1), Ya 01 is a single bond or a divalent linking group. The divalent linking group in Ya 01 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom, each of which is the same as described above.
式（ａ０－１）中、Ｙａ０１は、上記の中でも、エステル結合［－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－］、エーテル結合（－Ｏ－）、直鎖状若しくは分岐鎖状のアルキレン基、芳香族炭化水素基又はこれらの組合せ、あるいは単結合であることが好ましい。これらの中でも、Ｙａ０１としては、エステル結合［－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－］と直鎖状のアルキレン基との組み合わせ、又は単結合であることがより好ましく、単結合であることがさらに好ましい。
In formula (a0-1), Ya 01 is preferably an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group, or a combination thereof, or a single bond, among the above. Among these, Ya 01 is more preferably a combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group, or a single bond, and even more preferably a single bond.
式（ａ０－１）中、Ｒａ０１は酸解離性基である。
酸解離性基として、具体的には、以下に説明する「アセタール型酸解離性基」、「第３級アルキルエステル型酸解離性基」及び「第２級アルキルエステル型酸解離性基」等が挙げられる。 In formula (a0-1), Ra 01 represents an acid dissociable group.
Specific examples of the acid dissociable group include an "acetal type acid dissociable group," a "tertiary alkyl ester type acid dissociable group," and a "secondary alkyl ester type acid dissociable group," which will be described below.
酸解離性基として、具体的には、以下に説明する「アセタール型酸解離性基」、「第３級アルキルエステル型酸解離性基」及び「第２級アルキルエステル型酸解離性基」等が挙げられる。 In formula (a0-1), Ra 01 represents an acid dissociable group.
Specific examples of the acid dissociable group include an "acetal type acid dissociable group," a "tertiary alkyl ester type acid dissociable group," and a "secondary alkyl ester type acid dissociable group," which will be described below.
アセタール型酸解離性基：
Ｒａ０１における酸解離性基としては、例えば、下記一般式（ａ０－ｒ－１）で表される酸解離性基（以下「アセタール型酸解離性基」ということがある。）が挙げられる。 Acetal-type acid-dissociable group:
Examples of the acid dissociable group for Ra 01 include acid dissociable groups represented by the following general formula (a0-r-1) (hereinafter sometimes referred to as "acetal-type acid dissociable group").
Ｒａ０１における酸解離性基としては、例えば、下記一般式（ａ０－ｒ－１）で表される酸解離性基（以下「アセタール型酸解離性基」ということがある。）が挙げられる。 Acetal-type acid-dissociable group:
Examples of the acid dissociable group for Ra 01 include acid dissociable groups represented by the following general formula (a0-r-1) (hereinafter sometimes referred to as "acetal-type acid dissociable group").
式（ａ０－ｒ－１）中、Ｒａ０１及びＲａ０２は、それぞれ独立に、水素原子又はアルキル基である。
式（ａ０－ｒ－１）中、Ｒａ０１及びＲａ０２は、少なくとも一方が水素原子であることが好ましく、両方が水素原子であることがより好ましい。
Ｒａ０１又はＲａ０２がアルキル基である場合、該アルキル基としては、炭素数１～５のアルキル基が好ましい。具体的には、直鎖状または分岐鎖状のアルキル基が好ましく挙げられる。より具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基などが挙げられ、メチル基またはエチル基がより好ましく、メチル基が特に好ましい。
式（ａ０－ｒ－１）中、Ｒａ０１及びＲａ０２は、上記の中でも、それぞれ独立に、水素原子又は炭素数１～５のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましい。 In formula (a0-r-1), Ra 01 and Ra 02 each independently represent a hydrogen atom or an alkyl group.
In formula (a0-r-1), at least one of Ra 01 and Ra 02 is preferably a hydrogen atom, and more preferably both are hydrogen atoms.
When Ra 01 or Ra 02 is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. Specific examples of preferred alkyl groups include linear or branched alkyl groups. More specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. A methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.
In formula (a0-r-1), Ra 01 and Ra 02 are each preferably independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
式（ａ０－ｒ－１）中、Ｒａ０１及びＲａ０２は、少なくとも一方が水素原子であることが好ましく、両方が水素原子であることがより好ましい。
Ｒａ０１又はＲａ０２がアルキル基である場合、該アルキル基としては、炭素数１～５のアルキル基が好ましい。具体的には、直鎖状または分岐鎖状のアルキル基が好ましく挙げられる。より具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基などが挙げられ、メチル基またはエチル基がより好ましく、メチル基が特に好ましい。
式（ａ０－ｒ－１）中、Ｒａ０１及びＲａ０２は、上記の中でも、それぞれ独立に、水素原子又は炭素数１～５のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましい。 In formula (a0-r-1), Ra 01 and Ra 02 each independently represent a hydrogen atom or an alkyl group.
In formula (a0-r-1), at least one of Ra 01 and Ra 02 is preferably a hydrogen atom, and more preferably both are hydrogen atoms.
When Ra 01 or Ra 02 is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. Specific examples of preferred alkyl groups include linear or branched alkyl groups. More specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. A methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.
In formula (a0-r-1), Ra 01 and Ra 02 are each preferably independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
式（ａ０－ｒ－１）中、Ｒａ０３の炭化水素基としては、直鎖状もしくは分岐鎖状のアルキル基、又は環状の炭化水素基が挙げられる。
該直鎖状のアルキル基は、炭素数が１～５であることが好ましく、炭素数が１～４がより好ましく、炭素数１または２がさらに好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基等が挙げられる。これらの中でも、メチル基、エチル基またはｎ－ブチル基が好ましく、メチル基またはエチル基がより好ましい。 In formula (a0-r-1), examples of the hydrocarbon group for Ra 03 include a linear or branched alkyl group, or a cyclic hydrocarbon group.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably has 1 to 4 carbon atoms, and even more preferably has 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
該直鎖状のアルキル基は、炭素数が１～５であることが好ましく、炭素数が１～４がより好ましく、炭素数１または２がさらに好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基等が挙げられる。これらの中でも、メチル基、エチル基またはｎ－ブチル基が好ましく、メチル基またはエチル基がより好ましい。 In formula (a0-r-1), examples of the hydrocarbon group for Ra 03 include a linear or branched alkyl group, or a cyclic hydrocarbon group.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably has 1 to 4 carbon atoms, and even more preferably has 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
該分岐鎖状のアルキル基は、炭素数が３～１０であることが好ましく、炭素数３～５がより好ましい。具体的には、イソプロピル基、イソブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、ネオペンチル基、１，１－ジエチルプロピル基、２，２－ジメチルブチル基等が挙げられ、イソプロピル基であることが好ましい。
The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.
Ｒａ０３が環状の炭化水素基となる場合、該炭化水素基は、脂肪族炭化水素基でも芳香族炭化水素基でもよく、また、多環式基でも単環式基でもよい。
単環式基である脂肪族炭化水素基としては、モノシクロアルカンから１個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから１個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 When Ra 03 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
単環式基である脂肪族炭化水素基としては、モノシクロアルカンから１個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから１個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 When Ra 03 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
Ｒａ０３の環状の炭化水素基が芳香族炭化水素基となる場合、該芳香族炭化水素基は、芳香環を少なくとも１つ有する炭化水素基である。
この芳香環は、４ｎ＋２個のπ電子をもつ環状共役系であれば特に限定されず、単環式でも多環式でもよい。芳香環の炭素数は５～３０であることが好ましく、炭素数５～２０がより好ましく、炭素数６～１５がさらに好ましく、炭素数６～１２が特に好ましい。
芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
Ｒａ０３における芳香族炭化水素基として具体的には、前記芳香族炭化水素環または芳香族複素環から水素原子を１つ除いた基（アリール基またはヘテロアリール基）；２以上の芳香環を含む芳香族化合物（例えばビフェニル、フルオレン等）から水素原子を１つ除いた基；前記芳香族炭化水素環または芳香族複素環の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基など）等が挙げられる。前記芳香族炭化水素環または芳香族複素環に結合するアルキレン基の炭素数は、１～４であることが好ましく、炭素数１～２であることがより好ましく、炭素数１であることが特に好ましい。 When the cyclic hydrocarbon group of Ra 03 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group in Ra 03 include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably has 1 carbon atom.
この芳香環は、４ｎ＋２個のπ電子をもつ環状共役系であれば特に限定されず、単環式でも多環式でもよい。芳香環の炭素数は５～３０であることが好ましく、炭素数５～２０がより好ましく、炭素数６～１５がさらに好ましく、炭素数６～１２が特に好ましい。
芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
Ｒａ０３における芳香族炭化水素基として具体的には、前記芳香族炭化水素環または芳香族複素環から水素原子を１つ除いた基（アリール基またはヘテロアリール基）；２以上の芳香環を含む芳香族化合物（例えばビフェニル、フルオレン等）から水素原子を１つ除いた基；前記芳香族炭化水素環または芳香族複素環の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基など）等が挙げられる。前記芳香族炭化水素環または芳香族複素環に結合するアルキレン基の炭素数は、１～４であることが好ましく、炭素数１～２であることがより好ましく、炭素数１であることが特に好ましい。 When the cyclic hydrocarbon group of Ra 03 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group in Ra 03 include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably has 1 carbon atom.
Ｒａ０３における環状の炭化水素基は、置換基を有してもよい。この置換基としては、上述のＲａｘ５と同様の基が挙げられる。
The cyclic hydrocarbon group in Ra 03 may have a substituent. Examples of the substituent include the same groups as those in Ra x5 described above.
Ｒａ０３が、Ｒａ０１、Ｒａ０２のいずれかと結合して環を形成する場合、該環式基としては、４～７員環が好ましく、４～６員環がより好ましい。該環式基の具体例としては、テトラヒドロピラニル基、テトラヒドロフラニル基等が挙げられる。
When Ra 03 is bonded to either Ra 01 or Ra 02 to form a ring, the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.
アセタール型酸解離性基の具体例を以下に示す。＊は結合手を示す。
Specific examples of acetal-type acid-dissociable groups are shown below. * indicates a bond.
第３級アルキルエステル型酸解離性基：
Ｒａ０１における酸解離性基としては、例えば、下記一般式（ａ０－ｒ－２）で表される酸解離性基が挙げられる。
なお、下記式（ａ０－ｒ－２）で表される酸解離性基のうち、アルキル基により構成されるものを、以下、便宜上「第３級アルキルエステル型酸解離性基」ということがある。 Tertiary alkyl ester type acid-dissociable group:
Examples of the acid dissociable group for Ra 01 include acid dissociable groups represented by general formula (a0-r-2) shown below.
Among the acid-dissociable groups represented by the following formula (a0-r-2), those constituted by an alkyl group may be referred to as "tertiary alkyl ester-type acid-dissociable groups" hereinafter for convenience.
Ｒａ０１における酸解離性基としては、例えば、下記一般式（ａ０－ｒ－２）で表される酸解離性基が挙げられる。
なお、下記式（ａ０－ｒ－２）で表される酸解離性基のうち、アルキル基により構成されるものを、以下、便宜上「第３級アルキルエステル型酸解離性基」ということがある。 Tertiary alkyl ester type acid-dissociable group:
Examples of the acid dissociable group for Ra 01 include acid dissociable groups represented by general formula (a0-r-2) shown below.
Among the acid-dissociable groups represented by the following formula (a0-r-2), those constituted by an alkyl group may be referred to as "tertiary alkyl ester-type acid-dissociable groups" hereinafter for convenience.
Ｒａ０４の炭化水素基としては、直鎖状もしくは分岐鎖状のアルキル基、鎖状もしくは環状のアルケニル基、又は、環状の炭化水素基が挙げられる。
Ｒａ０４における直鎖状もしくは分岐鎖状のアルキル基、環状の炭化水素基（単環式基である脂肪族炭化水素基、多環式基である脂肪族炭化水素基、芳香族炭化水素基）は、前記Ｒａ０３と同様のものが挙げられる。
Ｒａ０４における鎖状もしくは環状のアルケニル基は、炭素数２～１０のアルケニル基が好ましい。
Ｒａ０５、Ｒａ０６の炭化水素基としては、前記Ｒａ０３と同様のものが挙げられる。 Examples of the hydrocarbon group for Ra 04 include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group.
Examples of the linear or branched alkyl group and cyclic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, and aromatic hydrocarbon group) in Ra 04 are the same as those in Ra 03 .
The chain or cyclic alkenyl group for Ra 04 is preferably an alkenyl group having 2 to 10 carbon atoms.
Examples of the hydrocarbon group for Ra 05 and Ra 06 include the same as those for Ra 03 .
Ｒａ０４における直鎖状もしくは分岐鎖状のアルキル基、環状の炭化水素基（単環式基である脂肪族炭化水素基、多環式基である脂肪族炭化水素基、芳香族炭化水素基）は、前記Ｒａ０３と同様のものが挙げられる。
Ｒａ０４における鎖状もしくは環状のアルケニル基は、炭素数２～１０のアルケニル基が好ましい。
Ｒａ０５、Ｒａ０６の炭化水素基としては、前記Ｒａ０３と同様のものが挙げられる。 Examples of the hydrocarbon group for Ra 04 include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group.
Examples of the linear or branched alkyl group and cyclic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, and aromatic hydrocarbon group) in Ra 04 are the same as those in Ra 03 .
The chain or cyclic alkenyl group for Ra 04 is preferably an alkenyl group having 2 to 10 carbon atoms.
Examples of the hydrocarbon group for Ra 05 and Ra 06 include the same as those for Ra 03 .
Ｒａ０５とＲａ０６とが互いに結合して環を形成する場合、下記一般式（ａ０－ｒ２－０１）で表される基、下記一般式（ａ０－ｒ２－０２）で表される基、下記一般式（ａ０－ｒ２－０３）で表される基が好適に挙げられる。
一方、Ｒａ０４～Ｒａ０６が互いに結合せず、独立した炭化水素基である場合、下記一般式（ａ０－ｒ２－０４）で表される基が好適に挙げられる。 When Ra 05 and Ra 06 are bonded to each other to form a ring, suitable examples of such a ring include a group represented by the following general formula (a0-r2-01), a group represented by the following general formula (a0-r2-02), and a group represented by the following general formula (a0-r2-03).
On the other hand, when Ra 04 to Ra 06 are not bonded to each other and are independent hydrocarbon groups, suitable examples include groups represented by the following general formula (a0-r2-04).
一方、Ｒａ０４～Ｒａ０６が互いに結合せず、独立した炭化水素基である場合、下記一般式（ａ０－ｒ２－０４）で表される基が好適に挙げられる。 When Ra 05 and Ra 06 are bonded to each other to form a ring, suitable examples of such a ring include a group represented by the following general formula (a0-r2-01), a group represented by the following general formula (a0-r2-02), and a group represented by the following general formula (a0-r2-03).
On the other hand, when Ra 04 to Ra 06 are not bonded to each other and are independent hydrocarbon groups, suitable examples include groups represented by the following general formula (a0-r2-04).
式（ａ０－ｒ２－０２）中、Ｙａｂ０は炭素原子である。Ｘａｂ０は、Ｙａｂ０と共に環状の炭化水素基を形成する基である。この環状の炭化水素基が有する水素原子の一部又は全部は置換されていてもよく、環を構成する炭素原子の一部がヘテロ原子で置換されていてもよい。Ｒａ００２～Ｒａ００４は、それぞれ独立して、水素原子、炭素原子数１～１０の１価の鎖状飽和炭化水素基又は炭素原子数３～２０の１価の脂肪族環状飽和炭化水素基である。この鎖状飽和炭化水素基及び脂肪族環状飽和炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ００２～Ｒａ００４の２つ以上が互いに結合して環状構造を形成してもよい。＊は結合手を示す。
式（ａ０－ｒ２－０３）中、Ｙａｃ０は炭素原子である。Ｘａｃ０は、Ｙａｃ０と共に環状の炭化水素基を形成する基である。この環状の炭化水素基が有する水素原子の一部又は全部は置換されていてもよく、環を構成する炭素原子の一部がヘテロ原子で置換されていてもよい。Ｒａ００５は、芳香族炭化水素基である。この芳香族炭化水素基が有する水素原子の一部又は全部は置換されていてもよく、環を構成する炭素原子の一部がヘテロ原子で置換されていてもよい。＊は結合手を示す。
式（ａ０－ｒ２－０４）中、Ｒａ００６及びＲａ００７は、それぞれ独立に、炭素数１～１０の１価の鎖状飽和炭化水素基である。この鎖状飽和炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ００８は、置換基を有してもよい炭化水素基である。＊は結合手を示す。］
In formula (a0-r2-02), Yab 0 is a carbon atom. Xab 0 is a group forming a cyclic hydrocarbon group together with Yab 0. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms. Ra 002 to Ra 004 are each independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent cyclic aliphatic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in this linear saturated hydrocarbon group and cyclic aliphatic saturated hydrocarbon group may be substituted. Two or more of Ra 002 to Ra 004 may be bonded to each other to form a cyclic structure. * indicates a bond.
In formula (a0-r2-03), Yac 0 is a carbon atom. Xac 0 is a group forming a cyclic hydrocarbon group together with Yac 0. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms. Ra 005 is an aromatic hydrocarbon group. Some or all of the hydrogen atoms in this aromatic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms. * indicates a bond.
In formula (a0-r2-04), Ra 006 and Ra 007 each independently represent a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may be substituted. Ra 008 represents a hydrocarbon group which may have a substituent. * represents a bond.]
式（ａ０－ｒ２－０１）中、Ｒａ００１は、置換を有してもよい直鎖状又は分岐鎖状のアルキル基である。
該直鎖状のアルキル基は、炭素原子数が１～５であることが好ましく、炭素原子数が１～４がより好ましく、炭素原子数１または２がさらに好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基等が挙げられる。これらの中でも、メチル基、エチル基またはｎ－ブチル基が好ましく、メチル基またはエチル基がより好ましい。 In formula (a0-r2-01), Ra 001 represents an optionally substituted straight-chain or branched-chain alkyl group.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Of these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.
該直鎖状のアルキル基は、炭素原子数が１～５であることが好ましく、炭素原子数が１～４がより好ましく、炭素原子数１または２がさらに好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基等が挙げられる。これらの中でも、メチル基、エチル基またはｎ－ブチル基が好ましく、メチル基またはエチル基がより好ましい。 In formula (a0-r2-01), Ra 001 represents an optionally substituted straight-chain or branched-chain alkyl group.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Of these, a methyl group, an ethyl group, or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.
該分岐鎖状のアルキル基は、炭素原子数が３～１０であることが好ましく、炭素原子数３～５がより好ましい。具体的には、イソプロピル基、イソブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、ネオペンチル基、１，１－ジエチルプロピル基、２，２－ジメチルブチル基等が挙げられる。
The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group.
Ｒａ００１における直鎖状又は分岐鎖状のアルキル基が有してもよい置換基としては、例えば、上述したＲａｘ５が挙げられる。
Examples of the substituent that the linear or branched alkyl group in Ra 001 may have include the above-mentioned Ra x5 .
式（ａ０－ｒ２－０１）中、Ｒａ００１は、上記の中でも、炭素原子数が１～５の直鎖状のアルキル基又は炭素原子数が３～１０の分岐鎖状のアルキル基であることが好ましく、炭素原子数が１～４の直鎖状のアルキル基又は炭素原子数が３～５の分岐鎖状のアルキル基であることがより好ましく、炭素原子数が１～３の直鎖状のアルキル基であることがさらに好ましい。
In formula (a0-r2-01), Ra 001 is preferably a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, and even more preferably a linear alkyl group having 1 to 3 carbon atoms.
式（ａ０－ｒ２－０１）中、Ｙａａ０は炭素原子であり、Ｘａａ０は、Ｙａａ０と共に環状の炭化水素基を形成する基である。
該環状の炭化水素基としては、脂肪族炭化水素基であっても、脂肪族炭化水素基と芳香族炭化水素基との縮合環式炭化水素基であってもよく、また、多環式基でも単環式基でもよい。 In formula (a0-r2-01), Yaa 0 is a carbon atom, and Xaa 0 is a group forming a cyclic hydrocarbon group together with Yaa 0 .
The cyclic hydrocarbon group may be an aliphatic hydrocarbon group or a condensed cyclic hydrocarbon group of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
該環状の炭化水素基としては、脂肪族炭化水素基であっても、脂肪族炭化水素基と芳香族炭化水素基との縮合環式炭化水素基であってもよく、また、多環式基でも単環式基でもよい。 In formula (a0-r2-01), Yaa 0 is a carbon atom, and Xaa 0 is a group forming a cyclic hydrocarbon group together with Yaa 0 .
The cyclic hydrocarbon group may be an aliphatic hydrocarbon group or a condensed cyclic hydrocarbon group of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
単環式基である脂肪族炭化水素基としては、モノシクロアルカンから２個以上の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数３～６のものが好ましく、炭素原子数５又は６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから２個以上の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 The monocyclic aliphatic hydrocarbon group is preferably a group in which two or more hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, more preferably 5 or 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which two or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから２個以上の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 The monocyclic aliphatic hydrocarbon group is preferably a group in which two or more hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, more preferably 5 or 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which two or more hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
脂肪族炭化水素基と芳香族炭化水素基との縮合環式炭化水素基における芳香族炭化水素基は、芳香環を少なくとも１つ有する炭化水素基である。
この芳香環は、４ｎ＋２個のπ電子をもつ環状共役系であれば特に限定されず、単環式でも多環式でもよい。芳香環の炭素数は５～３０であることが好ましく、炭素数５～２０がより好ましく、炭素数６～１５がさらに好ましく、炭素数６～１２が特に好ましい。
芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。 The aromatic hydrocarbon group in the condensed cyclic hydrocarbon group of an aliphatic hydrocarbon group and an aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
この芳香環は、４ｎ＋２個のπ電子をもつ環状共役系であれば特に限定されず、単環式でも多環式でもよい。芳香環の炭素数は５～３０であることが好ましく、炭素数５～２０がより好ましく、炭素数６～１５がさらに好ましく、炭素数６～１２が特に好ましい。
芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。 The aromatic hydrocarbon group in the condensed cyclic hydrocarbon group of an aliphatic hydrocarbon group and an aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
以下に、脂肪族炭化水素基と芳香族炭化水素基との縮合環式炭化水素基の具体例を示す。
Specific examples of condensed cyclic hydrocarbon groups consisting of an aliphatic hydrocarbon group and an aromatic hydrocarbon group are shown below.
上記環状の炭化水素基が有する水素原子の一部又は全部は置換されていてもよく、環を構成する炭素原子の一部がヘテロ原子で置換されていてもよい。
上記環状の炭化水素基が有する水素原子の一部又は全部を置換する置換基として、具体的には、上述したＲａｘ５が挙げられる。環を構成する炭素原子の一部がヘテロ原子で置換されていている場合、該ヘテロ原子としては、酸素原子、硫黄原子、窒素原子が挙げられる。 Some or all of the hydrogen atoms in the cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms.
Specific examples of the substituent that replaces a part or all of the hydrogen atoms of the cyclic hydrocarbon group include the above-mentioned Ra x5 . When a part of the carbon atoms constituting the ring is replaced with a heteroatom, examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.
上記環状の炭化水素基が有する水素原子の一部又は全部を置換する置換基として、具体的には、上述したＲａｘ５が挙げられる。環を構成する炭素原子の一部がヘテロ原子で置換されていている場合、該ヘテロ原子としては、酸素原子、硫黄原子、窒素原子が挙げられる。 Some or all of the hydrogen atoms in the cyclic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms.
Specific examples of the substituent that replaces a part or all of the hydrogen atoms of the cyclic hydrocarbon group include the above-mentioned Ra x5 . When a part of the carbon atoms constituting the ring is replaced with a heteroatom, examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.
式（ａ０－ｒ２－０１）中、Ｘａａ０と、Ｙａａ０とが形成する環状の炭化水素基としては、上記の中でも、単環式基又は多環式基の脂肪族炭化水素基が好ましく、単環式基の脂肪族炭化水素基がより好ましく、炭素原子数５又は６の単環式基の脂肪族炭化水素基がさらに好ましい。
In formula (a0-r2-01), the cyclic hydrocarbon group formed by Xaa0 and Yaa0 is preferably a monocyclic or polycyclic aliphatic hydrocarbon group, more preferably a monocyclic aliphatic hydrocarbon group, and still more preferably a monocyclic aliphatic hydrocarbon group having 5 or 6 carbon atoms.
式（ａ０－ｒ２－０２）中、Ｙａｂ０は炭素原子であり、Ｘａｂ０は、Ｙａｂ０と共に環状の炭化水素基を形成する基である。この環状の炭化水素基としては、上述したＸａａ０と、Ｙａａ０とが形成する環状の炭化水素基と同様のものが挙げられる。
In formula (a0-r2-02), Yab 0 is a carbon atom, and Xab 0 is a group forming a cyclic hydrocarbon group together with Yab 0. Examples of this cyclic hydrocarbon group include the same as the cyclic hydrocarbon group formed by Xaa 0 and Yaa 0 described above.
式（ａ０－ｒ２－０２）中、Ｒａ００２～Ｒａ００４は、それぞれ独立して、水素原子、炭素原子数１～１０の１価の鎖状飽和炭化水素基又は炭素原子数３～２０の１価の脂肪族環状飽和炭化水素基である。
In formula (a0-r2-02), Ra 002 to Ra 004 each independently represent a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent cyclic aliphatic saturated hydrocarbon group having 3 to 20 carbon atoms.
Ｒａ００２～Ｒａ００４における、炭素原子数１～１０の１価の鎖状飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基等が挙げられる。
Ｒａ００２～Ｒａ００４における、炭素原子数３～２０の１価の脂肪族環状飽和炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、シクロドデシル基等の単環式脂肪族飽和炭化水素基；ビシクロ［２．２．２］オクタニル基、トリシクロ［５．２．１．０２，６］デカニル基、トリシクロ［３．３．１．１３，７］デカニル基、テトラシクロ［６．２．１．１３，６．０２，７］ドデカニル基、アダマンチル基等の多環式脂肪族飽和炭化水素基等が挙げられる。 Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 002 to Ra 004 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group.
Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in Ra 002 to Ra 004 include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; and polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.0 2,6 ]decanyl group, a tricyclo[3.3.1.1 3,7 ]decanyl group, a tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodecanyl group, and an adamantyl group.
Ｒａ００２～Ｒａ００４における、炭素原子数３～２０の１価の脂肪族環状飽和炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、シクロドデシル基等の単環式脂肪族飽和炭化水素基；ビシクロ［２．２．２］オクタニル基、トリシクロ［５．２．１．０２，６］デカニル基、トリシクロ［３．３．１．１３，７］デカニル基、テトラシクロ［６．２．１．１３，６．０２，７］ドデカニル基、アダマンチル基等の多環式脂肪族飽和炭化水素基等が挙げられる。 Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 002 to Ra 004 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group.
Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in Ra 002 to Ra 004 include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; and polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.0 2,6 ]decanyl group, a tricyclo[3.3.1.1 3,7 ]decanyl group, a tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodecanyl group, and an adamantyl group.
Ｒａ００２～Ｒａ００４における、鎖状飽和炭化水素基及び脂肪族環状飽和炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。鎖状飽和炭化水素基及び脂肪族環状飽和炭化水素基が有する水素原子の一部又は全部を置換する置換基として、具体的には、上述したＲａｘ５が挙げられる。環を構成する炭素原子の一部がヘテロ原子で置換されていている場合、該ヘテロ原子としては、酸素原子、硫黄原子、窒素原子が挙げられる。
In Ra 002 to Ra 004 , some or all of the hydrogen atoms in the chain saturated hydrocarbon group and the alicyclic saturated hydrocarbon group may be substituted. Specific examples of the substituent substituting some or all of the hydrogen atoms in the chain saturated hydrocarbon group and the alicyclic saturated hydrocarbon group include the above-mentioned Ra x5 . When some of the carbon atoms constituting the ring are substituted with heteroatoms, examples of the heteroatom include oxygen atoms, sulfur atoms, and nitrogen atoms.
Ｒａ００２～Ｒａ００４の２つ以上が互いに結合して環状構造を形成することにより生じる炭素－炭素二重結合を含む基としては、例えば、シクロペンテニル基、シクロヘキセニル基、メチルシクロペンテニル基、メチルシクロヘキセニル基、シクロペンチリデンエテニル基、シクロへキシリデンエテニル基等が挙げられる。これらの中でも、合成容易性の観点から、シクロペンテニル基、シクロヘキセニル基、シクロペンチリデンエテニル基が好ましい。
Examples of groups containing a carbon-carbon double bond formed by two or more of Ra 002 to Ra 004 bonding to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylidene-ethenyl group, a cyclohexylidene-ethenyl group, etc. Among these, from the viewpoint of ease of synthesis, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylidene-ethenyl group are preferred.
式（ａ０－ｒ２－０２）中、Ｒａ００２～Ｒａ００４は、上記の中でも、それぞれ独立して、水素原子、炭素原子数１～１０の１価の鎖状飽和炭化水素基が好ましく、水素原子、メチル基、エチル基がより好ましく、水素原子がさらに好ましい。
In formula (a0-r2-02), Ra 002 to Ra 004 are each independently preferably a hydrogen atom or a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and still more preferably a hydrogen atom.
式（ａ０－ｒ２－０３）中、Ｙａｃ０は炭素原子であり、Ｘａｃ０は、Ｙａｃ０と共に環状の炭化水素基を形成する基である。この環状の炭化水素基としては、上述したＸａａ０と、Ｙａａ０とが形成する環状の炭化水素基と同様のものが挙げられる。
In formula (a0-r2-03), Yac 0 is a carbon atom, and Xac 0 is a group forming a cyclic hydrocarbon group together with Yac 0. Examples of this cyclic hydrocarbon group include the same as the cyclic hydrocarbon group formed by Xaa 0 and Yaa 0 described above.
式（ａ０－ｒ２－０３）中、Ｒａ００５は、芳香族炭化水素基としては、炭素原子数６～１５の芳香族炭化水素環から水素原子１個以上を除いた基が好ましく、ベンゼン、ナフタレン、アントラセン又はフェナントレンから水素原子１個以上を除いた基がより好ましく、ベンゼン又はナフタレンから水素原子１個以上を除いた基がさらに好ましく、ベンゼンから水素原子１個以上を除いた基が特に好ましい。
In formula (a0-r2-03), Ra 005 is preferably an aromatic hydrocarbon group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene, even more preferably a group obtained by removing one or more hydrogen atoms from benzene or naphthalene, and particularly preferably a group obtained by removing one or more hydrogen atoms from benzene.
上記芳香族炭化水素基が有する水素原子の一部又は全部は置換されていてもよく、環を構成する炭素原子の一部がヘテロ原子で置換されていてもよい。
上記芳香族炭化水素基が有する水素原子の一部又は全部を置換する置換基として、具体的には、上述したＲａｘ５が挙げられる。環を構成する炭素原子の一部がヘテロ原子で置換されていている場合、該ヘテロ原子としては、酸素原子、硫黄原子、窒素原子が挙げられる。 Some or all of the hydrogen atoms in the aromatic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms.
Specific examples of the substituent that replaces a part or all of the hydrogen atoms of the aromatic hydrocarbon group include the above-mentioned Ra x5 . When a part of the carbon atoms constituting the ring is replaced with a heteroatom, examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.
上記芳香族炭化水素基が有する水素原子の一部又は全部を置換する置換基として、具体的には、上述したＲａｘ５が挙げられる。環を構成する炭素原子の一部がヘテロ原子で置換されていている場合、該ヘテロ原子としては、酸素原子、硫黄原子、窒素原子が挙げられる。 Some or all of the hydrogen atoms in the aromatic hydrocarbon group may be substituted, and some of the carbon atoms constituting the ring may be substituted with heteroatoms.
Specific examples of the substituent that replaces a part or all of the hydrogen atoms of the aromatic hydrocarbon group include the above-mentioned Ra x5 . When a part of the carbon atoms constituting the ring is replaced with a heteroatom, examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.
式（ａ０－ｒ２－０４）中、Ｒａ００６及びＲａ００７は、それぞれ独立に、炭素数１～１０の１価の鎖状飽和炭化水素基である。
Ｒａ００６及びＲａ００７における、炭素数１～１０の１価の鎖状飽和炭化水素基としては、上述したＲａ００２～Ｒａ００４における炭素数１～１０の１価の鎖状飽和炭化水素基と同様のものが挙げられる。 In formula (a0-r2-04), Ra 006 and Ra 007 each independently represent a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms.
Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 006 and Ra 007 include the same monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms in Ra 002 to Ra 004 described above.
Ｒａ００６及びＲａ００７における、炭素数１～１０の１価の鎖状飽和炭化水素基としては、上述したＲａ００２～Ｒａ００４における炭素数１～１０の１価の鎖状飽和炭化水素基と同様のものが挙げられる。 In formula (a0-r2-04), Ra 006 and Ra 007 each independently represent a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms.
Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 006 and Ra 007 include the same monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms in Ra 002 to Ra 004 described above.
式（ａ０－ｒ２－０４）中、Ｒａ００６及びＲａ００７は、上記の中でも、炭素数１～５のアルキル基が好ましく、メチル基、エチル基がより好ましく、メチル基がさらに好ましい。
Ｒａ００６及びＲａ００７で表される鎖状飽和炭化水素基が置換されている場合、その置換基としては、例えば、上述のＲａｘ５と同様の基が挙げられる。 In formula (a0-r2-04), Ra 006 and Ra 007 are preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
When the chain saturated hydrocarbon groups represented by Ra 006 and Ra 007 are substituted, examples of the substituent include the same groups as those for Ra x5 above.
Ｒａ００６及びＲａ００７で表される鎖状飽和炭化水素基が置換されている場合、その置換基としては、例えば、上述のＲａｘ５と同様の基が挙げられる。 In formula (a0-r2-04), Ra 006 and Ra 007 are preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
When the chain saturated hydrocarbon groups represented by Ra 006 and Ra 007 are substituted, examples of the substituent include the same groups as those for Ra x5 above.
式（ａ０－ｒ２－０４）中、Ｒａ００８は、置換基を有してもよい炭化水素基である。Ｒａ００８における炭化水素基としては、直鎖状もしくは分岐鎖状のアルキル基、又は環状の炭化水素基が挙げられる。
In formula (a0-r2-04), Ra 008 represents a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group for Ra 008 include a linear or branched alkyl group, and a cyclic hydrocarbon group.
Ｒａ００８における直鎖状のアルキル基は、炭素数が１～５であることが好ましく、１～４がより好ましく、１又は２がさらに好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基等が挙げられる。これらの中でも、メチル基、エチル基又はｎ－ブチル基が好ましく、メチル基又はエチル基がより好ましい。
The linear alkyl group in Ra 008 preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and the like. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
Ｒａ００８における分岐鎖状のアルキル基は、炭素数が３～１０であることが好ましく、３～５がより好ましい。具体的には、イソプロピル基、イソブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、ネオペンチル基、１，１－ジエチルプロピル基、２，２－ジメチルブチル基等が挙げられ、イソプロピル基であることが好ましい。
The branched alkyl group in Ra 008 preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.
Ｒａ００８が環状の炭化水素基となる場合、該炭化水素基は、脂肪族炭化水素基でも芳香族炭化水素基でもよく、また、多環式基でも単環式基でもよい。
単環式基である脂肪族炭化水素基としては、モノシクロアルカンから１個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから１個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 When Ra 008 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
単環式基である脂肪族炭化水素基としては、モノシクロアルカンから１個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから１個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 When Ra 008 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
Ｒａ００８における芳香族炭化水素基としては、Ｒａ００５における芳香族炭化水素基と同様のものが挙げられる。中でも、Ｒａ００８は、炭素数６～１５の芳香族炭化水素環から水素原子１個以上を除いた基が好ましく、ベンゼン、ナフタレン、アントラセン又はフェナントレンから水素原子１個以上を除いた基がより好ましく、ベンゼン、ナフタレン又はアントラセンから水素原子１個以上を除いた基がさらに好ましく、ナフタレン又はアントラセンから水素原子１個以上を除いた基が特に好ましく、ナフタレンから水素原子１個以上を除いた基が最も好ましい。
Ｒａ００８が有していてもよい置換基としては、Ｒａ００５が有していてもよい置換基と同様のものが挙げられる。 Examples of the aromatic hydrocarbon group for Ra 008 include the same as the aromatic hydrocarbon group for Ra 005. Among them, Ra 008 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from naphthalene or anthracene, and most preferably a group in which one or more hydrogen atoms have been removed from naphthalene.
Examples of the substituent which Ra 008 may have include the same substituents as those which Ra 005 may have.
Ｒａ００８が有していてもよい置換基としては、Ｒａ００５が有していてもよい置換基と同様のものが挙げられる。 Examples of the aromatic hydrocarbon group for Ra 008 include the same as the aromatic hydrocarbon group for Ra 005. Among them, Ra 008 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from naphthalene or anthracene, and most preferably a group in which one or more hydrogen atoms have been removed from naphthalene.
Examples of the substituent which Ra 008 may have include the same substituents as those which Ra 005 may have.
式（ａ０－ｒ２－０４）中のＲａ００８がナフチル基である場合、前記式（ａ１－ｒ２－４）における第３級炭素原子と結合する位置は、ナフチル基の１位又は２位のいずれであってもよい。
式（ａ０－ｒ２－０４）中のＲａ００８がアントリル基である場合、前記式（ａ０－ｒ２－０４）における第３級炭素原子と結合する位置は、アントリル基の１位、２位又は９位のいずれであってもよい。 When Ra 008 in formula (a0-r2-04) is a naphthyl group, the position at which it bonds to the tertiary carbon atom in formula (a1-r2-4) may be either the 1st or 2nd position of the naphthyl group.
When Ra 008 in formula (a0-r2-04) is an anthryl group, the position at which it is bonded to the tertiary carbon atom in formula (a0-r2-04) may be any one of the 1-position, 2-position or 9-position of the anthryl group.
式（ａ０－ｒ２－０４）中のＲａ００８がアントリル基である場合、前記式（ａ０－ｒ２－０４）における第３級炭素原子と結合する位置は、アントリル基の１位、２位又は９位のいずれであってもよい。 When Ra 008 in formula (a0-r2-04) is a naphthyl group, the position at which it bonds to the tertiary carbon atom in formula (a1-r2-4) may be either the 1st or 2nd position of the naphthyl group.
When Ra 008 in formula (a0-r2-04) is an anthryl group, the position at which it is bonded to the tertiary carbon atom in formula (a0-r2-04) may be any one of the 1-position, 2-position or 9-position of the anthryl group.
式（ａ０－ｒ２－０４）中、Ｒａ００８は、上記の中でも、炭素数１～５のアルキル基が好ましく、メチル基、エチル基がより好ましく、メチル基がさらに好ましい。
In formula (a0-r2-04), Ra 008 is preferably an alkyl group having 1 to 5 carbon atoms among the above, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
前記式（ａ０－ｒ２－０１）で表される基の具体例を以下に挙げる。
Specific examples of the group represented by the formula (a0-r2-01) are given below.
前記式（ａ０－ｒ２－０２）で表される基の具体例を以下に挙げる。
Specific examples of the group represented by the formula (a0-r2-02) are given below.
前記式（ａ０－ｒ２－０３）で表される基の具体例を以下に挙げる。
Specific examples of the group represented by the formula (a0-r2-03) are given below.
前記式（ａ０－ｒ２－０４）で表される基の具体例を以下に挙げる。
Specific examples of the group represented by the formula (a0-r2-04) are given below.
第２級アルキルエステル型酸解離性基：
Ｒａ０１における酸解離性基としては、例えば、下記一般式（ａ０－ｒ－３）で表される酸解離性基が挙げられる。 Secondary alkyl ester type acid-dissociable group:
Examples of the acid dissociable group for Ra 01 include acid dissociable groups represented by general formula (a0-r-3) shown below.
Ｒａ０１における酸解離性基としては、例えば、下記一般式（ａ０－ｒ－３）で表される酸解離性基が挙げられる。 Secondary alkyl ester type acid-dissociable group:
Examples of the acid dissociable group for Ra 01 include acid dissociable groups represented by general formula (a0-r-3) shown below.
式中、Ｒａ０７及びＲａ０９における炭化水素基としては、前記Ｒａ０１と同様のものが挙げられる。
式中、Ｒａ０８ａ及びＲａ０８ｂにおけるアルキル基としては、前記Ｒａ０１におけるアルキル基と同様のものが挙げられる。
式中、Ｒａ０７及びＲａ０９における炭化水素基、並びに、Ｒａ０８ａ及びＲａ０８ｂにおけるアルキル基は置換基を有してもよい。この置換基としては、例えば、上述したＲａｘ５等が挙げられる。 In the formula, examples of the hydrocarbon group in Ra 07 and Ra 09 include the same as those in Ra 01 above.
In the formula, examples of the alkyl group in Ra 08a and Ra 08b include the same as the alkyl group in Ra 01 .
In the formula, the hydrocarbon groups in Ra 07 and Ra 09 , and the alkyl groups in Ra 08a and Ra 08b may have a substituent. Examples of the substituent include the above-mentioned Ra x5 .
式中、Ｒａ０８ａ及びＲａ０８ｂにおけるアルキル基としては、前記Ｒａ０１におけるアルキル基と同様のものが挙げられる。
式中、Ｒａ０７及びＲａ０９における炭化水素基、並びに、Ｒａ０８ａ及びＲａ０８ｂにおけるアルキル基は置換基を有してもよい。この置換基としては、例えば、上述したＲａｘ５等が挙げられる。 In the formula, examples of the hydrocarbon group in Ra 07 and Ra 09 include the same as those in Ra 01 above.
In the formula, examples of the alkyl group in Ra 08a and Ra 08b include the same as the alkyl group in Ra 01 .
In the formula, the hydrocarbon groups in Ra 07 and Ra 09 , and the alkyl groups in Ra 08a and Ra 08b may have a substituent. Examples of the substituent include the above-mentioned Ra x5 .
Ｒａ０７とＲａ０８ａ又はＲａ０８ｂとは、互いに結合して環を形成してもよい。該環は、多環であっても、単環であってもよく、脂環であっても、芳香環であってもよい。
該脂環及び芳香環は、ヘテロ原子を含むものでもよい。 Ra 07 and Ra 08a or Ra 08b may be bonded to each other to form a ring. The ring may be a polycyclic ring or a monocyclic ring, an alicyclic ring, or an aromatic ring.
The alicyclic and aromatic rings may contain heteroatoms.
該脂環及び芳香環は、ヘテロ原子を含むものでもよい。 Ra 07 and Ra 08a or Ra 08b may be bonded to each other to form a ring. The ring may be a polycyclic ring or a monocyclic ring, an alicyclic ring, or an aromatic ring.
The alicyclic and aromatic rings may contain heteroatoms.
Ｒａ０７とＲａ０８ａ又はＲａ０８ｂとが、互いに結合して形成する環としては、上記の中でも、モノシクロアルケン、モノシクロアルケンの炭素原子の一部がヘテロ原子（酸素原子、硫黄原子等）で置換された環、モノシクロアルカジエンが好ましく、炭素数３～６のシクロアルケンが好ましく、シクロペンテン又はシクロヘキセンが好ましい。
The ring formed by Ra 07 and Ra 08a or Ra 08b bonding to each other is preferably a monocycloalkene, a ring in which a portion of the carbon atoms of a monocycloalkene is substituted with a heteroatom (such as an oxygen atom or a sulfur atom), or a monocycloalkadiene, more preferably a cycloalkene having 3 to 6 carbon atoms, and more preferably cyclopentene or cyclohexene.
Ｒａ０７とＲａ０８ａ又はＲａ０８ｂとが、互いに結合して形成する環は、縮合環であってもよい。該縮合環として、具体的には、インダン等が挙げられる。
The ring formed by bonding between Ra 07 and Ra 08a or Ra 08b may be a condensed ring. Specific examples of the condensed ring include indan.
Ｒａ０７とＲａ０８ａ又はＲａ０８ｂとが、互いに結合して形成する環は、置換基を有してもよい。この置換基としては、例えば、上述したＲａｘ５等が挙げられる。
The ring formed by bonding Ra 07 and Ra 08a or Ra 08b together may have a substituent. Examples of the substituent include the above-mentioned Ra x5 .
