Method for manufacturing resist compositions and resist patterns

Abstract

To provide a resist composition from which a resist pattern having good line edge roughness can be produced.SOLUTION: The resist composition contains a compound represented by formula (I) and a resin having a first acid-labile group. The resin contains: at least one selected from the group consisting of structural units represented by formula (a1-1) and structural units represented by formula (a1-2); and a structural unit represented by formula (a3-4).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention provides a resist composition and a method for manufacturing a resist pattern using the resist composition. Regarding etc. [Background technology]

[0002] Patent Document 1 contains a compound with the following structural formula, a resin with the following structural formula, and an acid generator. A resist composition is described. TIFF0007927934000001.tif2789 [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2002-258483 [Overview of the project] [Problems that the invention aims to solve]

[0004] The resist pattern formed from the above resist composition has a higher line edge roughness ( The objective is to provide a resist composition in which LER forms a good resist pattern. ru. [Means for solving the problem]

[0005] This invention includes the following inventions. [1] A compound represented by formula (I), a resin having a primary acid-unstable group, and an acid generator. A resist composition having the resin having the first acid-unstable group is of formula (a1-1) A minimum number of structural units selected from the group consisting of the structural units represented and the structural units represented by formula (a1-2) A resist composition containing one type of resist. JPEG0007927934000002.jpg5258 [In formula (I), L 1 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms which may have a substituent. R 1 represents a second acid-labile group. R 2 represents *-L 1 -OH, *-L 1 -O-R 1 , *-X 1 -Ph-L 1 -OH or *- X 1 -Ph-L 1 -O-R 1 represents, and * represents a binding site to the benzene ring. R 1 and R 2 may together form a group having an acetal ring structure. X 1 represents a single bond, an alkanediyl group having 1 to 6 carbon atoms, -O-, -S-, -SO- or - SO2-. Ph represents a phenylene group which may have a substituent. m2 represents any integer of 0 to 3, when m2 is 1 or more, a plurality of L 1 and a plurality of R 1 may each be the same or different from each other, when m2 is 2 or more, a plurality of R 2 may be the same or different from each other. R 3 represents a halogen atom, a fluoroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and -CH2- contained in said alkyl group may be replaced by -O- or -CO- . m3 represents any integer of 0 to 5, when m3 is 2 or more, a plurality of R 3 may be the same or different from each other; provided that 0≦m2+m3≦5.] JPEG0007927934000003.jpg3884[In formula (a1-1) and formula (a1-2), La1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO-O- represents k1 represents an integer from 1 to 7, and * represents the bonding site with -CO-. R a4 and R a5 Each of these independently contains a hydrogen atom, a halogen atom, or a halogen atom. This represents an alkyl group that may have 1 to 6 carbon atoms. R a6 and R a7 These are, independently, alkyl groups with 1 to 8 carbon atoms and alkeh groups with 2 to 8 carbon atoms. Nyl group, alicyclic hydrocarbon group having 3 to 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms, or These represent the base formed by combining them. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3. [2] L 1 However, C1-C4 alkanediyls may have single bonds or halogen atoms. The resist composition described in [1] is a base. [3] R 1 However, the group is represented by formula (1a) or formula (2a) [1] or [2] The resist composition described in [2]. TIFF0007927934000004.tif2158 [In formula (1a), R aa1 , R aa2 and R aa3 Each of them independently has substituents A good C1-C8 alkyl group, or an alkenyl group that may have substituents C2-C8 , a cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms which may have substituents or which have substituents R represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may be present, or aa1 and R aa2 They are connected to each other together form an alicyclic hydrocarbon group having 3 to 20 carbon atoms with the carbon atom to which they bind . naa represents 0 or 1. * represents a binding site.] TIFF0007927934000005.tif2051[In formula (2a), R aa1’ and R aa2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 1 2 carbon atoms, R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ bind to each other and together with -C-X a - to which they bind form a heterocyclic group having 3 to 20 carbon atoms, and -CH₂- contained in said hydrocarbon group and said heterocyclic group may be replaced by -O- or - S-. X a represents an oxygen atom or a sulfur atom. * represents a binding site.] [4] R 1 is a group represented by formula (2a), and R aa2’ and R aa3’ bind to each other and together with -C-X a - to which they bind form a heterocyclic group having 3 to 20 carbon atoms, the resist composition according to [3].[[$END]] [5] m2 is 1 or 2, and at least one R 2 is *-L 1 -OH, the resist composition according to any one of [1] to [4] . [6] m2 is 1 or 2, and at least one R 2 is *-L 1 -O-R 1 , the resist composition according to any one of [1] to [4] . [7] m2 is 1 or 2, and at least one R 2 is *-X1 -Ph-L 1 -OR 1 [1] to [4] A resist composition as described below. [8] m3 is 1 or 2, R 3 A resist composition according to any of [1] to [7], wherein the atom is a halogen atom. [9] A resin having an acid-unstable group further comprises a structural unit represented by formula (a2-A) A resist composition according to any one of [1] to [8]. TIFF0007927934000006.tif3843[In formula (a2-A), R a50 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents an alkyl group. R a51 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxyalkyl group having 2 to 12 carbon atoms Lucoxy group, C2-C4 alkylcarbonyl group, C2-C4 alkylcarbonyl This represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or * -X a51 -(A a52 -X a52 ) nb - represents -R a50 they combine This represents the bonding site with the carbon atom. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent -O-, -CO-O-, or -O-CO- independently. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, Number Ra51 They may be identical or different from one another.