Ｒａ０８ａ又はＲａ０８ｂと、Ｒａ０９とは、互いに結合して環を形成してもよく、該環としては、Ｒａ０７とＲａ０８ａ又はＲａ０８ｂとが、互いに結合して形成する環と同様のものが挙げられる。
Ra 08a or Ra 08b and Ra 09 may be bonded to each other to form a ring, and examples of the ring include the same as the ring formed by Ra 07 and Ra 08a or Ra 08b being bonded to each other.
上記式（ａ０－ｒ－３）中、Ｒａ０７とＲａ０８ａ又はＲａ０８ｂとは、上記の中でも、互いに結合して環を形成することが好ましく、互いに結合して単環を形成することがより好ましく、互いに結合して単環の脂環を形成することがさらに好ましい。その場合、Ｒａ０９は、水素原子であることが好ましい。
また、Ｒａ０７とＲａ０８ａ又はＲａ０８ｂとが、互いに結合して形成する前記環は、置換基を有してもよく、該置換基としては、炭素原子数１～５のアルキル基が好ましく、炭素原子数１～３のアルキル基がより好ましく、メチル基又はエチル基がさらに好ましい。 In the above formula (a0-r-3), Ra 07 and Ra 08a or Ra 08b are preferably bonded to each other to form a ring, more preferably bonded to each other to form a monocyclic ring, and further preferably bonded to each other to form a monocyclic alicyclic ring. In that case, Ra 09 is preferably a hydrogen atom.
In addition, the ring formed by bonding Ra 07 and Ra 08a or Ra 08b to each other may have a substituent, and as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is further preferable.
また、Ｒａ０７とＲａ０８ａ又はＲａ０８ｂとが、互いに結合して形成する前記環は、置換基を有してもよく、該置換基としては、炭素原子数１～５のアルキル基が好ましく、炭素原子数１～３のアルキル基がより好ましく、メチル基又はエチル基がさらに好ましい。 In the above formula (a0-r-3), Ra 07 and Ra 08a or Ra 08b are preferably bonded to each other to form a ring, more preferably bonded to each other to form a monocyclic ring, and further preferably bonded to each other to form a monocyclic alicyclic ring. In that case, Ra 09 is preferably a hydrogen atom.
In addition, the ring formed by bonding Ra 07 and Ra 08a or Ra 08b to each other may have a substituent, and as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is further preferable.
前記式（ａ０－ｒ－３）で表される基の具体例を以下に挙げる。
Specific examples of the group represented by formula (a0-r-3) are given below.
上記式（ａ０－１）中、Ｒａ０１における酸解離性基としては、第３級アルキルエステル型酸解離性基であることが好ましく、上記式（ａ０－ｒ２－０１）又は（ａ０－ｒ２－０４）のいずれかで表される酸解離性基であることがより好ましく、上記式（ａ０－ｒ２－０１）で表される酸解離性基であることがさらに好ましい。
In the above formula (a0-1), the acid dissociable group for Ra 01 is preferably a tertiary alkyl ester type acid dissociable group, more preferably an acid dissociable group represented by the above formula (a0-r2-01) or (a0-r2-04), and even more preferably an acid dissociable group represented by the above formula (a0-r2-01).
上記式（ａ０－１）中、ｑは、０～３の整数である。ｑが０の場合は、ベンゼン構造、ｑが１の場合は、ナフタレン構造、ｑが２の場合は、アントラセン構造、ｑが３の場合は、テトラセン構造となる。
In the above formula (a0-1), q is an integer from 0 to 3. When q is 0, the structure is a benzene structure, when q is 1, the structure is a naphthalene structure, when q is 2, the structure is an anthracene structure, and when q is 3, the structure is a tetracene structure.
上記式（ａ０－１）中、ｎは、１以上の整数であり、好ましくは１～５であり、より好ましくは１～３であり、さらに好ましくは１又は２である。
In the above formula (a0-1), n is an integer of 1 or more, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.
上記式（ａ０－１）中、ｎ≦ｑ×２＋４である。
例えば、ｑが１でナフタレン構造である場合、該ナフタレンは、重合性基含有基（Ｗ０１）及び－Ｙａ０１－（Ｃ＝Ｏ）－Ｏ－Ｒａ０１基で置換されている水素原子以外の全ての水素原子がヒドロキシ基で置換されていてもよい。また、該ナフタレンにおいて、重合性基含有基（Ｗ０１）、－Ｙａ０１－（Ｃ＝Ｏ）－Ｏ－Ｒａ０１基、及びヒドロキシ基の置換位置は特に限定されない。 In the above formula (a0-1), n≦q×2+4.
For example, when q is 1 and the naphthalene structure is a naphthalene structure, all hydrogen atoms in the naphthalene other than those substituted with the polymerizable group-containing group (W 01 ) and the -Ya 01 -(C═O)-O-Ra 01 group may be substituted with hydroxy groups. In addition, in the naphthalene, the substitution positions of the polymerizable group-containing group (W 01 ), the -Ya 01 -(C═O)-O-Ra 01 group, and the hydroxy group are not particularly limited.
例えば、ｑが１でナフタレン構造である場合、該ナフタレンは、重合性基含有基（Ｗ０１）及び－Ｙａ０１－（Ｃ＝Ｏ）－Ｏ－Ｒａ０１基で置換されている水素原子以外の全ての水素原子がヒドロキシ基で置換されていてもよい。また、該ナフタレンにおいて、重合性基含有基（Ｗ０１）、－Ｙａ０１－（Ｃ＝Ｏ）－Ｏ－Ｒａ０１基、及びヒドロキシ基の置換位置は特に限定されない。 In the above formula (a0-1), n≦q×2+4.
For example, when q is 1 and the naphthalene structure is a naphthalene structure, all hydrogen atoms in the naphthalene other than those substituted with the polymerizable group-containing group (W 01 ) and the -Ya 01 -(C═O)-O-Ra 01 group may be substituted with hydroxy groups. In addition, in the naphthalene, the substitution positions of the polymerizable group-containing group (W 01 ), the -Ya 01 -(C═O)-O-Ra 01 group, and the hydroxy group are not particularly limited.
構成単位（ａ０１）は、上記の中でも、下記一般式（ａ０－１－１）で表される構成単位であることが好ましい。
Of the above, the structural unit (a01) is preferably a structural unit represented by the following general formula (a0-1-1):
式（ａ０－１－１）中、Ｒの炭素数１～５のアルキル基は、炭素数１～５の直鎖状または分岐鎖状のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。炭素数１～５のハロゲン化アルキル基は、前記炭素数１～５のアルキル基の水素原子の一部または全部がハロゲン原子で置換された基である。該ハロゲン原子としては、特にフッ素原子が好ましい。
Ｒとしては、水素原子、炭素数１～５のアルキル基又は炭素数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子又はメチル基が最も好ましい。 In formula (a0-1-1), the alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.
Ｒとしては、水素原子、炭素数１～５のアルキル基又は炭素数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子又はメチル基が最も好ましい。 In formula (a0-1-1), the alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.
式（ａ０－１－１）中、Ｙａ００１は、単結合又は２価の連結基である。
Ｙａ００１における２価の連結基としては、特に限定されないが、置換基を有してもよい２価の炭化水素基、及びヘテロ原子を含む２価の連結基等が好適なものとして挙げられ、それぞれＷ０１における２価の炭化水素基、及びヘテロ原子を含む２価の連結基と同様である。 In formula (a0-1-1), Ya 001 represents a single bond or a divalent linking group.
The divalent linking group for Ya 001 is not particularly limited, and preferred examples thereof include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom, which are the same as the divalent hydrocarbon group and the divalent linking group containing a hetero atom for W 01 , respectively.
Ｙａ００１における２価の連結基としては、特に限定されないが、置換基を有してもよい２価の炭化水素基、及びヘテロ原子を含む２価の連結基等が好適なものとして挙げられ、それぞれＷ０１における２価の炭化水素基、及びヘテロ原子を含む２価の連結基と同様である。 In formula (a0-1-1), Ya 001 represents a single bond or a divalent linking group.
The divalent linking group for Ya 001 is not particularly limited, and preferred examples thereof include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom, which are the same as the divalent hydrocarbon group and the divalent linking group containing a hetero atom for W 01 , respectively.
上記の中でも、Ｙａ００１としては、エステル結合［－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－］、エーテル結合（－Ｏ－）、直鎖状若しくは分岐鎖状のアルキレン基、芳香族炭化水素基又はこれらの組合せ、あるいは単結合であることが好ましい。これらの中でも、Ｙａ００１としては、エステル結合［－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－］と直鎖状のアルキレン基との組み合わせ、又は単結合であることがより好ましく、単結合であることがさらに好ましい。
Among the above, Ya 001 is preferably an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, an aromatic hydrocarbon group, or a combination thereof, or a single bond. Among these, Ya 001 is more preferably a combination of an ester bond [-C(=O)-O-, -O-C(=O)-] and a linear alkylene group, or a single bond, and even more preferably a single bond.
式（ａ０－１－１）中、Ｙａ０１は、上記式（ａ０－１）中のＹａ０１と同一である。
In formula (a0-1-1), Ya 01 is the same as Ya 01 in the above formula (a0-1).
式（ａ０－１－１）中、Ｒａｘ０１は上述した一般式（ａ０－ｒ－１）、（ａ０－ｒ－２）、又は、（ａ０－ｒ－３）で表される酸解離性基である。
式（ａ０－１－１）中、Ｒａｘ０１は、上記の中でも、上記式（ａ０－ｒ２－０１）又は（ａ０－ｒ２－０４）のいずれかで表される酸解離性基であることが好ましく、上記式（ａ０－ｒ２－０１）で表される酸解離性基であることがより好ましい。 In formula (a0-1-1), Rax01 is an acid dissociable group represented by the above-mentioned general formula (a0-r-1), (a0-r-2), or (a0-r-3).
In formula (a0-1-1), Rax 01 is preferably an acid dissociable group represented by any one of the above formulas (a0-r2-01) or (a0-r2-04), and more preferably an acid dissociable group represented by the above formula (a0-r2-01).
式（ａ０－１－１）中、Ｒａｘ０１は、上記の中でも、上記式（ａ０－ｒ２－０１）又は（ａ０－ｒ２－０４）のいずれかで表される酸解離性基であることが好ましく、上記式（ａ０－ｒ２－０１）で表される酸解離性基であることがより好ましい。 In formula (a0-1-1), Rax01 is an acid dissociable group represented by the above-mentioned general formula (a0-r-1), (a0-r-2), or (a0-r-3).
In formula (a0-1-1), Rax 01 is preferably an acid dissociable group represented by any one of the above formulas (a0-r2-01) or (a0-r2-04), and more preferably an acid dissociable group represented by the above formula (a0-r2-01).
式（ａ０－１－１）中、ｑ及びｎは、上記式（ａ０－１）中のｑ及びｎと同一である。
In formula (a0-1-1), q and n are the same as q and n in formula (a0-1) above.
以下に構成単位（ａ０１）の具体例を示す。以下の各式中、Ｒαは、水素原子、メチル基またはトリフルオロメチル基を示す。
Specific examples of structural unit (a01) are shown below. In each of the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
本実施形態のレジスト組成物における構成単位（ａ０１）としては、上記の中でも、上記式（ａ０１－１ａ－２）、（ａ０１－１ａ－８）、（ａ０１－１ａ－２８）、（ａ０１－１ａ－３１）、（ａ０１－１ａ－３４）、（ａ０１－１ａ－３７）のいずれかで表される構成単位であることが好ましく、上記式（ａ０１－１ａ－２）、（ａ０１－１ａ－３１）、（ａ０１－１ａ－３４）、（ａ０１－１ａ－３７）のいずれかで表される構成単位であることがより好ましい。
The structural unit (a01) in the resist composition of this embodiment is preferably a structural unit represented by any one of the above formulas (a01-1a-2), (a01-1a-8), (a01-1a-28), (a01-1a-31), (a01-1a-34), and (a01-1a-37), and more preferably a structural unit represented by any one of the above formulas (a01-1a-2), (a01-1a-31), (a01-1a-34), and (a01-1a-37).
（Ａ１）成分が有する構成単位（ａ０１）は、１種であってもよく２種以上であってもよい。
（Ａ１）成分中の構成単位（ａ０１）の割合は、該（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましく、３０モル％以上であることがさらに好ましく、１００モル％であってもよい。
構成単位（ａ０１）の割合を、前記の好ましい下限値以上にすることにより、解像性を低下させることなく、感度をより向上させることができる。また、現像液溶解性を適切に担保できるため、微細解像性をより向上させることができる。
例えば、（Ａ１）成分中の構成単位（ａ０１）の割合は、該（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％であることが好ましく、２０～８０モル％であることがより好ましく、３０～７０モル％であることがさらに好ましい。 The structural unit (a01) contained in the component (A1) may be of one type, or may be of two or more types.
The proportion of the structural unit (a01) in the component (A1) relative to the total (100 mol%) of all structural units constituting the component (A1), is preferably at least 10 mol%, more preferably at least 20 mol%, and even more preferably at least 30 mol%, or it may even be 100 mol%.
By making the proportion of the structural unit (a01) equal to or greater than the above-mentioned preferable lower limit, the sensitivity can be further improved without decreasing the resolution. In addition, since the solubility in the developer can be appropriately ensured, the fine resolution can be further improved.
For example, the amount of the structural unit (a01) in the component (A1) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %, relative to the total amount (100 mol %) of all structural units constituting the component (A1).
（Ａ１）成分中の構成単位（ａ０１）の割合は、該（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましく、３０モル％以上であることがさらに好ましく、１００モル％であってもよい。
構成単位（ａ０１）の割合を、前記の好ましい下限値以上にすることにより、解像性を低下させることなく、感度をより向上させることができる。また、現像液溶解性を適切に担保できるため、微細解像性をより向上させることができる。
例えば、（Ａ１）成分中の構成単位（ａ０１）の割合は、該（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％であることが好ましく、２０～８０モル％であることがより好ましく、３０～７０モル％であることがさらに好ましい。 The structural unit (a01) contained in the component (A1) may be of one type, or may be of two or more types.
The proportion of the structural unit (a01) in the component (A1) relative to the total (100 mol%) of all structural units constituting the component (A1), is preferably at least 10 mol%, more preferably at least 20 mol%, and even more preferably at least 30 mol%, or it may even be 100 mol%.
By making the proportion of the structural unit (a01) equal to or greater than the above-mentioned preferable lower limit, the sensitivity can be further improved without decreasing the resolution. In addition, since the solubility in the developer can be appropriately ensured, the fine resolution can be further improved.
For example, the amount of the structural unit (a01) in the component (A1) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol %, relative to the total amount (100 mol %) of all structural units constituting the component (A1).
≪その他構成単位≫
（Ａ１）成分は、前記構成単位（ａ０１）に加え、必要に応じてその他構成単位を有してもよい。
その他構成単位としては、例えば、酸の作用により極性が増大する酸分解性基を含む構成単位（ａ１）（但し、前記構成単位（ａ０１）に該当するものを除く）；後述の一般式（ａ１０－１）で表される構成単位（ａ１０）；ラクトン含有環式基を含む構成単位（ａ２）；後述の一般式（ａ８－１）で表される化合物から誘導される構成単位（ａ８）などが挙げられる。 Other structural units
The component (A1) may include other structural units, in addition to the structural unit (a01), as necessary.
Examples of other structural units include the structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of acid (provided that this does not fall under the category of the structural unit (a01) above); the structural unit (a10) represented by general formula (a10-1) described below; the structural unit (a2) containing a lactone-containing cyclic group; and the structural unit (a8) derived from a compound represented by general formula (a8-1) described below.
（Ａ１）成分は、前記構成単位（ａ０１）に加え、必要に応じてその他構成単位を有してもよい。
その他構成単位としては、例えば、酸の作用により極性が増大する酸分解性基を含む構成単位（ａ１）（但し、前記構成単位（ａ０１）に該当するものを除く）；後述の一般式（ａ１０－１）で表される構成単位（ａ１０）；ラクトン含有環式基を含む構成単位（ａ２）；後述の一般式（ａ８－１）で表される化合物から誘導される構成単位（ａ８）などが挙げられる。 Other structural units
The component (A1) may include other structural units, in addition to the structural unit (a01), as necessary.
Examples of other structural units include the structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of acid (provided that this does not fall under the category of the structural unit (a01) above); the structural unit (a10) represented by general formula (a10-1) described below; the structural unit (a2) containing a lactone-containing cyclic group; and the structural unit (a8) derived from a compound represented by general formula (a8-1) described below.
構成単位（ａ１）について：
（Ａ１）成分は、前記構成単位（ａ０１）に加え、さらに、構成単位（ａ１）を有するものでもよい。
構成単位（ａ１）は、酸の作用により極性が増大する酸分解性基を含む構成単位（但し、前記構成単位（ａ０１）に該当するものを除く）である。 Regarding the structural unit (a1):
The component (A1) may further contain a structural unit (a1) in addition to the structural unit (a01).
The structural unit (a1) is a structural unit (excluding those that fall under the category of the aforementioned structural unit (a01)) that contains an acid-decomposable group whose polarity increases when acted upon by an acid.
（Ａ１）成分は、前記構成単位（ａ０１）に加え、さらに、構成単位（ａ１）を有するものでもよい。
構成単位（ａ１）は、酸の作用により極性が増大する酸分解性基を含む構成単位（但し、前記構成単位（ａ０１）に該当するものを除く）である。 Regarding the structural unit (a1):
The component (A1) may further contain a structural unit (a1) in addition to the structural unit (a01).
The structural unit (a1) is a structural unit (excluding those that fall under the category of the aforementioned structural unit (a01)) that contains an acid-decomposable group whose polarity increases when acted upon by an acid.
酸解離性基としては、これまで、化学増幅型レジスト組成物用のベース樹脂の酸解離性基として提案されているものが挙げられる。
化学増幅型レジスト組成物用のベース樹脂の酸解離性基として提案されているものとして具体的には、上述した「アセタール型酸解離性基」、「第３級アルキルエステル型酸解離性基」及び「第２級アルキルエステル型酸解離性基」や以下に説明する「第３級アルキルオキシカルボニル酸解離性基」が挙げられる。 Examples of the acid-dissociable group include those that have been proposed as acid-dissociable groups in base resins for chemically amplified resist compositions.
Specific examples of groups that have been proposed as the acid dissociable group of the base resin for the chemically amplified resist composition include the above-mentioned "acetal type acid dissociable group,""tertiary alkyl ester type acid dissociable group," and "secondary alkyl ester type acid dissociable group," as well as the "tertiary alkyloxycarbonyl acid dissociable group" described below.
化学増幅型レジスト組成物用のベース樹脂の酸解離性基として提案されているものとして具体的には、上述した「アセタール型酸解離性基」、「第３級アルキルエステル型酸解離性基」及び「第２級アルキルエステル型酸解離性基」や以下に説明する「第３級アルキルオキシカルボニル酸解離性基」が挙げられる。 Examples of the acid-dissociable group include those that have been proposed as acid-dissociable groups in base resins for chemically amplified resist compositions.
Specific examples of groups that have been proposed as the acid dissociable group of the base resin for the chemically amplified resist composition include the above-mentioned "acetal type acid dissociable group,""tertiary alkyl ester type acid dissociable group," and "secondary alkyl ester type acid dissociable group," as well as the "tertiary alkyloxycarbonyl acid dissociable group" described below.
第３級アルキルオキシカルボニル酸解離性基：
水酸基を保護する酸解離性基としては、例えば、下記一般式（ａ１－ｒ－３）で表される酸解離性基（以下便宜上「第３級アルキルオキシカルボニル酸解離性基」ということがある）が挙げられる。 Tertiary alkyloxycarbonyl acid dissociating group:
Examples of the acid dissociable group for protecting a hydroxyl group include acid dissociable groups represented by the following general formula (a1-r-3) (hereinafter, for convenience, may be referred to as "tertiary alkyloxycarbonyl acid dissociable group").
水酸基を保護する酸解離性基としては、例えば、下記一般式（ａ１－ｒ－３）で表される酸解離性基（以下便宜上「第３級アルキルオキシカルボニル酸解離性基」ということがある）が挙げられる。 Tertiary alkyloxycarbonyl acid dissociating group:
Examples of the acid dissociable group for protecting a hydroxyl group include acid dissociable groups represented by the following general formula (a1-r-3) (hereinafter, for convenience, may be referred to as "tertiary alkyloxycarbonyl acid dissociable group").
式（ａ１－ｒ－３）中、Ｒａ’７～Ｒａ’９は、それぞれ炭素数１～５のアルキル基が好ましく、炭素数１～３のアルキル基がより好ましい。
また、各アルキル基の合計の炭素数は、３～７であることが好ましく、炭素数３～５であることがより好ましく、炭素数３～４であることが最も好ましい。 In formula (a1-r-3), Ra' 7 to Ra' 9 are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
The total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 or 4.
また、各アルキル基の合計の炭素数は、３～７であることが好ましく、炭素数３～５であることがより好ましく、炭素数３～４であることが最も好ましい。 In formula (a1-r-3), Ra' 7 to Ra' 9 are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
The total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 or 4.
構成単位（ａ１）としては、α位の炭素原子に結合した水素原子が置換基で置換されていてもよいアクリル酸エステルから誘導される構成単位、アクリルアミドから誘導される構成単位、ヒドロキシスチレン若しくはヒドロキシスチレン誘導体から誘導される構成単位の水酸基における水素原子の少なくとも一部が前記酸分解性基を含む置換基により保護された構成単位、ビニル安息香酸若しくはビニル安息香酸誘導体から誘導される構成単位の－Ｃ（＝Ｏ）－ＯＨにおける水素原子の少なくとも一部が前記酸分解性基を含む置換基により保護された構成単位等が挙げられる。
Examples of the structural unit (a1) include structural units derived from acrylic esters in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, structural units derived from acrylamide, structural units in which at least some of the hydrogen atoms in the hydroxyl groups of a structural unit derived from hydroxystyrene or a hydroxystyrene derivative are protected with a substituent containing the acid-decomposable group, and structural units in which at least some of the hydrogen atoms in -C(=O)-OH of a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative are protected with a substituent containing the acid-decomposable group.
構成単位（ａ１）としては、上記のなかでも、α位の炭素原子に結合した水素原子が置換基で置換されていてもよいアクリル酸エステルから誘導される構成単位が好ましい。
かかる構成単位（ａ１）の好ましい具体例としては、下記一般式（ａ１－１）又は（ａ１－２）で表される構成単位が挙げられる。 Of the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
Preferred specific examples of the structural unit (a1) include structural units represented by general formula (a1-1) or (a1-2) shown below.
かかる構成単位（ａ１）の好ましい具体例としては、下記一般式（ａ１－１）又は（ａ１－２）で表される構成単位が挙げられる。 Of the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
Preferred specific examples of the structural unit (a1) include structural units represented by general formula (a1-1) or (a1-2) shown below.
前記式（ａ１－１）中、Ｒの炭素数１～５のアルキル基は、炭素数１～５の直鎖状または分岐鎖状のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。炭素数１～５のハロゲン化アルキル基は、前記炭素数１～５のアルキル基の水素原子の一部または全部がハロゲン原子で置換された基である。該ハロゲン原子としては、特にフッ素原子が好ましい。
Ｒとしては、水素原子、炭素数１～５のアルキル基又は炭素数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子又はメチル基が最も好ましい。 In the formula (a1-1), the alkyl group having 1 to 5 carbon atoms represented by R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.
Ｒとしては、水素原子、炭素数１～５のアルキル基又は炭素数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子又はメチル基が最も好ましい。 In the formula (a1-1), the alkyl group having 1 to 5 carbon atoms represented by R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.
前記式（ａ１－１）中、Ｖａ１における２価の炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。
In the above formula (a1-1), the divalent hydrocarbon group for Va1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
Ｖａ１における２価の炭化水素基としての脂肪族炭化水素基は、飽和であってもよく、不飽和であってもよく、通常は飽和であることが好ましい。
該脂肪族炭化水素基として、より具体的には、直鎖状もしくは分岐鎖状の脂肪族炭化水素基、又は、構造中に環を含む脂肪族炭化水素基等が挙げられる。 The aliphatic hydrocarbon group as the divalent hydrocarbon group in Va1 may be saturated or unsaturated, and is usually preferably saturated.
More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.
該脂肪族炭化水素基として、より具体的には、直鎖状もしくは分岐鎖状の脂肪族炭化水素基、又は、構造中に環を含む脂肪族炭化水素基等が挙げられる。 The aliphatic hydrocarbon group as the divalent hydrocarbon group in Va1 may be saturated or unsaturated, and is usually preferably saturated.
More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.
前記直鎖状の脂肪族炭化水素基は、炭素数が１～１０であることが好ましく、炭素数１～６がより好ましく、炭素数１～４がさらに好ましく、炭素数１～３が最も好ましい。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基［－ＣＨ２－］、エチレン基［－（ＣＨ２）２－］、トリメチレン基［－（ＣＨ２）３－］、テトラメチレン基［－（ＣＨ２）４－］、ペンタメチレン基［－（ＣＨ２）５－］等が挙げられる。
前記分岐鎖状の脂肪族炭化水素基は、炭素数が２～１０であることが好ましく、炭素数３～６がより好ましく、炭素数３又は４がさらに好ましく、炭素数３が最も好ましい。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－Ｃ（ＣＨ２ＣＨ３）２－ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素数１～５の直鎖状のアルキル基が好ましい。 The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, further preferably has 1 to 4 carbon atoms, and most preferably has 1 to 3 carbon atoms.
As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably has 3 to 6 carbon atoms, even more preferably has 3 or 4 carbon atoms, and most preferably has 3 carbon atoms.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基［－ＣＨ２－］、エチレン基［－（ＣＨ２）２－］、トリメチレン基［－（ＣＨ２）３－］、テトラメチレン基［－（ＣＨ２）４－］、ペンタメチレン基［－（ＣＨ２）５－］等が挙げられる。
前記分岐鎖状の脂肪族炭化水素基は、炭素数が２～１０であることが好ましく、炭素数３～６がより好ましく、炭素数３又は４がさらに好ましく、炭素数３が最も好ましい。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－Ｃ（ＣＨ２ＣＨ３）２－ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素数１～５の直鎖状のアルキル基が好ましい。 The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, further preferably has 1 to 4 carbon atoms, and most preferably has 1 to 3 carbon atoms.
As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably has 3 to 6 carbon atoms, even more preferably has 3 or 4 carbon atoms, and most preferably has 3 carbon atoms.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
前記構造中に環を含む脂肪族炭化水素基としては、脂環式炭化水素基（脂肪族炭化水素環から水素原子を２個除いた基）、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の末端に結合した基、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。前記直鎖状または分岐鎖状の脂肪族炭化水素基としては、前記直鎖状の脂肪族炭化水素基または前記分岐鎖状の脂肪族炭化水素基と同様のものが挙げられる。
前記脂環式炭化水素基は、炭素数が３～２０であることが好ましく、炭素数３～１２であることがより好ましい。
前記脂環式炭化水素基は、多環式であってもよく、単環式であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから２個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては炭素数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから２個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては炭素数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
前記脂環式炭化水素基は、炭素数が３～２０であることが好ましく、炭素数３～１２であることがより好ましい。
前記脂環式炭化水素基は、多環式であってもよく、単環式であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから２個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては炭素数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから２個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては炭素数７～１２のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
Ｖａ１における２価の炭化水素基としての芳香族炭化水素基は、芳香環を有する炭化水素基である。
かかる芳香族炭化水素基は、炭素数が３～３０であることが好ましく、５～３０であることがより好ましく、５～２０がさらに好ましく、６～１５が特に好ましく、６～１２が最も好ましい。ただし、該炭素数には、置換基における炭素数を含まないものとする。
芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、ビフェニル、フルオレン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
該芳香族炭化水素基として具体的には、前記芳香族炭化水素環から水素原子を２つ除いた基（アリーレン基）；前記芳香族炭化水素環から水素原子を１つ除いた基（アリール基）の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基におけるアリール基から水素原子をさらに１つ除いた基）等が挙げられる。前記アルキレン基（アリールアルキル基中のアルキル鎖）の炭素数は、１～４であることが好ましく、１～２であることがより好ましく、１であることが特に好ましい。 The aromatic hydrocarbon group as the divalent hydrocarbon group in Va1 is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this carbon number does not include the number of carbon atoms in the substituents.
Specific examples of the aromatic ring contained in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring (arylene group); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring (aryl group) has been substituted with an alkylene group (for example, a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
かかる芳香族炭化水素基は、炭素数が３～３０であることが好ましく、５～３０であることがより好ましく、５～２０がさらに好ましく、６～１５が特に好ましく、６～１２が最も好ましい。ただし、該炭素数には、置換基における炭素数を含まないものとする。
芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、ビフェニル、フルオレン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
該芳香族炭化水素基として具体的には、前記芳香族炭化水素環から水素原子を２つ除いた基（アリーレン基）；前記芳香族炭化水素環から水素原子を１つ除いた基（アリール基）の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基におけるアリール基から水素原子をさらに１つ除いた基）等が挙げられる。前記アルキレン基（アリールアルキル基中のアルキル鎖）の炭素数は、１～４であることが好ましく、１～２であることがより好ましく、１であることが特に好ましい。 The aromatic hydrocarbon group as the divalent hydrocarbon group in Va1 is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this carbon number does not include the number of carbon atoms in the substituents.
Specific examples of the aromatic ring contained in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring (arylene group); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring (aryl group) has been substituted with an alkylene group (for example, a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
前記式（ａ１－１）中、Ｒａ１は、上記式（ａ０－ｒ－１）、（ａ０－ｒ－２）、又は、（ａ０－ｒ－３）で表される酸解離性基であり、その中でも、上記式（ａ０－ｒ－２）で表される酸解離性基であることが好ましく、上記式（ａ０－ｒ２－０１）又は（ａ０－ｒ２－０４）のいずれかで表される酸解離性基であることがより好ましく、上記式（ａ０－ｒ２－０１）で表される酸解離性基であることがさらに好ましい。
In the formula (a1-1), Ra 1 is an acid dissociable group represented by the above formula (a0-r-1), (a0-r-2), or (a0-r-3). Among these, an acid dissociable group represented by the above formula (a0-r-2) is preferable, an acid dissociable group represented by either of the above formulas (a0-r2-01) or (a0-r2-04) is more preferable, and an acid dissociable group represented by the above formula (a0-r2-01) is even more preferable.
前記式（ａ１－２）中、Ｗａ１におけるｎａ２＋１価の炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。該脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味し、飽和であってもよく、不飽和であってもよく、通常は飽和であることが好ましい。前記脂肪族炭化水素基としては、直鎖状または分岐鎖状の脂肪族炭化水素基、構造中に環を含む脂肪族炭化水素基、或いは直鎖状または分岐鎖状の脂肪族炭化水素基と構造中に環を含む脂肪族炭化水素基とを組み合わせた基が挙げられる。
前記ｎａ２＋１価は、２～４価が好ましく、２又は３価がより好ましい。 In the formula (a1-2), the n a2 +1 valent hydrocarbon group in Wa 1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in the structure, and groups that combine linear or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing a ring in the structure.
The n a2 +1 valency is preferably divalent to tetravalent, and more preferably divalent or trivalent.
前記ｎａ２＋１価は、２～４価が好ましく、２又は３価がより好ましい。 In the formula (a1-2), the n a2 +1 valent hydrocarbon group in Wa 1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in the structure, and groups that combine linear or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing a ring in the structure.
The n a2 +1 valency is preferably divalent to tetravalent, and more preferably divalent or trivalent.
前記式（ａ１－２）中、Ｒａ２は、上記の一般式（ａ０－ｒ－１）又は（ａ１－ｒ－３）で表される酸解離性基である。
In the formula (a1-2), Ra2 is an acid-dissociable group represented by the above general formula (a0-r-1) or (a1-r-3).
以下に前記式（ａ１－１）で表される構成単位の具体例を示す。以下の各式中、Ｒαは、水素原子、メチル基またはトリフルオロメチル基を示す。
Specific examples of the structural unit represented by formula (a1-1) are shown below: In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
（Ａ１）成分が有する構成単位（ａ１）は、１種でもよく２種以上でもよい。
構成単位（ａ１）としては、電子線やＥＵＶによるリソグラフィーでの特性（感度、形状等）をより高められやすいことから、前記式（ａ１－１）で表される構成単位がより好ましい。 The structural unit (a1) contained in the component (A1) may be of one type, or two or more types.
As the structural unit (a1), a structural unit represented by the above formula (a1-1) is more preferable, since it is easier to further improve the characteristics (sensitivity, shape, etc.) in electron beam or EUV lithography.
構成単位（ａ１）としては、電子線やＥＵＶによるリソグラフィーでの特性（感度、形状等）をより高められやすいことから、前記式（ａ１－１）で表される構成単位がより好ましい。 The structural unit (a1) contained in the component (A1) may be of one type, or two or more types.
As the structural unit (a1), a structural unit represented by the above formula (a1-1) is more preferable, since it is easier to further improve the characteristics (sensitivity, shape, etc.) in electron beam or EUV lithography.
（Ａ１）成分中の構成単位（ａ１）の割合は、該（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、１～８０モル％が好ましく、５～７０モル％がより好ましく、１０～６０モル％がさらに好ましい。
構成単位（ａ１）の割合を、前記の好ましい範囲の下限値以上とすることによって、解像性がより向上する。一方、前記の好ましい範囲の上限値以下であると、他の構成単位とのバランスを取ることができ、種々のリソグラフィー特性が良好となる。 The proportion of the structural unit (a1) in the component (A1) is preferably 1 to 80 mol %, more preferably 5 to 70 mol %, and even more preferably 10 to 60 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
By ensuring that the proportion of the structural unit (a1) is at least as large as the lower limit of the aforementioned preferred range, the resolution can be further improved, while by ensuring that the proportion is at most the upper limit of the aforementioned preferred range, a balance with other structural units can be achieved, resulting in various favorable lithography properties.
構成単位（ａ１）の割合を、前記の好ましい範囲の下限値以上とすることによって、解像性がより向上する。一方、前記の好ましい範囲の上限値以下であると、他の構成単位とのバランスを取ることができ、種々のリソグラフィー特性が良好となる。 The proportion of the structural unit (a1) in the component (A1) is preferably 1 to 80 mol %, more preferably 5 to 70 mol %, and even more preferably 10 to 60 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
By ensuring that the proportion of the structural unit (a1) is at least as large as the lower limit of the aforementioned preferred range, the resolution can be further improved, while by ensuring that the proportion is at most the upper limit of the aforementioned preferred range, a balance with other structural units can be achieved, resulting in various favorable lithography properties.
構成単位（ａ１０）について：
（Ａ１）成分は、さらに、下記一般式（ａ１０－１）で表される構成単位（ａ１０）（但し、構成単位（ａ０１）、又は、構成単位（ａ１）に該当するものを除く）を有するものでもよい。 Regarding the structural unit (a10):
The component (A1) may further include a structural unit (a10) represented by general formula (a10-1) below (provided that this does not include those corresponding to the structural unit (a01) or the structural unit (a1)).
（Ａ１）成分は、さらに、下記一般式（ａ１０－１）で表される構成単位（ａ１０）（但し、構成単位（ａ０１）、又は、構成単位（ａ１）に該当するものを除く）を有するものでもよい。 Regarding the structural unit (a10):
The component (A1) may further include a structural unit (a10) represented by general formula (a10-1) below (provided that this does not include those corresponding to the structural unit (a01) or the structural unit (a1)).
前記式（ａ１０－１）中、Ｒは、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基である。
Ｒとしては、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子、メチル基又はトリフルオロメチル基がより好ましく、水素原子又はメチル基がさらに好ましく、水素原子が特に好ましい。 In the above formula (a10-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom, a methyl group, or a trifluoromethyl group is more preferable, a hydrogen atom or a methyl group is still more preferable, and a hydrogen atom is particularly preferable.
Ｒとしては、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子、メチル基又はトリフルオロメチル基がより好ましく、水素原子又はメチル基がさらに好ましく、水素原子が特に好ましい。 In the above formula (a10-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom, a methyl group, or a trifluoromethyl group is more preferable, a hydrogen atom or a methyl group is still more preferable, and a hydrogen atom is particularly preferable.
前記式（ａ１０－１）中、Ｙａｘ１は、単結合又は２価の連結基である。
前記の化学式中、Ｙａｘ１における２価の連結基としては、特に限定されないが、置換基を有してもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基等が好適なものとして挙げられる。 In the above formula (a10-1), Ya x1 represents a single bond or a divalent linking group.
In the above chemical formula, the divalent linking group for Ya x1 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
前記の化学式中、Ｙａｘ１における２価の連結基としては、特に限定されないが、置換基を有してもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基等が好適なものとして挙げられる。 In the above formula (a10-1), Ya x1 represents a single bond or a divalent linking group.
In the above chemical formula, the divalent linking group for Ya x1 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
Ｙａｘ１としては、単結合、エステル結合［－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－］、エーテル結合（－Ｏ－）、直鎖状若しくは分岐鎖状のアルキレン基、又はこれらの組合せであることが好ましく、単結合、エステル結合［－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－］がより好ましく、単結合がさらに好ましい。
Ya x1 is preferably a single bond, an ester bond [-C(=O)-O-, -O-C(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof, more preferably a single bond or an ester bond [-C(=O)-O-, -O-C(=O)-], and still more preferably a single bond.
前記式（ａ１０－１）中、Ｗａｘ１は、置換基を有してもよい芳香族炭化水素基である。
Ｗａｘ１における芳香族炭化水素基としては、置換基を有してもよい芳香環から（ｎａｘ１＋１）個の水素原子を除いた基が挙げられる。ここでの芳香環は、４ｎ＋２個のπ電子をもつ環状共役系であれば特に限定されない。芳香環の炭素原子数は５～３０であることが好ましく、炭素原子数５～２０がより好ましく、炭素原子数６～１５がさらに好ましく、炭素原子数６～１２が特に好ましい。該芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
また、Ｗａｘ１における芳香族炭化水素基としては、２以上の置換基を有してもよい芳香環を含む芳香族化合物（例えばビフェニル、フルオレン等）から（ｎａｘ１＋１）個の水素原子を除いた基も挙げられる。
上記の中でも、Ｗａｘ１としては、ベンゼン、ナフタレン、アントラセンまたはビフェニルから（ｎａｘ１＋１）個の水素原子を除いた基が好ましく、ベンゼン又はナフタレンから（ｎａｘ１＋１）個の水素原子を除いた基がより好ましく、ベンゼンから（ｎａｘ１＋１）個の水素原子を除いた基がさらに好ましい。 In the above formula (a10-1), Wa x1 represents an aromatic hydrocarbon group which may have a substituent.
The aromatic hydrocarbon group in Wa x1 may be a group in which (n ax1 +1) hydrogen atoms have been removed from an aromatic ring which may have a substituent. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Further, examples of the aromatic hydrocarbon group in Wa x1 include groups in which (n ax1 +1) hydrogen atoms have been removed from an aromatic compound containing an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.).
Among the above, Wa x1 is preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene, naphthalene, anthracene or biphenyl, more preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene or naphthalene, and even more preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene.
Ｗａｘ１における芳香族炭化水素基としては、置換基を有してもよい芳香環から（ｎａｘ１＋１）個の水素原子を除いた基が挙げられる。ここでの芳香環は、４ｎ＋２個のπ電子をもつ環状共役系であれば特に限定されない。芳香環の炭素原子数は５～３０であることが好ましく、炭素原子数５～２０がより好ましく、炭素原子数６～１５がさらに好ましく、炭素原子数６～１２が特に好ましい。該芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環；前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
また、Ｗａｘ１における芳香族炭化水素基としては、２以上の置換基を有してもよい芳香環を含む芳香族化合物（例えばビフェニル、フルオレン等）から（ｎａｘ１＋１）個の水素原子を除いた基も挙げられる。
上記の中でも、Ｗａｘ１としては、ベンゼン、ナフタレン、アントラセンまたはビフェニルから（ｎａｘ１＋１）個の水素原子を除いた基が好ましく、ベンゼン又はナフタレンから（ｎａｘ１＋１）個の水素原子を除いた基がより好ましく、ベンゼンから（ｎａｘ１＋１）個の水素原子を除いた基がさらに好ましい。 In the above formula (a10-1), Wa x1 represents an aromatic hydrocarbon group which may have a substituent.
The aromatic hydrocarbon group in Wa x1 may be a group in which (n ax1 +1) hydrogen atoms have been removed from an aromatic ring which may have a substituent. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Further, examples of the aromatic hydrocarbon group in Wa x1 include groups in which (n ax1 +1) hydrogen atoms have been removed from an aromatic compound containing an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.).
Among the above, Wa x1 is preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene, naphthalene, anthracene or biphenyl, more preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene or naphthalene, and even more preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene.
Ｗａｘ１における芳香族炭化水素基は、置換基を有してもよく、有していなくてもよい。前記置換基としては、例えば、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基等が挙げられる。前記置換基としてのアルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基としては、Ｙａｘ１における環状の脂環式炭化水素基の置換基として挙げたものと同様のものが挙げられる。前記置換基は、炭素原子数１～５の直鎖状若しくは分岐鎖状のアルキル基が好ましく、炭素原子数１～３の直鎖状若しくは分岐鎖状のアルキル基がより好ましく、エチル基又はメチル基がさらに好ましく、メチル基が特に好ましい。Ｗａｘ１における芳香族炭化水素基は、置換基を有していないことが好ましい。
The aromatic hydrocarbon group in Wa x1 may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include the same as those exemplified as the substituent of the cyclic alicyclic hydrocarbon group in Ya x1 . The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, further preferably an ethyl group or a methyl group, and particularly preferably a methyl group. It is preferable that the aromatic hydrocarbon group in Wa x1 does not have a substituent.
前記式（ａ１０－１）中、ｎａｘ１は、１以上の整数であり、１～１０の整数が好ましく、１～５の整数がより好ましく、１、２又は３がさらに好ましく、１又は２が特に好ましい。
In the formula (a10-1), n ax1 represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1, 2 or 3, and particularly preferably 1 or 2.
以下に、前記式（ａ１０－１）で表される構成単位（ａ１０）の具体例を示す。
以下の各式中、Ｒαは、水素原子、メチル基又はトリフルオロメチル基を示す。 Specific examples of the structural unit (a10) represented by the aforementioned formula (a10-1) are shown below.
In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
以下の各式中、Ｒαは、水素原子、メチル基又はトリフルオロメチル基を示す。 Specific examples of the structural unit (a10) represented by the aforementioned formula (a10-1) are shown below.
In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
構成単位（ａ１０）としては、上記の中でも、上記式（ａ１０－１－１）で表される構成単位が好ましい。
As the structural unit (a10), the structural unit represented by the above formula (a10-1-1) is preferred.
（Ａ１）成分が有する構成単位（ａ１０）は、１種でもよく２種以上でもよい。
（Ａ１）成分が構成単位（ａ１０）を有する場合、（Ａ１）成分中の構成単位（ａ１０）の割合は、（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、２０～８０モル％が好ましく、２０～７０モル％がより好ましく、３０～６０モル％がさらに好ましい。
構成単位（ａ１０）の割合を下限値以上とすることにより、感度及びＣＤＵがより高められやすくなる。一方、上限値以下とすることにより、他の構成単位とのバランスをとりやすくなる。 The structural unit (a10) contained in the component (A1) may be of one type, or two or more types.
When the component (A1) contains the structural unit (a10), the proportion of the structural unit (a10) in the component (A1) is preferably 20 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 30 to 60 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
By ensuring that the proportion of the structural unit (a10) is at least as large as the lower limit of the above range, it is possible to increase the sensitivity and CDU, while by ensuring that the proportion is at most the upper limit of the above range, it is possible to easily achieve a balance with other structural units.
（Ａ１）成分が構成単位（ａ１０）を有する場合、（Ａ１）成分中の構成単位（ａ１０）の割合は、（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、２０～８０モル％が好ましく、２０～７０モル％がより好ましく、３０～６０モル％がさらに好ましい。
構成単位（ａ１０）の割合を下限値以上とすることにより、感度及びＣＤＵがより高められやすくなる。一方、上限値以下とすることにより、他の構成単位とのバランスをとりやすくなる。 The structural unit (a10) contained in the component (A1) may be of one type, or two or more types.
When the component (A1) contains the structural unit (a10), the proportion of the structural unit (a10) in the component (A1) is preferably 20 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 30 to 60 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
By ensuring that the proportion of the structural unit (a10) is at least as large as the lower limit of the above range, it is possible to increase the sensitivity and CDU, while by ensuring that the proportion is at most the upper limit of the above range, it is possible to easily achieve a balance with other structural units.
構成単位（ａ２）について：
（Ａ１）成分は、さらに、ラクトン含有環式基を含む構成単位（ａ２）（但し、構成単位（ａ１）に該当するものを除く）を有するものでもよい。
構成単位（ａ２）のラクトン含有環式基は、（Ａ１）成分をレジスト膜の形成に用いた場合に、レジスト膜の基板への密着性を高める上で有効なものである。また、構成単位（ａ２）を有することで、例えば酸拡散長を適切に調整する、レジスト膜の基板への密着性を高める、現像時の溶解性を適切に調整する等の効果により、リソグラフィー特性等が良好となる。 Regarding the structural unit (a2):
The component (A1) may further include a structural unit (a2) that contains a lactone-containing cyclic group (provided that this does not correspond to the structural unit (a1)).
The lactone-containing cyclic group of the structural unit (a2) is effective in improving the adhesion of the resist film to the substrate when the component (A1) is used to form a resist film. In addition, the structural unit (a2) has the effects of, for example, appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development, thereby improving the lithography properties, etc.
（Ａ１）成分は、さらに、ラクトン含有環式基を含む構成単位（ａ２）（但し、構成単位（ａ１）に該当するものを除く）を有するものでもよい。
構成単位（ａ２）のラクトン含有環式基は、（Ａ１）成分をレジスト膜の形成に用いた場合に、レジスト膜の基板への密着性を高める上で有効なものである。また、構成単位（ａ２）を有することで、例えば酸拡散長を適切に調整する、レジスト膜の基板への密着性を高める、現像時の溶解性を適切に調整する等の効果により、リソグラフィー特性等が良好となる。 Regarding the structural unit (a2):
The component (A1) may further include a structural unit (a2) that contains a lactone-containing cyclic group (provided that this does not correspond to the structural unit (a1)).
The lactone-containing cyclic group of the structural unit (a2) is effective in improving the adhesion of the resist film to the substrate when the component (A1) is used to form a resist film. In addition, the structural unit (a2) has the effects of, for example, appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development, thereby improving the lithography properties, etc.
「ラクトン含有環式基」とは、その環骨格中に－Ｏ－Ｃ（＝Ｏ）－を含む環（ラクトン環）を含有する環式基を示す。ラクトン環をひとつ目の環として数え、ラクトン環のみの場合は単環式基、さらに他の環構造を有する場合は、その構造に関わらず多環式基と称する。ラクトン含有環式基は、単環式基であってもよく、多環式基であってもよい。
構成単位（ａ２）におけるラクトン含有環式基としては、特に限定されることなく任意のものが使用可能である。具体的には、下記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表される基が挙げられる。 A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) that contains --O--C(=O)-- in its ring skeleton. The lactone ring is counted as the first ring, and when there is only a lactone ring, it is called a monocyclic group, and when there is further contained another ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
The lactone-containing cyclic group in the structural unit (a2) is not particularly limited and any suitable group can be used. Specific examples include the groups represented by the following general formulae (a2-r-1) to (a2-r-7).
構成単位（ａ２）におけるラクトン含有環式基としては、特に限定されることなく任意のものが使用可能である。具体的には、下記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表される基が挙げられる。 A "lactone-containing cyclic group" refers to a cyclic group that contains a ring (lactone ring) that contains --O--C(=O)-- in its ring skeleton. The lactone ring is counted as the first ring, and when there is only a lactone ring, it is called a monocyclic group, and when there is further contained another ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
The lactone-containing cyclic group in the structural unit (a2) is not particularly limited and any suitable group can be used. Specific examples include the groups represented by the following general formulae (a2-r-1) to (a2-r-7).
前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）中、Ｒａ’２１におけるアルキル基としては、炭素原子数１～６のアルキル基が好ましい。該アルキル基は、直鎖状または分岐鎖状であることが好ましい。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基等が挙げられる。これらの中でも、メチル基またはエチル基が好ましく、メチル基が特に好ましい。
Ｒａ’２１におけるアルコキシ基としては、炭素原子数１～６のアルコキシ基が好ましい。該アルコキシ基は、直鎖状または分岐鎖状であることが好ましい。具体的には、前記Ｒａ’２１におけるアルキル基として挙げたアルキル基と酸素原子（－Ｏ－）とが連結した基が挙げられる。
Ｒａ’２１におけるハロゲン原子としては、フッ素原子が好ましい。
Ｒａ’２１におけるハロゲン化アルキル基としては、前記Ｒａ’２１におけるアルキル基の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。該ハロゲン化アルキル基としては、フッ素化アルキル基が好ましく、特にパーフルオロアルキル基が好ましい。 In the general formulae (a2-r-1) to (a2-r-7), the alkyl group in Ra'21 is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Of these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.
The alkoxy group in Ra' 21 is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specific examples include groups in which the alkyl groups listed above as the alkyl groups in Ra' 21 are linked to an oxygen atom (-O-).
The halogen atom in Ra'21 is preferably a fluorine atom.
The halogenated alkyl group in Ra' 21 may be a group in which some or all of the hydrogen atoms in the alkyl group in Ra' 21 have been substituted with the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.
Ｒａ’２１におけるアルコキシ基としては、炭素原子数１～６のアルコキシ基が好ましい。該アルコキシ基は、直鎖状または分岐鎖状であることが好ましい。具体的には、前記Ｒａ’２１におけるアルキル基として挙げたアルキル基と酸素原子（－Ｏ－）とが連結した基が挙げられる。
Ｒａ’２１におけるハロゲン原子としては、フッ素原子が好ましい。
Ｒａ’２１におけるハロゲン化アルキル基としては、前記Ｒａ’２１におけるアルキル基の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。該ハロゲン化アルキル基としては、フッ素化アルキル基が好ましく、特にパーフルオロアルキル基が好ましい。 In the general formulae (a2-r-1) to (a2-r-7), the alkyl group in Ra'21 is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Of these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.
The alkoxy group in Ra' 21 is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specific examples include groups in which the alkyl groups listed above as the alkyl groups in Ra' 21 are linked to an oxygen atom (-O-).
The halogen atom in Ra'21 is preferably a fluorine atom.
The halogenated alkyl group in Ra' 21 may be a group in which some or all of the hydrogen atoms in the alkyl group in Ra' 21 have been substituted with the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.
Ｒａ’２１における－ＣＯＯＲ”、－ＯＣ（＝Ｏ）Ｒ”において、Ｒ”はいずれも水素原子、アルキル基、又は、ラクトン含有環式基である。
Ｒ”におけるアルキル基としては、直鎖状、分岐鎖状、環状のいずれでもよく、炭素原子数は１～１５が好ましい。
Ｒ”が直鎖状もしくは分岐鎖状のアルキル基の場合は、炭素原子数１～１０であることが好ましく、炭素原子数１～５であることがさらに好ましく、メチル基またはエチル基であることが特に好ましい。
Ｒ”が環状のアルキル基の場合は、炭素原子数３～１５であることが好ましく、炭素原子数４～１２であることがさらに好ましく、炭素原子数５～１０が最も好ましい。具体的には、フッ素原子またはフッ素化アルキル基で置換されていてもよいし、されていなくてもよいモノシクロアルカンから１個以上の水素原子を除いた基；ビシクロアルカン、トリシクロアルカン、テトラシクロアルカンなどのポリシクロアルカンから１個以上の水素原子を除いた基などを例示できる。より具体的には、シクロペンタン、シクロヘキサン等のモノシクロアルカンから１個以上の水素原子を除いた基；アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカンなどのポリシクロアルカンから１個以上の水素原子を除いた基などが挙げられる。
Ｒ”におけるラクトン含有環式基としては、前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表される基と同様のものが挙げられる。
Ｒａ’２１におけるヒドロキシアルキル基としては、炭素原子数が１～６であるものが好ましく、具体的には、前記Ｒａ’２１におけるアルキル基の水素原子の少なくとも１つが水酸基で置換された基が挙げられる。 In --COOR" and --OC(.dbd.O)R" in Ra' 21 , R" is both a hydrogen atom, an alkyl group, or a lactone-containing cyclic group.
The alkyl group for R″ may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms.
When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is particularly preferably a methyl group or an ethyl group.
When R" is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane. More specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane.
Examples of the lactone-containing cyclic group for R″ include the same groups as those represented by the general formulae (a2-r-1) to (a2-r-7).
The hydroxyalkyl group in Ra' 21 preferably has 1 to 6 carbon atoms, and specific examples include the alkyl group in Ra' 21 in which at least one hydrogen atom has been substituted with a hydroxyl group.
Ｒ”におけるアルキル基としては、直鎖状、分岐鎖状、環状のいずれでもよく、炭素原子数は１～１５が好ましい。
Ｒ”が直鎖状もしくは分岐鎖状のアルキル基の場合は、炭素原子数１～１０であることが好ましく、炭素原子数１～５であることがさらに好ましく、メチル基またはエチル基であることが特に好ましい。
Ｒ”が環状のアルキル基の場合は、炭素原子数３～１５であることが好ましく、炭素原子数４～１２であることがさらに好ましく、炭素原子数５～１０が最も好ましい。具体的には、フッ素原子またはフッ素化アルキル基で置換されていてもよいし、されていなくてもよいモノシクロアルカンから１個以上の水素原子を除いた基；ビシクロアルカン、トリシクロアルカン、テトラシクロアルカンなどのポリシクロアルカンから１個以上の水素原子を除いた基などを例示できる。より具体的には、シクロペンタン、シクロヘキサン等のモノシクロアルカンから１個以上の水素原子を除いた基；アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカンなどのポリシクロアルカンから１個以上の水素原子を除いた基などが挙げられる。
Ｒ”におけるラクトン含有環式基としては、前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表される基と同様のものが挙げられる。
Ｒａ’２１におけるヒドロキシアルキル基としては、炭素原子数が１～６であるものが好ましく、具体的には、前記Ｒａ’２１におけるアルキル基の水素原子の少なくとも１つが水酸基で置換された基が挙げられる。 In --COOR" and --OC(.dbd.O)R" in Ra' 21 , R" is both a hydrogen atom, an alkyl group, or a lactone-containing cyclic group.
The alkyl group for R″ may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms.
When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is particularly preferably a methyl group or an ethyl group.
When R" is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane. More specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane.
Examples of the lactone-containing cyclic group for R″ include the same groups as those represented by the general formulae (a2-r-1) to (a2-r-7).
The hydroxyalkyl group in Ra' 21 preferably has 1 to 6 carbon atoms, and specific examples include the alkyl group in Ra' 21 in which at least one hydrogen atom has been substituted with a hydroxyl group.
Ｒａ’２１としては、上記の中でも、それぞれ独立に水素原子又はシアノ基であることが好ましい。
Among the above, it is preferable that Ra'21 each independently represents a hydrogen atom or a cyano group.
前記一般式（ａ２－ｒ－２）、（ａ２－ｒ－３）、（ａ２－ｒ－５）中、Ａ”における炭素原子数１～５のアルキレン基としては、直鎖状または分岐鎖状のアルキレン基が好ましく、メチレン基、エチレン基、ｎ－プロピレン基、イソプロピレン基等が挙げられる。該アルキレン基が酸素原子または硫黄原子を含む場合、その具体例としては、前記アルキレン基の末端または炭素原子間に－Ｏ－または－Ｓ－が介在する基が挙げられ、例えば、－Ｏ－ＣＨ２－、－ＣＨ２－Ｏ－ＣＨ２－、－Ｓ－ＣＨ２－、－ＣＨ２－Ｓ－ＣＨ２－等が挙げられる。Ａ”としては、炭素原子数１～５のアルキレン基または－Ｏ－が好ましく、炭素原子数１～５のアルキレン基がより好ましく、メチレン基が最も好ましい。
In the general formulae (a2-r-2), (a2-r-3) and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A" is preferably a straight-chain or branched-chain alkylene group, such as a methylene group, an ethylene group, an n-propylene group or an isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is present at the terminal or between the carbon atoms of the alkylene group, such as -O-CH 2 -, -CH 2 -O-CH 2 -, -S-CH 2 - and -CH 2 -S-CH 2 -. A" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.
下記に一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表される基の具体例を挙げる。
Specific examples of the groups represented by general formulas (a2-r-1) to (a2-r-7) are listed below.
構成単位（ａ２）としては、なかでも、α位の炭素原子に結合した水素原子が置換基で置換されていてもよいアクリル酸エステルから誘導される構成単位が好ましい。
かかる構成単位（ａ２）は、下記一般式（ａ２－１）で表される構成単位であることが好ましい。 Of the various possibilities, the structural unit (a2) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
The structural unit (a2) is preferably a structural unit represented by general formula (a2-1) shown below.
かかる構成単位（ａ２）は、下記一般式（ａ２－１）で表される構成単位であることが好ましい。 Of the various possibilities, the structural unit (a2) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
The structural unit (a2) is preferably a structural unit represented by general formula (a2-1) shown below.
前記式（ａ２－１）中、Ｒは前記と同じである。Ｒとしては、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子又はメチル基が特に好ましい。
In the formula (a2-1), R is the same as above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferred.
前記式（ａ２－１）中、Ｙａ２１における２価の連結基としては、特に限定されないが、置換基を有してもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基等が好適に挙げられる。
In the formula (a2-1), the divalent linking group for Ya 21 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
Ｙａ２１としては、単結合、エステル結合［－Ｃ（＝Ｏ）－Ｏ－］、エーテル結合（－Ｏ－）、直鎖状若しくは分岐鎖状のアルキレン基、又はこれらの組合せであることが好ましい。
Ya 21 is preferably a single bond, an ester bond [--C(.dbd.O)--O--], an ether bond (--O--), a linear or branched alkylene group, or a combination thereof.
前記式（ａ２－１）中、Ｙａ２１は、単結合であり、Ｌａ２１は、－ＣＯＯ－、又は、－ＯＣＯ－、であることが好ましい。
In the formula (a2-1), it is preferable that Ya 21 is a single bond, and La 21 is --COO-- or --OCO--.
前記式（ａ２－１）中、Ｒａ２１はラクトン含有環式基である。
Ｒａ２１におけるラクトン含有環式基としてはそれぞれ、前述した一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表される基が好適に挙げられる。 In the above formula (a2-1), Ra 21 represents a lactone-containing cyclic group.
Suitable examples of the lactone-containing cyclic group for Ra 21 include the groups represented by the above-mentioned general formulae (a2-r-1) to (a2-r-7), respectively.
Ｒａ２１におけるラクトン含有環式基としてはそれぞれ、前述した一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表される基が好適に挙げられる。 In the above formula (a2-1), Ra 21 represents a lactone-containing cyclic group.
Suitable examples of the lactone-containing cyclic group for Ra 21 include the groups represented by the above-mentioned general formulae (a2-r-1) to (a2-r-7), respectively.
（Ａ１）成分が有する構成単位（ａ２）は、１種でもよく２種以上でもよい。
（Ａ１）成分が構成単位（ａ２）を有する場合、構成単位（ａ２）の割合は、当該（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、１～２０モル％であることが好ましく、１～１５モル％であることがより好ましく、１～１０モル％であることがさらに好ましい。
構成単位（ａ２）の割合を好ましい下限値以上とすると、前述した効果によって、構成単位（ａ２）を含有させることによる効果が充分に得られ、上限値以下であると、他の構成単位とのバランスを取ることができ、種々のリソグラフィー特性が良好となる。 The structural unit (a2) contained in the component (A1) may be of one type, or two or more types.
When the component (A1) contains the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 20 mol %, more preferably 1 to 15 mol %, and even more preferably 1 to 10 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
When the proportion of the structural unit (a2) is at least as large as the preferable lower limit, the effects achieved by including the structural unit (a2) can be fully obtained due to the effects described above. When the proportion of the structural unit (a2) is no more than the upper limit, a balance with other structural units can be achieved, and various lithography properties become favorable.
（Ａ１）成分が構成単位（ａ２）を有する場合、構成単位（ａ２）の割合は、当該（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、１～２０モル％であることが好ましく、１～１５モル％であることがより好ましく、１～１０モル％であることがさらに好ましい。
構成単位（ａ２）の割合を好ましい下限値以上とすると、前述した効果によって、構成単位（ａ２）を含有させることによる効果が充分に得られ、上限値以下であると、他の構成単位とのバランスを取ることができ、種々のリソグラフィー特性が良好となる。 The structural unit (a2) contained in the component (A1) may be of one type, or two or more types.
When the component (A1) contains the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 20 mol %, more preferably 1 to 15 mol %, and even more preferably 1 to 10 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
When the proportion of the structural unit (a2) is at least as large as the preferable lower limit, the effects achieved by including the structural unit (a2) can be fully obtained due to the effects described above. When the proportion of the structural unit (a2) is no more than the upper limit, a balance with other structural units can be achieved, and various lithography properties become favorable.
構成単位（ａ８）について：
構成単位（ａ８）は、下記一般式（ａ８－１）で表される化合物から誘導される構成単位である。
但し、構成単位（ａ０１）、又は、構成単位（ａ１）に該当するものを除かれる。 Regarding the structural unit (a8):
The structural unit (a8) is a structural unit derived from a compound represented by general formula (a8-1) shown below.
However, those corresponding to the structural unit (a01) or the structural unit (a1) are excluded.
構成単位（ａ８）は、下記一般式（ａ８－１）で表される化合物から誘導される構成単位である。
但し、構成単位（ａ０１）、又は、構成単位（ａ１）に該当するものを除かれる。 Regarding the structural unit (a8):
The structural unit (a8) is a structural unit derived from a compound represented by general formula (a8-1) shown below.
However, those corresponding to the structural unit (a01) or the structural unit (a1) are excluded.
Ｗ２の重合性基含有基における「重合性基」とは、重合性基を有する化合物がラジカル重合等により重合することを可能とする基であり、例えばエチレン性二重結合などの炭素原子間の多重結合を含む基をいう。
The "polymerizable group" in the polymerizable group-containing group of W2 is a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and is, for example, a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond.
重合性基含有基としては、重合性基のみから構成される基でもよいし、重合性基と該重合性基以外の他の基とから構成される基でもよい。該重合性基以外の他の基としては、置換基を有してもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基等が挙げられる。
重合性基含有基としては、例えば、化学式：Ｃ（ＲＸ１１）（ＲＸ１２）＝Ｃ（ＲＸ１３）－Ｙａｘ０－で表される基が好適に挙げられる。
この化学式中、ＲＸ１１、ＲＸ１２及びＲＸ１３は、それぞれ、水素原子、炭素数１～５のアルキル基又は炭素数１～５のハロゲン化アルキル基であり、Ｙａｘ０は、単結合または２価の連結基である。 The polymerizable group-containing group may be a group composed only of a polymerizable group, or may be a group composed of a polymerizable group and a group other than the polymerizable group. Examples of the group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
A suitable example of the polymerizable group-containing group is a group represented by the chemical formula: C(R x11 )(R x12 )=C(R x13 )-Ya x0 -.
In this chemical formula, R X11 , R X12 and R X13 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 represents a single bond or a divalent linking group.
重合性基含有基としては、例えば、化学式：Ｃ（ＲＸ１１）（ＲＸ１２）＝Ｃ（ＲＸ１３）－Ｙａｘ０－で表される基が好適に挙げられる。
この化学式中、ＲＸ１１、ＲＸ１２及びＲＸ１３は、それぞれ、水素原子、炭素数１～５のアルキル基又は炭素数１～５のハロゲン化アルキル基であり、Ｙａｘ０は、単結合または２価の連結基である。 The polymerizable group-containing group may be a group composed only of a polymerizable group, or may be a group composed of a polymerizable group and a group other than the polymerizable group. Examples of the group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
A suitable example of the polymerizable group-containing group is a group represented by the chemical formula: C(R x11 )(R x12 )=C(R x13 )-Ya x0 -.
In this chemical formula, R X11 , R X12 and R X13 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 represents a single bond or a divalent linking group.
Ｙａｘ２とＷ２とが形成する縮合環としては、Ｗ２部位の重合性基とＹａｘ２とが形成する縮合環、Ｗ２部位の重合性基以外の他の基とＹａｘ２とが形成する縮合環が挙げられる。
Ｙａｘ２とＷ２とが形成する縮合環は、置換基を有してもよい。 Examples of the fused ring formed by Ya x2 and W2 include a fused ring formed by the polymerizable group at the W2 site and Ya x2 , and a fused ring formed by Ya x2 and a group other than the polymerizable group at the W2 site.
The fused ring formed by Ya x2 and W 2 may have a substituent.
Ｙａｘ２とＷ２とが形成する縮合環は、置換基を有してもよい。 Examples of the fused ring formed by Ya x2 and W2 include a fused ring formed by the polymerizable group at the W2 site and Ya x2 , and a fused ring formed by Ya x2 and a group other than the polymerizable group at the W2 site.
The fused ring formed by Ya x2 and W 2 may have a substituent.
以下に、構成単位（ａ８）の具体例を示す。
下記の式中、Ｒαは、水素原子、メチル基又はトリフルオロメチル基を示す。 Specific examples of the structural unit (a8) are shown below.
In the following formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
下記の式中、Ｒαは、水素原子、メチル基又はトリフルオロメチル基を示す。 Specific examples of the structural unit (a8) are shown below.
In the following formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
上記例示の中でも、構成単位（ａ８）は、化学式（ａ８－１－０１）～（ａ８－１－０４）、(ａ８－１－０６)、(ａ８－１－０８)、(ａ８－１－０９)、及び、(ａ８－１－１０)でそれぞれ表される構成単位からなる群より選択される少なくとも１種が好ましく、化学式（ａ８－１－０１）～（ａ８－１－０４）、(ａ８－１－０９)でそれぞれ表される構成単位からなる群より選択される少なくとも１種がより好ましい。
Among the above examples, the structural unit (a8) is preferably at least one selected from the group consisting of structural units represented by the chemical formulas (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1-09), and (a8-1-10), and more preferably at least one selected from the group consisting of structural units represented by the chemical formulas (a8-1-01) to (a8-1-04), and (a8-1-09).
（Ａ１）成分が有する構成単位（ａ８）は、１種でもよく２種以上でもよい。
（Ａ１）成分における構成単位（ａ８）の割合は、当該（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、５０モル％以下であることが好ましく、０～３０モル％であることがより好ましい。 The structural unit (a8) contained in the component (A1) may be of one type, or two or more types.
The amount of the structural unit (a8) in the component (A1) relative to the total amount (100 mol %) of all structural units constituting the component (A1), is preferably no more than 50 mol %, and more preferably from 0 to 30 mol %.
（Ａ１）成分における構成単位（ａ８）の割合は、当該（Ａ１）成分を構成する全構成単位の合計（１００モル％）に対して、５０モル％以下であることが好ましく、０～３０モル％であることがより好ましい。 The structural unit (a8) contained in the component (A1) may be of one type, or two or more types.
The amount of the structural unit (a8) in the component (A1) relative to the total amount (100 mol %) of all structural units constituting the component (A1), is preferably no more than 50 mol %, and more preferably from 0 to 30 mol %.
レジスト組成物が含有する（Ａ１）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。
The resist composition may contain one type of component (A1) alone or two or more types in combination.
かかる（Ａ１）成分としては、構成単位（ａ０１）の繰り返し構造を有する高分子化合物が好ましく、構成単位（ａ０１）の繰り返し構造と、構成単位（ａ１０）の繰り返し構造とを有する高分子化合物；構成単位（ａ０１）の繰り返し構造と、構成単位（ａ１）の繰り返し構造とを有する高分子化合物がより好ましい。
より具体的に、（Ａ１）成分としては、構成単位（ａ０１）の繰り返し構造からなる高分子化合物；構成単位（ａ０１）の繰り返し構造、及び構成単位（ａ１）の繰り返し構造からなる高分子化合物；構成単位（ａ０１）の繰り返し構造、及び構成単位（ａ１０）の繰り返し構造からなる高分子化合物；構成単位（ａ０１）の繰り返し構造、構成単位（ａ１）の繰り返し構造及び構成単位（ａ１０）の繰り返し構造からなる高分子化合物が好ましい。 As the component (A1), a polymeric compound having a repeating structure of the structural unit (a01) is preferable, and a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a10) is more preferable; and a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a1).
More specifically, the component (A1) is preferably a polymeric compound having a repeating structure of the structural unit (a01); a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a1); a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a10); or a polymeric compound having a repeating structure of the structural unit (a01), a repeating structure of the structural unit (a1), and a repeating structure of the structural unit (a10).
より具体的に、（Ａ１）成分としては、構成単位（ａ０１）の繰り返し構造からなる高分子化合物；構成単位（ａ０１）の繰り返し構造、及び構成単位（ａ１）の繰り返し構造からなる高分子化合物；構成単位（ａ０１）の繰り返し構造、及び構成単位（ａ１０）の繰り返し構造からなる高分子化合物；構成単位（ａ０１）の繰り返し構造、構成単位（ａ１）の繰り返し構造及び構成単位（ａ１０）の繰り返し構造からなる高分子化合物が好ましい。 As the component (A1), a polymeric compound having a repeating structure of the structural unit (a01) is preferable, and a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a10) is more preferable; and a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a1).
More specifically, the component (A1) is preferably a polymeric compound having a repeating structure of the structural unit (a01); a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a1); a polymeric compound having a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a10); or a polymeric compound having a repeating structure of the structural unit (a01), a repeating structure of the structural unit (a1), and a repeating structure of the structural unit (a10).
構成単位（ａ０１）の繰り返し構造、及び構成単位（ａ１）の繰り返し構造からなる高分子化合物において、構成単位（ａ０１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％が好ましく、２０～８０モル％がより好ましく、３０～７０モル％がさらに好ましく、４０～６０モル％が特に好ましい。
また、該高分子化合物中の構成単位（ａ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％が好ましく、２０～８０モル％がより好ましく、３０～７０モル％がさらに好ましく、４０～６０モル％が特に好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a1), the proportion of the structural unit (a01) is preferably from 10 to 90 mol %, more preferably from 20 to 80 mol %, even more preferably from 30 to 70 mol %, and particularly preferably from 40 to 60 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a1) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, even more preferably from 30 to 70 mol%, and particularly preferably from 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
また、該高分子化合物中の構成単位（ａ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％が好ましく、２０～８０モル％がより好ましく、３０～７０モル％がさらに好ましく、４０～６０モル％が特に好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a1), the proportion of the structural unit (a01) is preferably from 10 to 90 mol %, more preferably from 20 to 80 mol %, even more preferably from 30 to 70 mol %, and particularly preferably from 40 to 60 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a1) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, even more preferably from 30 to 70 mol%, and particularly preferably from 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
構成単位（ａ０１）の繰り返し構造、及び構成単位（ａ１０）の繰り返し構造からなる高分子化合物において、構成単位（ａ０１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％が好ましく、２０～８０モル％がより好ましく、３０～７０モル％がさらに好ましく、４０～６０モル％が特に好ましい。
また、該高分子化合物中の構成単位（ａ１０）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％が好ましく、２０～８０モル％がより好ましく、３０～７０モル％がさらに好ましく、４０～６０モル％が特に好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a10), the proportion of the structural unit (a01) is preferably from 10 to 90 mol %, more preferably from 20 to 80 mol %, even more preferably from 30 to 70 mol %, and particularly preferably from 40 to 60 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a10) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, even more preferably from 30 to 70 mol%, and particularly preferably from 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
また、該高分子化合物中の構成単位（ａ１０）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％が好ましく、２０～８０モル％がより好ましく、３０～７０モル％がさらに好ましく、４０～６０モル％が特に好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (a01) and a repeating structure of the structural unit (a10), the proportion of the structural unit (a01) is preferably from 10 to 90 mol %, more preferably from 20 to 80 mol %, even more preferably from 30 to 70 mol %, and particularly preferably from 40 to 60 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a10) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, even more preferably from 30 to 70 mol%, and particularly preferably from 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
構成単位（ａ０１）の繰り返し構造、構成単位（ａ１）の繰り返し構造及び構成単位（ａ１０）の繰り返し構造からなる高分子化合物において、構成単位（ａ０１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％が好ましく、５～６０モル％がより好ましく、１０～５０モル％がさらに好ましく、２０～４０モル％が特に好ましい。
また、該高分子化合物中の構成単位（ａ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、５～７０モル％が好ましく、１０～６０モル％がより好ましく、３０～５０モル％がさらに好ましく、２０～４０モル％が特に好ましい。
また、該高分子化合物中の構成単位（ａ１０）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％が好ましく、２０～８０モル％がより好ましく、３０～７０モル％がさらに好ましく、４０～６０モル％が特に好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (a01), a repeating structure of the structural unit (a1), and a repeating structure of the structural unit (a10), the proportion of the structural unit (a01) is preferably from 10 to 90 mol %, more preferably from 5 to 60 mol %, even more preferably from 10 to 50 mol %, and particularly preferably from 20 to 40 mol %, based on the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a1) in the polymer compound is preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%, even more preferably from 30 to 50 mol%, and particularly preferably from 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
Furthermore, the proportion of the structural unit (a10) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, even more preferably from 30 to 70 mol%, and particularly preferably from 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
また、該高分子化合物中の構成単位（ａ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、５～７０モル％が好ましく、１０～６０モル％がより好ましく、３０～５０モル％がさらに好ましく、２０～４０モル％が特に好ましい。
また、該高分子化合物中の構成単位（ａ１０）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１０～９０モル％が好ましく、２０～８０モル％がより好ましく、３０～７０モル％がさらに好ましく、４０～６０モル％が特に好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (a01), a repeating structure of the structural unit (a1), and a repeating structure of the structural unit (a10), the proportion of the structural unit (a01) is preferably from 10 to 90 mol %, more preferably from 5 to 60 mol %, even more preferably from 10 to 50 mol %, and particularly preferably from 20 to 40 mol %, based on the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a1) in the polymer compound is preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%, even more preferably from 30 to 50 mol%, and particularly preferably from 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
Furthermore, the proportion of the structural unit (a10) in the polymer compound is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, even more preferably from 30 to 70 mol%, and particularly preferably from 40 to 60 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
かかる（Ａ１）成分は、各構成単位を誘導するモノマーを重合溶媒に溶解し、ここに、例えばアゾビスイソブチロニトリル（ＡＩＢＮ）、アゾビスイソ酪酸ジメチル（例えばＶ－６０１など）等のラジカル重合開始剤を加えて重合することにより製造することができる。
あるいは、かかる（Ａ１）成分は、構成単位（ａ０１）を誘導するモノマーと、必要に応じて他の構成単位を誘導するモノマー（例えば、構成単位（ａ１０）を誘導するモノマーの水酸基を保護した化合物）と、を重合溶媒に溶解し、ここに、上記のようなラジカル重合開始剤を加えて重合し、その後、必要に応じて脱保護反応を行うことにより製造することができる。
なお、重合の際に、例えば、ＨＳ－ＣＨ２－ＣＨ２－ＣＨ２－Ｃ（ＣＦ３）２－ＯＨのような連鎖移動剤を併用して用いることにより、末端に－Ｃ（ＣＦ３）２－ＯＨ基を導入してもよい。このように、アルキル基の水素原子の一部がフッ素原子で置換されたヒドロキシアルキル基が導入された共重合体は、現像欠陥の低減やＬＥＲ（ラインエッジラフネス：ライン側壁の不均一な凹凸）の低減に有効である。 The component (A1) can be produced by dissolving monomers from which each structural unit is derived in a polymerization solvent, and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601), and polymerizing the resulting mixture.
Alternatively, the component (A1) can be produced by dissolving a monomer that derives the structural unit (a01) and, if necessary, a monomer that derives other structural units (for example, a compound in which the hydroxyl group of the monomer that derives the structural unit (a10) is protected) in a polymerization solvent, adding the above-mentioned radical polymerization initiator to the mixture to polymerize, and then, if necessary, carrying out a deprotection reaction.
During polymerization, a chain transfer agent such as HS-CH 2 -CH 2 -CH 2 -C(CF 3 ) 2 -OH may be used in combination to introduce a -C(CF 3 ) 2 -OH group to the end. A copolymer having a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms in this way is effective in reducing development defects and LER (line edge roughness: non-uniform unevenness of the line sidewalls).
あるいは、かかる（Ａ１）成分は、構成単位（ａ０１）を誘導するモノマーと、必要に応じて他の構成単位を誘導するモノマー（例えば、構成単位（ａ１０）を誘導するモノマーの水酸基を保護した化合物）と、を重合溶媒に溶解し、ここに、上記のようなラジカル重合開始剤を加えて重合し、その後、必要に応じて脱保護反応を行うことにより製造することができる。
なお、重合の際に、例えば、ＨＳ－ＣＨ２－ＣＨ２－ＣＨ２－Ｃ（ＣＦ３）２－ＯＨのような連鎖移動剤を併用して用いることにより、末端に－Ｃ（ＣＦ３）２－ＯＨ基を導入してもよい。このように、アルキル基の水素原子の一部がフッ素原子で置換されたヒドロキシアルキル基が導入された共重合体は、現像欠陥の低減やＬＥＲ（ラインエッジラフネス：ライン側壁の不均一な凹凸）の低減に有効である。 The component (A1) can be produced by dissolving monomers from which each structural unit is derived in a polymerization solvent, and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601), and polymerizing the resulting mixture.
Alternatively, the component (A1) can be produced by dissolving a monomer that derives the structural unit (a01) and, if necessary, a monomer that derives other structural units (for example, a compound in which the hydroxyl group of the monomer that derives the structural unit (a10) is protected) in a polymerization solvent, adding the above-mentioned radical polymerization initiator to the mixture to polymerize, and then, if necessary, carrying out a deprotection reaction.
During polymerization, a chain transfer agent such as HS-CH 2 -CH 2 -CH 2 -C(CF 3 ) 2 -OH may be used in combination to introduce a -C(CF 3 ) 2 -OH group to the end. A copolymer having a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms in this way is effective in reducing development defects and LER (line edge roughness: non-uniform unevenness of the line sidewalls).
（Ａ１）成分の重量平均分子量（Ｍｗ）（ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算基準）は、特に限定されるものではなく、１０００～５００００が好ましく、２０００～３００００がより好ましく、３０００～２００００がさらに好ましい。
（Ａ１）成分のＭｗがこの範囲の好ましい上限値以下であると、レジストとして用いるのに充分なレジスト溶剤への溶解性があり、この範囲の好ましい下限値以上であると、耐ドライエッチング性やレジストパターン断面形状が良好である。
（Ａ１）成分の分散度（Ｍｗ／Ｍｎ）は、特に限定されず、１．０～４．０が好ましく、１．０～３．０がより好ましく、１．０～２．０が特に好ましい。なお、Ｍｎは数平均分子量を示す。 The weight average molecular weight (Mw) of the component (A1) (based on polystyrene equivalent by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000.
When the Mw of the component (A1) is no more than the preferred upper limit of this range, the compound has sufficient solubility in a resist solvent for use as a resist, and when it is no less than the preferred lower limit of this range, the compound has good dry etching resistance and good cross-sectional shape of the resist pattern.
The dispersity (Mw/Mn) of the component (A1) is not particularly limited, but is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and particularly preferably from 1.0 to 2.0, where Mn represents the number average molecular weight.
（Ａ１）成分のＭｗがこの範囲の好ましい上限値以下であると、レジストとして用いるのに充分なレジスト溶剤への溶解性があり、この範囲の好ましい下限値以上であると、耐ドライエッチング性やレジストパターン断面形状が良好である。
（Ａ１）成分の分散度（Ｍｗ／Ｍｎ）は、特に限定されず、１．０～４．０が好ましく、１．０～３．０がより好ましく、１．０～２．０が特に好ましい。なお、Ｍｎは数平均分子量を示す。 The weight average molecular weight (Mw) of the component (A1) (based on polystyrene equivalent by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000.
When the Mw of the component (A1) is no more than the preferred upper limit of this range, the compound has sufficient solubility in a resist solvent for use as a resist, and when it is no less than the preferred lower limit of this range, the compound has good dry etching resistance and good cross-sectional shape of the resist pattern.
The dispersity (Mw/Mn) of the component (A1) is not particularly limited, but is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and particularly preferably from 1.0 to 2.0, where Mn represents the number average molecular weight.
・（Ａ２）成分について
本実施形態のレジスト組成物は、（Ａ）成分として、前記（Ａ１）成分に該当しない、酸の作用により現像液に対する溶解性が変化する基材成分（以下「（Ａ２）成分」という。）を併用してもよい。
（Ａ２）成分としては、特に限定されず、化学増幅型レジスト組成物用の基材成分として従来から知られている多数のものから任意に選択して用いればよい。
（Ａ２）成分は、高分子化合物又は低分子化合物の１種を単独で用いてもよく２種以上を組み合わせて用いてもよい。 Regarding the Component (A2) The resist composition of this embodiment may also use, as the component (A), a base component (A2) (hereafter referred to as the component (A2)) that does not fall under the category of the component (A1) above and whose solubility in a developer changes under the action of an acid.
There are no particular restrictions on the component (A2), and it may be any compound selected from the many compounds conventionally known as base components for chemically amplified resist compositions.
The component (A2) may be a polymeric compound or a low molecular weight compound, and may be a combination of two or more of these.
本実施形態のレジスト組成物は、（Ａ）成分として、前記（Ａ１）成分に該当しない、酸の作用により現像液に対する溶解性が変化する基材成分（以下「（Ａ２）成分」という。）を併用してもよい。
（Ａ２）成分としては、特に限定されず、化学増幅型レジスト組成物用の基材成分として従来から知られている多数のものから任意に選択して用いればよい。
（Ａ２）成分は、高分子化合物又は低分子化合物の１種を単独で用いてもよく２種以上を組み合わせて用いてもよい。 Regarding the Component (A2) The resist composition of this embodiment may also use, as the component (A), a base component (A2) (hereafter referred to as the component (A2)) that does not fall under the category of the component (A1) above and whose solubility in a developer changes under the action of an acid.
There are no particular restrictions on the component (A2), and it may be any compound selected from the many compounds conventionally known as base components for chemically amplified resist compositions.
The component (A2) may be a polymeric compound or a low molecular weight compound, and may be a combination of two or more of these.
（Ａ）成分中の（Ａ１）成分の割合は、（Ａ）成分の総質量に対し、２５質量％以上が好ましく、５０質量％以上がより好ましく、７５質量％以上がさらに好ましく、１００質量％であってもよい。該割合が２５質量％以上であると、高感度化やＣＤＵ、解像性、ラフネス改善などの種々のリソグラフィー特性に優れたレジストパターンが形成されやすくなる。
The proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of component (A). When the proportion is 25% by mass or more, a resist pattern that is excellent in various lithography properties such as high sensitivity, CDU, resolution, and improved roughness is easily formed.
本実施形態のレジスト組成物中、（Ａ）成分の含有量は、形成しようとするレジスト膜厚等に応じて調整すればよい。
The content of component (A) in the resist composition of this embodiment may be adjusted according to the thickness of the resist film to be formed, etc.
＜（Ｆ）成分＞
本実施形態のレジスト組成物において、（Ｆ）成分は、下記一般式（ｆ１）で表される構成単位を有するフッ素樹脂成分（Ｆ１）（以下「（Ｆ１）成分」ともいう）を含む。 <Component (F)>
In the resist composition of this embodiment, the component (F) includes a fluororesin component (F1) (hereinafter also referred to as “component (F1)”) that has a structural unit represented by general formula (f1) below.
本実施形態のレジスト組成物において、（Ｆ）成分は、下記一般式（ｆ１）で表される構成単位を有するフッ素樹脂成分（Ｆ１）（以下「（Ｆ１）成分」ともいう）を含む。 <Component (F)>
In the resist composition of this embodiment, the component (F) includes a fluororesin component (F1) (hereinafter also referred to as “component (F1)”) that has a structural unit represented by general formula (f1) below.
上記一般式（ｆ１）中、Ｒは、水素原子、炭素数１～５のアルキル基又は炭素数１～５のハロゲン化アルキル基である。
Ｒにおける炭素数１～５のアルキル基は、炭素数１～５の直鎖状又は分岐鎖状のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。
Ｒにおける炭素数１～５のハロゲン化アルキル基は、前記炭素数１～５のアルキル基の水素原子の一部又は全部がハロゲン原子で置換された基である。該ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、特にフッ素原子が好ましい。
Ｒとしては、水素原子、炭素数１～５のアルキル基又は炭素数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子、メチル基又はトリフルオロメチル基がより好ましく、水素原子又はメチル基がさらに好ましく、メチル基が特に好ましい。 In the above general formula (f1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
The halogenated alkyl group having 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, is more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, is further preferably a hydrogen atom or a methyl group, and is particularly preferably a methyl group.
Ｒにおける炭素数１～５のアルキル基は、炭素数１～５の直鎖状又は分岐鎖状のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。
Ｒにおける炭素数１～５のハロゲン化アルキル基は、前記炭素数１～５のアルキル基の水素原子の一部又は全部がハロゲン原子で置換された基である。該ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、特にフッ素原子が好ましい。
Ｒとしては、水素原子、炭素数１～５のアルキル基又は炭素数１～５のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子、メチル基又はトリフルオロメチル基がより好ましく、水素原子又はメチル基がさらに好ましく、メチル基が特に好ましい。 In the above general formula (f1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
The halogenated alkyl group having 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, is more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, is further preferably a hydrogen atom or a methyl group, and is particularly preferably a methyl group.
上記一般式（ｆ１）中、Ｘ０は、酸解離性部位を有さない２価の連結基である。
「酸解離性部位」とは、上述した「酸解離性基」のように当該有機基内における、露光により発生する酸が作用して解離する部位をいう。すなわち、主鎖に結合している（－Ｃ（＝Ｏ）－Ｏ－）のＯ原子とＲｆ０とが、酸の作用により解離することはない。 In the above general formula (f1), X 0 is a divalent linking group that does not have an acid dissociable site.
The "acid dissociable site" refers to a site in the organic group that dissociates due to the action of an acid generated by exposure, like the above-mentioned "acid dissociable group." In other words, the O atom of (-C(=O)-O-) bonded to the main chain and Rf0 do not dissociate due to the action of an acid.
「酸解離性部位」とは、上述した「酸解離性基」のように当該有機基内における、露光により発生する酸が作用して解離する部位をいう。すなわち、主鎖に結合している（－Ｃ（＝Ｏ）－Ｏ－）のＯ原子とＲｆ０とが、酸の作用により解離することはない。 In the above general formula (f1), X 0 is a divalent linking group that does not have an acid dissociable site.
The "acid dissociable site" refers to a site in the organic group that dissociates due to the action of an acid generated by exposure, like the above-mentioned "acid dissociable group." In other words, the O atom of (-C(=O)-O-) bonded to the main chain and Rf0 do not dissociate due to the action of an acid.
Ｘ０における酸解離性部位を有さない２価の連結基としては、置換基を有していてもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基等が挙げられる。
Examples of the divalent linking group not having an acid dissociable site for X 0 include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
・置換基を有していてもよい炭化水素基
重合性基以外の他の基において、炭化水素基が「置換基を有する」とは、該炭化水素基における水素原子の一部または全部が、水素原子以外の基または原子で置換されていることを意味する。
炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。
脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。かかる脂肪族炭化水素基は、飽和であってもよく、不飽和であってもよく、通常は飽和であることが好ましい。 Hydrocarbon Group Which Optionally Has a Substituent With respect to groups other than polymerizable groups, the term "having a substituent" in the hydrocarbon group means that some or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Such an aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
重合性基以外の他の基において、炭化水素基が「置換基を有する」とは、該炭化水素基における水素原子の一部または全部が、水素原子以外の基または原子で置換されていることを意味する。
炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。
脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。かかる脂肪族炭化水素基は、飽和であってもよく、不飽和であってもよく、通常は飽和であることが好ましい。 Hydrocarbon Group Which Optionally Has a Substituent With respect to groups other than polymerizable groups, the term "having a substituent" in the hydrocarbon group means that some or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Such an aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
脂肪族炭化水素基として、より具体的には、直鎖状または分岐鎖状の脂肪族炭化水素基、構造中に環を含む脂肪族炭化水素基等が挙げられる。
Specific examples of aliphatic hydrocarbon groups include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups that contain a ring in the structure.