[10] The acid generator contains a salt represented by formula (B1) as described in any of [1] to [9]. A resist composition. TIFF0007927934000007.tif2859[In formula (B1), Q b1 and Q b2 Each of these independently comprises a fluorine atom or a perfluorinated atom having 1 to 6 carbon atoms. This represents a luquill group. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and this divalent saturated hydrocarbon group The -CH2- contained may be replaced by -O- or -CO-, and the divalent saturated carbon The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms or hydroxyl groups. Y is a methyl group which may have substituents or a C3-C2 group which may have substituents 4 represents an alicyclic hydrocarbon group, and the -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced with SO2- or -CO-. Z + This represents an organic cation.

[11] Further contains a salt that generates an acid that is less acidic than the acid generated by the acid generator. A resist composition according to any one of [1] to

[10] .

[12] (1) Apply the resist composition described in any of [1] to

[11] onto the substrate. The process, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) A method for manufacturing a resist pattern, comprising the step of developing the composition layer after heating. [Effects of the Invention]

[0006] By using the resist composition of the present invention, a resist pattern with favorable line edge roughness (LER) can be produced. DESCRIPTION OF EMBODIMENTS

[0007] In the present specification, the term "(meth)acrylic monomer" refers to CH2=CH-CO- a monomer having the structure and a monomer having the structure CH2=C(CH3)-CO- selected from the group consisting of the foregoing, meaning at least one species selected therefrom. Similarly, "(meth)acrylate" and "(meth)acrylic acid" mean at least one species selected from the group consisting of acrylate and methacrylate, and at least one species selected from the group consisting of acrylic acid and methacrylic acid, respectively. When a structural unit having CH2=C(CH3)-CO- or CH2=CH-C O- is exemplified, structural units having both groups shall also be considered similarly exemplified. Further, for groups described in the present specification that can have both a linear structure and a branched structure, either structure is acceptable. The term "combined group" means a group obtained by bonding two or more of the exemplified groups, and the valence of these groups may be changed appropriately depending on the bonding form. The terms "derived from" or "derived" mean that the polymerizable C=C bond contained in the molecule is converted into a -C-C- group via polymerization. When stereoisomers exist, all stereoisomers are included. In the present specification, the "solid content of the resist composition" means the total of components obtained by removing the solvent (E) described below from the total amount of the resist composition.

[0008] <Resist Composition> The resist composition of the present invention comprises a compound represented by formula (I) (hereinafter referred to as "compound (I)")[[$END]] ​(In some cases) and structural units represented by formula (a1-1) and structures represented by formula (a1-2) A resin having an acid-unstable group that includes at least one selected from the group consisting of units (hereinafter referred to as "resin") (A) may be used as an acid generator (hereinafter referred to as "acid generator (B)"). . ) contains. Here, "acid-unstable group" refers to a group that has a leaving group and leaves when in contact with an acid. The group is removed, transforming into a constituent unit having a hydrophilic group (e.g., a hydroxyl group or a carboxyl group). It means the base to be replaced. The resist composition of the present invention may further contain resins other than resin (A). The resist composition of the present invention generates an acid that is less acidic than the acid generated by the acid generator. It may contain a quencher such as salt (hereinafter sometimes referred to as "quencher (C)"). Preferably, it contains a solvent (which may be referred to as "solvent (E)" below).