直鎖状または分岐鎖状の脂肪族炭化水素基は、炭素数が１～１０であることが好ましく、１～８がより好ましく、１～５がさらに好ましく、１～３が特に好ましく、２が最も好ましい。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基、エチレン基［－（ＣＨ２）２－］、トリメチレン基［－（ＣＨ２）３－］、テトラメチレン基［－（ＣＨ２）４－］、ペンタメチレン基［－（ＣＨ２）５－］等が挙げられる。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素数１～５の直鎖状のアルキル基が好ましい。
鎖状（直鎖状、分岐鎖状）の脂肪族炭化水素基は、置換基を有していてもよく、有していなくてもよい。該置換基としては、フッ素原子、フッ素原子で置換された炭素数１～５のフッ素化低級アルキル基、酸素原子（＝Ｏ）等が挙げられる。 The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms, and most preferably 2 carbon atoms.
As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group, an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C ( CH3 ) ( CH2CH3 )-, -C( CH3 )( CH2CH2CH3 ) - , -C( CH2CH3 ) 2- , and the like; alkylethylene groups such as -CH( CH3 ) CH2- , -CH ( CH3 ) CH( CH3 )-, -C ( CH3 )2CH2- , -CH ( CH2CH3 ) CH2- , and the like ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. As the alkyl group in the alkyl alkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.
The chain (straight-chain or branched-chain) aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom (═O).
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基、エチレン基［－（ＣＨ２）２－］、トリメチレン基［－（ＣＨ２）３－］、テトラメチレン基［－（ＣＨ２）４－］、ペンタメチレン基［－（ＣＨ２）５－］等が挙げられる。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素数１～５の直鎖状のアルキル基が好ましい。
鎖状（直鎖状、分岐鎖状）の脂肪族炭化水素基は、置換基を有していてもよく、有していなくてもよい。該置換基としては、フッ素原子、フッ素原子で置換された炭素数１～５のフッ素化低級アルキル基、酸素原子（＝Ｏ）等が挙げられる。 The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms, and most preferably 2 carbon atoms.
As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group, an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C ( CH3 ) ( CH2CH3 )-, -C( CH3 )( CH2CH2CH3 ) - , -C( CH2CH3 ) 2- , and the like; alkylethylene groups such as -CH( CH3 ) CH2- , -CH ( CH3 ) CH( CH3 )-, -C ( CH3 )2CH2- , -CH ( CH2CH3 ) CH2- , and the like ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. As the alkyl group in the alkyl alkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.
The chain (straight-chain or branched-chain) aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom (═O).
環を含む脂肪族炭化水素基としては、環状の脂肪族炭化水素基（脂肪族炭化水素環から水素原子２個を除いた基）、該環状の脂肪族炭化水素基が前述した鎖状の脂肪族炭化水素基の末端に結合するか又は鎖状の脂肪族炭化水素基の途中に介在する基等が挙げられる。
環状の脂肪族炭化水素基は、炭素数が３～２０であることが好ましく、３～１２であることがより好ましい。
環状の脂肪族炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式基としては、炭素数３～６のモノシクロアルカンから２個の水素原子を除いた基が好ましく、該モノシクロアルカンとしてはシクロペンタン、シクロヘキサン等が例示できる。
多環式基としては、炭素数７～１２のポリシクロアルカンから２個の水素原子を除いた基が好ましく、該ポリシクロアルカンとして具体的には、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。
環状の脂肪族炭化水素基は、置換基を有していてもよいし、有していなくてもよい。置換基としては、炭素数１～５の低級アルキル基、フッ素原子、フッ素原子で置換された炭素数１～５のフッ素化低級アルキル基、酸素原子（＝Ｏ）等が挙げられる。 Examples of the aliphatic hydrocarbon group containing a ring include a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring) and a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of the aforementioned chain-like aliphatic hydrocarbon group or is present in the middle of the chain-like aliphatic hydrocarbon group.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic group, a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane.
The polycyclic group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of such polycycloalkanes include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom (═O).
環状の脂肪族炭化水素基は、炭素数が３～２０であることが好ましく、３～１２であることがより好ましい。
環状の脂肪族炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式基としては、炭素数３～６のモノシクロアルカンから２個の水素原子を除いた基が好ましく、該モノシクロアルカンとしてはシクロペンタン、シクロヘキサン等が例示できる。
多環式基としては、炭素数７～１２のポリシクロアルカンから２個の水素原子を除いた基が好ましく、該ポリシクロアルカンとして具体的には、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。
環状の脂肪族炭化水素基は、置換基を有していてもよいし、有していなくてもよい。置換基としては、炭素数１～５の低級アルキル基、フッ素原子、フッ素原子で置換された炭素数１～５のフッ素化低級アルキル基、酸素原子（＝Ｏ）等が挙げられる。 Examples of the aliphatic hydrocarbon group containing a ring include a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring) and a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of the aforementioned chain-like aliphatic hydrocarbon group or is present in the middle of the chain-like aliphatic hydrocarbon group.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic group, a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane.
The polycyclic group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of such polycycloalkanes include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom (═O).
芳香族炭化水素基としては、例えば、フェニル基、ビフェニル（ｂｉｐｈｅｎｙｌ）基、フルオレニル（ｆｌｕｏｒｅｎｙｌ）基、ナフチル基、アントリル（ａｎｔｈｒｙｌ）基、フェナントリル基等の、１価の芳香族炭化水素基の芳香族炭化水素の核から水素原子をさらに１つ除いた２価の芳香族炭化水素基；
当該２価の芳香族炭化水素基の環を構成する炭素原子の一部が酸素原子、硫黄原子、窒素原子等のヘテロ原子で置換された芳香族炭化水素基；
ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基等でかつその芳香族炭化水素の核から水素原子をさらに１つ除いた芳香族炭化水素基等が挙げられる。
なかでも、前記２価の芳香族炭化水素基が好ましく、フェニル基から水素原子をさらに１つ除いた芳香族炭化水素基、ナフチル基から水素原子をさらに１つ除いた芳香族炭化水素基が特に好ましい。
前記アリールアルキル基中のアルキル鎖の炭素数は、１～４であることが好ましく、１～２であることがより好ましく、１であることが特に好ましい。
芳香族炭化水素基は、置換基を有していてもよいし、有していなくてもよい。置換基としては、炭素数１～５の低級アルキル基、フッ素原子、フッ素原子で置換された炭素数１～５のフッ素化低級アルキル基、酸素原子（＝Ｏ）等が挙げられる。 Examples of the aromatic hydrocarbon group include divalent aromatic hydrocarbon groups in which one hydrogen atom has been further removed from the aromatic hydrocarbon nucleus of a monovalent aromatic hydrocarbon group, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group;
an aromatic hydrocarbon group in which a part of the carbon atoms constituting the ring of the divalent aromatic hydrocarbon group is substituted with a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom;
Examples of the arylalkyl group include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl groups, and aromatic hydrocarbon groups in which one hydrogen atom has been further removed from the aromatic hydrocarbon nucleus.
Of these, the above-mentioned divalent aromatic hydrocarbon groups are preferred, and aromatic hydrocarbon groups in which a further hydrogen atom has been removed from a phenyl group and aromatic hydrocarbon groups in which a further hydrogen atom has been removed from a naphthyl group are particularly preferred.
The alkyl chain in the arylalkyl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.
The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom (═O).
当該２価の芳香族炭化水素基の環を構成する炭素原子の一部が酸素原子、硫黄原子、窒素原子等のヘテロ原子で置換された芳香族炭化水素基；
ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基等でかつその芳香族炭化水素の核から水素原子をさらに１つ除いた芳香族炭化水素基等が挙げられる。
なかでも、前記２価の芳香族炭化水素基が好ましく、フェニル基から水素原子をさらに１つ除いた芳香族炭化水素基、ナフチル基から水素原子をさらに１つ除いた芳香族炭化水素基が特に好ましい。
前記アリールアルキル基中のアルキル鎖の炭素数は、１～４であることが好ましく、１～２であることがより好ましく、１であることが特に好ましい。
芳香族炭化水素基は、置換基を有していてもよいし、有していなくてもよい。置換基としては、炭素数１～５の低級アルキル基、フッ素原子、フッ素原子で置換された炭素数１～５のフッ素化低級アルキル基、酸素原子（＝Ｏ）等が挙げられる。 Examples of the aromatic hydrocarbon group include divalent aromatic hydrocarbon groups in which one hydrogen atom has been further removed from the aromatic hydrocarbon nucleus of a monovalent aromatic hydrocarbon group, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group;
an aromatic hydrocarbon group in which a part of the carbon atoms constituting the ring of the divalent aromatic hydrocarbon group is substituted with a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom;
Examples of the arylalkyl group include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl groups, and aromatic hydrocarbon groups in which one hydrogen atom has been further removed from the aromatic hydrocarbon nucleus.
Of these, the above-mentioned divalent aromatic hydrocarbon groups are preferred, and aromatic hydrocarbon groups in which a further hydrogen atom has been removed from a phenyl group and aromatic hydrocarbon groups in which a further hydrogen atom has been removed from a naphthyl group are particularly preferred.
The alkyl chain in the arylalkyl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.
The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom (═O).
上記のなかでも、置換基を有していてもよい炭化水素基としては、直鎖状、分岐鎖状または環状の脂肪族炭化水素基、２価の芳香族炭化水素基がより好ましく、メチレン基、エチレン基、－ＣＨ（ＣＨ３）－、テトラシクロドデカニル基から水素原子をさらに１つ除いた基、フェニル基から水素原子をさらに１つ除いた芳香族炭化水素基が特に好ましい。
Among the above, as the hydrocarbon group which may have a substituent, a linear, branched or cyclic aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group are more preferred, and a methylene group, an ethylene group, -CH(CH 3 )-, a group in which one further hydrogen atom has been removed from a tetracyclododecanyl group, and an aromatic hydrocarbon group in which one further hydrogen atom has been removed from a phenyl group are particularly preferred.
・ヘテロ原子を含む２価の連結基
ヘテロ原子とは、炭素原子および水素原子以外の原子であり、たとえば酸素原子、窒素原子、硫黄原子、ハロゲン原子等が挙げられる。
ヘテロ原子を含む２価の連結基としては、たとえば、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、カーボネート結合（－Ｏ－Ｃ（＝Ｏ）－Ｏ－）、－ＮＨ－、－ＮＲ０４（Ｒ０４はアルキル基）－、－ＮＨ－Ｃ（＝Ｏ）－、＝Ｎ－、または「これらの基」と２価の炭化水素基との組み合わせ等が挙げられる。
２価の炭化水素基としては、上述した置換基を有していてもよい炭化水素基と同様のものが挙げられ、直鎖状または分岐鎖状の脂肪族炭化水素基が好ましい。
なかでも、ヘテロ原子を含む２価の連結基としては、前記「これらの基」と２価の炭化水素基との組み合わせがより好ましく、具体的には、前記「これらの基」と上記脂肪族炭化水素基との組み合わせ、上記脂肪族炭化水素基と前記「これらの基」と上記脂肪族炭化水素基との組み合わせが特に好ましい。 Divalent Linking Group Containing a Heteroatom A heteroatom is an atom other than carbon and hydrogen atoms, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
Examples of divalent linking groups containing a heteroatom include -O-, -C(=O)-, -C(=O)-O-, a carbonate bond (-O-C(=O)-O-), -NH-, -NR 04 (R 04 is an alkyl group)-, -NH-C(=O)-, =N-, and combinations of "these groups" with divalent hydrocarbon groups.
The divalent hydrocarbon group may be the same as the above-mentioned hydrocarbon group which may have a substituent, and a straight-chain or branched-chain aliphatic hydrocarbon group is preferred.
Among these, as the divalent linking group containing a heteroatom, a combination of the above-mentioned "these groups" and a divalent hydrocarbon group is more preferable, and specifically, a combination of the above-mentioned "these groups" and the above-mentioned aliphatic hydrocarbon group, and a combination of the above-mentioned aliphatic hydrocarbon group, the above-mentioned "these groups" and the above-mentioned aliphatic hydrocarbon group are particularly preferable.
ヘテロ原子とは、炭素原子および水素原子以外の原子であり、たとえば酸素原子、窒素原子、硫黄原子、ハロゲン原子等が挙げられる。
ヘテロ原子を含む２価の連結基としては、たとえば、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、カーボネート結合（－Ｏ－Ｃ（＝Ｏ）－Ｏ－）、－ＮＨ－、－ＮＲ０４（Ｒ０４はアルキル基）－、－ＮＨ－Ｃ（＝Ｏ）－、＝Ｎ－、または「これらの基」と２価の炭化水素基との組み合わせ等が挙げられる。
２価の炭化水素基としては、上述した置換基を有していてもよい炭化水素基と同様のものが挙げられ、直鎖状または分岐鎖状の脂肪族炭化水素基が好ましい。
なかでも、ヘテロ原子を含む２価の連結基としては、前記「これらの基」と２価の炭化水素基との組み合わせがより好ましく、具体的には、前記「これらの基」と上記脂肪族炭化水素基との組み合わせ、上記脂肪族炭化水素基と前記「これらの基」と上記脂肪族炭化水素基との組み合わせが特に好ましい。 Divalent Linking Group Containing a Heteroatom A heteroatom is an atom other than carbon and hydrogen atoms, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
Examples of divalent linking groups containing a heteroatom include -O-, -C(=O)-, -C(=O)-O-, a carbonate bond (-O-C(=O)-O-), -NH-, -NR 04 (R 04 is an alkyl group)-, -NH-C(=O)-, =N-, and combinations of "these groups" with divalent hydrocarbon groups.
The divalent hydrocarbon group may be the same as the above-mentioned hydrocarbon group which may have a substituent, and a straight-chain or branched-chain aliphatic hydrocarbon group is preferred.
Among these, as the divalent linking group containing a heteroatom, a combination of the above-mentioned "these groups" and a divalent hydrocarbon group is more preferable, and specifically, a combination of the above-mentioned "these groups" and the above-mentioned aliphatic hydrocarbon group, and a combination of the above-mentioned aliphatic hydrocarbon group, the above-mentioned "these groups" and the above-mentioned aliphatic hydrocarbon group are particularly preferable.
上記一般式（ｆ１）中、Ｒｆ０は、フッ素原子を有する有機基であり、フッ素原子を含む炭化水素基であることが好ましい。
フッ素原子を含む炭化水素基としては、直鎖状、分岐鎖状または環状のいずれであってもよく、炭素原子数は１～２０であることが好ましく、炭素原子数１～１５であることがより好ましく、炭素原子数１～１０がさらに好ましく、炭素原子数１～５が特に好ましい。
また、フッ素原子を含む炭化水素基中のフッ素原子の数は、１～１０であることが好ましく、１～６であることがより好ましく、１～３であることがさらに好ましい。
また、フッ素原子を含む炭化水素基は、当該炭化水素基における水素原子の２５％以上がフッ素化されていることが好ましく、４０％以上がフッ素化されていることがより好ましい。
なかでも、Ｒｆ０としては、炭素原子数１～６のフッ素化炭化水素基がより好ましく、トリフルオロメチル基、－ＣＨ２－ＣＦ３、－ＣＨ２－ＣＨ２－ＣＦ３、－ＣＨ２－ＣＦ２－ＣＦ３、－ＣＨ（ＣＦ３）２が好ましい。 In the above general formula (f1), Rf 0 is an organic group having a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom.
The fluorine atom-containing hydrocarbon group may be linear, branched, or cyclic and preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, still more preferably has 1 to 10 carbon atoms, and particularly preferably has 1 to 5 carbon atoms.
The number of fluorine atoms in the fluorine-containing hydrocarbon group is preferably 1-10, more preferably 1-6, and even more preferably 1-3.
In addition, in the hydrocarbon group containing a fluorine atom, preferably 25% or more, and more preferably 40% or more of the hydrogen atoms in the hydrocarbon group are fluorinated.
Among these, Rf 0 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and a trifluoromethyl group, -CH 2 -CF 3 , -CH 2 -CH 2 -CF 3 , -CH 2 -CF 2 -CF 3 , or -CH(CF 3 ) 2 is preferred.
フッ素原子を含む炭化水素基としては、直鎖状、分岐鎖状または環状のいずれであってもよく、炭素原子数は１～２０であることが好ましく、炭素原子数１～１５であることがより好ましく、炭素原子数１～１０がさらに好ましく、炭素原子数１～５が特に好ましい。
また、フッ素原子を含む炭化水素基中のフッ素原子の数は、１～１０であることが好ましく、１～６であることがより好ましく、１～３であることがさらに好ましい。
また、フッ素原子を含む炭化水素基は、当該炭化水素基における水素原子の２５％以上がフッ素化されていることが好ましく、４０％以上がフッ素化されていることがより好ましい。
なかでも、Ｒｆ０としては、炭素原子数１～６のフッ素化炭化水素基がより好ましく、トリフルオロメチル基、－ＣＨ２－ＣＦ３、－ＣＨ２－ＣＨ２－ＣＦ３、－ＣＨ２－ＣＦ２－ＣＦ３、－ＣＨ（ＣＦ３）２が好ましい。 In the above general formula (f1), Rf 0 is an organic group having a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom.
The fluorine atom-containing hydrocarbon group may be linear, branched, or cyclic and preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, still more preferably has 1 to 10 carbon atoms, and particularly preferably has 1 to 5 carbon atoms.
The number of fluorine atoms in the fluorine-containing hydrocarbon group is preferably 1-10, more preferably 1-6, and even more preferably 1-3.
In addition, in the hydrocarbon group containing a fluorine atom, preferably 25% or more, and more preferably 40% or more of the hydrogen atoms in the hydrocarbon group are fluorinated.
Among these, Rf 0 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and a trifluoromethyl group, -CH 2 -CF 3 , -CH 2 -CH 2 -CF 3 , -CH 2 -CF 2 -CF 3 , or -CH(CF 3 ) 2 is preferred.
（Ｆ１）成分は、下記一般式（ｆ１－１）で表される構成単位、又は、下記一般式（ｆ１－２）で表される構成単位を有することが好ましい。
The (F1) component preferably has a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).
≪一般式（ｆ１－１）で表される構成単位≫
<Constituent unit represented by general formula (f1-1)>
上記一般式（ｆ１－１）中のＲは、上述した式（ｆ１）中のＲと同一である。
R in the above general formula (f1-1) is the same as R in the above formula (f1).
上記一般式（ｆ１－１）中のＸ０１における酸解離性部位を有さない２価の連結基としては、上述した式（ｆ１）中のＸ０と同様のものが挙げられる。
Examples of the divalent linking group not having an acid dissociable site in X 01 in the above general formula (f1-1) include the same as X 0 in the above formula (f1).
上記一般式（ｆ１－１）中のＸ０１における酸解離性部位を有さない２価の連結基として、具体的には、置換基を有してもよい直鎖状若しくは分岐鎖状の脂肪族炭化水素基、又は、置換基を有してもよい芳香族炭化水素基であることが好ましく、フッ素原子を有してもよい直鎖状若しくは分岐鎖状の脂肪族炭化水素基、又は、置換基を有してもよい芳香族炭化水素基であることがより好ましく、直鎖状の脂肪族炭化水素基、フッ素原子を有する分岐鎖状の脂肪族炭化水素基、又は、置換基を有してもよい芳香族炭化水素基であることがさらに好ましい。
該脂肪族炭化水素基は、炭素原子数が１～１０であることが好ましく、炭素原子数が１～８がより好ましく、炭素原子数が１～５がさらに好ましい。
該置換基を有してもよい芳香族炭化水素基として、具体的には、＊＊－（ＡｒＸ）－Ｏ－ＲＺ－*で表される基であることが好ましい。式中、ＡｒＸは、２価の芳香族炭化水素基であり、ＲＺは、２価の直鎖状又は分岐鎖状の脂肪族炭化水素基であり、＊＊は、式（ｆ１－１）中の（－Ｏ－）との結合手を示し、＊は、式（ｆ１－１）中の－（Ｃ＝Ｏ）－Ｏ－の炭素原子との結合手を示す。
ＡｒＸとしては、フェニレン基が好ましい。
ＲＺは、炭素原子数が１～５の２価の直鎖状の脂肪族炭化水素基であることが好ましく、炭素原子数が１～３の２価の直鎖状の脂肪族炭化水素基であることがより好ましい。 Specifically, the divalent linking group having no acid dissociable site in X 01 in general formula (f1-1) is preferably a linear or branched aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent, more preferably a linear or branched aliphatic hydrocarbon group which may have a fluorine atom, or an aromatic hydrocarbon group which may have a substituent, and even more preferably a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group having a fluorine atom, or an aromatic hydrocarbon group which may have a substituent.
The aliphatic hydrocarbon group preferably contains 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms.
Specifically, the aromatic hydrocarbon group which may have a substituent is preferably a group represented by **-(ArX)-O-RZ-*, where ArX is a divalent aromatic hydrocarbon group, RZ is a divalent linear or branched aliphatic hydrocarbon group, ** represents a bond to (-O-) in formula (f1-1), and * represents a bond to the carbon atom of -(C=O)-O- in formula (f1-1).
ArX is preferably a phenylene group.
RZ is preferably a divalent linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably a divalent linear aliphatic hydrocarbon group having 1 to 3 carbon atoms.
該脂肪族炭化水素基は、炭素原子数が１～１０であることが好ましく、炭素原子数が１～８がより好ましく、炭素原子数が１～５がさらに好ましい。
該置換基を有してもよい芳香族炭化水素基として、具体的には、＊＊－（ＡｒＸ）－Ｏ－ＲＺ－*で表される基であることが好ましい。式中、ＡｒＸは、２価の芳香族炭化水素基であり、ＲＺは、２価の直鎖状又は分岐鎖状の脂肪族炭化水素基であり、＊＊は、式（ｆ１－１）中の（－Ｏ－）との結合手を示し、＊は、式（ｆ１－１）中の－（Ｃ＝Ｏ）－Ｏ－の炭素原子との結合手を示す。
ＡｒＸとしては、フェニレン基が好ましい。
ＲＺは、炭素原子数が１～５の２価の直鎖状の脂肪族炭化水素基であることが好ましく、炭素原子数が１～３の２価の直鎖状の脂肪族炭化水素基であることがより好ましい。 Specifically, the divalent linking group having no acid dissociable site in X 01 in general formula (f1-1) is preferably a linear or branched aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent, more preferably a linear or branched aliphatic hydrocarbon group which may have a fluorine atom, or an aromatic hydrocarbon group which may have a substituent, and even more preferably a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group having a fluorine atom, or an aromatic hydrocarbon group which may have a substituent.
The aliphatic hydrocarbon group preferably contains 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms.
Specifically, the aromatic hydrocarbon group which may have a substituent is preferably a group represented by **-(ArX)-O-RZ-*, where ArX is a divalent aromatic hydrocarbon group, RZ is a divalent linear or branched aliphatic hydrocarbon group, ** represents a bond to (-O-) in formula (f1-1), and * represents a bond to the carbon atom of -(C=O)-O- in formula (f1-1).
ArX is preferably a phenylene group.
RZ is preferably a divalent linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably a divalent linear aliphatic hydrocarbon group having 1 to 3 carbon atoms.
上記一般式（ｆ１－１）中のＲｆ０１としては、上述した式（ｆ１）中のＲｆ０と同様のものが挙げられ、炭素原子数１～６のフッ素化炭化水素基が好ましく、トリフルオロメチル基、－ＣＨ２－ＣＦ３、－ＣＨ２－ＣＨ２－ＣＦ３、－ＣＨ２－ＣＦ２－ＣＦ３、－ＣＨ（ＣＦ３）２がより好ましく、－ＣＨ２－ＣＦ３、－ＣＨ２－ＣＨ２－ＣＦ３、－ＣＨ（ＣＦ３）２がさらに好ましい。
Examples of Rf 01 in the above general formula (f1-1) include the same as Rf 0 in the above formula (f1), and are preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, more preferably a trifluoromethyl group, -CH 2 -CF 3 , -CH 2 -CH 2 -CF 3 , -CH 2 -CF 2 -CF 3 , -CH(CF 3 ) 2 , and even more preferably -CH 2 -CF 3 , -CH 2 -CH 2 -CF 3 , -CH(CF 3 ) 2 .
一般式（ｆ１－１）で表される構成単位の好ましい具体例を以下に示す。
以下の各式中、Ｒαは、水素原子、メチル基又はトリフルオロメチル基を示す。 Preferred specific examples of the structural unit represented by general formula (f1-1) are shown below.
In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
以下の各式中、Ｒαは、水素原子、メチル基又はトリフルオロメチル基を示す。 Preferred specific examples of the structural unit represented by general formula (f1-1) are shown below.
In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
一般式（ｆ１－１）で表される構成単位としては、上記の中でも、上記式（ｆ１－１－２）で表される構成単位が好ましい。
As the structural unit represented by general formula (f1-1), the structural unit represented by formula (f1-1-2) is preferred among the above.
≪一般式（ｆ１－２）で表される構成単位≫
<Constituent unit represented by general formula (f1-2)>
上記一般式（ｆ１－２）中のＲは、上述した式（ｆ１）中のＲと同一である。
R in the above general formula (f1-2) is the same as R in the above formula (f1).
上記一般式（ｆ１－２）中のＸ０２１は、環式基であり、前記環式基が有する水素原子の一部又は全部は置換基で置換されていてもよい。該置換基としては、炭素数１～５の低級アルキル基、フッ素原子、フッ素原子で置換された炭素数１～５のフッ素化低級アルキル基、酸素原子（＝Ｏ）等が挙げられる。
該環式基として、具体的には、脂肪族環式基、アリーレン基、ヘテロアリーレン基等が挙げられる。 X in the above general formula (f1-2) is a cyclic group, and some or all of the hydrogen atoms of the cyclic group may be substituted with a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom (=O).
Specific examples of the cyclic group include an aliphatic cyclic group, an arylene group, and a heteroarylene group.
該環式基として、具体的には、脂肪族環式基、アリーレン基、ヘテロアリーレン基等が挙げられる。 X in the above general formula (f1-2) is a cyclic group, and some or all of the hydrogen atoms of the cyclic group may be substituted with a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and an oxygen atom (=O).
Specific examples of the cyclic group include an aliphatic cyclic group, an arylene group, and a heteroarylene group.
該脂肪族環式基としては、多環式基であってもよく、単環式基であってもよい。単環式基としては、炭素数３～６のモノシクロアルカンから２個の水素原子を除いた基が好ましく、該モノシクロアルカンとしてはシクロペンタン、シクロヘキサン等が例示できる。
多環式基としては、炭素数７～１２のポリシクロアルカンから２個の水素原子を除いた基が好ましく、該ポリシクロアルカンとして具体的には、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 The aliphatic cyclic group may be a polycyclic group or a monocyclic group. The monocyclic group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms, and examples of the monocycloalkane include cyclopentane and cyclohexane.
The polycyclic group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of such polycycloalkanes include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
多環式基としては、炭素数７～１２のポリシクロアルカンから２個の水素原子を除いた基が好ましく、該ポリシクロアルカンとして具体的には、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等が挙げられる。 The aliphatic cyclic group may be a polycyclic group or a monocyclic group. The monocyclic group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms, and examples of the monocycloalkane include cyclopentane and cyclohexane.
The polycyclic group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of such polycycloalkanes include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
アリーレン基としては、フェニレン基が好ましい。
ヘテロアリーレン基としては、チエニレン基、イソキサゾレン基等が挙げられる。 The arylene group is preferably a phenylene group.
Examples of the heteroarylene group include a thienylene group and an isoxazolene group.
ヘテロアリーレン基としては、チエニレン基、イソキサゾレン基等が挙げられる。 The arylene group is preferably a phenylene group.
Examples of the heteroarylene group include a thienylene group and an isoxazolene group.
上記一般式（ｆ１－２）中のＸ０２１としては、上記の中でも、アリーレン基であることが好ましく、フェニレン基であることがより好ましい。
Among the above, X 021 in general formula (f1-2) is preferably an arylene group, and more preferably a phenylene group.
上記一般式（ｆ１－２）中のＸ０２２における酸解離性部位を有さない２価の連結基としては、上述した式（ｆ１）中のＸ０と同様のものが挙げられる。
Examples of the divalent linking group not having an acid dissociable site in X 022 in the above general formula (f1-2) include the same as X 0 in the above formula (f1).
上記一般式（ｆ１－１）中のＸ０２２における酸解離性部位を有さない２価の連結基として、具体的には、置換基を有してもよい直鎖状若しくは分岐鎖状の脂肪族炭化水素基が好ましく、置換基を有してもよい直鎖状の脂肪族炭化水素基がより好ましい。
該脂肪族炭化水素基は、炭素原子数が１～１０であることが好ましく、炭素原子数が１～８がより好ましく、炭素原子数が１～５がさらに好ましい。
該置換基を有してもよい直鎖状の脂肪族炭化水素基として、具体的には、＊＊－Ｏ－ＲＹ－＊で表される基であることが好ましい。式中、ＲＹは、２価の直鎖状又は分岐鎖状の脂肪族炭化水素基であり、＊＊は、式（ｆ１－１）中の（－Ｏ－）との結合手を示し、＊は、式（ｆ１－１）中の－（Ｃ＝Ｏ）－Ｏ－の炭素原子との結合手を示す。
ＲＹは、炭素原子数が１～５の２価の直鎖状の脂肪族炭化水素基であることが好ましく、炭素原子数が１～３の２価の直鎖状の脂肪族炭化水素基であることがより好ましい。 As the divalent linking group having no acid dissociable site for X 022 in general formula (f1-1), specifically, a linear or branched aliphatic hydrocarbon group which may have a substituent is preferable, and a linear aliphatic hydrocarbon group which may have a substituent is more preferable.
The aliphatic hydrocarbon group preferably contains 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms.
The optionally substituted straight-chain aliphatic hydrocarbon group is specifically preferably a group represented by **-O-RY-*, in which RY is a divalent straight-chain or branched-chain aliphatic hydrocarbon group, ** represents a bond to (-O-) in formula (f1-1), and * represents a bond to the carbon atom of -(C=O)-O- in formula (f1-1).
RY is preferably a divalent linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably a divalent linear aliphatic hydrocarbon group having 1 to 3 carbon atoms.
該脂肪族炭化水素基は、炭素原子数が１～１０であることが好ましく、炭素原子数が１～８がより好ましく、炭素原子数が１～５がさらに好ましい。
該置換基を有してもよい直鎖状の脂肪族炭化水素基として、具体的には、＊＊－Ｏ－ＲＹ－＊で表される基であることが好ましい。式中、ＲＹは、２価の直鎖状又は分岐鎖状の脂肪族炭化水素基であり、＊＊は、式（ｆ１－１）中の（－Ｏ－）との結合手を示し、＊は、式（ｆ１－１）中の－（Ｃ＝Ｏ）－Ｏ－の炭素原子との結合手を示す。
ＲＹは、炭素原子数が１～５の２価の直鎖状の脂肪族炭化水素基であることが好ましく、炭素原子数が１～３の２価の直鎖状の脂肪族炭化水素基であることがより好ましい。 As the divalent linking group having no acid dissociable site for X 022 in general formula (f1-1), specifically, a linear or branched aliphatic hydrocarbon group which may have a substituent is preferable, and a linear aliphatic hydrocarbon group which may have a substituent is more preferable.
The aliphatic hydrocarbon group preferably contains 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms.
The optionally substituted straight-chain aliphatic hydrocarbon group is specifically preferably a group represented by **-O-RY-*, in which RY is a divalent straight-chain or branched-chain aliphatic hydrocarbon group, ** represents a bond to (-O-) in formula (f1-1), and * represents a bond to the carbon atom of -(C=O)-O- in formula (f1-1).
RY is preferably a divalent linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably a divalent linear aliphatic hydrocarbon group having 1 to 3 carbon atoms.
上記一般式（ｆ１－２）中のＲｆ０１としては、上述した式（ｆ１）中のＲｆ０と同様のものが挙げられ、炭素原子数１～６のフッ素化炭化水素基が好ましく、トリフルオロメチル基、－ＣＨ２－ＣＦ３、－ＣＨ２－ＣＨ２－ＣＦ３、－ＣＨ２－ＣＦ２－ＣＦ３、－ＣＨ（ＣＦ３）２がより好ましく、－ＣＨ２－ＣＦ２－ＣＦ３がさらに好ましい。
Rf 01 in the above general formula (f1-2) may be the same as Rf 0 in the above formula (f1), and is preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, more preferably a trifluoromethyl group, -CH 2 -CF 3 , -CH 2 -CH 2 -CF 3 , -CH 2 -CF 2 -CF 3 , -CH(CF 3 ) 2 , and even more preferably -CH 2 -CF 2 -CF 3 .
一般式（ｆ１－２）で表される構成単位の好ましい具体例を以下に示す。
以下の各式中、Ｒαは、水素原子、メチル基又はトリフルオロメチル基を示す。 Preferred specific examples of the structural unit represented by general formula (f1-2) are shown below.
In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
以下の各式中、Ｒαは、水素原子、メチル基又はトリフルオロメチル基を示す。 Preferred specific examples of the structural unit represented by general formula (f1-2) are shown below.
In each of the following formulas, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
≪その他構成単位≫
（Ｆ１）成分は、上記の一般式（ｆ１－１）で表される構成単位、又は一般式（ｆ１－２）で表される構成単位に加え、必要に応じてその他構成単位を有してもよい。
ここでのその他構成単位としては、例えば、上記構成単位（ａ１）、上記構成単位（ａ２）、アクリル酸から誘導される構成単位、メタクリル酸から誘導される構成単位などが挙げられる。 Other structural units
The component (F1) may have other structural units, as well as the structural unit represented by general formula (f1-1) or the structural unit represented by general formula (f1-2) above, if necessary.
Examples of the other structural units include the above-mentioned structural unit (a1), the above-mentioned structural unit (a2), a structural unit derived from acrylic acid, and a structural unit derived from methacrylic acid.
（Ｆ１）成分は、上記の一般式（ｆ１－１）で表される構成単位、又は一般式（ｆ１－２）で表される構成単位に加え、必要に応じてその他構成単位を有してもよい。
ここでのその他構成単位としては、例えば、上記構成単位（ａ１）、上記構成単位（ａ２）、アクリル酸から誘導される構成単位、メタクリル酸から誘導される構成単位などが挙げられる。 Other structural units
The component (F1) may have other structural units, as well as the structural unit represented by general formula (f1-1) or the structural unit represented by general formula (f1-2) above, if necessary.
Examples of the other structural units include the above-mentioned structural unit (a1), the above-mentioned structural unit (a2), a structural unit derived from acrylic acid, and a structural unit derived from methacrylic acid.
（Ｆ１）成分として、具体的には、構成単位（ｆ１）の繰り返し構造を有する高分子化合物が好ましく、構成単位（ｆ１）の繰り返し構造と、構成単位（ａ１）又は（ａ２）の繰り返し構造とを有する高分子化合物がより好ましく、構成単位（ｆ１）の繰り返し構造と、構成単位（ａ１）又は（ａ２）の繰り返し構造と、アクリル酸又はメタクリル酸から誘導される構成単位とを有する高分子化合物がさらに好ましい。
より具体的に、（Ｆ１）成分としては、構成単位（ｆ１）の繰り返し構造からなる高分子化合物；構成単位（ｆ１）の繰り返し構造、及び構成単位（ａ１）の繰り返し構造からなる高分子化合物；構成単位（ｆ１）の繰り返し構造、及び構成単位（ａ２）の繰り返し構造からなる高分子化合物；構成単位（ｆ１）の繰り返し構造、構成単位（ａ１）の繰り返し構造及びアクリル酸又はメタクリル酸から誘導される構成単位の繰り返し構造からなる高分子化合物が好ましく、構成単位（ｆ１）の繰り返し構造、及び構成単位（ａ１）の繰り返し構造からなる高分子化合物；構成単位（ｆ１）の繰り返し構造、構成単位（ａ１）の繰り返し構造及びアクリル酸又はメタクリル酸から誘導される構成単位の繰り返し構造からなる高分子化合物がより好ましく、構成単位（ｆ１）の繰り返し構造、構成単位（ａ１）の繰り返し構造及びアクリル酸又はメタクリル酸から誘導される構成単位の繰り返し構造からなる高分子化合物がさらに好ましい。
ここで、該構成単位（ｆ１）と共重合される前記構成単位（ａ１）としては、上記一般式（ａ１－１）で表される構成単位であり、式中のＲａ１が、上述した一般式（ａ０－ｒ－１）で表される酸解離性基である構成単位が好ましい。
また、該構成単位（ｆ１）は、上述した一般式（ｆ１－１）又は（ｆ１－２）で表される構成単位であることが好ましい。 Specifically, the component (F1) is preferably a polymeric compound having a repeating structure of the structural unit (f1), more preferably a polymeric compound having a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1) or (a2), and even more preferably a polymeric compound having a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1) or (a2), and a structural unit derived from acrylic acid or methacrylic acid.
More specifically, the component (F1) is preferably a polymeric compound comprising a repeating structure of the structural unit (f1); a polymeric compound comprising a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1); a polymeric compound comprising a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a2); a polymeric compound comprising a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid, more preferably a polymeric compound comprising a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1); a polymeric compound comprising a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid, and even more preferably a polymeric compound comprising a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid.
Here, the structural unit (a1) that is copolymerized with the structural unit (f1) is preferably a structural unit represented by the above general formula (a1-1), in which Ra 1 in the formula is an acid-dissociable group represented by the above-mentioned general formula (a0-r-1).
Furthermore, the structural unit (f1) is preferably a structural unit represented by the above-mentioned general formula (f1-1) or (f1-2).
より具体的に、（Ｆ１）成分としては、構成単位（ｆ１）の繰り返し構造からなる高分子化合物；構成単位（ｆ１）の繰り返し構造、及び構成単位（ａ１）の繰り返し構造からなる高分子化合物；構成単位（ｆ１）の繰り返し構造、及び構成単位（ａ２）の繰り返し構造からなる高分子化合物；構成単位（ｆ１）の繰り返し構造、構成単位（ａ１）の繰り返し構造及びアクリル酸又はメタクリル酸から誘導される構成単位の繰り返し構造からなる高分子化合物が好ましく、構成単位（ｆ１）の繰り返し構造、及び構成単位（ａ１）の繰り返し構造からなる高分子化合物；構成単位（ｆ１）の繰り返し構造、構成単位（ａ１）の繰り返し構造及びアクリル酸又はメタクリル酸から誘導される構成単位の繰り返し構造からなる高分子化合物がより好ましく、構成単位（ｆ１）の繰り返し構造、構成単位（ａ１）の繰り返し構造及びアクリル酸又はメタクリル酸から誘導される構成単位の繰り返し構造からなる高分子化合物がさらに好ましい。
ここで、該構成単位（ｆ１）と共重合される前記構成単位（ａ１）としては、上記一般式（ａ１－１）で表される構成単位であり、式中のＲａ１が、上述した一般式（ａ０－ｒ－１）で表される酸解離性基である構成単位が好ましい。
また、該構成単位（ｆ１）は、上述した一般式（ｆ１－１）又は（ｆ１－２）で表される構成単位であることが好ましい。 Specifically, the component (F1) is preferably a polymeric compound having a repeating structure of the structural unit (f1), more preferably a polymeric compound having a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1) or (a2), and even more preferably a polymeric compound having a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1) or (a2), and a structural unit derived from acrylic acid or methacrylic acid.
More specifically, the component (F1) is preferably a polymeric compound comprising a repeating structure of the structural unit (f1); a polymeric compound comprising a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1); a polymeric compound comprising a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a2); a polymeric compound comprising a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid, more preferably a polymeric compound comprising a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1); a polymeric compound comprising a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid, and even more preferably a polymeric compound comprising a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid.
Here, the structural unit (a1) that is copolymerized with the structural unit (f1) is preferably a structural unit represented by the above general formula (a1-1), in which Ra 1 in the formula is an acid-dissociable group represented by the above-mentioned general formula (a0-r-1).
Furthermore, the structural unit (f1) is preferably a structural unit represented by the above-mentioned general formula (f1-1) or (f1-2).
構成単位（ｆ１）の繰り返し構造、及び構成単位（ａ１）の繰り返し構造からなる高分子化合物において、構成単位（ｆ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、４０～９５モル％が好ましく、５０～９０モル％がより好ましく、６０～８０モル％がさらに好ましい。
また、該高分子化合物中の構成単位（ａ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、５～６０モル％が好ましく、１０～５０モル％がより好ましく、２０～４０モル％がさらに好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1), the proportion of the structural unit (f1) is preferably 40 to 95 mol %, more preferably 50 to 90 mol %, and even more preferably 60 to 80 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a1) in the polymer compound is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, and even more preferably from 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
また、該高分子化合物中の構成単位（ａ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、５～６０モル％が好ましく、１０～５０モル％がより好ましく、２０～４０モル％がさらに好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a1), the proportion of the structural unit (f1) is preferably 40 to 95 mol %, more preferably 50 to 90 mol %, and even more preferably 60 to 80 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a1) in the polymer compound is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, and even more preferably from 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
構成単位（ｆ１）の繰り返し構造、及び構成単位（ａ２）の繰り返し構造からなる高分子化合物において、構成単位（ｆ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、４０～９５モル％が好ましく、５０～９０モル％がより好ましく、６０～８０モル％がさらに好ましい。
また、該高分子化合物中の構成単位（ａ２）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、５～６０モル％が好ましく、１０～５０モル％がより好ましく、２０～４０モル％がさらに好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a2), the proportion of the structural unit (f1) is preferably 40 to 95 mol %, more preferably 50 to 90 mol %, and even more preferably 60 to 80 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a2) in the polymer compound is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, and even more preferably from 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
また、該高分子化合物中の構成単位（ａ２）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、５～６０モル％が好ましく、１０～５０モル％がより好ましく、２０～４０モル％がさらに好ましい。 In a polymeric compound consisting of a repeating structure of the structural unit (f1) and a repeating structure of the structural unit (a2), the proportion of the structural unit (f1) is preferably 40 to 95 mol %, more preferably 50 to 90 mol %, and even more preferably 60 to 80 mol %, relative to the total (100 mol %) of all structural units constituting the polymeric compound.
Furthermore, the proportion of the structural unit (a2) in the polymer compound is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, and even more preferably from 20 to 40 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
構成単位（ｆ１）の繰り返し構造、構成単位（ａ１）の繰り返し構造、及び、アクリル酸又はメタクリル酸から誘導される構成単位の繰り返し構造からなる高分子化合物において、構成単位（ｆ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、４０～９５モル％が好ましく、５０～９０モル％がより好ましく、６０～８０モル％がさらに好ましい。
また、該高分子化合物中の構成単位（ａ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１～５０モル％が好ましく、５～４０モル％がより好ましく、１０～３０モル％がさらに好ましい。
また、該高分子化合物中のアクリル酸又はメタクリル酸から誘導される構成単位の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１～４０モル％が好ましく、１～３０モル％がより好ましく、５～２０モル％がさらに好ましい。 In a polymeric compound which is composed of a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid, the proportion of the structural unit (f1) relative to the total (100 mol%) of all structural units constituting the polymeric compound is preferably 40 to 95 mol%, more preferably 50 to 90 mol%, and even more preferably 60 to 80 mol%.
Furthermore, the proportion of the structural unit (a1) in the polymer compound is preferably from 1 to 50 mol%, more preferably from 5 to 40 mol%, and even more preferably from 10 to 30 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
Furthermore, the proportion of structural units derived from acrylic acid or methacrylic acid in the polymer compound is preferably 1 to 40 mol %, more preferably 1 to 30 mol %, and even more preferably 5 to 20 mol %, relative to the total (100 mol %) of all structural units constituting the polymer compound.
また、該高分子化合物中の構成単位（ａ１）の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１～５０モル％が好ましく、５～４０モル％がより好ましく、１０～３０モル％がさらに好ましい。
また、該高分子化合物中のアクリル酸又はメタクリル酸から誘導される構成単位の割合は、該高分子化合物を構成する全構成単位の合計（１００モル％）に対して、１～４０モル％が好ましく、１～３０モル％がより好ましく、５～２０モル％がさらに好ましい。 In a polymeric compound which is composed of a repeating structure of the structural unit (f1), a repeating structure of the structural unit (a1), and a repeating structure of a structural unit derived from acrylic acid or methacrylic acid, the proportion of the structural unit (f1) relative to the total (100 mol%) of all structural units constituting the polymeric compound is preferably 40 to 95 mol%, more preferably 50 to 90 mol%, and even more preferably 60 to 80 mol%.
Furthermore, the proportion of the structural unit (a1) in the polymer compound is preferably from 1 to 50 mol%, more preferably from 5 to 40 mol%, and even more preferably from 10 to 30 mol%, based on the total (100 mol%) of all structural units constituting the polymer compound.
Furthermore, the proportion of structural units derived from acrylic acid or methacrylic acid in the polymer compound is preferably 1 to 40 mol %, more preferably 1 to 30 mol %, and even more preferably 5 to 20 mol %, relative to the total (100 mol %) of all structural units constituting the polymer compound.
（Ｆ１）成分の重量平均分子量（Ｍｗ）（ゲルパーミエーションクロマトグラフィーによるポリスチレン換算基準）は、１０００～５００００が好ましく、５０００～４００００がより好ましく、１００００～３００００が最も好ましい。この範囲の上限値以下であると、レジストとして用いるのにレジスト用溶剤への充分な溶解性があり、この範囲の下限値以上であると、レジスト膜の撥水性が良好である。
（Ｆ１）成分の分散度（Ｍｗ／Ｍｎ）は、１．０～５．０が好ましく、１．０～３．０がより好ましく、１．０～２．５が最も好ましい。 The weight average molecular weight (Mw) of component (F1) (based on polystyrene equivalent measured by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. When it is below the upper limit of this range, the compound has sufficient solubility in a resist solvent for use as a resist, and when it is above the lower limit of this range, the resist film has good water repellency.
The dispersity (Mw/Mn) of the component (F1) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0, and most preferably from 1.0 to 2.5.
（Ｆ１）成分の分散度（Ｍｗ／Ｍｎ）は、１．０～５．０が好ましく、１．０～３．０がより好ましく、１．０～２．５が最も好ましい。 The weight average molecular weight (Mw) of component (F1) (based on polystyrene equivalent measured by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. When it is below the upper limit of this range, the compound has sufficient solubility in a resist solvent for use as a resist, and when it is above the lower limit of this range, the resist film has good water repellency.
The dispersity (Mw/Mn) of the component (F1) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0, and most preferably from 1.0 to 2.5.
本実施形態のレジスト組成物において、（Ｆ１）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。
本実施形態のレジスト組成物において、（Ｆ１）成分の含有量は、（Ａ１）成分１００質量部に対して、０．５～１５質量部であることが好ましく、１～１０質量部であることがより好ましく、３～７質量部であることがさらに好ましい。
（Ｆ１）成分の含有量が、上記の好ましい下限値以上であれば、解像性及びＣＤＵがより向上する。
また、（Ｆ１）成分の含有量が、上記の好ましい上限値以下であれば、感度がより向上する。 In the resist composition of this embodiment, the component (F1) may use either a single type, or a combination of two or more types.
In the resist composition of this embodiment, the amount of the component (F1) relative to 100 parts by mass of the component (A1) is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 3 to 7 parts by mass.
When the content of the component (F1) is at least the above preferable lower limit, the resolution and CDU are further improved.
Furthermore, when the content of the component (F1) is equal to or less than the above preferred upper limit, the sensitivity is further improved.
本実施形態のレジスト組成物において、（Ｆ１）成分の含有量は、（Ａ１）成分１００質量部に対して、０．５～１５質量部であることが好ましく、１～１０質量部であることがより好ましく、３～７質量部であることがさらに好ましい。
（Ｆ１）成分の含有量が、上記の好ましい下限値以上であれば、解像性及びＣＤＵがより向上する。
また、（Ｆ１）成分の含有量が、上記の好ましい上限値以下であれば、感度がより向上する。 In the resist composition of this embodiment, the component (F1) may use either a single type, or a combination of two or more types.
In the resist composition of this embodiment, the amount of the component (F1) relative to 100 parts by mass of the component (A1) is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 3 to 7 parts by mass.
When the content of the component (F1) is at least the above preferable lower limit, the resolution and CDU are further improved.
Furthermore, when the content of the component (F1) is equal to or less than the above preferred upper limit, the sensitivity is further improved.
本実施形態のレジスト組成物は、（Ｆ）成分として、前記（Ｆ１）成分に該当しないフッ素樹脂成分（Ｆ２）（以下「（Ｆ２）成分」という）を併用してもよいが、フッ素樹脂成分としては、（Ｆ１）成分のみからなることが好ましい。
一実施形態のレジスト組成物としては、（Ｆ２）成分を含有するレジスト組成物は除かれる。 In the resist composition of this embodiment, a fluororesin component (F2) (hereafter referred to as "component (F2)") that does not fall under the category of the component (F1) may be used in combination as the component (F). However, it is preferable that the fluororesin component consist solely of the component (F1).
The resist composition of one embodiment excludes resist compositions that contain the component (F2).
一実施形態のレジスト組成物としては、（Ｆ２）成分を含有するレジスト組成物は除かれる。 In the resist composition of this embodiment, a fluororesin component (F2) (hereafter referred to as "component (F2)") that does not fall under the category of the component (F1) may be used in combination as the component (F). However, it is preferable that the fluororesin component consist solely of the component (F1).
The resist composition of one embodiment excludes resist compositions that contain the component (F2).
（Ｆ）成分中の（Ｆ１）成分の割合は、（Ｆ）成分の総質量に対し、２５質量％以上が好ましく、５０質量％以上がより好ましく、７５質量％以上がさらに好ましく、１００質量％であってもよい。該割合が２５質量％以上であると、高感度化や解像性、ラフネス改善などの種々のリソグラフィー特性に優れたレジストパターンが形成されやすくなる。
The proportion of component (F1) in component (F) is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of component (F). If the proportion is 25% by mass or more, a resist pattern that is excellent in various lithography properties such as high sensitivity, resolution, and improved roughness is easily formed.
＜その他成分＞
本実施形態のレジスト組成物は、上述した（Ａ）成分及び（Ｆ）成分、に加え、その他成分をさらに含有してもよい。その他成分としては、例えば以下に示す（Ｂ）成分、（Ｄ）成分、（Ｅ）成分、（Ｓ）成分などが挙げられる。 <Other ingredients>
The resist composition of this embodiment may further contain other components in addition to the above-mentioned components (A) and (F). Examples of other components include the following components (B), (D), (E), and (S).
本実施形態のレジスト組成物は、上述した（Ａ）成分及び（Ｆ）成分、に加え、その他成分をさらに含有してもよい。その他成分としては、例えば以下に示す（Ｂ）成分、（Ｄ）成分、（Ｅ）成分、（Ｓ）成分などが挙げられる。 <Other ingredients>
The resist composition of this embodiment may further contain other components in addition to the above-mentioned components (A) and (F). Examples of other components include the following components (B), (D), (E), and (S).
≪酸発生剤成分（Ｂ）≫
本実施形態のレジスト組成物は、さらに、露光により酸を発生する酸発生剤成分（Ｂ）を含有することが好ましい。
（Ｂ）成分としては、特に限定されず、これまで化学増幅型レジスト組成物用の酸発生剤として提案されているものを用いることができる。
このような酸発生剤としては、ヨードニウム塩やスルホニウム塩などのオニウム塩系酸発生剤、オキシムスルホネート系酸発生剤；ビスアルキル又はビスアリールスルホニルジアゾメタン類、ポリ（ビススルホニル）ジアゾメタン類などのジアゾメタン系酸発生剤；ニトロベンジルスルホネート系酸発生剤、イミノスルホネート系酸発生剤、ジスルホン系酸発生剤など多種のものが挙げられる。 <Acid generator component (B)>
The resist composition of this embodiment preferably further contains an acid generator component (B) that generates an acid upon exposure.
There are no particular limitations on the component (B), and any of the acid generators that have been proposed so far for use in chemically amplified resist compositions can be used.
Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl- or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.
本実施形態のレジスト組成物は、さらに、露光により酸を発生する酸発生剤成分（Ｂ）を含有することが好ましい。
（Ｂ）成分としては、特に限定されず、これまで化学増幅型レジスト組成物用の酸発生剤として提案されているものを用いることができる。
このような酸発生剤としては、ヨードニウム塩やスルホニウム塩などのオニウム塩系酸発生剤、オキシムスルホネート系酸発生剤；ビスアルキル又はビスアリールスルホニルジアゾメタン類、ポリ（ビススルホニル）ジアゾメタン類などのジアゾメタン系酸発生剤；ニトロベンジルスルホネート系酸発生剤、イミノスルホネート系酸発生剤、ジスルホン系酸発生剤など多種のものが挙げられる。 <Acid generator component (B)>
The resist composition of this embodiment preferably further contains an acid generator component (B) that generates an acid upon exposure.
There are no particular limitations on the component (B), and any of the acid generators that have been proposed so far for use in chemically amplified resist compositions can be used.
Examples of such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl- or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.
オニウム塩系酸発生剤としては、例えば、下記の一般式（ｂ－１）で表される化合物（以下「（ｂ－１）成分」ともいう）、一般式（ｂ－２）で表される化合物（以下「（ｂ－２）成分」ともいう）又は一般式（ｂ－３）で表される化合物（以下「（ｂ－３）成分」ともいう）が挙げられる。
Examples of onium salt acid generators include a compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), a compound represented by general formula (b-2) (hereinafter also referred to as "component (b-2)"), or a compound represented by general formula (b-3) (hereinafter also referred to as "component (b-3)").
｛アニオン部｝
・（ｂ－１）成分におけるアニオン
式（ｂ－１）中、Ｒ１０１は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。 {anion portion}
Anion in Component (b-1) In formula (b-1), R 101 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.
・（ｂ－１）成分におけるアニオン
式（ｂ－１）中、Ｒ１０１は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。 {anion portion}
Anion in Component (b-1) In formula (b-1), R 101 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.
置換基を有してもよい環式基：
該環式基は、環状の炭化水素基であることが好ましく、該環状の炭化水素基は、芳香族炭化水素基であってもよく、脂肪族炭化水素基であってもよい。脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。また、脂肪族炭化水素基は、飽和であることが好ましい。 Optionally substituted cyclic group:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. In addition, the aliphatic hydrocarbon group is preferably saturated.
該環式基は、環状の炭化水素基であることが好ましく、該環状の炭化水素基は、芳香族炭化水素基であってもよく、脂肪族炭化水素基であってもよい。脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。また、脂肪族炭化水素基は、飽和であることが好ましい。 Optionally substituted cyclic group:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. In addition, the aliphatic hydrocarbon group is preferably saturated.
Ｒ１０１における芳香族炭化水素基は、芳香環を有する炭化水素基である。該芳香族炭化水素基の炭素原子数は３～３０であることが好ましく、５～３０であることがより好ましく、５～２０がさらに好ましく、６～１５が特に好ましく、６～１０が最も好ましい。但し、該炭素原子数には、置換基における炭素原子数を含まないものとする。
Ｒ１０１における芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、フルオレン、ナフタレン、アントラセン、フェナントレン、ビフェニル、又はこれらの芳香環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環などが挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
Ｒ１０１における芳香族炭化水素基として具体的には、前記芳香環から水素原子を１つ除いた基（アリール基：例えば、フェニル基、ナフチル基など）、前記芳香環の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基など）等が挙げられる。前記アルキレン基（アリールアルキル基中のアルキル鎖）の炭素原子数は、１～４であることが好ましく、１～２であることがより好ましく、１であることが特に好ましい。 The aromatic hydrocarbon group for R 101 is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.
Specific examples of the aromatic ring contained in the aromatic hydrocarbon group of R 101 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which a part of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group for R 101 include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, etc.), etc. The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
Ｒ１０１における芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、フルオレン、ナフタレン、アントラセン、フェナントレン、ビフェニル、又はこれらの芳香環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環などが挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
Ｒ１０１における芳香族炭化水素基として具体的には、前記芳香環から水素原子を１つ除いた基（アリール基：例えば、フェニル基、ナフチル基など）、前記芳香環の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基など）等が挙げられる。前記アルキレン基（アリールアルキル基中のアルキル鎖）の炭素原子数は、１～４であることが好ましく、１～２であることがより好ましく、１であることが特に好ましい。 The aromatic hydrocarbon group for R 101 is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.
Specific examples of the aromatic ring contained in the aromatic hydrocarbon group of R 101 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which a part of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group for R 101 include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, etc.), etc. The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
Ｒ１０１における環状の脂肪族炭化水素基は、構造中に環を含む脂肪族炭化水素基が挙げられる。
この構造中に環を含む脂肪族炭化水素基としては、脂環式炭化水素基（脂肪族炭化水素環から水素原子を１個除いた基）、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の末端に結合した基、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。
前記脂環式炭化水素基は、炭素原子数が３～２０であることが好ましく、３～１２であることがより好ましい。
前記脂環式炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから１個以上の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから１個以上の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数７～３０のものが好ましい。中でも、該ポリシクロアルカンとしては、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等の架橋環系の多環式骨格を有するポリシクロアルカン；ステロイド骨格を有する環式基等の縮合環系の多環式骨格を有するポリシクロアルカンがより好ましい。 The cyclic aliphatic hydrocarbon group for R 101 includes an aliphatic hydrocarbon group containing a ring in the structure.
Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
この構造中に環を含む脂肪族炭化水素基としては、脂環式炭化水素基（脂肪族炭化水素環から水素原子を１個除いた基）、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の末端に結合した基、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。
前記脂環式炭化水素基は、炭素原子数が３～２０であることが好ましく、３～１２であることがより好ましい。
前記脂環式炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから１個以上の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから１個以上の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数７～３０のものが好ましい。中でも、該ポリシクロアルカンとしては、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等の架橋環系の多環式骨格を有するポリシクロアルカン；ステロイド骨格を有する環式基等の縮合環系の多環式骨格を有するポリシクロアルカンがより好ましい。 The cyclic aliphatic hydrocarbon group for R 101 includes an aliphatic hydrocarbon group containing a ring in the structure.
Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
なかでも、Ｒ１０１における環状の脂肪族炭化水素基としては、モノシクロアルカンまたはポリシクロアルカンから水素原子を１つ以上除いた基が好ましく、ポリシクロアルカンから水素原子を１つ除いた基がより好ましく、アダマンチル基、ノルボルニル基がさらに好ましく、アダマンチル基が特に好ましい。
Among these, the cyclic aliphatic hydrocarbon group for R 101 is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, further preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.
脂環式炭化水素基に結合してもよい、直鎖状の脂肪族炭化水素基は、炭素原子数が１～１０であることが好ましく、１～６がより好ましく、１～４がさらに好ましく、１～３が最も好ましい。直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基［－ＣＨ２－］、エチレン基［－（ＣＨ２）２－］、トリメチレン基［－（ＣＨ２）３－］、テトラメチレン基［－（ＣＨ２）４－］、ペンタメチレン基［－（ＣＨ２）５－］等が挙げられる。
脂環式炭化水素基に結合してもよい、分岐鎖状の脂肪族炭化水素基は、炭素原子数が２～１０であることが好ましく、３～６がより好ましく、３又は４がさらに好ましく、３が最も好ましい。分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－Ｃ（ＣＨ２ＣＨ３）２－ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数１～５の直鎖状のアルキル基が好ましい。 The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], and the like.
The branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
脂環式炭化水素基に結合してもよい、分岐鎖状の脂肪族炭化水素基は、炭素原子数が２～１０であることが好ましく、３～６がより好ましく、３又は４がさらに好ましく、３が最も好ましい。分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－Ｃ（ＣＨ２ＣＨ３）２－ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数１～５の直鎖状のアルキル基が好ましい。 The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], and the like.
The branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
また、Ｒ１０１における環状の炭化水素基は、複素環等のようにヘテロ原子を含んでもよい。具体的には、前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表されるラクトン含有環式基、下記一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－４）でそれぞれ表される－ＳＯ２－含有環式基、その他下記化学式（ｒ－ｈｒ－１）～（ｒ－ｈｒ－１６）でそれぞれ表される複素環式基が挙げられる。式中＊は、式（ｂ－１）中のＹ１０１に結合する結合手を表す。
Furthermore, the cyclic hydrocarbon group in R 101 may contain a heteroatom, such as a heterocycle. Specific examples include the lactone-containing cyclic groups represented by the above general formulae (a2-r-1) to (a2-r-7), the -SO 2 -containing cyclic groups represented by the following general formulae (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the following chemical formulae (r-hr-1) to (r-hr-16). In the formulae, * represents a bond bonded to Y 101 in formula (b-1).
前記一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－２）中、Ｂ”は、酸素原子もしくは硫黄原子を含んでいてもよい炭素原子数１～５のアルキレン基、酸素原子または硫黄原子である。
Ｂ”としては、炭素原子数１～５のアルキレン基または－Ｏ－が好ましく、炭素原子数１～５のアルキレン基がより好ましく、メチレン基がさらに好ましい。 In the general formulae (b5-r-1) and (b5-r-2), B" represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom.
B" is preferably an alkylene group having 1 to 5 carbon atoms or --O--, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.
Ｂ”としては、炭素原子数１～５のアルキレン基または－Ｏ－が好ましく、炭素原子数１～５のアルキレン基がより好ましく、メチレン基がさらに好ましい。 In the general formulae (b5-r-1) and (b5-r-2), B" represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom.
B" is preferably an alkylene group having 1 to 5 carbon atoms or --O--, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.
前記一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－４）中、Ｒｂ’５１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、－ＣＯＯＲ”、－ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり、その中でも、それぞれ独立に水素原子又はシアノ基であることが好ましい。
In the general formulae (b5-r-1) to (b5-r-4), Rb'51 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group, and among these, it is preferable that they each independently represent a hydrogen atom or a cyano group.
下記に一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－４）でそれぞれ表される基の具体例を挙げる。式中の「Ａｃ」は、アセチル基を示す。
Specific examples of groups represented by general formulas (b5-r-1) to (b5-r-4) are listed below. "Ac" in the formulas represents an acetyl group.
Ｒ１０１の環式基における置換基としては、例えば、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、カルボニル基、ニトロ基等が挙げられる。
置換基としてのアルキル基としては、炭素原子数１～５のアルキル基が好ましい。
置換基としてのアルコキシ基としては、炭素原子数１～５のアルコキシ基が好ましく、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基がより好ましく、メトキシ基、エトキシ基が最も好ましい。
置換基としてのハロゲン原子としては、フッ素原子、臭素原子、ヨウ素原子が好ましい。
置換基としてのハロゲン化アルキル基としては、炭素原子数１～５のアルキル基、例えばメチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基等の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。
置換基としてのカルボニル基は、環状の炭化水素基を構成するメチレン基（－ＣＨ２－）を置換する基である。 Examples of the substituent in the cyclic group of R 101 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms.
The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
As the halogen atom as a substituent, a fluorine atom, a bromine atom or an iodine atom is preferred.
Examples of the halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.
The carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) that constitutes a cyclic hydrocarbon group.
置換基としてのアルキル基としては、炭素原子数１～５のアルキル基が好ましい。
置換基としてのアルコキシ基としては、炭素原子数１～５のアルコキシ基が好ましく、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基がより好ましく、メトキシ基、エトキシ基が最も好ましい。
置換基としてのハロゲン原子としては、フッ素原子、臭素原子、ヨウ素原子が好ましい。
置換基としてのハロゲン化アルキル基としては、炭素原子数１～５のアルキル基、例えばメチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基等の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。
置換基としてのカルボニル基は、環状の炭化水素基を構成するメチレン基（－ＣＨ２－）を置換する基である。 Examples of the substituent in the cyclic group of R 101 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms.
The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
As the halogen atom as a substituent, a fluorine atom, a bromine atom or an iodine atom is preferred.
Examples of the halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.
The carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) that constitutes a cyclic hydrocarbon group.
Ｒ１０１における環状の炭化水素基は、脂肪族炭化水素環と芳香環とが縮合した縮合環を含む縮合環式基であってもよい。前記縮合環としては、例えば、架橋環系の多環式骨格を有するポリシクロアルカンに、１個以上の芳香環が縮合したもの等が挙げられる。前記架橋環系ポリシクロアルカンの具体例としては、ビシクロ［２．２．１］ヘプタン（ノルボルナン）、ビシクロ［２．２．２］オクタン等のビシクロアルカンが挙げられる。前記縮合環式としては、ビシクロアルカンに２個又は３個の芳香環が縮合した縮合環を含む基が好ましく、ビシクロ［２．２．２］オクタンに２個又は３個の芳香環が縮合した縮合環を含む基がより好ましい。Ｒ１０１における縮合環式基の具体例としては、下記式（ｒ－ｂｒ－１）～（ｒ－ｂｒ－２）で表されるが挙げられる。式中＊は、式（ｂ－１）中のＹ１０１に結合する結合手を表す。
The cyclic hydrocarbon group in R 101 may be a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused. Examples of the fused ring include a polycycloalkane having a polycyclic skeleton of a bridged ring system to which one or more aromatic rings are fused. Specific examples of the bridged ring polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane, and more preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicyclo[2.2.2]octane. Specific examples of the fused ring group in R 101 include those represented by the following formulae (r-br-1) to (r-br-2). In the formulae, * represents a bond bonded to Y 101 in formula (b-1).
Ｒ１０１における縮合環式基が有していてもよい置換基としては、例えば、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、カルボニル基、ニトロ基、芳香族炭化水素基、脂環式炭化水素基等が挙げられる。
前記縮合環式基の置換基としてのアルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基は、上記Ｒ１０１における環式基の置換基として挙げたものと同様のものが挙げられる。
前記縮合環式基の置換基としての芳香族炭化水素基としては、芳香環から水素原子を１つ除いた基（アリール基：例えば、フェニル基、ナフチル基など）、前記芳香環の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基など）、上記式（ｒ－ｈｒ－１）～（ｒ－ｈｒ－６）でそれぞれ表される複素環式基等が挙げられる。
前記縮合環式基の置換基としての脂環式炭化水素基としては、シクロペンタン、シクロヘキサン等のモノシクロアルカンから１個の水素原子を除いた基；アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等のポリシクロアルカンから１個の水素原子を除いた基；前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表されるラクトン含有環式基；前記一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－４）でそれぞれ表される－ＳＯ２－含有環式基；前記式（ｒ－ｈｒ－７）～（ｒ－ｈｒ－１６）でそれぞれ表される複素環式基等が挙げられる。 Examples of the substituent that the fused cyclic group for R 101 may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.
Examples of the alkyl group, alkoxy group, halogen atom and halogenated alkyl group as the substituent of the condensed cyclic group include the same as those exemplified as the substituent of the cyclic group in R 101 above.
Examples of the aromatic hydrocarbon group as the substituent of the fused ring group include a group in which one hydrogen atom has been removed from an aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), and the heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6), respectively.
Examples of the alicyclic hydrocarbon group as a substituent of the fused cyclic group include groups obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane or cyclohexane; groups obtained by removing one hydrogen atom from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane or tetracyclododecane; lactone-containing cyclic groups represented by each of the general formulae (a2-r-1) to (a2-r-7); —SO 2 -containing cyclic groups represented by each of the general formulae (b5-r-1) to (b5-r-4); and heterocyclic groups represented by each of the formulae (r-hr-7) to (r-hr-16).
前記縮合環式基の置換基としてのアルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基は、上記Ｒ１０１における環式基の置換基として挙げたものと同様のものが挙げられる。
前記縮合環式基の置換基としての芳香族炭化水素基としては、芳香環から水素原子を１つ除いた基（アリール基：例えば、フェニル基、ナフチル基など）、前記芳香環の水素原子の１つがアルキレン基で置換された基（例えば、ベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基など）、上記式（ｒ－ｈｒ－１）～（ｒ－ｈｒ－６）でそれぞれ表される複素環式基等が挙げられる。
前記縮合環式基の置換基としての脂環式炭化水素基としては、シクロペンタン、シクロヘキサン等のモノシクロアルカンから１個の水素原子を除いた基；アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等のポリシクロアルカンから１個の水素原子を除いた基；前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表されるラクトン含有環式基；前記一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－４）でそれぞれ表される－ＳＯ２－含有環式基；前記式（ｒ－ｈｒ－７）～（ｒ－ｈｒ－１６）でそれぞれ表される複素環式基等が挙げられる。 Examples of the substituent that the fused cyclic group for R 101 may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.
Examples of the alkyl group, alkoxy group, halogen atom and halogenated alkyl group as the substituent of the condensed cyclic group include the same as those exemplified as the substituent of the cyclic group in R 101 above.
Examples of the aromatic hydrocarbon group as the substituent of the fused ring group include a group in which one hydrogen atom has been removed from an aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), and the heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6), respectively.
Examples of the alicyclic hydrocarbon group as a substituent of the fused cyclic group include groups obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane or cyclohexane; groups obtained by removing one hydrogen atom from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane or tetracyclododecane; lactone-containing cyclic groups represented by each of the general formulae (a2-r-1) to (a2-r-7); —SO 2 -containing cyclic groups represented by each of the general formulae (b5-r-1) to (b5-r-4); and heterocyclic groups represented by each of the formulae (r-hr-7) to (r-hr-16).
置換基を有してもよい鎖状のアルキル基：
Ｒ１０１の鎖状のアルキル基としては、直鎖状又は分岐鎖状のいずれでもよい。
直鎖状のアルキル基としては、炭素原子数が１～２０であることが好ましく、１～１５であることがより好ましく、１～１０が最も好ましい。
分岐鎖状のアルキル基としては、炭素原子数が３～２０であることが好ましく、３～１５であることがより好ましく、３～１０が最も好ましい。具体的には、例えば、１－メチルエチル基、１－メチルプロピル基、２－メチルプロピル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１－エチルブチル基、２－エチルブチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基などが挙げられる。 A chain alkyl group which may have a substituent:
The chain alkyl group for R 101 may be either a straight chain or a branched chain.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
Ｒ１０１の鎖状のアルキル基としては、直鎖状又は分岐鎖状のいずれでもよい。
直鎖状のアルキル基としては、炭素原子数が１～２０であることが好ましく、１～１５であることがより好ましく、１～１０が最も好ましい。
分岐鎖状のアルキル基としては、炭素原子数が３～２０であることが好ましく、３～１５であることがより好ましく、３～１０が最も好ましい。具体的には、例えば、１－メチルエチル基、１－メチルプロピル基、２－メチルプロピル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１－エチルブチル基、２－エチルブチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基などが挙げられる。 A chain alkyl group which may have a substituent:
The chain alkyl group for R 101 may be either a straight chain or a branched chain.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
置換基を有してもよい鎖状のアルケニル基：
Ｒ１０１の鎖状のアルケニル基としては、直鎖状又は分岐鎖状のいずれでもよく、炭素原子数が２～１０であることが好ましく、２～５がより好ましく、２～４がさらに好ましく、３が特に好ましい。直鎖状のアルケニル基としては、例えば、ビニル基、プロペニル基（アリル基）、ブテニル基などが挙げられる。分岐鎖状のアルケニル基としては、例えば、１－メチルビニル基、２－メチルビニル基、１－メチルプロペニル基、２－メチルプロペニル基などが挙げられる。
鎖状のアルケニル基としては、上記の中でも、直鎖状のアルケニル基が好ましく、ビニル基、プロペニル基がより好ましく、ビニル基が特に好ましい。 A chain alkenyl group which may have a substituent:
The chain alkenyl group for R 101 may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups.
Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.
Ｒ１０１の鎖状のアルケニル基としては、直鎖状又は分岐鎖状のいずれでもよく、炭素原子数が２～１０であることが好ましく、２～５がより好ましく、２～４がさらに好ましく、３が特に好ましい。直鎖状のアルケニル基としては、例えば、ビニル基、プロペニル基（アリル基）、ブテニル基などが挙げられる。分岐鎖状のアルケニル基としては、例えば、１－メチルビニル基、２－メチルビニル基、１－メチルプロペニル基、２－メチルプロペニル基などが挙げられる。
鎖状のアルケニル基としては、上記の中でも、直鎖状のアルケニル基が好ましく、ビニル基、プロペニル基がより好ましく、ビニル基が特に好ましい。 A chain alkenyl group which may have a substituent:
The chain alkenyl group for R 101 may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups.
Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.
Ｒ１０１の鎖状のアルキル基またはアルケニル基における置換基としては、例えば、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、カルボニル基、ニトロ基、アミノ基、上記Ｒ１０１における環式基等が挙げられる。
Examples of the substituent in the chain alkyl or alkenyl group of R 101 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic groups in R 101 above.
上記の中でも、Ｒ１０１は、置換基を有してもよい環式基が好ましく、置換基を有してもよい環状の炭化水素基であることがより好ましい。また、該環式基又は該環状の炭化水素基が置換基を有する場合、置換基としては、ヨウ素原子が好ましい。
環状の炭化水素基として、より具体的には、フェニル基、ナフチル基、ポリシクロアルカンから１個以上の水素原子を除いた基；前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表されるラクトン含有環式基；前記一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－４）でそれぞれ表される－ＳＯ２－含有環式基が好ましく、フェニル基、ポリシクロアルカンから１個以上の水素原子を除いた基がより好ましく、フェニル基、アダマンチル基がさらに好ましい。 Among the above, R 101 is preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent. When the cyclic group or the cyclic hydrocarbon group has a substituent, the substituent is preferably an iodine atom.
More specifically, the cyclic hydrocarbon group is preferably a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane; a lactone-containing cyclic group represented by each of the general formulas (a2-r-1) to (a2-r-7); or an —SO 2 —-containing cyclic group represented by each of the general formulas (b5-r-1) to (b5-r-4), more preferably a phenyl group or a group in which one or more hydrogen atoms have been removed from a polycycloalkane, and even more preferably a phenyl group or an adamantyl group.
環状の炭化水素基として、より具体的には、フェニル基、ナフチル基、ポリシクロアルカンから１個以上の水素原子を除いた基；前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表されるラクトン含有環式基；前記一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－４）でそれぞれ表される－ＳＯ２－含有環式基が好ましく、フェニル基、ポリシクロアルカンから１個以上の水素原子を除いた基がより好ましく、フェニル基、アダマンチル基がさらに好ましい。 Among the above, R 101 is preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent. When the cyclic group or the cyclic hydrocarbon group has a substituent, the substituent is preferably an iodine atom.
More specifically, the cyclic hydrocarbon group is preferably a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane; a lactone-containing cyclic group represented by each of the general formulas (a2-r-1) to (a2-r-7); or an —SO 2 —-containing cyclic group represented by each of the general formulas (b5-r-1) to (b5-r-4), more preferably a phenyl group or a group in which one or more hydrogen atoms have been removed from a polycycloalkane, and even more preferably a phenyl group or an adamantyl group.
式（ｂ－１）中、Ｙ１０１は、単結合または酸素原子を含む２価の連結基である。
Ｙ１０１が酸素原子を含む２価の連結基である場合、該Ｙ１０１は、酸素原子以外の原子を含有してもよい。酸素原子以外の原子としては、例えば炭素原子、水素原子、硫黄原子、窒素原子等が挙げられる。
酸素原子を含む２価の連結基としては、例えば下記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）でそれぞれ表される連結基が挙げられる。なお、下記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）において、上記式（ｂ－１）中のＲ１０１と結合するのが、下記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）中のＶ’１０１である。 In formula (b-1), Y 101 is a single bond or a divalent linking group containing an oxygen atom.
When Y 101 is a divalent linking group containing an oxygen atom, Y 101 may contain an atom other than an oxygen atom. Examples of the atom other than an oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.
Examples of the divalent linking group containing an oxygen atom include linking groups represented by the following general formulae (y-al-1) to (y-al-7), respectively. In the following general formulae (y-al-1) to (y-al-7), what is bonded to R 101 in the above formula (b-1) is V' 101 in the following general formulae (y-al-1) to (y-al-7).
Ｙ１０１が酸素原子を含む２価の連結基である場合、該Ｙ１０１は、酸素原子以外の原子を含有してもよい。酸素原子以外の原子としては、例えば炭素原子、水素原子、硫黄原子、窒素原子等が挙げられる。
酸素原子を含む２価の連結基としては、例えば下記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）でそれぞれ表される連結基が挙げられる。なお、下記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）において、上記式（ｂ－１）中のＲ１０１と結合するのが、下記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）中のＶ’１０１である。 In formula (b-1), Y 101 is a single bond or a divalent linking group containing an oxygen atom.
When Y 101 is a divalent linking group containing an oxygen atom, Y 101 may contain an atom other than an oxygen atom. Examples of the atom other than an oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.
Examples of the divalent linking group containing an oxygen atom include linking groups represented by the following general formulae (y-al-1) to (y-al-7), respectively. In the following general formulae (y-al-1) to (y-al-7), what is bonded to R 101 in the above formula (b-1) is V' 101 in the following general formulae (y-al-1) to (y-al-7).
Ｖ’１０２における２価の飽和炭化水素基は、炭素原子数１～３０のアルキレン基であることが好ましく、炭素原子数１～１０のアルキレン基であることがより好ましく、炭素原子数１～５のアルキレン基であることがさらに好ましい。
The divalent saturated hydrocarbon group for V' 102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.
Ｖ’１０１およびＶ’１０２におけるアルキレン基としては、直鎖状のアルキレン基でもよく分岐鎖状のアルキレン基でもよく、直鎖状のアルキレン基が好ましい。
Ｖ’１０１およびＶ’１０２におけるアルキレン基として、具体的には、メチレン基［－ＣＨ２－］；－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；エチレン基［－ＣＨ２ＣＨ２－］；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－等のアルキルエチレン基；トリメチレン基（ｎ－プロピレン基）［－ＣＨ２ＣＨ２ＣＨ２－］；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；テトラメチレン基［－ＣＨ２ＣＨ２ＣＨ２ＣＨ２－］；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基；ペンタメチレン基［－ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２－］等が挙げられる。
また、Ｖ’１０１又はＶ’１０２における前記アルキレン基における一部のメチレン基が、炭素原子数５～１０の２価の脂肪族環式基で置換されていてもよい。当該脂肪族環式基は、前記式（ａ１－ｒ－１）中のＲａ’３の環状の脂肪族炭化水素基（単環式の脂肪族炭化水素基、多環式の脂肪族炭化水素基）から水素原子をさらに１つ除いた２価の基が好ましく、シクロへキシレン基、１，５－アダマンチレン基または２，６－アダマンチレン基がより好ましい。 The alkylene group in V'101 and V'102 may be a linear alkylene group or a branched alkylene group, with a linear alkylene group being preferred.
Specific examples of the alkylene group in V' 101 and V' 102 include a methylene group [-CH 2 -]; alkylmethylene groups such as -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, and -C(CH 2 CH 3 ) 2 -; an ethylene group [-CH 2 CH 2 -]; alkylethylene groups such as -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, and -CH(CH 2 CH 3 )CH 2 -; a trimethylene group (n-propylene group) [-CH 2 CH 2 CH 2- ] ; alkyl trimethylene groups such as -CH( CH3 ) CH2CH2- and -CH2CH ( CH3 ) CH2- ; tetramethylene group [ -CH2CH2CH2CH2- ]; alkyl tetramethylene groups such as -CH ( CH3 ) CH2CH2CH2- and -CH2CH ( CH3 ) CH2CH2- ; pentamethylene group [ -CH2CH2CH2CH2CH2CH2- ].
In addition, some of the methylene groups in the alkylene group in V'101 or V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra'3 in formula (a1-r-1), and more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.
Ｖ’１０１およびＶ’１０２におけるアルキレン基として、具体的には、メチレン基［－ＣＨ２－］；－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；エチレン基［－ＣＨ２ＣＨ２－］；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－等のアルキルエチレン基；トリメチレン基（ｎ－プロピレン基）［－ＣＨ２ＣＨ２ＣＨ２－］；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；テトラメチレン基［－ＣＨ２ＣＨ２ＣＨ２ＣＨ２－］；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基；ペンタメチレン基［－ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２－］等が挙げられる。
また、Ｖ’１０１又はＶ’１０２における前記アルキレン基における一部のメチレン基が、炭素原子数５～１０の２価の脂肪族環式基で置換されていてもよい。当該脂肪族環式基は、前記式（ａ１－ｒ－１）中のＲａ’３の環状の脂肪族炭化水素基（単環式の脂肪族炭化水素基、多環式の脂肪族炭化水素基）から水素原子をさらに１つ除いた２価の基が好ましく、シクロへキシレン基、１，５－アダマンチレン基または２，６－アダマンチレン基がより好ましい。 The alkylene group in V'101 and V'102 may be a linear alkylene group or a branched alkylene group, with a linear alkylene group being preferred.
Specific examples of the alkylene group in V' 101 and V' 102 include a methylene group [-CH 2 -]; alkylmethylene groups such as -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, and -C(CH 2 CH 3 ) 2 -; an ethylene group [-CH 2 CH 2 -]; alkylethylene groups such as -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, and -CH(CH 2 CH 3 )CH 2 -; a trimethylene group (n-propylene group) [-CH 2 CH 2 CH 2- ] ; alkyl trimethylene groups such as -CH( CH3 ) CH2CH2- and -CH2CH ( CH3 ) CH2- ; tetramethylene group [ -CH2CH2CH2CH2- ]; alkyl tetramethylene groups such as -CH ( CH3 ) CH2CH2CH2- and -CH2CH ( CH3 ) CH2CH2- ; pentamethylene group [ -CH2CH2CH2CH2CH2CH2- ].
In addition, some of the methylene groups in the alkylene group in V'101 or V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra'3 in formula (a1-r-1), and more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.
Ｙ１０１としては、エステル結合を含む２価の連結基、またはエーテル結合を含む２価の連結基が好ましく、上記式（ｙ－ａｌ－１）～（ｙ－ａｌ－５）でそれぞれ表される連結基がより好ましく、上記式（ｙ－ａｌ－１）で表される連結基がさらに好ましい。
Y 101 is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, more preferably a linking group represented by each of the above formulas (y-al-1) to (y-al-5), and still more preferably a linking group represented by the above formula (y-al-1).
式（ｂ－１）中、Ｖ１０１は、単結合、アルキレン基又はフッ素化アルキレン基である。Ｖ１０１におけるアルキレン基、フッ素化アルキレン基は、炭素原子数１～４であることが好ましい。なかでも、Ｖ１０１は、単結合、又は炭素原子数１～４の直鎖状のフッ素化アルキレン基であることが好ましい。
In formula (b-1), V 101 is a single bond, an alkylene group, or a fluorinated alkylene group. The alkylene group or fluorinated alkylene group in V 101 preferably has 1 to 4 carbon atoms. In particular, V 101 is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.
式（ｂ－１）中、Ｒ１０２は、フッ素原子又は炭素原子数１～５のフッ素化アルキル基である。Ｒ１０２は、フッ素原子または炭素原子数１～５のパーフルオロアルキル基であることが好ましく、フッ素原子であることがより好ましい。
In formula (b-1), R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.
前記式（ｂ－１）で表されるアニオン部の具体例としては、例えば、Ｙ１０１が単結合となる場合、トリフルオロメタンスルホネートアニオンやパーフルオロブタンスルホネートアニオン等のフッ素化アルキルスルホネートアニオンが挙げられ；Ｙ１０１が酸素原子を含む２価の連結基である場合、下記式（ａｎ－１）～（ａｎ－３）のいずれかで表されるアニオンが挙げられる。
Specific examples of the anion moiety represented by formula (b-1) include, for example, when Y 101 is a single bond, fluorinated alkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion; and, when Y 101 is a divalent linking group containing an oxygen atom, anions represented by any of the following formulas (an-1) to (an-3) are included.
Ｒ”１０１、Ｒ”１０２およびＲ”１０３の置換基を有してもよい脂肪族環式基は、前記式（ｂ－１）中のＲ１０１における環状の脂肪族炭化水素基として例示した基であることが好ましい。前記置換基としては、前記式（ｂ－１）中のＲ１０１における環状の脂肪族炭化水素基を置換してもよい置換基と同様のものが挙げられる。
The aliphatic cyclic groups which may have a substituent of R" 101 , R" 102 and R" 103 are preferably the groups exemplified as the cyclic aliphatic hydrocarbon group in R 101 in formula (b-1) above. Examples of the substituent include the same as the substituents which may substitute the cyclic aliphatic hydrocarbon group in R 101 in formula (b-1) above.
Ｒ”１０１およびＲ”１０３における置換基を有してもよい芳香族環式基は、前記式（ｂ－１）中のＲ１０１における環状の炭化水素基における芳香族炭化水素基として例示した基であることが好ましい。前記置換基としては、前記式（ｂ－１）中のＲ１０１における該芳香族炭化水素基を置換してもよい置換基と同様のものが挙げられる。
The aromatic cyclic group which may have a substituent in R" 101 and R" 103 is preferably a group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R101 in the above formula (b-1). Examples of the substituent include the same as the substituent which may substitute the aromatic hydrocarbon group in R101 in the above formula (b-1).
Ｒ”１０１における置換基を有してもよい鎖状のアルキル基は、前記式（ｂ－１）中のＲ１０１における鎖状のアルキル基として例示した基であることが好ましい。
Ｒ”１０３における置換基を有してもよい鎖状のアルケニル基は、前記式（ｂ－１）中のＲ１０１における鎖状のアルケニル基として例示した基であることが好ましい。 The chain alkyl group which may have a substituent in R″ 101 is preferably a group exemplified as the chain alkyl group in R 101 in the above formula (b-1).
The chain alkenyl group which may have a substituent in R″ 103 is preferably a group exemplified as the chain alkenyl group in R 101 in the above formula (b-1).
Ｒ”１０３における置換基を有してもよい鎖状のアルケニル基は、前記式（ｂ－１）中のＲ１０１における鎖状のアルケニル基として例示した基であることが好ましい。 The chain alkyl group which may have a substituent in R″ 101 is preferably a group exemplified as the chain alkyl group in R 101 in the above formula (b-1).
The chain alkenyl group which may have a substituent in R″ 103 is preferably a group exemplified as the chain alkenyl group in R 101 in the above formula (b-1).
・（ｂ－２）成分におけるアニオン
式（ｂ－２）中、Ｒ１０４、Ｒ１０５は、それぞれ独立に、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、または置換基を有してもよい鎖状のアルケニル基であり、それぞれ、式（ｂ－１）中のＲ１０１と同様のものが挙げられる。ただし、Ｒ１０４、Ｒ１０５は、相互に結合して環を形成していてもよい。
Ｒ１０４、Ｒ１０５は、置換基を有してもよい鎖状のアルキル基が好ましく、直鎖状若しくは分岐鎖状のアルキル基、又は直鎖状若しくは分岐鎖状のフッ素化アルキル基であることがより好ましい。
該鎖状のアルキル基の炭素原子数は、１～１０であることが好ましく、より好ましくは炭素原子数１～７、さらに好ましくは炭素原子数１～３である。Ｒ１０４、Ｒ１０５の鎖状のアルキル基の炭素原子数は、上記炭素原子数の範囲内において、レジスト用溶剤への溶解性も良好である等の理由により、小さいほど好ましい。また、Ｒ１０４、Ｒ１０５の鎖状のアルキル基においては、フッ素原子で置換されている水素原子の数が多いほど、酸の強度が強くなり、また、２５０ｎｍ以下の高エネルギー光や電子線に対する透明性が向上するため好ましい。前記鎖状のアルキル基中のフッ素原子の割合、すなわちフッ素化率は、好ましくは７０～１００％、さらに好ましくは９０～１００％であり、最も好ましくは、全ての水素原子がフッ素原子で置換されたパーフルオロアルキル基である。
式（ｂ－２）中、Ｖ１０２、Ｖ１０３は、それぞれ独立に、単結合、アルキレン基、またはフッ素化アルキレン基であり、それぞれ、式（ｂ－１）中のＶ１０１と同様のものが挙げられる。
式（ｂ－２）中、Ｌ１０１、Ｌ１０２は、それぞれ独立に単結合又は酸素原子である。 Anion in Component (b-2) In formula (b-2), R 104 and R 105 each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples of these include the same as R 101 in formula (b-1). However, R 104 and R 105 may be bonded to each other to form a ring.