[0009] <Compound (I)> The resist composition of the present invention contains compound (I). TIFF0007927934000008.tif5158[In formula (I), all symbols have the same meaning as described above.]

[0010] L 1 The alkanediyl groups in this context include methylene, ethylene, and propane-1,3. -diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1, Linear alkanediyl groups such as 6-diyl groups; and Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Examples include branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group. The number of carbon atoms in the lucandiyl group is preferably 1 to 4, and more preferably 1 to 3. L 1 The alkanediyl group may have substituents such as halogen atoms and hydroxyl groups. cyano group, carboxyl group, alkyl group with 1 to 12 carbon atoms, alkyl fluoride with 1 to 6 carbon atoms A C1 group, an alkoxy group having 1 to 12 carbon atoms, and a group formed by combining two or more of these groups. It can be listed. Examples of halogen atoms mentioned above include fluorine, chlorine, bromine, and iodine. It can be done. The C1-C12 alkyl groups mentioned above include methyl, ethyl, propyl, and iso Propyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, Examples include octyl groups and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9. , more preferably 1 to 6, even more preferably 1 to 4, even more The answer is 1 to 3. The above-mentioned C1-C6 alkyl fluorides include trifluoromethyl groups and difluoromethyl groups. Methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2 -Tetrafluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafull Oropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-Octaful Olobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonaph Examples include fluoride alkyl groups such as ruolopentyl group and perfluorohexyl group. The number of carbon atoms in the alkyl group is preferably 1 to 4, and more preferably 1 to 3. The above-mentioned alkoxy groups having 1 to 12 carbon atoms include methoxy groups, ethoxy groups, and propoxy groups. Group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethyl Hexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group Examples include xy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 4, and more preferably The values ​​are 1 to 3. Groups that combine two or more of the above-mentioned types include alkoxycarbonyl groups having 2 to 13 carbon atoms. , alkylcarbonyl groups having 2 to 13 carbon atoms and alkylcarbonyl oxyl groups having 2 to 13 carbon atoms Examples include the C group. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and Alkylcarbonyloxy groups having 2 to 13 carbon atoms are the alkyl or alkoxy groups mentioned above. This represents a group in which a carbonyl group or a carbonyloxy group is bonded to a cy group. Examples of alkoxycarbonyl groups with 2 to 13 carbon atoms include the methoxycarbonyl group and the ethoxycarbonyl group. Examples include carbonyl groups and butoxycarbonyl groups, which are alkylcarbonyl groups with 2 to 13 carbon atoms. Examples of acetyl groups include acetyl groups, propionyl groups, and butyryl groups, with 2 to 1 carbon atoms. 3. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, Examples include butyryloxy groups. L 1 This is an alkanediyl group having 1 to 4 carbon atoms, which may have single bonds or substituents. Preferably, a C1-C4 alkanediyl group which may have a single bond or a halogen atom. It is more preferable that there be a bond, and even more preferable that it be a single bond or -(CF3)2C-.

[0011] R 1 The second acid-unstable group is R when it comes into contact with an acid (e.g., p-toluenesulfonic acid). 1 in This refers to a group that, when detached, forms a hydroxyl group. Examples of the second acid-unstable group include the group represented by formula (1a) (hereinafter, depending on the case, "acid-unstable"). This is called a "stable group (1a)" (or, depending on the circumstances, an "acid-unstable group"), a group represented by formula (2a) (hereinafter referred to as an "acid-unstable group"). (2a) is an example of this. TIFF0007927934000009.tif2159 [In formula (1a), R aa1 , R aa2 and R aa3 Each of them independently has substituents A good C1-C8 alkyl group, or an alkenyl group that may have substituents C2-C8 , a cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms which may have substituents or which have substituents R represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may be present, or aa1 and R aa2 They are connected to each other Together, they form alicyclic hydrocarbon groups with 3 to 20 carbon atoms, along with the carbon atoms to which they are bonded. . naa represents 0 or 1. * indicates a connection site. TIFF0007927934000010.tif2051 [In formula (2a), R aa1’ and R aa2’ Each of these is independently a hydrogen atom or a carbon atom with 1 to 1 carbon atoms. Represents two hydrocarbon groups, R aa3’ represents a hydrocarbon group with 1 to 20 carbon atoms, or R aa2’ and R aa3’ They combine with each other and they join together -CX a -along with 3 to 20 carbon atoms A heterocyclic group is formed, and the hydrocarbon group and the -CH2- contained in the heterocyclic group are -O- or - It may be replaced with S-. Note that X a and the -C contained in the hydrocarbon group or the heterocyclic group The -O- and -S- that replaced H2- were each replaced by one carbon atom, and the number of carbon atoms and The calculation shall be performed as follows. Unless otherwise specified, the method for counting the number of carbon atoms is the same hereafter, and description thereof will be omitted . X a represents an oxygen atom or a sulfur atom. * represents a binding site.]

[0012] R aa1 , R aa2 and R aa3 examples of the alkyl group for include a methyl group, an ethyl group, a propyl group, n -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like . For R aa1 , R aa2 and R aa3 , the number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3. R aa1 , R aa2 and R aa3 examples of the alkenyl group for include an ethenyl group, a propenyl group, an isoprop enyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hex enyl group, a heptenyl group, an octynyl group, an isooctynyl group, and a nonenyl group. R aa1 , R aa2 and R aa3 the alicyclic hydrocarbon group for may be either monocyclic or polycyclic. examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cyclohep tyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include, for example, a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a binding site), and the like. For R aa1 , R aa2 and R aa3 , the alicyclic hydrocarbon the number of carbon atoms in the group is preferably 3 to 16, and more preferably 3 to 12. TIFF0007927934000011.tif9159R aa1 , R aa2 and R aa3 Examples of aromatic hydrocarbon groups include phenyl group, naphthyl group, and ammonium group. Examples of aryl groups include tolyl groups, biphenyl groups, and phenanthryl groups. Note, R aa1 , R aa2 and R aa3 These are alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, and aromatic groups. It may also be a combination of aromatic hydrocarbon groups. The combined groups in this case will be described later. Examples similar to those exemplified in formula (1) can be given.

[0013] A substituent on an alkyl group having 1 to 8 carbon atoms may include a substituent having 2 to 8 carbon atoms. Alkenyl groups, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, aromatic hydrocarbons with 6 to 18 carbon atoms Examples include the group, which may have substituents as a substituent of an alkenyl group having 2 to 8 carbon atoms. These are alkyl groups with 1 to 8 carbon atoms, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, and groups with 6 to 18 carbon atoms. Examples include aromatic hydrocarbon groups. Alicyclic carbon groups having 3 to 20 carbon atoms, which may have substituents. Substituents for the hydrogen group include alkyl groups with 1 to 8 carbon atoms, alkenyl groups with 2 to 8 carbon atoms, and carbon atoms. Examples include aromatic hydrocarbon groups with 6 to 18 prime numbers. These may have substituents, or have 6 to 1 carbon atoms. The substituents on the aromatic hydrocarbon group 8 include alkyl groups with 1 to 8 carbon atoms and alkyl groups with 2 to 8 carbon atoms. Examples include lukenyl groups and alicyclic hydrocarbon groups having 3 to 20 carbon atoms. More specifically, alkyl A group that combines a cyclohexyl group and an alicyclic hydrocarbon group (methylcyclohexyl group, dimethylcyclohexyl group) Hexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, (Alkylcycloalkyl groups such as norbornyl ethyl group or cycloalkylalkyl groups), Aromatic hydrocarbon groups having aralkyl groups such as benzyl groups and alkyl groups (p-methylphenyl butyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group (e.g., 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group), alicyclic carbon Aromatic hydrocarbon groups containing hydrogen groups (p-cyclohexylphenyl group, p-adamantilphanic group) Examples include phenyl groups, phenylcyclohexyl groups, and other aryl-cycloalkyl groups. ru. naa is preferably 1.

[0014] R aa1 and R aa2 -C(R aa1 )( R aa2 )(R aa3 Examples of such groups include the following: Alicyclic hydrocarbon groups are preferably carbon The number of prime numbers is 3 to 16, and more preferably 3 to 12 carbon atoms. * indicates the bond site with -O- represent. TIFF0007927934000012.tif30140

[0015] The group represented by formula (1a) is the 1,1-dialkylalkoxycarbonyl group (formula ( 1a) In R aa1 , R aa2 and R aa A group in which is an alkyl group, preferably tert-br Toxycarbonyl group), 2-alkyladamantan-2-yloxycarbonyl group (formula ( 1a) Medium, R aa1 , R aa2 And the carbon atoms to which these are bonded form an adamantyl group, R aa 3 (A group in which is an alkyl group) and 1-(adamantan-1-yl)-1-alkylalkoxy cycarbonyl group (in formula (1a), Raa1 and R aa2 is an alkyl group, R aa3 Adamant Examples include groups that are chill groups.