R 104 and R 105 are preferably a chain alkyl group which may have a substituent, and more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group.
The number of carbon atoms in the chain-like alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. The number of carbon atoms in the chain-like alkyl group of R 104 and R 105 is preferably as small as possible within the above range of the number of carbon atoms, for reasons such as good solubility in a resist solvent. In addition, in the chain-like alkyl group of R 104 and R 105 , the more hydrogen atoms substituted with fluorine atoms, the stronger the acid strength becomes, and the more the transparency to high-energy light and electron beams of 250 nm or less is improved, which is preferable. The ratio of fluorine atoms in the chain-like alkyl group, i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
In formula (b-2), V 102 and V 103 each independently represent a single bond, an alkylene group, or a fluorinated alkylene group, and examples of V 101 in formula (b-1) include the same as those described above.
In formula (b-2), L 101 and L 102 each independently represent a single bond or an oxygen atom.
式（ｂ－２）中、Ｒ１０４、Ｒ１０５は、それぞれ独立に、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、または置換基を有してもよい鎖状のアルケニル基であり、それぞれ、式（ｂ－１）中のＲ１０１と同様のものが挙げられる。ただし、Ｒ１０４、Ｒ１０５は、相互に結合して環を形成していてもよい。
Ｒ１０４、Ｒ１０５は、置換基を有してもよい鎖状のアルキル基が好ましく、直鎖状若しくは分岐鎖状のアルキル基、又は直鎖状若しくは分岐鎖状のフッ素化アルキル基であることがより好ましい。
該鎖状のアルキル基の炭素原子数は、１～１０であることが好ましく、より好ましくは炭素原子数１～７、さらに好ましくは炭素原子数１～３である。Ｒ１０４、Ｒ１０５の鎖状のアルキル基の炭素原子数は、上記炭素原子数の範囲内において、レジスト用溶剤への溶解性も良好である等の理由により、小さいほど好ましい。また、Ｒ１０４、Ｒ１０５の鎖状のアルキル基においては、フッ素原子で置換されている水素原子の数が多いほど、酸の強度が強くなり、また、２５０ｎｍ以下の高エネルギー光や電子線に対する透明性が向上するため好ましい。前記鎖状のアルキル基中のフッ素原子の割合、すなわちフッ素化率は、好ましくは７０～１００％、さらに好ましくは９０～１００％であり、最も好ましくは、全ての水素原子がフッ素原子で置換されたパーフルオロアルキル基である。
式（ｂ－２）中、Ｖ１０２、Ｖ１０３は、それぞれ独立に、単結合、アルキレン基、またはフッ素化アルキレン基であり、それぞれ、式（ｂ－１）中のＶ１０１と同様のものが挙げられる。
式（ｂ－２）中、Ｌ１０１、Ｌ１０２は、それぞれ独立に単結合又は酸素原子である。 Anion in Component (b-2) In formula (b-2), R 104 and R 105 each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples of these include the same as R 101 in formula (b-1). However, R 104 and R 105 may be bonded to each other to form a ring.
R 104 and R 105 are preferably a chain alkyl group which may have a substituent, and more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group.
The number of carbon atoms in the chain-like alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. The number of carbon atoms in the chain-like alkyl group of R 104 and R 105 is preferably as small as possible within the above range of the number of carbon atoms, for reasons such as good solubility in a resist solvent. In addition, in the chain-like alkyl group of R 104 and R 105 , the more hydrogen atoms substituted with fluorine atoms, the stronger the acid strength becomes, and the more the transparency to high-energy light and electron beams of 250 nm or less is improved, which is preferable. The ratio of fluorine atoms in the chain-like alkyl group, i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
In formula (b-2), V 102 and V 103 each independently represent a single bond, an alkylene group, or a fluorinated alkylene group, and examples of V 101 in formula (b-1) include the same as those described above.
In formula (b-2), L 101 and L 102 each independently represent a single bond or an oxygen atom.
・（ｂ－３）成分におけるアニオン
式（ｂ－３）中、Ｒ１０６～Ｒ１０８は、それぞれ独立に、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、それぞれ、式（ｂ－１）中のＲ１０１と同様のものが挙げられる。
式（ｂ－３）中、Ｌ１０３～Ｌ１０５は、それぞれ独立に、単結合、－ＣＯ－又は－ＳＯ２－である。 Anion in Component (b-3) In formula (b- 3 ), R to R each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples of these include the same as R 101 in formula (b-1).
In formula (b-3), L 103 to L 105 each independently represent a single bond, —CO— or —SO 2 —.
式（ｂ－３）中、Ｒ１０６～Ｒ１０８は、それぞれ独立に、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、それぞれ、式（ｂ－１）中のＲ１０１と同様のものが挙げられる。
式（ｂ－３）中、Ｌ１０３～Ｌ１０５は、それぞれ独立に、単結合、－ＣＯ－又は－ＳＯ２－である。 Anion in Component (b-3) In formula (b- 3 ), R to R each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples of these include the same as R 101 in formula (b-1).
In formula (b-3), L 103 to L 105 each independently represent a single bond, —CO— or —SO 2 —.
上記の中でも、（Ｂ）成分のアニオン部としては、（ｂ－１）成分におけるアニオンが好ましい。
Among the above, the anion in component (b-1) is preferred as the anion portion of component (B).
｛カチオン部｝
前記の式（ｂ－１）、式（ｂ－２）、式（ｂ－３）中、Ｍ’ｍ＋は、ｍ価のオニウムカチオンを表す。この中でも、スルホニウムカチオン、ヨードニウムカチオンが好ましい。
ｍは、１以上の整数である。 {Cation part}
In the above formulae (b-1), (b-2) and (b-3), M'm+ represents an m-valent onium cation, of which sulfonium cation and iodonium cation are preferred.
m is an integer of 1 or more.
前記の式（ｂ－１）、式（ｂ－２）、式（ｂ－３）中、Ｍ’ｍ＋は、ｍ価のオニウムカチオンを表す。この中でも、スルホニウムカチオン、ヨードニウムカチオンが好ましい。
ｍは、１以上の整数である。 {Cation part}
In the above formulae (b-1), (b-2) and (b-3), M'm+ represents an m-valent onium cation, of which sulfonium cation and iodonium cation are preferred.
m is an integer of 1 or more.
好ましいカチオン部（（Ｍ’ｍ＋）１／ｍ）としては、下記の一般式（ｃａ－１）～（ｃａ－３）でそれぞれ表される有機カチオンが挙げられる。
Preferred cationic moieties ((M'm + ) 1/m ) include organic cations represented by the following general formulas (ca-1) to (ca-3).
上記の一般式（ｃａ－１）～（ｃａ－３）中、Ｒ２０１～Ｒ２０７におけるアリール基としては、炭素原子数６～２０の無置換のアリール基が挙げられ、フェニル基、ナフチル基が好ましい。
Ｒ２０１～Ｒ２０７におけるアルキル基としては、鎖状又は環状のアルキル基であって、炭素原子数１～３０のものが好ましい。
Ｒ２０１～Ｒ２０７におけるアルケニル基としては、炭素原子数が２～１０であることが好ましい。
Ｒ２０１～Ｒ２０７、およびＲ２１０が有していてもよい置換基としては、例えば、アルキル基、ハロゲン原子、ハロゲン化アルキル基、カルボニル基、シアノ基、アミノ基、アリール基、下記の一般式（ｃａ－ｒ－１）～（ｃａ－ｒ－７）でそれぞれ表される基等が挙げられる。 In the above general formulae (ca-1) to (ca-3), the aryl group for R 201 to R 207 can be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferable.
The alkyl group for R 201 to R 207 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R 201 to R 207 preferably has 2 to 10 carbon atoms.
Examples of the substituent that R 201 to R 207 and R 210 may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulas (ca-r-1) to (ca-r-7), respectively.
Ｒ２０１～Ｒ２０７におけるアルキル基としては、鎖状又は環状のアルキル基であって、炭素原子数１～３０のものが好ましい。
Ｒ２０１～Ｒ２０７におけるアルケニル基としては、炭素原子数が２～１０であることが好ましい。
Ｒ２０１～Ｒ２０７、およびＲ２１０が有していてもよい置換基としては、例えば、アルキル基、ハロゲン原子、ハロゲン化アルキル基、カルボニル基、シアノ基、アミノ基、アリール基、下記の一般式（ｃａ－ｒ－１）～（ｃａ－ｒ－７）でそれぞれ表される基等が挙げられる。 In the above general formulae (ca-1) to (ca-3), the aryl group for R 201 to R 207 can be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferable.
The alkyl group for R 201 to R 207 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R 201 to R 207 preferably has 2 to 10 carbon atoms.
Examples of the substituent that R 201 to R 207 and R 210 may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulas (ca-r-1) to (ca-r-7), respectively.
置換基を有してもよい環式基：
該環式基は、環状の炭化水素基であることが好ましく、該環状の炭化水素基は、芳香族炭化水素基であってもよく、脂肪族炭化水素基であってもよい。脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。また、脂肪族炭化水素基は、飽和であってもよく、不飽和であってもよく、通常は飽和であることが好ましい。 Optionally substituted cyclic group:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
該環式基は、環状の炭化水素基であることが好ましく、該環状の炭化水素基は、芳香族炭化水素基であってもよく、脂肪族炭化水素基であってもよい。脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。また、脂肪族炭化水素基は、飽和であってもよく、不飽和であってもよく、通常は飽和であることが好ましい。 Optionally substituted cyclic group:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Ｒ’２０１における芳香族炭化水素基は、芳香環を有する炭化水素基である。該芳香族炭化水素基の炭素原子数は３～３０であることが好ましく、炭素原子数５～３０がより好ましく、炭素原子数５～２０がさらに好ましく、炭素原子数６～１５が特に好ましく、炭素原子数６～１０が最も好ましい。ただし、該炭素原子数には、置換基における炭素原子数を含まないものとする。
Ｒ’２０１における芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、フルオレン、ナフタレン、アントラセン、フェナントレン、ビフェニル、又はこれらの芳香環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環などが挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
Ｒ’２０１における芳香族炭化水素基として具体的には、前記芳香環から水素原子を１つ除いた基（アリール基：例えばフェニル基、ナフチル基など）、前記芳香環の水素原子の１つがアルキレン基で置換された基（例えばベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基など）等が挙げられる。前記アルキレン基（アリールアルキル基中のアルキル鎖）の炭素原子数は、１～４であることが好ましく、炭素原子数１～２がより好ましく、炭素原子数１が特に好ましい。 The aromatic hydrocarbon group in R'201 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, even more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.
Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in R'201 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group for R'201 include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
Ｒ’２０１における芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、フルオレン、ナフタレン、アントラセン、フェナントレン、ビフェニル、又はこれらの芳香環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環などが挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
Ｒ’２０１における芳香族炭化水素基として具体的には、前記芳香環から水素原子を１つ除いた基（アリール基：例えばフェニル基、ナフチル基など）、前記芳香環の水素原子の１つがアルキレン基で置換された基（例えばベンジル基、フェネチル基、１－ナフチルメチル基、２－ナフチルメチル基、１－ナフチルエチル基、２－ナフチルエチル基等のアリールアルキル基など）等が挙げられる。前記アルキレン基（アリールアルキル基中のアルキル鎖）の炭素原子数は、１～４であることが好ましく、炭素原子数１～２がより好ましく、炭素原子数１が特に好ましい。 The aromatic hydrocarbon group in R'201 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, even more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.
Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in R'201 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group for R'201 include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
Ｒ’２０１における環状の脂肪族炭化水素基は、構造中に環を含む脂肪族炭化水素基が挙げられる。
この構造中に環を含む脂肪族炭化水素基としては、脂環式炭化水素基（脂肪族炭化水素環から水素原子を１個除いた基）、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の末端に結合した基、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。
前記脂環式炭化水素基は、炭素原子数が３～２０であることが好ましく、３～１２であることがより好ましい。
前記脂環式炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから１個以上の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから１個以上の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数７～３０のものが好ましい。中でも、該ポリシクロアルカンとしては、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等の架橋環系の多環式骨格を有するポリシクロアルカン；ステロイド骨格を有する環式基等の縮合環系の多環式骨格を有するポリシクロアルカンがより好ましい。 The cyclic aliphatic hydrocarbon group for R'201 includes an aliphatic hydrocarbon group containing a ring in the structure.
Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
この構造中に環を含む脂肪族炭化水素基としては、脂環式炭化水素基（脂肪族炭化水素環から水素原子を１個除いた基）、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の末端に結合した基、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。
前記脂環式炭化水素基は、炭素原子数が３～２０であることが好ましく、３～１２であることがより好ましい。
前記脂環式炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから１個以上の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数３～６のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから１個以上の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数７～３０のものが好ましい。中でも、該ポリシクロアルカンとしては、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等の架橋環系の多環式骨格を有するポリシクロアルカン；ステロイド骨格を有する環式基等の縮合環系の多環式骨格を有するポリシクロアルカンがより好ましい。 The cyclic aliphatic hydrocarbon group for R'201 includes an aliphatic hydrocarbon group containing a ring in the structure.
Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
なかでも、Ｒ’２０１における環状の脂肪族炭化水素基としては、モノシクロアルカンまたはポリシクロアルカンから水素原子を１つ以上除いた基が好ましく、ポリシクロアルカンから水素原子を１つ除いた基がより好ましく、アダマンチル基、ノルボルニル基が特に好ましく、アダマンチル基が最も好ましい。
Among these, the cyclic aliphatic hydrocarbon group for R'201 is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.
脂環式炭化水素基に結合してもよい、直鎖状または分岐鎖状の脂肪族炭化水素基は、炭素原子数が１～１０であることが好ましく、炭素原子数１～６がより好ましく、炭素原子数１～４がさらに好ましく、炭素原子数１～３が特に好ましい。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基［－ＣＨ２－］、エチレン基［－（ＣＨ２）２－］、トリメチレン基［－（ＣＨ２）３－］、テトラメチレン基［－（ＣＨ２）４－］、ペンタメチレン基［－（ＣＨ２）５－］等が挙げられる。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－Ｃ（ＣＨ２ＣＨ３）２－ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数１～５の直鎖状のアルキル基が好ましい。 The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基［－ＣＨ２－］、エチレン基［－（ＣＨ２）２－］、トリメチレン基［－（ＣＨ２）３－］、テトラメチレン基［－（ＣＨ２）４－］、ペンタメチレン基［－（ＣＨ２）５－］等が挙げられる。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ３）（ＣＨ２ＣＨ２ＣＨ３）－、－Ｃ（ＣＨ２ＣＨ３）２－等のアルキルメチレン基；－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２ＣＨ２－、－ＣＨ（ＣＨ２ＣＨ３）ＣＨ２－、－Ｃ（ＣＨ２ＣＨ３）２－ＣＨ２－等のアルキルエチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－等のアルキルトリメチレン基；－ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２－等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数１～５の直鎖状のアルキル基が好ましい。 The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkylmethylene groups such as -CH( CH3 )-, -CH( CH2CH3 )-, -C( CH3 ) 2- , -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3 ) 2- ; alkylethylene groups such as -CH ( CH3 ) CH2- , -CH( CH3 )CH( CH3 ) - , -C( CH3 ) 2CH2- , -CH ( CH2CH3 ) CH2- , and -C( CH2CH3 ) 2 - CH2- ; and alkyl alkylene groups such as alkyl trimethylene groups such as -CH (CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 -, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
また、Ｒ’２０１における環状の炭化水素基は、複素環等のようにヘテロ原子を含んでもよい。具体的には、前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表されるラクトン含有環式基、前記一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－４）でそれぞれ表される－ＳＯ２－含有環式基、その他上記の化学式（ｒ－ｈｒ－１）～（ｒ－ｈｒ－１６）でそれぞれ表される複素環式基が挙げられる。
Furthermore, the cyclic hydrocarbon group in R'201 may contain a heteroatom, such as a heterocycle. Specific examples include the lactone-containing cyclic groups represented by the general formulae (a2-r-1) to (a2-r-7) above, the -SO 2 -containing cyclic groups represented by the general formulae (b5-r-1) to (b5-r-4) above, and the heterocyclic groups represented by the chemical formulae (r-hr-1) to (r-hr-16) above.
Ｒ’２０１の環式基における置換基としては、たとえば、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、カルボニル基、ニトロ基等が挙げられる。
置換基としてのアルキル基としては、炭素原子数１～５のアルキル基が好ましく、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基が最も好ましい。
置換基としてのアルコキシ基としては、炭素原子数１～５のアルコキシ基が好ましく、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基がより好ましく、メトキシ基、エトキシ基が最も好ましい。
置換基としてのハロゲン原子としては、フッ素原子が好ましい。
置換基としてのハロゲン化アルキル基としては、炭素原子数１～５のアルキル基、たとえばメチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基等の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。
置換基としてのカルボニル基は、環状の炭化水素基を構成するメチレン基（－ＣＨ２－）を置換する基である。 Examples of the substituent in the cyclic group of R'201 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
As the halogen atom as a substituent, a fluorine atom is preferred.
Examples of the halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.
The carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) that constitutes a cyclic hydrocarbon group.
置換基としてのアルキル基としては、炭素原子数１～５のアルキル基が好ましく、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基が最も好ましい。
置換基としてのアルコキシ基としては、炭素原子数１～５のアルコキシ基が好ましく、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基がより好ましく、メトキシ基、エトキシ基が最も好ましい。
置換基としてのハロゲン原子としては、フッ素原子が好ましい。
置換基としてのハロゲン化アルキル基としては、炭素原子数１～５のアルキル基、たとえばメチル基、エチル基、プロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基等の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。
置換基としてのカルボニル基は、環状の炭化水素基を構成するメチレン基（－ＣＨ２－）を置換する基である。 Examples of the substituent in the cyclic group of R'201 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
As the halogen atom as a substituent, a fluorine atom is preferred.
Examples of the halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.
The carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) that constitutes a cyclic hydrocarbon group.
置換基を有してもよい鎖状のアルキル基：
Ｒ’２０１の鎖状のアルキル基としては、直鎖状又は分岐鎖状のいずれでもよい。
直鎖状のアルキル基としては、炭素原子数が１～２０であることが好ましく、炭素原子数１～１５であることがより好ましく、炭素原子数１～１０が最も好ましい。
分岐鎖状のアルキル基としては、炭素原子数が３～２０であることが好ましく、炭素原子数３～１５であることがより好ましく、炭素原子数３～１０が最も好ましい。具体的には、例えば、１－メチルエチル基、１－メチルプロピル基、２－メチルプロピル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１－エチルブチル基、２－エチルブチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基などが挙げられる。 A chain alkyl group which may have a substituent:
The chain alkyl group of R'201 may be either linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and most preferably has 1 to 10 carbon atoms.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 15 carbon atoms, and most preferably has 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
Ｒ’２０１の鎖状のアルキル基としては、直鎖状又は分岐鎖状のいずれでもよい。
直鎖状のアルキル基としては、炭素原子数が１～２０であることが好ましく、炭素原子数１～１５であることがより好ましく、炭素原子数１～１０が最も好ましい。
分岐鎖状のアルキル基としては、炭素原子数が３～２０であることが好ましく、炭素原子数３～１５であることがより好ましく、炭素原子数３～１０が最も好ましい。具体的には、例えば、１－メチルエチル基、１－メチルプロピル基、２－メチルプロピル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１－エチルブチル基、２－エチルブチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基などが挙げられる。 A chain alkyl group which may have a substituent:
The chain alkyl group of R'201 may be either linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and most preferably has 1 to 10 carbon atoms.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 15 carbon atoms, and most preferably has 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
置換基を有してもよい鎖状のアルケニル基：
Ｒ’２０１の鎖状のアルケニル基としては、直鎖状又は分岐鎖状のいずれでもよく、炭素原子数が２～１０であることが好ましく、炭素原子数２～５がより好ましく、炭素原子数２～４がさらに好ましく、炭素原子数３が特に好ましい。直鎖状のアルケニル基としては、例えば、ビニル基、プロペニル基（アリル基）、ブテニル基などが挙げられる。分岐鎖状のアルケニル基としては、例えば、１－メチルビニル基、２－メチルビニル基、１－メチルプロペニル基、２－メチルプロペニル基などが挙げられる。
鎖状のアルケニル基としては、上記の中でも、直鎖状のアルケニル基が好ましく、ビニル基、プロペニル基がより好ましく、ビニル基が特に好ましい。 A chain alkenyl group which may have a substituent:
The chain alkenyl group of R'201 may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups.
Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.
Ｒ’２０１の鎖状のアルケニル基としては、直鎖状又は分岐鎖状のいずれでもよく、炭素原子数が２～１０であることが好ましく、炭素原子数２～５がより好ましく、炭素原子数２～４がさらに好ましく、炭素原子数３が特に好ましい。直鎖状のアルケニル基としては、例えば、ビニル基、プロペニル基（アリル基）、ブテニル基などが挙げられる。分岐鎖状のアルケニル基としては、例えば、１－メチルビニル基、２－メチルビニル基、１－メチルプロペニル基、２－メチルプロペニル基などが挙げられる。
鎖状のアルケニル基としては、上記の中でも、直鎖状のアルケニル基が好ましく、ビニル基、プロペニル基がより好ましく、ビニル基が特に好ましい。 A chain alkenyl group which may have a substituent:
The chain alkenyl group of R'201 may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butenyl groups. Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups.
Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.
Ｒ’２０１の鎖状のアルキル基またはアルケニル基における置換基としては、たとえば、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、カルボニル基、ニトロ基、アミノ基、上記Ｒ’２０１における環式基等が挙げられる。
Examples of the substituent in the chain alkyl or alkenyl group of R'201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic groups in R'201 described above.
Ｒ’２０１の置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基は、上述したものの他、置換基を有してもよい環式基又は置換基を有してもよい鎖状のアルキル基として、上述の式（ａ１－ｒ－２）で表される酸解離性基と同様のものも挙げられる。
The optionally substituted cyclic group, optionally substituted chain alkyl group, or optionally substituted chain alkenyl group for R'201 is as described above, and examples of the optionally substituted cyclic group or optionally substituted chain alkyl group include the same as the acid dissociable group represented by formula (a1-r-2) above.
なかでも、Ｒ’２０１は、置換基を有してもよい環式基が好ましく、置換基を有してもよい環状の炭化水素基であることがより好ましい。より具体的には、例えば、フェニル基、ナフチル基、ポリシクロアルカンから１個以上の水素原子を除いた基；前記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表されるラクトン含有環式基；前記一般式（ｂ５－ｒ－１）～（ｂ５－ｒ－４）でそれぞれ表される－ＳＯ２－含有環式基などが好ましい。
Among these, R'201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane, a lactone-containing cyclic group represented by each of the general formulae (a2-r-1) to (a2-r-7), an -SO 2 --containing cyclic group represented by each of the general formulae (b5-r-1) to (b5-r-4), etc. are preferred.
上記の一般式（ｃａ－１）～（ｃａ－３）中、Ｒ２０１～Ｒ２０３、Ｒ２０６～Ｒ２０７は、相互に結合して式中のイオウ原子と共に環を形成する場合、硫黄原子、酸素原子、窒素原子等のヘテロ原子や、カルボニル基、－ＳＯ－、－ＳＯ２－、－ＳＯ３－、－ＣＯＯ－、－ＣＯＮＨ－または－Ｎ（ＲＮ）－（該ＲＮは炭素原子数１～５のアルキル基である。）等の官能基を介して結合してもよい。形成される環としては、式中のイオウ原子をその環骨格に含む１つの環が、イオウ原子を含めて、３～１０員環であることが好ましく、５～７員環であることが特に好ましい。形成される環の具体例としては、例えばチオフェン環、チアゾール環、ベンゾチオフェン環、ジベンゾチオフェン環、９Ｈ－チオキサンテン環、チオキサントン環、チアントレン環、フェノキサチイン環、テトラヒドロチオフェニウム環、テトラヒドロチオピラニウム環等が挙げられる。
In the above general formulae (ca-1) to (ca-3), when R 201 to R 203 and R 206 to R 207 are bonded to each other to form a ring together with the sulfur atom in the formula, they may be bonded via a heteroatom such as a sulfur atom, an oxygen atom or a nitrogen atom, or a functional group such as a carbonyl group, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )- (wherein R N is an alkyl group having 1 to 5 carbon atoms). As for the ring formed, one ring containing the sulfur atom in the ring skeleton in the formula is preferably a 3- to 10-membered ring including the sulfur atom, and particularly preferably a 5- to 7-membered ring. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.
Ｒ２０８～Ｒ２０９は、それぞれ独立に、水素原子または炭素原子数１～５のアルキル基を表し、水素原子又は炭素原子数１～３のアルキル基が好ましく、アルキル基となる場合、相互に結合して環を形成してもよい。
R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they represent an alkyl group, they may be bonded to each other to form a ring.
Ｒ２１０は、置換基を有してもよいアリール基、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、又は置換基を有してもよい－ＳＯ２－含有環式基である。
Ｒ２１０におけるアリール基としては、炭素原子数６～２０の無置換のアリール基が挙げられ、フェニル基、ナフチル基が好ましい。
Ｒ２１０におけるアルキル基としては、鎖状又は環状のアルキル基であって、炭素原子数１～３０のものが好ましい。
Ｒ２１０におけるアルケニル基としては、炭素原子数が２～１０であることが好ましい。
Ｒ２１０における、置換基を有してもよい－ＳＯ２－含有環式基としては、「－ＳＯ２－含有多環式基」が好ましく、上記一般式（ｂ５－ｒ－１）で表される基がより好ましい。 R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an --SO 2 -- containing cyclic group which may have a substituent.
The aryl group for R 210 includes unsubstituted aryl groups having 6 to 20 carbon atoms, and is preferably a phenyl group or a naphthyl group.
The alkyl group for R 210 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R 210 preferably has 2 to 10 carbon atoms.
As the -SO 2 -containing cyclic group for R 210 which may have a substituent, a "-SO 2 -containing polycyclic group" is preferable, and a group represented by the above general formula (b5-r-1) is more preferable.
Ｒ２１０におけるアリール基としては、炭素原子数６～２０の無置換のアリール基が挙げられ、フェニル基、ナフチル基が好ましい。
Ｒ２１０におけるアルキル基としては、鎖状又は環状のアルキル基であって、炭素原子数１～３０のものが好ましい。
Ｒ２１０におけるアルケニル基としては、炭素原子数が２～１０であることが好ましい。
Ｒ２１０における、置換基を有してもよい－ＳＯ２－含有環式基としては、「－ＳＯ２－含有多環式基」が好ましく、上記一般式（ｂ５－ｒ－１）で表される基がより好ましい。 R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an --SO 2 -- containing cyclic group which may have a substituent.
The aryl group for R 210 includes unsubstituted aryl groups having 6 to 20 carbon atoms, and is preferably a phenyl group or a naphthyl group.
The alkyl group for R 210 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R 210 preferably has 2 to 10 carbon atoms.
As the -SO 2 -containing cyclic group for R 210 which may have a substituent, a "-SO 2 -containing polycyclic group" is preferable, and a group represented by the above general formula (b5-r-1) is more preferable.
前記式（ｃａ－１）で表されるカチオンの具体例を以下に示す。
Specific examples of the cations represented by formula (ca-1) are shown below.
前記式（ｃａ－１）で表される好適なカチオンとして具体的には、下記の化学式（ｃａ－１－１）～（ｃａ－１－７０）でそれぞれ表されるカチオンが挙げられる。
Specific examples of suitable cations represented by the formula (ca-1) include the cations represented by the following chemical formulas (ca-1-1) to (ca-1-70).
前記式（ｃａ－２）で表される好適なカチオンとして具体的には、ジフェニルヨードニウムカチオン、ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムカチオン等が挙げられる。
Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, etc.
前記式（ｃａ－３）で表される好適なカチオンとして具体的には、下記式（ｃａ－３－１）～（ｃａ－３－６）でそれぞれ表されるカチオンが挙げられる。
Specific examples of suitable cations represented by the formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).
本実施形態のレジスト組成物において、（Ｂ）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。
レジスト組成物が（Ｂ）成分を含有する場合、レジスト組成物中、（Ｂ）成分の含有量は、（Ａ１）成分１００質量部に対して、５～４０質量部が好ましく、１０～４０質量部がより好ましく、１０～３０質量部がさらに好ましい。
（Ｂ）成分の含有量が、前記の好ましい範囲の下限値以上であると、レジストパターン形成において、感度、ＣＤＵ、解像性能、ＬＷＲ（ラインワイズラフネス）低減性等のリソグラフィー特性がより向上する。一方、好ましい範囲の上限値以下であると、レジスト組成物の各成分を有機溶剤に溶解した際、均一な溶液が得られやすく、レジスト組成物としての保存安定性がより高まる。 In the resist composition of this embodiment, the component (B) may use either a single type, or a combination of two or more types.
When the resist composition contains the component (B), the amount of the component (B) in the resist composition is preferably 5 to 40 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the component (A1).
When the content of component (B) is at least the lower limit of the aforementioned preferred range, lithography properties such as sensitivity, CDU, resolution performance, and LWR (line width roughness) reduction are further improved during resist pattern formation. On the other hand, when the content is no more than the upper limit of the preferred range, a homogeneous solution is more easily obtained when the components of the resist composition are dissolved in an organic solvent, and the storage stability of the resist composition is further improved.
レジスト組成物が（Ｂ）成分を含有する場合、レジスト組成物中、（Ｂ）成分の含有量は、（Ａ１）成分１００質量部に対して、５～４０質量部が好ましく、１０～４０質量部がより好ましく、１０～３０質量部がさらに好ましい。
（Ｂ）成分の含有量が、前記の好ましい範囲の下限値以上であると、レジストパターン形成において、感度、ＣＤＵ、解像性能、ＬＷＲ（ラインワイズラフネス）低減性等のリソグラフィー特性がより向上する。一方、好ましい範囲の上限値以下であると、レジスト組成物の各成分を有機溶剤に溶解した際、均一な溶液が得られやすく、レジスト組成物としての保存安定性がより高まる。 In the resist composition of this embodiment, the component (B) may use either a single type, or a combination of two or more types.
When the resist composition contains the component (B), the amount of the component (B) in the resist composition is preferably 5 to 40 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the component (A1).
When the content of component (B) is at least the lower limit of the aforementioned preferred range, lithography properties such as sensitivity, CDU, resolution performance, and LWR (line width roughness) reduction are further improved during resist pattern formation. On the other hand, when the content is no more than the upper limit of the preferred range, a homogeneous solution is more easily obtained when the components of the resist composition are dissolved in an organic solvent, and the storage stability of the resist composition is further improved.
≪塩基成分（Ｄ）≫
本実施形態のレジスト組成物は、さらに、露光により発生する酸をトラップ（すなわち、酸の拡散を制御）する塩基成分（以下「（Ｄ）成分」ともいう）を含有することが好ましい。（Ｄ）成分は、レジスト組成物において露光により発生する酸をトラップするクエンチャー（酸拡散制御剤）として作用するものである。
（Ｄ）成分としては、例えば、露光により分解して酸拡散制御性を失う光崩壊性塩基（Ｄ１）（以下「（Ｄ１）成分」という。）、該（Ｄ１）成分に該当しない含窒素有機化合物（Ｄ２）（以下「（Ｄ２）成分」という。）等が挙げられる。これらの中でも、ラフネス低減性を高められやすいことから、光崩壊性塩基（（Ｄ１）成分）が好ましい。また、（Ｄ１）成分を含有させることで、高感度化、塗布欠陥の発生の抑制の特性をいずれも高めやすくなる。 <<Base component (D)>>
The resist composition of this embodiment preferably further contains a base component (hereinafter also referred to as "component (D)") that traps acid generated upon exposure (i.e., controls the diffusion of acid). The component (D) acts as a quencher (acid diffusion controller) that traps acid generated in the resist composition upon exposure.
Examples of the component (D) include a photodegradable base (D1) (hereinafter referred to as "component (D1)") that decomposes upon exposure to light and loses its acid diffusion controllability, and a nitrogen-containing organic compound (D2) (hereinafter referred to as "component (D2)") that does not fall under the category of component (D1). Among these, the photodegradable base (component (D1)) is preferred because it is likely to enhance the roughness reduction properties. In addition, by including component (D1), it is possible to easily enhance both the properties of increasing sensitivity and suppressing the occurrence of coating defects.
本実施形態のレジスト組成物は、さらに、露光により発生する酸をトラップ（すなわち、酸の拡散を制御）する塩基成分（以下「（Ｄ）成分」ともいう）を含有することが好ましい。（Ｄ）成分は、レジスト組成物において露光により発生する酸をトラップするクエンチャー（酸拡散制御剤）として作用するものである。
（Ｄ）成分としては、例えば、露光により分解して酸拡散制御性を失う光崩壊性塩基（Ｄ１）（以下「（Ｄ１）成分」という。）、該（Ｄ１）成分に該当しない含窒素有機化合物（Ｄ２）（以下「（Ｄ２）成分」という。）等が挙げられる。これらの中でも、ラフネス低減性を高められやすいことから、光崩壊性塩基（（Ｄ１）成分）が好ましい。また、（Ｄ１）成分を含有させることで、高感度化、塗布欠陥の発生の抑制の特性をいずれも高めやすくなる。 <<Base component (D)>>
The resist composition of this embodiment preferably further contains a base component (hereinafter also referred to as "component (D)") that traps acid generated upon exposure (i.e., controls the diffusion of acid). The component (D) acts as a quencher (acid diffusion controller) that traps acid generated in the resist composition upon exposure.
Examples of the component (D) include a photodegradable base (D1) (hereinafter referred to as "component (D1)") that decomposes upon exposure to light and loses its acid diffusion controllability, and a nitrogen-containing organic compound (D2) (hereinafter referred to as "component (D2)") that does not fall under the category of component (D1). Among these, the photodegradable base (component (D1)) is preferred because it is likely to enhance the roughness reduction properties. In addition, by including component (D1), it is possible to easily enhance both the properties of increasing sensitivity and suppressing the occurrence of coating defects.
・（Ｄ１）成分について
（Ｄ１）成分を含有するレジスト組成物とすることで、レジストパターンを形成する際に、レジスト膜の露光部と未露光部とのコントラストをより向上させることができる。
（Ｄ１）成分としては、露光により分解して酸拡散制御性を失うものであれば特に限定されず、下記一般式（ｄ１－１）で表される化合物（以下「（ｄ１－１）成分」という。）、下記一般式（ｄ１－２）で表される化合物（以下「（ｄ１－２）成分」という。）及び下記一般式（ｄ１－３）で表される化合物（以下「（ｄ１－３）成分」という。）からなる群より選ばれる１種以上の化合物が好ましい。
（ｄ１－１）～（ｄ１－３）成分は、レジスト膜の露光部においては分解して酸拡散制御性（塩基性）を失うためクエンチャーとして作用せず、レジスト膜の未露光部においてクエンチャーとして作用する。 - Component (D1) By using a resist composition that contains the component (D1), the contrast between exposed and unexposed areas of the resist film can be further improved when forming a resist pattern.
The component (D1) is not particularly limited as long as it decomposes upon exposure to light and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "component (d1-1)"), a compound represented by the following general formula (d1-2) (hereinafter referred to as "component (d1-2)"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "component (d1-3)"):
The components (d1-1) to (d1-3) do not act as quenchers in the exposed areas of the resist film because they decompose and lose their acid diffusion control ability (basicity), but act as quenchers in the unexposed areas of the resist film.
（Ｄ１）成分を含有するレジスト組成物とすることで、レジストパターンを形成する際に、レジスト膜の露光部と未露光部とのコントラストをより向上させることができる。
（Ｄ１）成分としては、露光により分解して酸拡散制御性を失うものであれば特に限定されず、下記一般式（ｄ１－１）で表される化合物（以下「（ｄ１－１）成分」という。）、下記一般式（ｄ１－２）で表される化合物（以下「（ｄ１－２）成分」という。）及び下記一般式（ｄ１－３）で表される化合物（以下「（ｄ１－３）成分」という。）からなる群より選ばれる１種以上の化合物が好ましい。
（ｄ１－１）～（ｄ１－３）成分は、レジスト膜の露光部においては分解して酸拡散制御性（塩基性）を失うためクエンチャーとして作用せず、レジスト膜の未露光部においてクエンチャーとして作用する。 - Component (D1) By using a resist composition that contains the component (D1), the contrast between exposed and unexposed areas of the resist film can be further improved when forming a resist pattern.
The component (D1) is not particularly limited as long as it decomposes upon exposure to light and loses its acid diffusion controllability, and is preferably one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "component (d1-1)"), a compound represented by the following general formula (d1-2) (hereinafter referred to as "component (d1-2)"), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "component (d1-3)"):
The components (d1-1) to (d1-3) do not act as quenchers in the exposed areas of the resist film because they decompose and lose their acid diffusion control ability (basicity), but act as quenchers in the unexposed areas of the resist film.
｛（ｄ１－１）成分｝
・・アニオン部
式（ｄ１－１）中、Ｒｄ１は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、それぞれ前記Ｒ’２０１と同様のものが挙げられる。
これらのなかでも、Ｒｄ１としては、置換基を有してもよい芳香族炭化水素基、置換基を有してもよい脂肪族環式基、又は置換基を有してもよい鎖状のアルキル基が好ましい。これらの基が有していてもよい置換基としては、水酸基、オキソ基、アルキル基、アリール基、フッ素原子、フッ素化アルキル基、上記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表されるラクトン含有環式基、エーテル結合、エステル結合、またはこれらの組み合わせが挙げられる。エーテル結合やエステル結合を置換基として含む場合、アルキレン基を介していてもよく、この場合の置換基としては、上記式（ｙ－ａｌ－１）～（ｙ－ａｌ－５）でそれぞれ表される連結基が好ましい。なお、Ｒｄ１における芳香族炭化水素基、脂肪族環式基、又は鎖状のアルキル基が、置換基として、上記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）でそれぞれ表される連結基を有する場合、上記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）において、式（ｄ３－１）中のＲｄ１における芳香族炭化水素基、脂肪族環式基、又は鎖状のアルキル基を構成する炭素原子に結合するのが、上記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）中のＶ’１０１である。
前記芳香族炭化水素基としては、フェニル基、ナフチル基、ビシクロオクタン骨格を含む多環構造（ビシクロオクタン骨格とこれ以外の環構造とからなる多環構造）が好適に挙げられる。
前記脂肪族環式基としては、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等のポリシクロアルカンから１個以上の水素原子を除いた基であることがより好ましい。
前記鎖状のアルキル基としては、炭素原子数が１～１０であることが好ましく、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の直鎖状のアルキル基；１－メチルエチル基、１－メチルプロピル基、２－メチルプロピル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１－エチルブチル基、２－エチルブチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基等の分岐鎖状のアルキル基が挙げられる。 {(d1-1) component}
In formula (d1-1), Rd 1 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples of these groups include the same as those for R' 201 described above.
Among these, Rd 1 is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, a lactone-containing cyclic group represented by each of the above general formulas (a2-r-1) to (a2-r-7), an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the above formulas (y-al-1) to (y-al-5). When the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 1 has a linking group represented by each of the general formulae (y-al-1) to (y-al-7) as a substituent, in the general formulae (y-al-1) to (y-al-7), V' 101 in the general formulae (y-al-1) to (y-al-7) is bonded to a carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 1 in formula (d3-1).
Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and another ring structure).
The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane.
The chain alkyl group preferably has 1 to 10 carbon atoms. Specific examples of the chain alkyl group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched alkyl groups such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
・・アニオン部
式（ｄ１－１）中、Ｒｄ１は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、それぞれ前記Ｒ’２０１と同様のものが挙げられる。
これらのなかでも、Ｒｄ１としては、置換基を有してもよい芳香族炭化水素基、置換基を有してもよい脂肪族環式基、又は置換基を有してもよい鎖状のアルキル基が好ましい。これらの基が有していてもよい置換基としては、水酸基、オキソ基、アルキル基、アリール基、フッ素原子、フッ素化アルキル基、上記一般式（ａ２－ｒ－１）～（ａ２－ｒ－７）でそれぞれ表されるラクトン含有環式基、エーテル結合、エステル結合、またはこれらの組み合わせが挙げられる。エーテル結合やエステル結合を置換基として含む場合、アルキレン基を介していてもよく、この場合の置換基としては、上記式（ｙ－ａｌ－１）～（ｙ－ａｌ－５）でそれぞれ表される連結基が好ましい。なお、Ｒｄ１における芳香族炭化水素基、脂肪族環式基、又は鎖状のアルキル基が、置換基として、上記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）でそれぞれ表される連結基を有する場合、上記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）において、式（ｄ３－１）中のＲｄ１における芳香族炭化水素基、脂肪族環式基、又は鎖状のアルキル基を構成する炭素原子に結合するのが、上記一般式（ｙ－ａｌ－１）～（ｙ－ａｌ－７）中のＶ’１０１である。
前記芳香族炭化水素基としては、フェニル基、ナフチル基、ビシクロオクタン骨格を含む多環構造（ビシクロオクタン骨格とこれ以外の環構造とからなる多環構造）が好適に挙げられる。
前記脂肪族環式基としては、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等のポリシクロアルカンから１個以上の水素原子を除いた基であることがより好ましい。
前記鎖状のアルキル基としては、炭素原子数が１～１０であることが好ましく、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の直鎖状のアルキル基；１－メチルエチル基、１－メチルプロピル基、２－メチルプロピル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１－エチルブチル基、２－エチルブチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基等の分岐鎖状のアルキル基が挙げられる。 {(d1-1) component}
In formula (d1-1), Rd 1 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples of these groups include the same as those for R' 201 described above.
Among these, Rd 1 is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, a lactone-containing cyclic group represented by each of the above general formulas (a2-r-1) to (a2-r-7), an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, it may be via an alkylene group, and in this case, the substituent is preferably a linking group represented by each of the above formulas (y-al-1) to (y-al-5). When the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 1 has a linking group represented by each of the general formulae (y-al-1) to (y-al-7) as a substituent, in the general formulae (y-al-1) to (y-al-7), V' 101 in the general formulae (y-al-1) to (y-al-7) is bonded to a carbon atom constituting the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 1 in formula (d3-1).
Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and another ring structure).
The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane.
The chain alkyl group preferably has 1 to 10 carbon atoms. Specific examples of the chain alkyl group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and branched alkyl groups such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
前記鎖状のアルキル基が置換基としてフッ素原子又はフッ素化アルキル基を有するフッ素化アルキル基である場合、フッ素化アルキル基の炭素原子数は、１～１１が好ましく、１～８がより好ましく、１～４がさらに好ましい。該フッ素化アルキル基は、フッ素原子以外の原子を含有してもよい。フッ素原子以外の原子としては、例えば酸素原子、硫黄原子、窒素原子等が挙げられる。
When the chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.
以下に（ｄ１－１）成分のアニオン部の好ましい具体例を示す。
The following are preferred examples of the anion portion of component (d1-1):
・・カチオン部
式（ｄ１－１）中、Ｍｍ＋は、ｍ価の有機カチオンである。
Ｍｍ＋の有機カチオンとしては、前記一般式（ｃａ－１）～（ｃａ－３）でそれぞれ表されるカチオンと同様のものが好適に挙げられ、前記一般式（ｃａ－１）で表されるカチオンがより好ましく、上記一般式（ｃａ－１－１）～（ｃａ－１－７０）でそれぞれ表されるカチオンがさらに好ましい。 In formula (d1-1), M m+ represents an m-valent organic cation.
Suitable examples of the organic cation of M m+ include the same cations as those represented by the general formulas (ca-1) to (ca-3), respectively, more preferably the cation represented by the general formula (ca-1), and even more preferably the cations represented by the general formulas (ca-1-1) to (ca-1-70), respectively.
式（ｄ１－１）中、Ｍｍ＋は、ｍ価の有機カチオンである。
Ｍｍ＋の有機カチオンとしては、前記一般式（ｃａ－１）～（ｃａ－３）でそれぞれ表されるカチオンと同様のものが好適に挙げられ、前記一般式（ｃａ－１）で表されるカチオンがより好ましく、上記一般式（ｃａ－１－１）～（ｃａ－１－７０）でそれぞれ表されるカチオンがさらに好ましい。 In formula (d1-1), M m+ represents an m-valent organic cation.