[0016] R aa1' , R aa2' and R aa3' Examples of hydrocarbon groups include alkyl groups, alicyclic hydrocarbon groups, and aromatic groups. Examples include aromatic hydrocarbon groups and groups formed by combining them. Alkyl and alicyclic hydrocarbon groups are R aa1 , R aa2 and R aa3 The same base as the one mentioned above It can be listed. Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, alkylcycloalkyl groups or cycloalkylalkyl groups), benzyl groups, etc. Aromatic hydrocarbon groups having a alkyl group (p-methylphenyl group, p-ter) t-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-die Fragrances having alicyclic hydrocarbon groups (such as ethylphenyl group and 2-methyl-6-ethylphenyl group) Fragrance group hydrocarbons (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), f Examples include aryl-cycloalkyl groups such as phenylcyclohexyl groups. R aa2' and R aa3' They bond with each other, and the carbon atoms and X that they bond to are bonded together. a along with complex algebras When forming a group, -C(R aa1' )(R aa2' )-X a -(R aa3' ) The following are the basis These can be listed. * indicates a binding site. R aa2' and R aa3' They combine with each other and combine them carbon atoms and X a When forming a heterocyclic group together, it forms a heterocyclic group with 3 to 8 carbon atoms. It is preferable to do so. TIFF0007927934000013.tif22152R aa1' and R aa2' Preferably, at least one of them is a hydrogen atom.

[0017] Specific examples of acid-unstable groups (1a) include the following groups. * indicates a bonding site. TIFF0007927934000014.tif91154

[0018] Specific examples of acid-unstable groups (2a) include the following groups. * indicates a bonding site. TIFF0007927934000015.tif57163R 1 and R 2 When these groups combine to form a group having an acetal ring structure, see below. Examples include compounds that are used. TIFF0007927934000016.tif29133

[0019] X 1 The alkanediyl groups in this context include methylene, ethylene, and propane-1,3. -diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1, Linear alkanediyl groups such as 6-diyl groups; and Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Examples include branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group. The number of carbon atoms in the lucandiyl group is preferably 1 to 4, and more preferably 1 to 3.

[0020] R 2 The substituents that the pH may have include halogen atoms, hydroxyl groups, cyano groups, Carboxylic group, alkyl group with 1 to 12 carbon atoms, alkyl fluoride with 1 to 6 carbon atoms, carbon number Examples include 1 to 12 alkoxy groups and groups formed by combining two or more of these groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. The C1-C12 alkyl groups mentioned above include methyl, ethyl, propyl, and iso Propyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, Examples include octyl groups and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9. , more preferably 1 to 6, even more preferably 1 to 4, even more The answer is 1 to 3. The above-mentioned C1-C6 alkyl fluorides include trifluoromethyl groups and difluoromethyl groups. Methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2 -Tetrafluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafull Oropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-Octaful Olobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonaph Examples include fluoride alkyl groups such as ruolopentyl group and perfluorohexyl group. The number of carbon atoms in the alkyl group is preferably 1 to 4, and more preferably 1 to 3. The above-mentioned alkoxy groups having 1 to 12 carbon atoms include methoxy groups, ethoxy groups, and propoxy groups. Group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethyl Hexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group Examples include xy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 4, and more preferably The values ​​are 1 to 3. Groups that combine two or more of the above-mentioned types include alkoxycarbonyl groups having 2 to 13 carbon atoms. , alkylcarbonyl groups having 2 to 13 carbon atoms and alkylcarbonyl oxyl groups having 2 to 13 carbon atoms Examples include the C group. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and Alkylcarbonyloxy groups having 2 to 13 carbon atoms are the alkyl or alkoxy groups mentioned above. This represents a group in which a carbonyl group or a carbonyloxy group is bonded to a cy group. The above-mentioned alkoxycarbonyl groups having 2 to 13 carbon atoms include the methoxycarbonyl group, and Examples include toxiccarbonyl groups and butoxycarbonyl groups, and alkyl groups having 2 to 13 carbon atoms. Examples of rubonyl groups include acetyl groups, propionyl groups, and butyryl groups, and the number of carbon atoms Examples of alkylcarbonyloxy groups 2-13 include acetyloxy groups and propionyloxy groups. Examples include the cy group and the butyryloxy group. Note that X is bonded to the phenylene group. 1 and L 1 This refers to the ortho, meta, and para positions of the phenylene group. The atoms may be bonded at any of these positions, but it is preferable that they be bonded at the para position.

[0021] R 3 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. It can be done. R 3Examples of C1-C6 alkyl fluorides include trifluoromethyl groups and difluoromethyl groups. Methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2 -Tetrafluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafull Oropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-Octaful Olobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonaph Examples include fluoride alkyl groups such as ruolopentyl group and perfluorohexyl group. The number of carbon atoms in the alkyl group is preferably 1 to 4, and more preferably 1 to 3. R 3 Examples of alkyl groups with 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, iso Propyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, Examples of alkyl groups include octyl groups and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more Preferably, it is 1 to 3.

[0022] R 3 In the alkyl group, the -CH2- is replaced by -O- or -CO-. In addition, the number of carbon atoms before replacement shall be the total number of carbon atoms of the alkyl group. 3 The alkyl group is , hydroxyl group (a group in which the -CH2- contained in the methyl group is replaced by -O-), A boxyl group (a group in which the -CH2-CH2- contained in the ethyl group is replaced with -O-CO-). ), alkoxy group (where any -CH2- in the alkyl group is replaced by -O-) (a split group), an alkoxycarbonyl group (a -CH2- at any position within the alkyl group) CH2- is replaced by -O-CO-, alkylcarbonyl group (with alkyl group) (A group in which any -CH2- at any position is replaced by -CO-), alkylcarbonyl The oxy group (where any -CH2-CH2- in the alkyl group is replaced by -CO-O-) It may have a replaced group. Examples of alkoxy groups include alkoxy groups having 1 to 11 carbon atoms, such as methoxy. Groups such as ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy groups It can be listed. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups are A carbonyl group or carbonyloxy group is bonded to the alkyl group or alkoxy group mentioned above. It represents the basis. Examples of alkoxycarbonyl groups include alkoxycarbonyl groups having 2 to 11 carbon atoms. For example, methoxycarbonyl groups, ethoxycarbonyl groups, butoxycarbonyl groups, etc. Examples include alkylcarbonyl groups with 2 to 12 carbon atoms. Examples include acetyl groups, propionyl groups, and butyryl groups. Examples of carbonyloxy groups include alkylcarbonyloxy groups having 2 to 11 carbon atoms. Examples include acetyloxy groups, propionyloxy groups, and butyryloxy groups. ru.

[0023] R 3 Each of these is independently preferably a fluorine atom, an iodine atom, a hydroxyl group, and a carbon number Fluoride alkyl groups of 1 to 3 carbon atoms or alkyl groups having 1 to 3 carbon atoms (the alkyl group contains -C H2- may be replaced by -O- or -CO-), and more preferably H2- It is an elementary atom, an iodine atom, or a trifluoromethyl group, and more preferably a fluorine atom or It is an iodine atom. m2 is preferably an integer from 0 to 2, more preferably 1 or 2, and even more preferably 1. It seems so. R 2 At least one of the bonding sites in the benzene ring is L 1 Being in position p relative to It is preferable. m3 is preferably an integer from 0 to 4, and more preferably an integer from 0 to 2. 1 or 2 is even more preferable.

[0024] Compound (I) includes compounds represented by the following formula. TIFF0007927934000017.tif165132

[0025] TIFF0007927934000018.tif221144

[0026] TIFF0007927934000019.tif138129

[0027] TIFF0007927934000020.tif85150

[0028] TIFF0007927934000021.tif141129

[0029] The content of compound (I) is typically 0.001 to 20 based on the solid content of the resist composition. The amount is in mass%, preferably 0.005 to 15 mass%, more preferably 0.01 to 10 mass%. ru.