Suitable examples of the organic cation of M m+ include the same cations as those represented by the general formulas (ca-1) to (ca-3), respectively, more preferably the cation represented by the general formula (ca-1), and even more preferably the cations represented by the general formulas (ca-1-1) to (ca-1-70), respectively.
（ｄ１－１）成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The (d1-1) component may be used alone or in combination of two or more types.
｛（ｄ１－２）成分｝
・・アニオン部
式（ｄ１－２）中、Ｒｄ２は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、前記Ｒ’２０１と同様のものが挙げられる。
但し、Ｒｄ２における、Ｓ原子に隣接する炭素原子にはフッ素原子は結合していない（フッ素置換されていない）ものとする。これにより、（ｄ１－２）成分のアニオンが適度な弱酸アニオンとなり、（Ｄ）成分としてのクエンチング能が向上する。
Ｒｄ２としては、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい脂肪族環式基であることが好ましく、置換基を有してもよい脂肪族環式基であることがより好ましい。 {(d1-2) component}
In formula (d1-2), Rd2 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples of R'201 include the same as those described above for R'201 .
However, in Rd2 , the carbon atom adjacent to the S atom does not have a fluorine atom bonded thereto (is not substituted with fluorine), whereby the anion of the component (d1-2) becomes an appropriately weak acid anion, and the quenching ability of the component (D) is improved.
Rd2 is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent, and more preferably an aliphatic cyclic group which may have a substituent.
・・アニオン部
式（ｄ１－２）中、Ｒｄ２は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、前記Ｒ’２０１と同様のものが挙げられる。
但し、Ｒｄ２における、Ｓ原子に隣接する炭素原子にはフッ素原子は結合していない（フッ素置換されていない）ものとする。これにより、（ｄ１－２）成分のアニオンが適度な弱酸アニオンとなり、（Ｄ）成分としてのクエンチング能が向上する。
Ｒｄ２としては、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい脂肪族環式基であることが好ましく、置換基を有してもよい脂肪族環式基であることがより好ましい。 {(d1-2) component}
In formula (d1-2), Rd2 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples of R'201 include the same as those described above for R'201 .
However, in Rd2 , the carbon atom adjacent to the S atom does not have a fluorine atom bonded thereto (is not substituted with fluorine), whereby the anion of the component (d1-2) becomes an appropriately weak acid anion, and the quenching ability of the component (D) is improved.
Rd2 is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent, and more preferably an aliphatic cyclic group which may have a substituent.
該鎖状のアルキル基としては、炭素原子数１～１０であることが好ましく、３～１０であることがより好ましい。
該脂肪族環式基としては、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等から１個以上の水素原子を除いた基（置換基を有してもよい）；カンファーから１個以上の水素原子を除いた基であることがより好ましい。 The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 3 to 10 carbon atoms.
The aliphatic cyclic group is preferably a group (which may have a substituent) in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, tetracyclododecane, or the like; or a group in which one or more hydrogen atoms have been removed from camphor.
該脂肪族環式基としては、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等から１個以上の水素原子を除いた基（置換基を有してもよい）；カンファーから１個以上の水素原子を除いた基であることがより好ましい。 The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 3 to 10 carbon atoms.
The aliphatic cyclic group is preferably a group (which may have a substituent) in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, tetracyclododecane, or the like; or a group in which one or more hydrogen atoms have been removed from camphor.
Ｒｄ２の炭化水素基は、置換基を有していてもよく、該置換基としては、前記式（ｄ１－１）のＲｄ１における炭化水素基（芳香族炭化水素基、脂肪族環式基、鎖状のアルキル基）が有していてもよい置換基と同様のものが挙げられる。
The hydrocarbon group of Rd2 may have a substituent, and examples of the substituent include the same as the substituents that may be possessed by the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in Rd1 of the above formula (d1-1).
以下に（ｄ１－２）成分のアニオン部の好ましい具体例を示す。
The following are preferred examples of the anion portion of component (d1-2):
・・カチオン部
式（ｄ１－２）中、Ｍｍ＋は、ｍ価の有機カチオンであり、前記式（ｄ１－１）中のＭｍ＋と同様である。
（ｄ１－２）成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Cation Moiety In formula (d1-2), M m+ represents an m-valent organic cation and is the same as M m+ in formula (d1-1).
The component (d1-2) may be used alone or in combination of two or more.
式（ｄ１－２）中、Ｍｍ＋は、ｍ価の有機カチオンであり、前記式（ｄ１－１）中のＭｍ＋と同様である。
（ｄ１－２）成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Cation Moiety In formula (d1-2), M m+ represents an m-valent organic cation and is the same as M m+ in formula (d1-1).
The component (d1-2) may be used alone or in combination of two or more.
｛（ｄ１－３）成分｝
・・アニオン部
式（ｄ１－３）中、Ｒｄ３は置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、前記Ｒ’２０１と同様のものが挙げられ、フッ素原子を含む環式基、鎖状のアルキル基、又は鎖状のアルケニル基であることが好ましい。中でも、フッ素化アルキル基が好ましく、前記Ｒｄ１のフッ素化アルキル基と同様のものがより好ましい。 {(d1-3) component}
In formula (d1-3), Rd 3 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof include the same as those of R' 201 , and is preferably a cyclic group, chain alkyl group, or chain alkenyl group containing a fluorine atom. Among these, a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group of Rd 1 is more preferable.
・・アニオン部
式（ｄ１－３）中、Ｒｄ３は置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、前記Ｒ’２０１と同様のものが挙げられ、フッ素原子を含む環式基、鎖状のアルキル基、又は鎖状のアルケニル基であることが好ましい。中でも、フッ素化アルキル基が好ましく、前記Ｒｄ１のフッ素化アルキル基と同様のものがより好ましい。 {(d1-3) component}
In formula (d1-3), Rd 3 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples thereof include the same as those of R' 201 , and is preferably a cyclic group, chain alkyl group, or chain alkenyl group containing a fluorine atom. Among these, a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group of Rd 1 is more preferable.
式（ｄ１－３）中、Ｒｄ４は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、前記Ｒ’２０１と同様のものが挙げられる。
なかでも、置換基を有してもよいアルキル基、アルコキシ基、アルケニル基、環式基であることが好ましい。
Ｒｄ４におけるアルキル基は、炭素原子数１～５の直鎖状又は分岐鎖状のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。Ｒｄ４のアルキル基の水素原子の一部が水酸基、シアノ基等で置換されていてもよい。
Ｒｄ４におけるアルコキシ基は、炭素原子数１～５のアルコキシ基が好ましく、炭素原子数１～５のアルコキシ基として具体的には、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基が挙げられる。なかでも、メトキシ基、エトキシ基が好ましい。 In formula (d1-3), Rd4 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples of R'201 include the same as those described above.
Among these, an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group, which may have a substituent, is preferable.
The alkyl group in Rd 4 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. A portion of the hydrogen atoms of the alkyl group in Rd 4 may be substituted with a hydroxyl group, a cyano group, etc.
The alkoxy group in Rd 4 is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferred.
なかでも、置換基を有してもよいアルキル基、アルコキシ基、アルケニル基、環式基であることが好ましい。
Ｒｄ４におけるアルキル基は、炭素原子数１～５の直鎖状又は分岐鎖状のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。Ｒｄ４のアルキル基の水素原子の一部が水酸基、シアノ基等で置換されていてもよい。
Ｒｄ４におけるアルコキシ基は、炭素原子数１～５のアルコキシ基が好ましく、炭素原子数１～５のアルコキシ基として具体的には、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基が挙げられる。なかでも、メトキシ基、エトキシ基が好ましい。 In formula (d1-3), Rd4 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and examples of R'201 include the same as those described above.
Among these, an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group, which may have a substituent, is preferable.
The alkyl group in Rd 4 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. A portion of the hydrogen atoms of the alkyl group in Rd 4 may be substituted with a hydroxyl group, a cyano group, etc.
The alkoxy group in Rd 4 is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferred.
Ｒｄ４におけるアルケニル基は、前記Ｒ’２０１におけるアルケニル基と同様のものが挙げられ、ビニル基、プロペニル基（アリル基）、１－メチルプロペニル基、２－メチルプロペニル基が好ましい。これらの基はさらに置換基として、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基を有していてもよい。
The alkenyl group in Rd4 may be the same as the alkenyl group in R'201 , and preferably a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, or a 2-methylpropenyl group. These groups may further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.
Ｒｄ４における環式基は、前記Ｒ’２０１における環式基と同様のものが挙げられ、シクロペンタン、シクロヘキサン、アダマンタン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０２，６］デカン、テトラシクロドデカン等のシクロアルカンから１個以上の水素原子を除いた脂環式基、又は、フェニル基、ナフチル基等の芳香族基が好ましい。Ｒｄ４が脂環式基である場合、レジスト組成物が有機溶剤に良好に溶解することにより、リソグラフィー特性が良好となる。また、Ｒｄ４が芳香族基である場合、ＥＵＶ等を露光光源とするリソグラフィーにおいて、該レジスト組成物が光吸収効率に優れ、感度やリソグラフィー特性が良好となる。
The cyclic group in Rd 4 may be the same as the cyclic group in R' 201 , and is preferably an alicyclic group obtained by removing one or more hydrogen atoms from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, or tetracyclododecane, or an aromatic group such as a phenyl group or naphthyl group. When Rd 4 is an alicyclic group, the resist composition dissolves well in an organic solvent, resulting in good lithography properties. In addition, when Rd 4 is an aromatic group, in lithography using EUV or the like as an exposure light source, the resist composition has excellent light absorption efficiency, and the sensitivity and lithography properties are good.
式（ｄ１－３）中、Ｙｄ１は、単結合または２価の連結基である。
Ｙｄ１における２価の連結基としては、特に限定されないが、置換基を有してもよい２価の炭化水素基（脂肪族炭化水素基、芳香族炭化水素基）、ヘテロ原子を含む２価の連結基等が挙げられる。これらはそれぞれ、上記式（ａ２－１）中のＹａ２１における２価の連結基についての説明のなかで挙げた、置換基を有してもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基と同様のものが挙げられる。
Ｙｄ１としては、カルボニル基、エステル結合、アミド結合、アルキレン基又はこれらの組み合わせであることが好ましい。アルキレン基としては、直鎖状又は分岐鎖状のアルキレン基であることがより好ましく、メチレン基又はエチレン基であることがさらに好ましい。 In formula (d1-3), Yd1 represents a single bond or a divalent linking group.
The divalent linking group in Yd 1 is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent (an aliphatic hydrocarbon group, an aromatic hydrocarbon group), a divalent linking group containing a hetero atom, etc. These include the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom mentioned in the description of the divalent linking group in Ya 21 in the above formula (a2-1).
Yd1 is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and further preferably a methylene group or an ethylene group.
Ｙｄ１における２価の連結基としては、特に限定されないが、置換基を有してもよい２価の炭化水素基（脂肪族炭化水素基、芳香族炭化水素基）、ヘテロ原子を含む２価の連結基等が挙げられる。これらはそれぞれ、上記式（ａ２－１）中のＹａ２１における２価の連結基についての説明のなかで挙げた、置換基を有してもよい２価の炭化水素基、ヘテロ原子を含む２価の連結基と同様のものが挙げられる。
Ｙｄ１としては、カルボニル基、エステル結合、アミド結合、アルキレン基又はこれらの組み合わせであることが好ましい。アルキレン基としては、直鎖状又は分岐鎖状のアルキレン基であることがより好ましく、メチレン基又はエチレン基であることがさらに好ましい。 In formula (d1-3), Yd1 represents a single bond or a divalent linking group.
The divalent linking group in Yd 1 is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent (an aliphatic hydrocarbon group, an aromatic hydrocarbon group), a divalent linking group containing a hetero atom, etc. These include the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom mentioned in the description of the divalent linking group in Ya 21 in the above formula (a2-1).
Yd1 is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and further preferably a methylene group or an ethylene group.
以下に（ｄ１－３）成分のアニオン部の好ましい具体例を示す。
The following are preferred examples of the anion portion of component (d1-3):
・・カチオン部
式（ｄ１－３）中、Ｍｍ＋は、ｍ価の有機カチオンであり、前記式（ｄ１－１）中のＭｍ＋と同様である。
（ｄ１－３）成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Cation Moiety In formula (d1-3), M m+ represents an m-valent organic cation and is the same as M m+ in formula (d1-1).
The component (d1-3) may be used alone or in combination of two or more.
式（ｄ１－３）中、Ｍｍ＋は、ｍ価の有機カチオンであり、前記式（ｄ１－１）中のＭｍ＋と同様である。
（ｄ１－３）成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Cation Moiety In formula (d1-3), M m+ represents an m-valent organic cation and is the same as M m+ in formula (d1-1).
The component (d1-3) may be used alone or in combination of two or more.
（Ｄ１）成分は、上記（ｄ１－１）～（ｄ１－３）成分のいずれか１種のみを用いてもよく、２種以上を組み合わせて用いてもよい。
レジスト組成物が（Ｄ１）成分を含有する場合、レジスト組成物中、（Ｄ１）成分の含有量は、（Ａ１）成分１００質量部に対して、０．５～１５質量部が好ましく、１～１０質量部がより好ましく、２～８質量部がさらに好ましい。
（Ｄ１）成分の含有量が好ましい下限値以上であると、特に良好なリソグラフィー特性及びレジストパターン形状が得られやすい。一方、上限値以下であると、感度を良好に維持でき、スループットにも優れる。 The component (D1) may be any one of the above components (d1-1) to (d1-3), or a combination of two or more of them.
When the resist composition contains the component (D1), the amount of the component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, relative to 100 parts by mass of the component (A1).
When the amount of the component (D1) is at least as large as the preferred lower limit, particularly good lithography properties and resist pattern shape are likely to be obtained, while when the amount is no more than the upper limit, good sensitivity can be maintained and excellent throughput is also achieved.
レジスト組成物が（Ｄ１）成分を含有する場合、レジスト組成物中、（Ｄ１）成分の含有量は、（Ａ１）成分１００質量部に対して、０．５～１５質量部が好ましく、１～１０質量部がより好ましく、２～８質量部がさらに好ましい。
（Ｄ１）成分の含有量が好ましい下限値以上であると、特に良好なリソグラフィー特性及びレジストパターン形状が得られやすい。一方、上限値以下であると、感度を良好に維持でき、スループットにも優れる。 The component (D1) may be any one of the above components (d1-1) to (d1-3), or a combination of two or more of them.
When the resist composition contains the component (D1), the amount of the component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, relative to 100 parts by mass of the component (A1).
When the amount of the component (D1) is at least as large as the preferred lower limit, particularly good lithography properties and resist pattern shape are likely to be obtained, while when the amount is no more than the upper limit, good sensitivity can be maintained and excellent throughput is also achieved.
本実施形態のレジスト組成物において、（Ｄ１）成分は、上記（ｄ１－１）成分を含むことが好ましい。
本実施形態のレジスト組成物が含有する（Ｄ）成分全体のうち、（ｄ１－１）成分の含有量は、５０質量％以上であることが好ましく、７０質量％以上であることが好ましく、９０質量％以上であることがさらに好ましく、（Ｄ）成分は化合物（ｄ１－１）成分のみからなるものであってもよい。 In the resist composition of this embodiment, the component (D1) preferably includes the component (d1-1) above.
In the resist composition of this embodiment, the content of the component (d1-1) in the entire component (D) is preferably 50 mass % or more, preferably 70 mass % or more, and more preferably 90 mass % or more. The component (D) may consist solely of the compound (d1-1).
本実施形態のレジスト組成物が含有する（Ｄ）成分全体のうち、（ｄ１－１）成分の含有量は、５０質量％以上であることが好ましく、７０質量％以上であることが好ましく、９０質量％以上であることがさらに好ましく、（Ｄ）成分は化合物（ｄ１－１）成分のみからなるものであってもよい。 In the resist composition of this embodiment, the component (D1) preferably includes the component (d1-1) above.
In the resist composition of this embodiment, the content of the component (d1-1) in the entire component (D) is preferably 50 mass % or more, preferably 70 mass % or more, and more preferably 90 mass % or more. The component (D) may consist solely of the compound (d1-1).
（Ｄ１）成分の製造方法：
前記の（ｄ１－１）成分、（ｄ１－２）成分の製造方法は、特に限定されず、公知の方法により製造することができる。
また、（ｄ１－３）成分の製造方法は、特に限定されず、例えば、ＵＳ２０１２－０１４９９１６号公報に記載の方法と同様にして製造される。 Production method of component (D1):
The method for producing the components (d1-1) and (d1-2) is not particularly limited, and they can be produced by known methods.
The method for producing the component (d1-3) is not particularly limited, and it can be produced, for example, in the same manner as the method described in US 2012-0149916.
前記の（ｄ１－１）成分、（ｄ１－２）成分の製造方法は、特に限定されず、公知の方法により製造することができる。
また、（ｄ１－３）成分の製造方法は、特に限定されず、例えば、ＵＳ２０１２－０１４９９１６号公報に記載の方法と同様にして製造される。 Production method of component (D1):
The method for producing the components (d1-1) and (d1-2) is not particularly limited, and they can be produced by known methods.
The method for producing the component (d1-3) is not particularly limited, and it can be produced, for example, in the same manner as the method described in US 2012-0149916.
・（Ｄ２）成分について
（Ｄ）成分としては、上記の（Ｄ１）成分に該当しない含窒素有機化合物成分（以下「（Ｄ２）成分」という。）を含有してもよい。
（Ｄ２）成分としては、酸拡散制御剤として作用するもので、かつ、（Ｄ１）成分に該当しないものであれば特に限定されず、公知のものから任意に用いればよい。なかでも、脂肪族アミンが好ましく、この中でも特に第２級脂肪族アミンや第３級脂肪族アミンがより好ましい。
脂肪族アミンとは、１つ以上の脂肪族基を有するアミンであり、該脂肪族基は炭素原子数が１～１２であることが好ましい。
脂肪族アミンとしては、アンモニアＮＨ３の水素原子の少なくとも１つを、炭素原子数１２以下のアルキル基もしくはヒドロキシアルキル基で置換したアミン（アルキルアミンもしくはアルキルアルコールアミン）又は環式アミンが挙げられる。
アルキルアミンおよびアルキルアルコールアミンの具体例としては、ｎ－ヘキシルアミン、ｎ－ヘプチルアミン、ｎ－オクチルアミン、ｎ－ノニルアミン、ｎ－デシルアミン等のモノアルキルアミン；ジエチルアミン、ジ－ｎ－プロピルアミン、ジ－ｎ－ヘプチルアミン、ジ－ｎ－オクチルアミン、ジシクロヘキシルアミン等のジアルキルアミン；トリメチルアミン、トリエチルアミン、トリ－ｎ－プロピルアミン、トリ－ｎ－ブチルアミン、トリ－ｎ－ペンチルアミン、トリ－ｎ－ヘキシルアミン、トリ－ｎ－ヘプチルアミン、トリ－ｎ－オクチルアミン、トリ－ｎ－ノニルアミン、トリ－ｎ－デシルアミン、トリ－ｎ－ドデシルアミン等のトリアルキルアミン；ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、ジ－ｎ－オクタノールアミン、トリ－ｎ－オクタノールアミン等のアルキルアルコールアミンが挙げられる。これらの中でも、炭素原子数６～３０のトリアルキルアミンがさらに好ましく、トリ－ｎ－ペンチルアミン又はトリ－ｎ－オクチルアミンが特に好ましい。 Regarding Component (D2) The component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as “component (D2)”) that does not fall under the category of the above-mentioned component (D1).
The component (D2) is not particularly limited as long as it acts as an acid diffusion controller and does not fall under the category of component (D1), and any known component may be used. Among these, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred.
Aliphatic amines are amines that have one or more aliphatic groups, preferably having 1 to 12 carbon atoms.
Examples of aliphatic amines include amines in which at least one of the hydrogen atoms of ammonia NH3 is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms (alkylamines or alkyl alcohol amines), or cyclic amines.
Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 6 to 30 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.
（Ｄ）成分としては、上記の（Ｄ１）成分に該当しない含窒素有機化合物成分（以下「（Ｄ２）成分」という。）を含有してもよい。
（Ｄ２）成分としては、酸拡散制御剤として作用するもので、かつ、（Ｄ１）成分に該当しないものであれば特に限定されず、公知のものから任意に用いればよい。なかでも、脂肪族アミンが好ましく、この中でも特に第２級脂肪族アミンや第３級脂肪族アミンがより好ましい。
脂肪族アミンとは、１つ以上の脂肪族基を有するアミンであり、該脂肪族基は炭素原子数が１～１２であることが好ましい。
脂肪族アミンとしては、アンモニアＮＨ３の水素原子の少なくとも１つを、炭素原子数１２以下のアルキル基もしくはヒドロキシアルキル基で置換したアミン（アルキルアミンもしくはアルキルアルコールアミン）又は環式アミンが挙げられる。
アルキルアミンおよびアルキルアルコールアミンの具体例としては、ｎ－ヘキシルアミン、ｎ－ヘプチルアミン、ｎ－オクチルアミン、ｎ－ノニルアミン、ｎ－デシルアミン等のモノアルキルアミン；ジエチルアミン、ジ－ｎ－プロピルアミン、ジ－ｎ－ヘプチルアミン、ジ－ｎ－オクチルアミン、ジシクロヘキシルアミン等のジアルキルアミン；トリメチルアミン、トリエチルアミン、トリ－ｎ－プロピルアミン、トリ－ｎ－ブチルアミン、トリ－ｎ－ペンチルアミン、トリ－ｎ－ヘキシルアミン、トリ－ｎ－ヘプチルアミン、トリ－ｎ－オクチルアミン、トリ－ｎ－ノニルアミン、トリ－ｎ－デシルアミン、トリ－ｎ－ドデシルアミン等のトリアルキルアミン；ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、ジ－ｎ－オクタノールアミン、トリ－ｎ－オクタノールアミン等のアルキルアルコールアミンが挙げられる。これらの中でも、炭素原子数６～３０のトリアルキルアミンがさらに好ましく、トリ－ｎ－ペンチルアミン又はトリ－ｎ－オクチルアミンが特に好ましい。 Regarding Component (D2) The component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as “component (D2)”) that does not fall under the category of the above-mentioned component (D1).
The component (D2) is not particularly limited as long as it acts as an acid diffusion controller and does not fall under the category of component (D1), and any known component may be used. Among these, aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred.
Aliphatic amines are amines that have one or more aliphatic groups, preferably having 1 to 12 carbon atoms.
Examples of aliphatic amines include amines in which at least one of the hydrogen atoms of ammonia NH3 is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms (alkylamines or alkyl alcohol amines), or cyclic amines.
Specific examples of alkylamines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having 6 to 30 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.
環式アミンとしては、例えば、ヘテロ原子として窒素原子を含む複素環化合物が挙げられる。該複素環化合物としては、単環式のもの（脂肪族単環式アミン）であっても多環式のもの（脂肪族多環式アミン）であってもよい。
脂肪族単環式アミンとして、具体的には、ピペリジン、ピペラジン等が挙げられる。
脂肪族多環式アミンとしては、炭素原子数が６～１０のものが好ましく、具体的には、１，５－ジアザビシクロ［４．３．０］－５－ノネン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセン、ヘキサメチレンテトラミン、１，４－ジアザビシクロ［２．２．２］オクタン等が挙げられる。 Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
The aliphatic polycyclic amine is preferably one having 6 to 10 carbon atoms, and specific examples thereof include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.
脂肪族単環式アミンとして、具体的には、ピペリジン、ピペラジン等が挙げられる。
脂肪族多環式アミンとしては、炭素原子数が６～１０のものが好ましく、具体的には、１，５－ジアザビシクロ［４．３．０］－５－ノネン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセン、ヘキサメチレンテトラミン、１，４－ジアザビシクロ［２．２．２］オクタン等が挙げられる。 Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
The aliphatic polycyclic amine is preferably one having 6 to 10 carbon atoms, and specific examples thereof include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.
その他の脂肪族アミンとしては、トリス（２－メトキシメトキシエチル）アミン、トリス｛２－（２－メトキシエトキシ）エチル｝アミン、トリス｛２－（２－メトキシエトキシメトキシ）エチル｝アミン、トリス｛２－（１－メトキシエトキシ）エチル｝アミン、トリス｛２－（１－エトキシエトキシ）エチル｝アミン、トリス｛２－（１－エトキシプロポキシ）エチル｝アミン、トリス［２－｛２－（２－ヒドロキシエトキシ）エトキシ｝エチル］アミン、トリエタノールアミントリアセテート等が挙げられ、トリエタノールアミントリアセテートが好ましい。
Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.
また、（Ｄ２）成分としては、芳香族アミンを用いてもよい。
芳香族アミンとしては、４－ジメチルアミノピリジン、ピロール、インドール、ピラゾール、イミダゾールまたはこれらの誘導体、トリベンジルアミン、２，６－ジイソプロピルアニリン、Ｎ－ｔｅｒｔ－ブトキシカルボニルピロリジン、２，６－ジ－ｔｅｒｔ－ブチルピリジン等が挙げられる。 Furthermore, an aromatic amine may be used as the component (D2).
Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and 2,6-di-tert-butylpyridine.
芳香族アミンとしては、４－ジメチルアミノピリジン、ピロール、インドール、ピラゾール、イミダゾールまたはこれらの誘導体、トリベンジルアミン、２，６－ジイソプロピルアニリン、Ｎ－ｔｅｒｔ－ブトキシカルボニルピロリジン、２，６－ジ－ｔｅｒｔ－ブチルピリジン等が挙げられる。 Furthermore, an aromatic amine may be used as the component (D2).
Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and 2,6-di-tert-butylpyridine.
上記の中でも、（Ｄ２）成分は、アルキルアミンであることが好ましく、炭素原子数６～３０のトリアルキルアミンがより好ましい。
Among the above, component (D2) is preferably an alkylamine, more preferably a trialkylamine having 6 to 30 carbon atoms.
（Ｄ２）成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
レジスト組成物が（Ｄ２）成分を含有する場合、レジスト組成物中、（Ｄ２）成分の含有量は、（Ａ１）成分１００質量部に対して、０．０１～５質量部が好ましく、０．１～５質量部がより好ましく、０．５～５質量部がさらに好ましい。
（Ｄ２）成分の含有量が好ましい下限値以上であると、特に良好なリソグラフィー特性及びレジストパターン形状が得られやすい。一方、上限値以下であると、感度を良好に維持でき、スループットにも優れる。 The component (D2) may be used alone or in combination of two or more types.
When the resist composition contains the component (D2), the amount of the component (D2) in the resist composition is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the component (A1).
When the amount of the component (D2) is at least as large as the preferred lower limit, particularly good lithography properties and resist pattern shape are likely to be obtained, while when the amount is no more than the upper limit, good sensitivity can be maintained and excellent throughput is also achieved.
レジスト組成物が（Ｄ２）成分を含有する場合、レジスト組成物中、（Ｄ２）成分の含有量は、（Ａ１）成分１００質量部に対して、０．０１～５質量部が好ましく、０．１～５質量部がより好ましく、０．５～５質量部がさらに好ましい。
（Ｄ２）成分の含有量が好ましい下限値以上であると、特に良好なリソグラフィー特性及びレジストパターン形状が得られやすい。一方、上限値以下であると、感度を良好に維持でき、スループットにも優れる。 The component (D2) may be used alone or in combination of two or more types.
When the resist composition contains the component (D2), the amount of the component (D2) in the resist composition is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the component (A1).
When the amount of the component (D2) is at least as large as the preferred lower limit, particularly good lithography properties and resist pattern shape are likely to be obtained, while when the amount is no more than the upper limit, good sensitivity can be maintained and excellent throughput is also achieved.
≪有機カルボン酸、並びにリンのオキソ酸及びその誘導体からなる群より選択される少なくとも１種の化合物（Ｅ）≫
本実施形態のレジスト組成物には、感度劣化の防止や、レジストパターン形状、引き置き経時安定性等の向上の目的で、任意の成分として、有機カルボン酸、並びにリンのオキソ酸及びその誘導体からなる群より選択される少なくとも１種の化合物（Ｅ）（以下「（Ｅ）成分」という）を含有させることができる。
有機カルボン酸として、具体的には、酢酸、マロン酸、クエン酸、リンゴ酸、コハク酸、安息香酸、サリチル酸等が挙げられ、その中でも、サリチル酸が好ましい。
リンのオキソ酸としては、リン酸、ホスホン酸、ホスフィン酸等が挙げられ、これらの中でも特にホスホン酸が好ましい。 <At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxoacids and derivatives thereof>
For the purposes of preventing deterioration of sensitivity and improving the resist pattern shape and storage stability, etc., the resist composition of this embodiment may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids, and phosphorus oxoacids and derivatives thereof (hereafter referred to as "component (E)").
Specific examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, and among these, salicylic acid is preferred.
Examples of phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred.
本実施形態のレジスト組成物には、感度劣化の防止や、レジストパターン形状、引き置き経時安定性等の向上の目的で、任意の成分として、有機カルボン酸、並びにリンのオキソ酸及びその誘導体からなる群より選択される少なくとも１種の化合物（Ｅ）（以下「（Ｅ）成分」という）を含有させることができる。
有機カルボン酸として、具体的には、酢酸、マロン酸、クエン酸、リンゴ酸、コハク酸、安息香酸、サリチル酸等が挙げられ、その中でも、サリチル酸が好ましい。
リンのオキソ酸としては、リン酸、ホスホン酸、ホスフィン酸等が挙げられ、これらの中でも特にホスホン酸が好ましい。 <At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxoacids and derivatives thereof>
For the purposes of preventing deterioration of sensitivity and improving the resist pattern shape and storage stability, etc., the resist composition of this embodiment may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids, and phosphorus oxoacids and derivatives thereof (hereafter referred to as "component (E)").
Specific examples of the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, and among these, salicylic acid is preferred.
Examples of phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred.
本実施形態のレジスト組成物において、（Ｅ）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。
レジスト組成物が（Ｅ）成分を含有する場合、（Ｅ）成分の含有量は、（Ａ１）成分１００質量部に対して、０．０１～５質量部が好ましく、０．０５～３質量部がより好ましい。上記範囲とすることにより、リソグラフィー特性がより向上する。 In the resist composition of this embodiment, the component (E) may use either a single type, or a combination of two or more types.
When the resist composition contains the component (E), the amount of the component (E) per 100 parts by mass of the component (A1) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass. By ensuring that the amount is within this range, lithography properties are further improved.
レジスト組成物が（Ｅ）成分を含有する場合、（Ｅ）成分の含有量は、（Ａ１）成分１００質量部に対して、０．０１～５質量部が好ましく、０．０５～３質量部がより好ましい。上記範囲とすることにより、リソグラフィー特性がより向上する。 In the resist composition of this embodiment, the component (E) may use either a single type, or a combination of two or more types.
When the resist composition contains the component (E), the amount of the component (E) per 100 parts by mass of the component (A1) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass. By ensuring that the amount is within this range, lithography properties are further improved.
≪有機溶剤成分（Ｓ）≫
本実施形態のレジスト組成物は、レジスト材料を有機溶剤成分（以下「（Ｓ）成分」という）に溶解させて製造することができる。
本実施形態のレジスト組成物において、（Ｓ）成分は、１種単独で用いてもよく、２種以上の混合溶剤として用いてもよい。なかでも、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）、プロピレングリコールモノメチルエーテル、γ－ブチロラクトン、ジアセトンアルコール、乳酸エチル（ＥＬ）、シクロヘキサノンが好ましい。 <Organic solvent component (S)>
The resist composition of this embodiment can be produced by dissolving the resist materials in an organic solvent component (hereafter referred to as “component (S)”).
In the resist composition of this embodiment, the component (S) may be used alone or as a mixed solvent of two or more kinds. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, γ-butyrolactone, diacetone alcohol, ethyl lactate (EL), and cyclohexanone are preferable.
本実施形態のレジスト組成物は、レジスト材料を有機溶剤成分（以下「（Ｓ）成分」という）に溶解させて製造することができる。
本実施形態のレジスト組成物において、（Ｓ）成分は、１種単独で用いてもよく、２種以上の混合溶剤として用いてもよい。なかでも、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）、プロピレングリコールモノメチルエーテル、γ－ブチロラクトン、ジアセトンアルコール、乳酸エチル（ＥＬ）、シクロヘキサノンが好ましい。 <Organic solvent component (S)>
The resist composition of this embodiment can be produced by dissolving the resist materials in an organic solvent component (hereafter referred to as “component (S)”).
In the resist composition of this embodiment, the component (S) may be used alone or as a mixed solvent of two or more kinds. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, γ-butyrolactone, diacetone alcohol, ethyl lactate (EL), and cyclohexanone are preferable.
また、（Ｓ）成分としては、ＰＧＭＥＡと極性溶剤とを混合した混合溶剤も好ましい。その配合比（質量比）は、ＰＧＭＥＡと極性溶剤との相溶性等を考慮して適宜決定すればよい。
また、（Ｓ）成分として、その他には、ＰＧＭＥＡ及びＥＬの中から選ばれる少なくとも１種とγ－ブチロラクトンとの混合溶剤も好ましい。この場合、混合割合としては、前者と後者との質量比が、好ましくは７０：３０～９５：５とされる。
（Ｓ）成分の使用量は、特に限定されず、基板等に塗布可能な濃度で、塗布膜厚に応じて適宜設定される。一般的にはレジスト組成物の固形分濃度が０．１～２０質量％、好ましくは０．２～１５質量％の範囲内となるように（Ｓ）成分は用いられる。 As the component (S), a mixed solvent of PGMEA and a polar solvent is also preferred. The blending ratio (mass ratio) may be appropriately determined taking into consideration the compatibility between PGMEA and the polar solvent, etc.
As the component (S), a mixed solvent of at least one selected from PGMEA and EL with γ-butyrolactone is also preferred. In this case, the mixing ratio of the former to the latter is preferably 70:30 to 95:5 by mass.
There are no particular limitations on the amount of the component (S) used, and it is set appropriately depending on the coating film thickness so as to provide a concentration that allows application to a substrate, etc. In general, the component (S) is used so that the solids concentration of the resist composition falls within the range of 0.1 to 20 mass %, and preferably 0.2 to 15 mass %.
また、（Ｓ）成分として、その他には、ＰＧＭＥＡ及びＥＬの中から選ばれる少なくとも１種とγ－ブチロラクトンとの混合溶剤も好ましい。この場合、混合割合としては、前者と後者との質量比が、好ましくは７０：３０～９５：５とされる。
（Ｓ）成分の使用量は、特に限定されず、基板等に塗布可能な濃度で、塗布膜厚に応じて適宜設定される。一般的にはレジスト組成物の固形分濃度が０．１～２０質量％、好ましくは０．２～１５質量％の範囲内となるように（Ｓ）成分は用いられる。 As the component (S), a mixed solvent of PGMEA and a polar solvent is also preferred. The blending ratio (mass ratio) may be appropriately determined taking into consideration the compatibility between PGMEA and the polar solvent, etc.
As the component (S), a mixed solvent of at least one selected from PGMEA and EL with γ-butyrolactone is also preferred. In this case, the mixing ratio of the former to the latter is preferably 70:30 to 95:5 by mass.
There are no particular limitations on the amount of the component (S) used, and it is set appropriately depending on the coating film thickness so as to provide a concentration that allows application to a substrate, etc. In general, the component (S) is used so that the solids concentration of the resist composition falls within the range of 0.1 to 20 mass %, and preferably 0.2 to 15 mass %.
本実施形態のレジスト組成物は、上記レジスト材料を（Ｓ）成分に溶解させた後、ポリイミド多孔質膜、ポリアミドイミド多孔質膜等を用いて、不純物等の除去を行ってもよい。例えば、ポリイミド多孔質膜からなるフィルター、ポリアミドイミド多孔質膜からなるフィルター、ポリイミド多孔質膜及びポリアミドイミド多孔質膜からなるフィルター等を用いて、レジスト組成物の濾過を行ってもよい。前記ポリイミド多孔質膜及び前記ポリアミドイミド多孔質膜としては、例えば、特開２０１６－１５５１２１号公報に記載のもの等が例示される。
In the resist composition of this embodiment, after dissolving the resist material in the component (S), impurities and the like may be removed using a polyimide porous film, a polyamideimide porous film, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous film, a filter made of a polyamideimide porous film, or a filter made of a polyimide porous film and a polyamideimide porous film. Examples of the polyimide porous film and the polyamideimide porous film include those described in JP 2016-155121 A.
以上説明した本実施形態のレジスト組成物は、上述した構成単位（ａ０１）を有する樹脂成分（Ａ１）と、一般式（ｆ１）で表される構成単位を有するフッ素樹脂成分（Ｆ１）とを含有する。
構成単位（ａ０１）は、酸解離性基と、フェノール性水酸基とをいずれも有するため、樹脂成分（Ａ１）中の酸解離性基の含有率を減らすことなく、フェノール性水酸基の含有率を高めることができる。そのため、解像性を低下させることなく、感度を向上させることができる。一方で、構成単位（ａ０１）は、比較的疎水性の高い構造を有するため、現像液親和性、及び、親水性が比較的低い。そこで、アルカリ現像液に対して分解性を示す特定の構成単位を有するフッ素樹脂成分（Ｆ１）を組み合わせることで、現像液親和性、及び、親水性が向上し、アルカリ現像プロセス、水リンスプロセスにおいて、レジスト膜を均一に溶解させることができ、ＣＤＵの改善、及び、さらなる解像性の向上を図ることができる。
したがって、本実施形態のレジスト組成物によれば、高感度化が図れ、解像性及びラフネスの低減性が良好なレジストパターンを形成することができる。 The resist composition of the present embodiment described above contains a resin component (A1) having the structural unit (a01) described above, and a fluororesin component (F1) having a structural unit represented by general formula (f1).
Since the structural unit (a01) has both an acid dissociable group and a phenolic hydroxyl group, the content of the phenolic hydroxyl group can be increased without decreasing the content of the acid dissociable group in the resin component (A1). Therefore, the sensitivity can be improved without decreasing the resolution. On the other hand, since the structural unit (a01) has a relatively highly hydrophobic structure, the developer affinity and hydrophilicity are relatively low. Therefore, by combining with a fluororesin component (F1) having a specific structural unit that shows decomposition in an alkaline developer, the developer affinity and hydrophilicity are improved, and the resist film can be uniformly dissolved in the alkaline development process and the water rinsing process, and the CDU can be improved and the resolution can be further improved.
Therefore, according to the resist composition of this embodiment, it is possible to achieve high sensitivity and form a resist pattern with excellent resolution and reduced roughness.
構成単位（ａ０１）は、酸解離性基と、フェノール性水酸基とをいずれも有するため、樹脂成分（Ａ１）中の酸解離性基の含有率を減らすことなく、フェノール性水酸基の含有率を高めることができる。そのため、解像性を低下させることなく、感度を向上させることができる。一方で、構成単位（ａ０１）は、比較的疎水性の高い構造を有するため、現像液親和性、及び、親水性が比較的低い。そこで、アルカリ現像液に対して分解性を示す特定の構成単位を有するフッ素樹脂成分（Ｆ１）を組み合わせることで、現像液親和性、及び、親水性が向上し、アルカリ現像プロセス、水リンスプロセスにおいて、レジスト膜を均一に溶解させることができ、ＣＤＵの改善、及び、さらなる解像性の向上を図ることができる。
したがって、本実施形態のレジスト組成物によれば、高感度化が図れ、解像性及びラフネスの低減性が良好なレジストパターンを形成することができる。 The resist composition of the present embodiment described above contains a resin component (A1) having the structural unit (a01) described above, and a fluororesin component (F1) having a structural unit represented by general formula (f1).
Since the structural unit (a01) has both an acid dissociable group and a phenolic hydroxyl group, the content of the phenolic hydroxyl group can be increased without decreasing the content of the acid dissociable group in the resin component (A1). Therefore, the sensitivity can be improved without decreasing the resolution. On the other hand, since the structural unit (a01) has a relatively highly hydrophobic structure, the developer affinity and hydrophilicity are relatively low. Therefore, by combining with a fluororesin component (F1) having a specific structural unit that shows decomposition in an alkaline developer, the developer affinity and hydrophilicity are improved, and the resist film can be uniformly dissolved in the alkaline development process and the water rinsing process, and the CDU can be improved and the resolution can be further improved.
Therefore, according to the resist composition of this embodiment, it is possible to achieve high sensitivity and form a resist pattern with excellent resolution and reduced roughness.
（レジストパターン形成方法）
本発明の第２の態様に係るレジストパターン形成方法は、支持体上に、上述した本発明の第１の態様に係るレジスト組成物を用いてレジスト膜を形成する工程、前記レジスト膜を露光する工程、及び前記露光後のレジスト膜を現像してレジストパターンを形成する工程を有する方法である。
かかるレジストパターン形成方法の一実施形態としては、例えば以下のようにして行うレジストパターン形成方法が挙げられる。 (Method of forming a resist pattern)
A method for forming a resist pattern according to the second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition according to the first aspect of the present invention, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.
One embodiment of the resist pattern forming method is, for example, a resist pattern forming method carried out as follows.
本発明の第２の態様に係るレジストパターン形成方法は、支持体上に、上述した本発明の第１の態様に係るレジスト組成物を用いてレジスト膜を形成する工程、前記レジスト膜を露光する工程、及び前記露光後のレジスト膜を現像してレジストパターンを形成する工程を有する方法である。
かかるレジストパターン形成方法の一実施形態としては、例えば以下のようにして行うレジストパターン形成方法が挙げられる。 (Method of forming a resist pattern)
A method for forming a resist pattern according to the second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition according to the first aspect of the present invention, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.
One embodiment of the resist pattern forming method is, for example, a resist pattern forming method carried out as follows.
まず、上述した実施形態のレジスト組成物を、支持体上にスピンナー等で塗布し、ベーク（ポストアプライベーク（ＰＡＢ））処理を、例えば８０～１５０℃の温度条件にて４０～１２０秒間、好ましくは６０～９０秒間施してレジスト膜を形成する。
次に、該レジスト膜に対し、例えば電子線描画装置、ＡｒＦ露光装置等の露光装置を用いて、所定のパターンが形成されたマスク（マスクパターン）を介した露光またはマスクパターンを介さない電子線の直接照射による描画等による選択的露光を行った後、ベーク（ポストエクスポージャーベーク（ＰＥＢ））処理を、例えば８０～１５０℃の温度条件にて４０～１２０秒間、好ましくは６０～９０秒間施す。
次に、前記レジスト膜を現像処理する。現像処理は、アルカリ現像プロセスの場合は、アルカリ現像液を用い、溶剤現像プロセスの場合は、有機溶剤を含有する現像液（有機系現像液）を用いて行う。 First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and then baked (post-applied bake (PAB)) at a temperature of, for example, 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film.
Next, the resist film is selectively exposed using an exposure device such as an electron beam lithography device or an ArF lithography device, either through a mask (mask pattern) on which a predetermined pattern has been formed, or by lithography using direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150° C.
Next, the resist film is developed using an alkaline developer in the case of an alkaline development process, or a developer containing an organic solvent (organic developer) in the case of a solvent development process.
次に、該レジスト膜に対し、例えば電子線描画装置、ＡｒＦ露光装置等の露光装置を用いて、所定のパターンが形成されたマスク（マスクパターン）を介した露光またはマスクパターンを介さない電子線の直接照射による描画等による選択的露光を行った後、ベーク（ポストエクスポージャーベーク（ＰＥＢ））処理を、例えば８０～１５０℃の温度条件にて４０～１２０秒間、好ましくは６０～９０秒間施す。
次に、前記レジスト膜を現像処理する。現像処理は、アルカリ現像プロセスの場合は、アルカリ現像液を用い、溶剤現像プロセスの場合は、有機溶剤を含有する現像液（有機系現像液）を用いて行う。 First, the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and then baked (post-applied bake (PAB)) at a temperature of, for example, 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film.
Next, the resist film is selectively exposed using an exposure device such as an electron beam lithography device or an ArF lithography device, either through a mask (mask pattern) on which a predetermined pattern has been formed, or by lithography using direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of, for example, 80 to 150° C.
Next, the resist film is developed using an alkaline developer in the case of an alkaline development process, or a developer containing an organic solvent (organic developer) in the case of a solvent development process.
現像処理後、好ましくはリンス処理を行う。リンス処理は、アルカリ現像プロセスの場合は、純水を用いた水リンスが好ましく、溶剤現像プロセスの場合は、有機溶剤を含有するリンス液を用いることが好ましい。
溶剤現像プロセスの場合、前記現像処理またはリンス処理の後に、パターン上に付着している現像液またはリンス液を、超臨界流体により除去する処理を行ってもよい。
現像処理後またはリンス処理後、乾燥を行う。また、場合によっては、上記現像処理後にベーク処理（ポストベーク）を行ってもよい。 After the development process, a rinse process is preferably carried out. In the case of an alkaline development process, the rinse process is preferably a water rinse using pure water, and in the case of a solvent development process, a rinse liquid containing an organic solvent is preferably used.
In the case of a solvent development process, after the development treatment or rinsing treatment, a treatment may be carried out in which the developer or rinsing liquid adhering to the pattern is removed by using a supercritical fluid.
After the development or rinsing treatment, the resist is dried. In some cases, a baking treatment (post-baking) may be performed after the development treatment.
溶剤現像プロセスの場合、前記現像処理またはリンス処理の後に、パターン上に付着している現像液またはリンス液を、超臨界流体により除去する処理を行ってもよい。
現像処理後またはリンス処理後、乾燥を行う。また、場合によっては、上記現像処理後にベーク処理（ポストベーク）を行ってもよい。 After the development process, a rinse process is preferably carried out. In the case of an alkaline development process, the rinse process is preferably a water rinse using pure water, and in the case of a solvent development process, a rinse liquid containing an organic solvent is preferably used.
In the case of a solvent development process, after the development treatment or rinsing treatment, a treatment may be carried out in which the developer or rinsing liquid adhering to the pattern is removed by using a supercritical fluid.
After the development or rinsing treatment, the resist is dried. In some cases, a baking treatment (post-baking) may be performed after the development treatment.
支持体としては、特に限定されず、従来公知のものを用いることができ、例えば、電子部品用の基板や、これに所定の配線パターンが形成されたもの等が挙げられる。より具体的には、シリコンウェーハ、銅、クロム、鉄、アルミニウム等の金属製の基板や、ガラス基板等が挙げられる。配線パターンの材料としては、例えば銅、アルミニウム、ニッケル、金等が使用可能である。
The support is not particularly limited, and conventionally known materials can be used, such as substrates for electronic components and substrates on which a predetermined wiring pattern is formed. More specifically, examples include silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, and glass substrates. Materials that can be used for the wiring pattern include, for example, copper, aluminum, nickel, and gold.
露光に用いる波長は、特に限定されず、ＡｒＦエキシマレーザー、ＫｒＦエキシマレーザー、Ｆ２エキシマレーザー、ＥＵＶ（極端紫外線）、ＶＵＶ（真空紫外線）、ＥＢ（電子線）、Ｘ線、軟Ｘ線等の放射線を用いて行うことができる。
The wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays can be used.
レジスト膜の露光方法は、空気や窒素等の不活性ガス中で行う通常の露光（ドライ露光）であってもよく、液浸露光（Ｌｉｑｕｉｄ Ｉｍｍｅｒｓｉｏｎ Ｌｉｔｈｏｇｒａｐｈｙ）であってもよい。
液浸露光は、予めレジスト膜と露光装置の最下位置のレンズ間を、空気の屈折率よりも大きい屈折率を有する溶媒（液浸媒体）で満たし、その状態で露光（浸漬露光）を行う露光方法である。
液浸媒体としては、空気の屈折率よりも大きく、かつ、露光されるレジスト膜の屈折率よりも小さい屈折率を有する溶媒が好ましく、例えば、水、フッ素系不活性液体、シリコン系溶剤、炭化水素系溶剤等が挙げられる。
液浸媒体としては、水が好ましく用いられる。 The exposure method for the resist film may be a normal exposure method (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion exposure (liquid immersion lithography).
Immersion exposure is an exposure method in which the space between the resist film and the lowest lens of the exposure tool is filled with a solvent (immersion medium) that has a refractive index greater than that of air, and exposure (immersion exposure) is then performed in that state.
The immersion medium is preferably a solvent having a refractive index greater than that of air and less than that of the resist film to be exposed, and examples of such a solvent include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
As the liquid immersion medium, water is preferably used.
液浸露光は、予めレジスト膜と露光装置の最下位置のレンズ間を、空気の屈折率よりも大きい屈折率を有する溶媒（液浸媒体）で満たし、その状態で露光（浸漬露光）を行う露光方法である。
液浸媒体としては、空気の屈折率よりも大きく、かつ、露光されるレジスト膜の屈折率よりも小さい屈折率を有する溶媒が好ましく、例えば、水、フッ素系不活性液体、シリコン系溶剤、炭化水素系溶剤等が挙げられる。
液浸媒体としては、水が好ましく用いられる。 The exposure method for the resist film may be a normal exposure method (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion exposure (liquid immersion lithography).
Immersion exposure is an exposure method in which the space between the resist film and the lowest lens of the exposure tool is filled with a solvent (immersion medium) that has a refractive index greater than that of air, and exposure (immersion exposure) is then performed in that state.
The immersion medium is preferably a solvent having a refractive index greater than that of air and less than that of the resist film to be exposed, and examples of such a solvent include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
As the liquid immersion medium, water is preferably used.
アルカリ現像プロセスで現像処理に用いるアルカリ現像液としては、例えば０．１～１０質量％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液が挙げられる。
溶剤現像プロセスで現像処理に用いる有機系現像液が含有する有機溶剤としては、（Ａ）成分（露光前の（Ａ）成分）を溶解し得るものであればよく、公知の有機溶剤の中から適宜選択できる。具体的には、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、ニトリル系溶剤、アミド系溶剤、エーテル系溶剤等の極性溶剤、炭化水素系溶剤等が挙げられる。 The alkaline developer used in the development treatment in the alkaline development process may be, for example, a 0.1 to 10% by weight aqueous solution of tetramethylammonium hydroxide (TMAH).
The organic solvent contained in the organic developer used in the development treatment in the solvent development process may be any organic solvent capable of dissolving the component (A) (the component (A) before exposure), and may be appropriately selected from known organic solvents. Specific examples of the organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.
溶剤現像プロセスで現像処理に用いる有機系現像液が含有する有機溶剤としては、（Ａ）成分（露光前の（Ａ）成分）を溶解し得るものであればよく、公知の有機溶剤の中から適宜選択できる。具体的には、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、ニトリル系溶剤、アミド系溶剤、エーテル系溶剤等の極性溶剤、炭化水素系溶剤等が挙げられる。 The alkaline developer used in the development treatment in the alkaline development process may be, for example, a 0.1 to 10% by weight aqueous solution of tetramethylammonium hydroxide (TMAH).
The organic solvent contained in the organic developer used in the development treatment in the solvent development process may be any organic solvent capable of dissolving the component (A) (the component (A) before exposure), and may be appropriately selected from known organic solvents. Specific examples of the organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.
エステル系溶剤としては、例えば、酢酸メチル、酢酸ブチル、酢酸エチル、酢酸イソプロピル、酢酸ペンチル、酢酸イソペンチル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチルー３－エトキシプロピオネート、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル、ブタン酸ブチル、２－ヒドロキシイソ酪酸メチル、酢酸イソアミル、イソ酪酸イソブチル、及び、プロピオン酸ブチルが挙げられる。
Ester solvents include, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
ニトリル系溶剤としては、例えば、アセトニトリル、プロピオニトリル、バレロニトリル、ブチロニトリル等が挙げられる。
Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, butyronitrile, etc.
有機系現像液には、必要に応じて公知の添加剤を配合できる。該添加剤としては、例えば界面活性剤が挙げられる。界面活性剤としては、特に限定されないが、例えばイオン性や非イオン性のフッ素系及び／又はシリコン系界面活性剤等を用いることができる。
Known additives can be added to the organic developer as necessary. Examples of such additives include surfactants. There are no particular limitations on the surfactants, but examples of surfactants that can be used include ionic or non-ionic fluorine-based and/or silicon-based surfactants.
現像処理は、公知の現像方法により実施することが可能であり、例えば現像液中に支持体を一定時間浸漬する方法（ディップ法）、支持体表面に現像液を表面張力によって盛り上げて一定時間静止する方法（パドル法）、支持体表面に現像液を噴霧する方法（スプレー法）、一定速度で回転している支持体上に一定速度で現像液塗出ノズルをスキャンしながら現像液を塗出し続ける方法（ダイナミックディスペンス法）等が挙げられる。
The development process can be carried out by a known development method, such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it still for a certain period of time (paddle method), a method of spraying the developer on the surface of the support (spray method), or a method of continuously applying developer while scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method).
溶剤現像プロセスで現像処理後のリンス処理に用いるリンス液が含有する有機溶剤としては、例えば前記有機系現像液に用いる有機溶剤として挙げた有機溶剤のうち、レジストパターンを溶解しにくいものを適宜選択して使用できる。通常、炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤およびエーテル系溶剤から選択される少なくとも１種類の溶剤を使用する。
これらの有機溶剤は、いずれか１種を単独で用いてもよく、２種以上を併用してもよい。また、上記以外の有機溶剤や水と混合して用いてもよい。 The organic solvent contained in the rinse solution used in the rinsing treatment after the development treatment in the solvent development process can be appropriately selected from the organic solvents listed above as the organic solvents used in the organic developer, which do not easily dissolve the resist pattern. Usually, at least one solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used.
These organic solvents may be used alone or in combination of two or more thereof, and may be used in combination with other organic solvents or water.
これらの有機溶剤は、いずれか１種を単独で用いてもよく、２種以上を併用してもよい。また、上記以外の有機溶剤や水と混合して用いてもよい。 The organic solvent contained in the rinse solution used in the rinsing treatment after the development treatment in the solvent development process can be appropriately selected from the organic solvents listed above as the organic solvents used in the organic developer, which do not easily dissolve the resist pattern. Usually, at least one solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used.
These organic solvents may be used alone or in combination of two or more thereof, and may be used in combination with other organic solvents or water.
リンス液を用いたリンス処理（洗浄処理）は、公知のリンス方法により実施できる。該リンス処理の方法としては、例えば一定速度で回転している支持体上にリンス液を塗出し続ける方法（回転塗布法）、リンス液中に支持体を一定時間浸漬する方法（ディップ法）、支持体表面にリンス液を噴霧する方法（スプレー法）等が挙げられる。
The rinse treatment (cleaning treatment) using a rinse solution can be carried out by a known rinse method. Examples of the rinse treatment method include a method in which the rinse solution is continuously applied onto a support rotating at a constant speed (spin coating method), a method in which the support is immersed in the rinse solution for a certain period of time (dip method), and a method in which the rinse solution is sprayed onto the surface of the support (spray method).
以上説明した本実施形態のレジストパターン形成方法によれば、上述したレジスト組成物が用いられているため、高感度であり、かつ、解像性及びＣＤＵが良好なレジストパターンを形成することができる。
The resist pattern forming method of this embodiment described above uses the resist composition described above, making it possible to form a resist pattern that is highly sensitive and has good resolution and CDU.
上述した実施形態のレジスト組成物、及び、上述した実施形態のパターン形成方法において使用される各種材料（例えば、レジスト溶剤、現像液、リンス液、反射防止膜形成用組成物、トップコート形成用組成物など）は、金属、ハロゲンを含む金属塩、酸、アルカリ、硫黄原子又はリン原子を含む成分等の不純物を含まないことが好ましい。ここで、金属原子を含む不純物としては、Ｎａ、Ｋ、Ｃａ、Ｆｅ、Ｃｕ、Ｍｎ、Ｍｇ、Ａｌ、Ｃｒ、Ｎｉ、Ｚｎ、Ａｇ、Ｓｎ、Ｐｂ、Ｌｉ、またはこれらの塩などを挙げることができる。これら材料に含まれる不純物の含有量としては、２００ｐｐｂ以下が好ましく、１ｐｐｂ以下がより好ましく、１００ｐｐｔ（ｐａｒｔｓ ｐｅｒ ｔｒｉｌｌｉｏｎ）以下が更に好ましく、１０ｐｐｔ以下が特に好ましく、実質的に含まないこと（測定装置の検出限界以下であること）が最も好ましい。
The resist composition of the above-mentioned embodiment and the various materials used in the pattern formation method of the above-mentioned embodiment (e.g., resist solvent, developer, rinse solution, anti-reflective film forming composition, top coat forming composition, etc.) preferably do not contain impurities such as metals, metal salts containing halogens, acids, alkalis, and components containing sulfur atoms or phosphorus atoms. Here, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof. The content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free (below the detection limit of the measuring device).
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの例によって限定されるものではない。
The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.
＜レジスト組成物の調製＞
（実施例１～１８、比較例１～４）
表１～３に示す各成分を混合して溶解し、各例のレジスト組成物をそれぞれ調製した。 <Preparation of Resist Composition>
(Examples 1 to 18, Comparative Examples 1 to 4)
The components shown in Tables 1 to 3 were mixed and dissolved to prepare resist compositions of each example.
（実施例１～１８、比較例１～４）
表１～３に示す各成分を混合して溶解し、各例のレジスト組成物をそれぞれ調製した。 <Preparation of Resist Composition>
(Examples 1 to 18, Comparative Examples 1 to 4)
The components shown in Tables 1 to 3 were mixed and dissolved to prepare resist compositions of each example.
表１～３中、各略号はそれぞれ以下の意味を有する。［ ］内の数値は配合量（質量部）である。
In Tables 1 to 3, the abbreviations have the following meanings. The numbers in brackets [ ] are the amounts used (parts by mass).
・（Ａ）成分
（Ａ）成分の略号の意味、ＧＰＣ測定により求めた標準ポリスチレン換算の重量平均分子量（Ｍｗ）、分子量分散度（Ｍｗ／Ｍｎ）、及び１３Ｃ－ＮＭＲにより求められた共重合組成比（構造式中の各構成単位の割合（モル比））を以下に示す。 Component (A) The meaning of the abbreviation for component (A), the weight average molecular weight (Mw) and molecular weight dispersity (Mw/Mn) calculated in terms of standard polystyrene determined by GPC measurement, and the copolymerization composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) determined by C -NMR are shown below.
（Ａ）成分の略号の意味、ＧＰＣ測定により求めた標準ポリスチレン換算の重量平均分子量（Ｍｗ）、分子量分散度（Ｍｗ／Ｍｎ）、及び１３Ｃ－ＮＭＲにより求められた共重合組成比（構造式中の各構成単位の割合（モル比））を以下に示す。 Component (A) The meaning of the abbreviation for component (A), the weight average molecular weight (Mw) and molecular weight dispersity (Mw/Mn) calculated in terms of standard polystyrene determined by GPC measurement, and the copolymerization composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) determined by C -NMR are shown below.
（Ａ１）－１：下記の化学式（Ａ１－１）で表される高分子化合物。高分子化合物（Ａ１－１）の重量平均分子量（Ｍｗ）は６６００、分子量分散度（Ｍｗ／Ｍｎ）は１．５６。
（Ａ１）－２：下記の化学式（Ａ１－２）で表される高分子化合物。高分子化合物（Ａ１－２）の重量平均分子量（Ｍｗ）は６４００、分子量分散度（Ｍｗ／Ｍｎ）は１．５７。
（Ａ１）－３：下記の化学式（Ａ１－３）で表される高分子化合物。高分子化合物（Ａ１－３）の重量平均分子量（Ｍｗ）は６５００、分子量分散度（Ｍｗ／Ｍｎ）は１．６３、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－４：下記の化学式（Ａ１－４）で表される高分子化合物。高分子化合物（Ａ１－４）の重量平均分子量（Ｍｗ）は６８００、分子量分散度（Ｍｗ／Ｍｎ）は１．６７、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－５：下記の化学式（Ａ１－５）で表される高分子化合物。高分子化合物（Ａ１－５）の重量平均分子量（Ｍｗ）は６９００、分子量分散度（Ｍｗ／Ｍｎ）は１．６０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－６：下記の化学式（Ａ１－６）で表される高分子化合物。高分子化合物（Ａ１－６）の重量平均分子量（Ｍｗ）は６８００、分子量分散度（Ｍｗ／Ｍｎ）は１．６２、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－７：下記の化学式（Ａ１－７）で表される高分子化合物。高分子化合物（Ａ１－７）の重量平均分子量（Ｍｗ）は７２００、分子量分散度（Ｍｗ／Ｍｎ）は１．６８、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。 (A1)-1: A polymeric compound represented by the following chemical formula (A1-1): The polymeric compound (A1-1) has a weight average molecular weight (Mw) of 6,600 and a molecular weight dispersity (Mw/Mn) of 1.56.
(A1)-2: A polymeric compound represented by the following chemical formula (A1-2): The polymeric compound (A1-2) has a weight average molecular weight (Mw) of 6,400 and a molecular weight dispersity (Mw/Mn) of 1.57.
(A1)-3: A polymeric compound represented by the following chemical formula (A1-3): The polymeric compound (A1-3) has a weight average molecular weight (Mw) of 6,500, a molecular weight dispersity (Mw/Mn) of 1.63, and a copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
(A1)-4: A polymeric compound represented by the following chemical formula (A1-4): The polymeric compound (A1-4) has a weight average molecular weight (Mw) of 6,800, a molecular weight dispersity (Mw/Mn) of 1.67, and a copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
(A1)-5: A polymeric compound represented by the following chemical formula (A1-5): The polymeric compound (A1-5) has a weight average molecular weight (Mw) of 6,900, a molecular weight dispersity (Mw/Mn) of 1.60, and a copolymerization composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
(A1)-6: A polymeric compound represented by the following chemical formula (A1-6): The polymeric compound (A1-6) has a weight average molecular weight (Mw) of 6,800, a molecular weight dispersity (Mw/Mn) of 1.62, and a copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
(A1)-7: A polymeric compound represented by the following chemical formula (A1-7): The polymeric compound (A1-7) has a weight average molecular weight (Mw) of 7,200, a molecular weight dispersity (Mw/Mn) of 1.68, and a copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
（Ａ１）－２：下記の化学式（Ａ１－２）で表される高分子化合物。高分子化合物（Ａ１－２）の重量平均分子量（Ｍｗ）は６４００、分子量分散度（Ｍｗ／Ｍｎ）は１．５７。
（Ａ１）－３：下記の化学式（Ａ１－３）で表される高分子化合物。高分子化合物（Ａ１－３）の重量平均分子量（Ｍｗ）は６５００、分子量分散度（Ｍｗ／Ｍｎ）は１．６３、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－４：下記の化学式（Ａ１－４）で表される高分子化合物。高分子化合物（Ａ１－４）の重量平均分子量（Ｍｗ）は６８００、分子量分散度（Ｍｗ／Ｍｎ）は１．６７、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－５：下記の化学式（Ａ１－５）で表される高分子化合物。高分子化合物（Ａ１－５）の重量平均分子量（Ｍｗ）は６９００、分子量分散度（Ｍｗ／Ｍｎ）は１．６０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－６：下記の化学式（Ａ１－６）で表される高分子化合物。高分子化合物（Ａ１－６）の重量平均分子量（Ｍｗ）は６８００、分子量分散度（Ｍｗ／Ｍｎ）は１．６２、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－７：下記の化学式（Ａ１－７）で表される高分子化合物。高分子化合物（Ａ１－７）の重量平均分子量（Ｍｗ）は７２００、分子量分散度（Ｍｗ／Ｍｎ）は１．６８、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。 (A1)-1: A polymeric compound represented by the following chemical formula (A1-1): The polymeric compound (A1-1) has a weight average molecular weight (Mw) of 6,600 and a molecular weight dispersity (Mw/Mn) of 1.56.
(A1)-2: A polymeric compound represented by the following chemical formula (A1-2): The polymeric compound (A1-2) has a weight average molecular weight (Mw) of 6,400 and a molecular weight dispersity (Mw/Mn) of 1.57.
(A1)-3: A polymeric compound represented by the following chemical formula (A1-3): The polymeric compound (A1-3) has a weight average molecular weight (Mw) of 6,500, a molecular weight dispersity (Mw/Mn) of 1.63, and a copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
(A1)-4: A polymeric compound represented by the following chemical formula (A1-4): The polymeric compound (A1-4) has a weight average molecular weight (Mw) of 6,800, a molecular weight dispersity (Mw/Mn) of 1.67, and a copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
(A1)-5: A polymeric compound represented by the following chemical formula (A1-5): The polymeric compound (A1-5) has a weight average molecular weight (Mw) of 6,900, a molecular weight dispersity (Mw/Mn) of 1.60, and a copolymerization composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
(A1)-6: A polymeric compound represented by the following chemical formula (A1-6): The polymeric compound (A1-6) has a weight average molecular weight (Mw) of 6,800, a molecular weight dispersity (Mw/Mn) of 1.62, and a copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
(A1)-7: A polymeric compound represented by the following chemical formula (A1-7): The polymeric compound (A1-7) has a weight average molecular weight (Mw) of 7,200, a molecular weight dispersity (Mw/Mn) of 1.68, and a copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 50/50.
（Ａ１）－８：下記の化学式（Ａ１－８）で表される高分子化合物。高分子化合物（Ａ１－８）の重量平均分子量（Ｍｗ）は６８００、分子量分散度（Ｍｗ／Ｍｎ）は１．５８、
共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－９：下記の化学式（Ａ１－９）で表される高分子化合物。高分子化合物（Ａ１－９）の重量平均分子量（Ｍｗ）は６８００、分子量分散度（Ｍｗ／Ｍｎ）は１．７１、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ／ｎ＝５０／３０／２０。
（Ａ２）－１：下記の化学式（Ａ２－１）で表される高分子化合物。高分子化合物（Ａ２－１）の重量平均分子量（Ｍｗ）は６６００、分子量分散度（Ｍｗ／Ｍｎ）は１．６６、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。 (A1)-8: A polymer compound represented by the following chemical formula (A1-8). The weight average molecular weight (Mw) of the polymer compound (A1-8) is 6,800, and the molecular weight dispersity (Mw/Mn) is 1.58.
The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) was l/m = 50/50.
(A1)-9: Polymer compound represented by the following chemical formula (A1-9): Polymer compound (A1-9) has a weight average molecular weight (Mw) of 6,800, a molecular weight dispersity (Mw/Mn) of 1.71, and a copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) of l/m/n=50/30/20.
(A2)-1: A polymeric compound represented by the following chemical formula (A2-1): The polymeric compound (A2-1) has a weight average molecular weight (Mw) of 6,600, a molecular weight dispersity (Mw/Mn) of 1.66, and a copolymerization composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) of l/m=50/50.
共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。
（Ａ１）－９：下記の化学式（Ａ１－９）で表される高分子化合物。高分子化合物（Ａ１－９）の重量平均分子量（Ｍｗ）は６８００、分子量分散度（Ｍｗ／Ｍｎ）は１．７１、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ／ｎ＝５０／３０／２０。
（Ａ２）－１：下記の化学式（Ａ２－１）で表される高分子化合物。高分子化合物（Ａ２－１）の重量平均分子量（Ｍｗ）は６６００、分子量分散度（Ｍｗ／Ｍｎ）は１．６６、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝５０／５０。 (A1)-8: A polymer compound represented by the following chemical formula (A1-8). The weight average molecular weight (Mw) of the polymer compound (A1-8) is 6,800, and the molecular weight dispersity (Mw/Mn) is 1.58.
The copolymerization composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) was l/m = 50/50.
(A1)-9: Polymer compound represented by the following chemical formula (A1-9): Polymer compound (A1-9) has a weight average molecular weight (Mw) of 6,800, a molecular weight dispersity (Mw/Mn) of 1.71, and a copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) of l/m/n=50/30/20.
(A2)-1: A polymeric compound represented by the following chemical formula (A2-1): The polymeric compound (A2-1) has a weight average molecular weight (Mw) of 6,600, a molecular weight dispersity (Mw/Mn) of 1.66, and a copolymerization composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) of l/m=50/50.
（Ｂ）－１：下記化学式（Ｂ－１）で表される化合物からなる酸発生剤。
（Ｄ）－１：下記化学式（Ｄ－１）で表される化合物からなる酸拡散制御剤。 (B)-1: An acid generator comprising a compound represented by the following chemical formula (B-1).
(D)-1: An acid diffusion controller consisting of a compound represented by the following chemical formula (D-1).
（Ｄ）－１：下記化学式（Ｄ－１）で表される化合物からなる酸拡散制御剤。 (B)-1: An acid generator comprising a compound represented by the following chemical formula (B-1).
(D)-1: An acid diffusion controller consisting of a compound represented by the following chemical formula (D-1).
（Ｆ１）－１：下記の化学式（Ｆ１－１）で表される高分子化合物。高分子化合物（Ｆ１－１）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－２：下記の化学式（Ｆ１－２）で表される高分子化合物。高分子化合物（Ｆ１－２）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－３：下記の化学式（Ｆ１－３）で表される高分子化合物。高分子化合物（Ｆ１－３）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－４：下記の化学式（Ｆ１－４）で表される高分子化合物。高分子化合物（Ｆ１－４）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。 (F1)-1: A polymer compound represented by the following chemical formula (F1-1): The polymer compound (F1-1) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-2: A polymer compound represented by the following chemical formula (F1-2): The polymer compound (F1-2) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-3: A polymer compound represented by the following chemical formula (F1-3): The polymer compound (F1-3) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-4: A polymer compound represented by the following chemical formula (F1-4): The polymer compound (F1-4) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
（Ｆ１）－２：下記の化学式（Ｆ１－２）で表される高分子化合物。高分子化合物（Ｆ１－２）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－３：下記の化学式（Ｆ１－３）で表される高分子化合物。高分子化合物（Ｆ１－３）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－４：下記の化学式（Ｆ１－４）で表される高分子化合物。高分子化合物（Ｆ１－４）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。 (F1)-1: A polymer compound represented by the following chemical formula (F1-1): The polymer compound (F1-1) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-2: A polymer compound represented by the following chemical formula (F1-2): The polymer compound (F1-2) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-3: A polymer compound represented by the following chemical formula (F1-3): The polymer compound (F1-3) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-4: A polymer compound represented by the following chemical formula (F1-4): The polymer compound (F1-4) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
（Ｆ１）－５：下記の化学式（Ｆ１－５）で表される高分子化合物。高分子化合物（Ｆ１－５）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ／ｎ＝７０／２０／１０。
（Ｆ１）－６：下記の化学式（Ｆ１－６）で表される高分子化合物。高分子化合物（Ｆ１－６）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－７：下記の化学式（Ｆ１－７）で表される高分子化合物。高分子化合物（Ｆ１－７）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－８：下記の化学式（Ｆ１－８）で表される高分子化合物。高分子化合物（Ｆ１－８）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。 (F1)-5: Polymer compound represented by the following chemical formula (F1-5): Polymer compound (F1-5) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) of l/m/n=70/20/10.
(F1)-6: A polymer compound represented by the following chemical formula (F1-6): The polymer compound (F1-6) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-7: A polymer compound represented by the following chemical formula (F1-7): The polymer compound (F1-7) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-8: A polymer compound represented by the following chemical formula (F1-8): The polymer compound (F1-8) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
（Ｆ１）－６：下記の化学式（Ｆ１－６）で表される高分子化合物。高分子化合物（Ｆ１－６）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－７：下記の化学式（Ｆ１－７）で表される高分子化合物。高分子化合物（Ｆ１－７）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－８：下記の化学式（Ｆ１－８）で表される高分子化合物。高分子化合物（Ｆ１－８）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。 (F1)-5: Polymer compound represented by the following chemical formula (F1-5): Polymer compound (F1-5) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) of l/m/n=70/20/10.
(F1)-6: A polymer compound represented by the following chemical formula (F1-6): The polymer compound (F1-6) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-7: A polymer compound represented by the following chemical formula (F1-7): The polymer compound (F1-7) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-8: A polymer compound represented by the following chemical formula (F1-8): The polymer compound (F1-8) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
（Ｆ１）－９：下記の化学式（Ｆ１－９）で表される高分子化合物。高分子化合物（Ｆ１－９）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。
（Ｆ１）－１０：下記の化学式（Ｆ１－１０）で表される高分子化合物。高分子化合物（Ｆ１－１０）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ／ｎ＝７０／２０／１０。
（Ｆ２）－１：下記の化学式（Ｆ２－１）で表される高分子化合物。高分子化合物（Ｆ２－１）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。 (F1)-9: Polymer compound represented by the following chemical formula (F1-9): Polymer compound (F1-9) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-10: Polymer compound represented by the following chemical formula (F1-10): Polymer compound (F1-10) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) of l/m/n=70/20/10.
(F2)-1: A polymer compound represented by the following chemical formula (F2-1): The polymer compound (F2-1) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
（Ｆ１）－１０：下記の化学式（Ｆ１－１０）で表される高分子化合物。高分子化合物（Ｆ１－１０）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ／ｎ＝７０／２０／１０。
（Ｆ２）－１：下記の化学式（Ｆ２－１）で表される高分子化合物。高分子化合物（Ｆ２－１）の重量平均分子量（Ｍｗ）は１５０００、分子量分散度（Ｍｗ／Ｍｎ）は１．７０、共重合組成比（構造式中の各構成単位の割合（モル比））はｌ／ｍ＝７０／３０。 (F1)-9: Polymer compound represented by the following chemical formula (F1-9): Polymer compound (F1-9) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
(F1)-10: Polymer compound represented by the following chemical formula (F1-10): Polymer compound (F1-10) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) of l/m/n=70/20/10.
(F2)-1: A polymer compound represented by the following chemical formula (F2-1): The polymer compound (F2-1) has a weight average molecular weight (Mw) of 15,000, a molecular weight dispersity (Mw/Mn) of 1.70, and a copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of l/m = 70/30.
（Ｓ）－１：プロピレングリコールモノメチルエーテルアセテート／プロピレングリコールモノメチルエーテル／乳酸エチル／ジアセトンアルコール＝４５／２５／１５／１５（質量比）の混合溶剤。
(S)-1: A mixed solvent of propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether/ethyl lactate/diacetone alcohol = 45/25/15/15 (mass ratio).
＜レジストパターンの形成＞
ヘキサメチルジシラザン（ＨＭＤＳ）処理を施した８インチシリコン基板上に、各例のレジスト組成物をそれぞれ、スピンナーを用いて塗布し、ホットプレート上で、温度１１０℃で６０秒間のプレベーク（ＰＡＢ）処理を行い、乾燥することにより、膜厚５０ｎｍのレジスト膜を形成した。
次に、前記レジスト膜に対し、電子線描画装置ＪＥＯＬ－ＪＢＸ－９３００ＦＳ（日本電子株式会社製）を用い、加速電圧１００ｋＶにて、直径３２ｎｍのホールが等間隔（ピッチ６４ｎｍ）に配置されたコンタクトホールパターン（以下「ＣＨパターン」という。）とする描画（露光）を行った。その後、１００℃で６０秒間の露光後加熱（ＰＥＢ）処理を行った。
次いで、２３℃にて、２．３８質量％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液「ＮＭＤ－３」（商品名、東京応化工業株式会社製）を用いて、６０秒間のアルカリ現像を行った。その後、純水を用いて１５秒間水リンス処理を行った。
その結果、直径３２ｎｍのホールが等間隔（ピッチ６４ｎｍ）に配置されたＣＨパターンが形成された。 <Formation of Resist Pattern>
Each resist composition of the examples was applied using a spinner onto an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and the substrate was pre-baked (PAB) on a hot plate at a temperature of 110° C. for 60 seconds, followed by drying to form a resist film with a thickness of 50 nm.
Next, the resist film was exposed to light using an electron beam lithography system JEOL-JBX-9300FS (manufactured by JEOL Ltd.) at an acceleration voltage of 100 kV to form a contact hole pattern (hereinafter referred to as a "CH pattern") in which holes with a diameter of 32 nm were arranged at equal intervals (pitch of 64 nm).Then, a post-exposure bake (PEB) treatment was performed at 100° C. for 60 seconds.
Next, alkaline development was carried out for 60 seconds using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C. After that, a water rinsing treatment was carried out for 15 seconds using pure water.
As a result, a CH pattern was formed in which holes having a diameter of 32 nm were arranged at equal intervals (pitch 64 nm).
ヘキサメチルジシラザン（ＨＭＤＳ）処理を施した８インチシリコン基板上に、各例のレジスト組成物をそれぞれ、スピンナーを用いて塗布し、ホットプレート上で、温度１１０℃で６０秒間のプレベーク（ＰＡＢ）処理を行い、乾燥することにより、膜厚５０ｎｍのレジスト膜を形成した。
次に、前記レジスト膜に対し、電子線描画装置ＪＥＯＬ－ＪＢＸ－９３００ＦＳ（日本電子株式会社製）を用い、加速電圧１００ｋＶにて、直径３２ｎｍのホールが等間隔（ピッチ６４ｎｍ）に配置されたコンタクトホールパターン（以下「ＣＨパターン」という。）とする描画（露光）を行った。その後、１００℃で６０秒間の露光後加熱（ＰＥＢ）処理を行った。
次いで、２３℃にて、２．３８質量％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液「ＮＭＤ－３」（商品名、東京応化工業株式会社製）を用いて、６０秒間のアルカリ現像を行った。その後、純水を用いて１５秒間水リンス処理を行った。
その結果、直径３２ｎｍのホールが等間隔（ピッチ６４ｎｍ）に配置されたＣＨパターンが形成された。 <Formation of Resist Pattern>
Each resist composition of the examples was applied using a spinner onto an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and the substrate was pre-baked (PAB) on a hot plate at a temperature of 110° C. for 60 seconds, followed by drying to form a resist film with a thickness of 50 nm.
Next, the resist film was exposed to light using an electron beam lithography system JEOL-JBX-9300FS (manufactured by JEOL Ltd.) at an acceleration voltage of 100 kV to form a contact hole pattern (hereinafter referred to as a "CH pattern") in which holes with a diameter of 32 nm were arranged at equal intervals (pitch of 64 nm).Then, a post-exposure bake (PEB) treatment was performed at 100° C. for 60 seconds.
Next, alkaline development was carried out for 60 seconds using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C. After that, a water rinsing treatment was carried out for 15 seconds using pure water.
As a result, a CH pattern was formed in which holes having a diameter of 32 nm were arranged at equal intervals (pitch 64 nm).
［最適露光量（Ｅｏｐ）の評価］
前記のレジストパターンの形成方法によってターゲットサイズのＣＨパターンが形成される最適露光量Ｅｏｐ（μＣ／ｃｍ２）を求めた。その結果を表４及び５を示す。 [Evaluation of Optimal Exposure (Eop)]
The optimum exposure dose Eop (μC/cm 2 ) at which a CH pattern of the target size was formed by the above resist pattern forming method was determined. The results are shown in Tables 4 and 5.
前記のレジストパターンの形成方法によってターゲットサイズのＣＨパターンが形成される最適露光量Ｅｏｐ（μＣ／ｃｍ２）を求めた。その結果を表４及び５を示す。 [Evaluation of Optimal Exposure (Eop)]
The optimum exposure dose Eop (μC/cm 2 ) at which a CH pattern of the target size was formed by the above resist pattern forming method was determined. The results are shown in Tables 4 and 5.
［パターン寸法の面内均一性（ＣＤＵ）の評価］
上記の＜レジストパターンの形成＞によって形成されたＣＨパターンについて、測長ＳＥＭ（走査型電子顕微鏡、加速電圧８００Ｖ、商品名：Ｓ－９３８０ 、日立ハイテク社製）により、ＣＨパターン上空から観察し、各ホールのホール直径（ｎｍ）を測定した。そして、その測定結果から算出した標準偏差（σ）の３倍値（３σ）を求めた。その結果を「ＣＤＵ（ｎｍ）」として表４及び５に示す。
このようにして求められる３σは、その値が小さいほど、該レジスト膜に形成された複数のホールの寸法（ＣＤ）均一性が高いことを意味する。 [Evaluation of in-plane uniformity (CDU) of pattern dimensions]
The CH pattern formed by the above <Formation of Resist Pattern> was observed from above the CH pattern using a length measuring SEM (scanning electron microscope, accelerating voltage 800V, product name: S-9380, manufactured by Hitachi High-Technologies Corporation), and the hole diameter (nm) of each hole was measured. Then, a triple value (3σ) of the standard deviation (σ) calculated from the measurement results was obtained. The results are shown in Tables 4 and 5 as "CDU (nm)".
The smaller the value of 3σ thus determined, the higher the uniformity of the dimensions (CD) of the multiple holes formed in the resist film.
上記の＜レジストパターンの形成＞によって形成されたＣＨパターンについて、測長ＳＥＭ（走査型電子顕微鏡、加速電圧８００Ｖ、商品名：Ｓ－９３８０ 、日立ハイテク社製）により、ＣＨパターン上空から観察し、各ホールのホール直径（ｎｍ）を測定した。そして、その測定結果から算出した標準偏差（σ）の３倍値（３σ）を求めた。その結果を「ＣＤＵ（ｎｍ）」として表４及び５に示す。
このようにして求められる３σは、その値が小さいほど、該レジスト膜に形成された複数のホールの寸法（ＣＤ）均一性が高いことを意味する。 [Evaluation of in-plane uniformity (CDU) of pattern dimensions]
The CH pattern formed by the above <Formation of Resist Pattern> was observed from above the CH pattern using a length measuring SEM (scanning electron microscope, accelerating voltage 800V, product name: S-9380, manufactured by Hitachi High-Technologies Corporation), and the hole diameter (nm) of each hole was measured. Then, a triple value (3σ) of the standard deviation (σ) calculated from the measurement results was obtained. The results are shown in Tables 4 and 5 as "CDU (nm)".
The smaller the value of 3σ thus determined, the higher the uniformity of the dimensions (CD) of the multiple holes formed in the resist film.
［限界解像性の評価］
上記ＣＨパターンが形成される最適露光量（Ｅｏｐ）における限界解像度、具体的には、最適露光量（Ｅｏｐ）から露光量を少しずつ減少させてＣＨパターンを形成していく際に、解像するパターンのホール直径（ｎｍ）を、走査型電子顕微鏡Ｓ－９３８０（日立ハイテク社製）を用いて求めた。その結果を表４及び５を示す。 [Evaluation of limiting resolution]
The limiting resolution at the optimum exposure dose (Eop) at which the above CH pattern is formed, specifically, the hole diameter (nm) of the resolved pattern when the exposure dose is gradually decreased from the optimum exposure dose (Eop) to form the CH pattern, was determined using a scanning electron microscope S-9380 (manufactured by Hitachi High-Tech Corporation). The results are shown in Tables 4 and 5.
上記ＣＨパターンが形成される最適露光量（Ｅｏｐ）における限界解像度、具体的には、最適露光量（Ｅｏｐ）から露光量を少しずつ減少させてＣＨパターンを形成していく際に、解像するパターンのホール直径（ｎｍ）を、走査型電子顕微鏡Ｓ－９３８０（日立ハイテク社製）を用いて求めた。その結果を表４及び５を示す。 [Evaluation of limiting resolution]
The limiting resolution at the optimum exposure dose (Eop) at which the above CH pattern is formed, specifically, the hole diameter (nm) of the resolved pattern when the exposure dose is gradually decreased from the optimum exposure dose (Eop) to form the CH pattern, was determined using a scanning electron microscope S-9380 (manufactured by Hitachi High-Tech Corporation). The results are shown in Tables 4 and 5.
表４及び５に示す通り、実施例のレジスト組成物は、比較例のレジスト組成物に比べて、高感度化を図りつつ、解像性及びＣＤＵがいずれも良好であることが確認できた。
As shown in Tables 4 and 5, it was confirmed that the resist compositions of the examples had higher sensitivity and better resolution and CDU than the resist compositions of the comparative examples.
以上、本発明の好ましい実施例を説明したが、本発明はこれら実施例に限定されることはない。本発明の趣旨を逸脱しない範囲で、構成の付加、省略、置換、およびその他の変更が可能である。本発明は前述した説明によって限定されることはなく、添付のクレームの範囲によってのみ限定される。
The above describes preferred embodiments of the present invention, but the present invention is not limited to these embodiments. Addition, omission, substitution, and other modifications of the configuration are possible without departing from the spirit of the present invention. The present invention is not limited by the above description, but is limited only by the scope of the attached claims.
Claims (7)
- 露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化するレジスト組成物であって、
酸の作用により現像液に対する溶解性が変化する樹脂成分（Ａ１）と、
アルカリ現像液に対して分解性を示すフッ素添加剤成分（Ｆ）とを含有し、
前記樹脂成分（Ａ１）は、下記一般式（ａ０－１）で表される化合物から誘導される構成単位（ａ０１）を有し、
前記フッ素添加剤成分（Ｆ）は、下記一般式（ｆ１）で表される構成単位を有するフッ素樹脂成分（Ｆ１）を含む、レジスト組成物。
a resin component (A1) whose solubility in a developer changes under the action of an acid;
and a fluorine additive component (F) that is decomposable in an alkaline developer,
The resin component (A1) has a structural unit (a01) derived from a compound represented by the following general formula (a0-1):
The resist composition, wherein the fluorine additive component (F) comprises a fluorine resin component (F1) having a structural unit represented by the following general formula (f1):
- 前記フッ素樹脂成分（Ｆ１）は、下記一般式（ｆ１－１）で表される構成単位を有する、請求項１に記載のレジスト組成物。
- 前記フッ素樹脂成分（Ｆ１）は、下記一般式（ｆ１－２）で表される構成単位を有する、請求項１に記載のレジスト組成物。
- 前記フッ素樹脂成分（Ｆ１）は、さらに、酸の作用により極性が増大する酸分解性基を含む構成単位（ａ１）を有する、請求項１に記載のレジスト組成物。 The resist composition according to claim 1, wherein the fluororesin component (F1) further comprises a structural unit (a1) containing an acid-decomposable group whose polarity increases under the action of an acid.
- 前記構成単位（ａ０１）は、下記一般式（ａ０－１－１）で表される構成単位である、請求項１に記載のレジスト組成物。
式（ａ０－ｒ－２）中、Ｒａ０４～Ｒａ０６は、それぞれ独立に、炭化水素基であり、Ｒａ０５及びＲａ０６は互いに結合して環を形成してもよい。＊は結合手を示す。
式（ａ０－ｒ－３）中、Ｒａ０７は、炭化水素基である。Ｒａ０８ａ及びＲａ０８ｂは、それぞれ独立に、水素原子、ハロゲン原子又はアルキル基である。Ｒａ０９は、水素原子又は炭化水素基である。Ｒａ０７とＲａ０８ａ又はＲａ０８ｂとは、互いに結合して環を形成してもよい。Ｒａ０８ａ又はＲａ０８ｂと、Ｒａ０９とは、互いに結合して環を形成してもよい。＊は結合手を示す。］ 2. The resist composition according to claim 1, wherein the structural unit (a01) is a structural unit represented by the following general formula (a0-1-1):
In formula (a0-r-2), Ra 04 to Ra 06 each independently represent a hydrocarbon group, and Ra 05 and Ra 06 may be bonded to each other to form a ring. * represents a bond.
In formula (a0-r-3), Ra 07 is a hydrocarbon group. Ra 08a and Ra 08b are each independently a hydrogen atom, a halogen atom, or an alkyl group. Ra 09 is a hydrogen atom or a hydrocarbon group. Ra 07 and Ra 08a or Ra 08b may be bonded to each other to form a ring. Ra 08a or Ra 08b and Ra 09 may be bonded to each other to form a ring. * indicates a bond.] - 支持体上に、請求項１に記載のレジスト組成物を用いてレジスト膜を形成する工程、前記レジスト膜を露光する工程、及び前記露光後のレジスト膜を現像してレジストパターンを形成する工程を有する、レジストパターン形成方法。 A method for forming a resist pattern, comprising the steps of forming a resist film on a support using the resist composition according to claim 1, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.
- 前記のレジスト膜を露光する工程において、前記レジスト膜に、ＥＵＶ（極端紫外線）又はＥＢ（電子線）を露光する、請求項６に記載のレジストパターン形成方法。 The method for forming a resist pattern according to claim 6, wherein in the step of exposing the resist film, the resist film is exposed to EUV (extreme ultraviolet) or EB (electron beam).
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