[0030] <Resin (A)> Resin (A) is a structural unit having an acid-unstable group (hereinafter referred to as "structural unit (a1)"). It has a structural unit represented by formula (a1-1) and formula (a1-2) described later. It includes at least one selected from the group consisting of structural units. The resin (A) further comprises structural It is preferable to include structural units other than unit (a1). In this regard, structural units that do not have acid-unstable groups (hereinafter sometimes referred to as "structural units (s)"), Structural units other than structural unit (a1) and structural unit (s) (for example, halogen atoms as described later) The structural units (hereinafter sometimes referred to as "structural units (a4)") and the non-desorbed carbonized water described later. Structural units having elementary elements (hereinafter sometimes referred to as "structural units (a5)") and other such Examples include structural units derived from monomers known in the field.

[0031] <Structural unit (a1)> Structural unit (a1) is a monomer having an acid-unstable group (hereinafter referred to as "monomer (a1)"). It is derived from (in some cases). The acid-unstable group contained in resin (A) is the group represented by formula (1) (hereinafter also referred to as group (1)). ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferred. TIFF0007927934000022.tif1988[In formula (1), R a1 , R a2 and R a3 These are, independently, alkyl groups with 1 to 8 carbon atoms. C1-C2 group, C2-C8 alkenyl group, C3-C20 alicyclic hydrocarbon group, C6-C1 8 represents aromatic hydrocarbon groups or groups formed by combining them, or R a1 and R a2 they are connected to each other They then form a non-aromatic hydrocarbon ring with 3 to 20 carbon atoms, together with the carbon atoms to which they bond. . ma and na each independently represent 0 or 1, and at least one of ma and na This represents 1. * indicates a connection site. TIFF0007927934000023.tif2171[In formula (2), R a1’ and R a2’ Each of these is independently a hydrogen atom or a carbon atom with 1 to 1 carbon atoms. Represents two hydrocarbon groups, R a3’ R represents a hydrocarbon group with 1 to 20 carbon atoms. a2’ Reach biR a3’ They bond with each other, and together with the carbon atoms and X they bond to, they have 3 to 20 carbon atoms. A heterocycle is formed, and the hydrocarbon group and the -CH2- contained in the heterocycle are -O- or -S- It can be replaced with this. X represents either an oxygen atom or a sulfur atom. 'na' represents either 0 or 1. * indicates a connection site.

[0032] R a1 , R a2 and R a3 Examples of alkyl groups in this context include methyl group, ethyl group, and propyl group. Examples include the hydroxyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group. R a1 , R a2 and R a3 The alkenyl groups in this context include the ethenyl group and the propenyl group. isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl Examples include the hexenyl group, heptenyl group, octinyl group, isooctinyl group, and nonenyl group. It is possible. R a1 , R a2 and R a3 In this context, the alicyclic hydrocarbon group is either monocyclic or polycyclic. This is also acceptable. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl group, cyclohexyl group, and cyclopentyl group. Examples include cycloalkyl groups such as chloroheptyl and cyclooctyl groups. Polycyclic and alicyclic groups. The hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following: Examples include the base (* indicates a binding site). a1 , R a2 and R a3 Alicyclic carbonization The number of carbon atoms in the hydrogen group is preferably 3 to 16. TIFF0007927934000024.tif10150R a1 , R a2 and R a3 Aromatic hydrocarbon groups in this context include phenyl groups and naphthyl groups. Examples of aryl groups include anthryl, biphenyl, and phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) Cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbol Alkylcycloalkyl groups such as ylethyl groups or cycloalkylalkyl groups), benzyl Aralkyl groups such as p-methylphenyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p -tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2, 6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc., alicyclic hydrocarbon group Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) Examples include aryl-cycloalkyl groups such as phenylcyclohexyl groups. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 )(R a2 )(R a3 Examples of such rings include the following: The non-aromatic hydrocarbon ring is preferably carbon The numbers range from 3 to 12. * represents the bonding site with -O-. TIFF0007927934000025.tif31139

[0033] R a1’ , R a2’ and R a3’ Examples of hydrocarbon groups in this context include alkyl groups and alicyclic carbon groups. Examples include hydrogenated groups, aromatic hydrocarbon groups, and groups formed by combining these. It is possible. Alkyl and alicyclic hydrocarbon groups are R a1 , R a2 and R a3 Similar to the base mentioned above This is one example. Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) Cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbol Alkylcycloalkyl groups such as ylethyl groups or cycloalkylalkyl groups), benzyl Aralkyl groups such as p-methylphenyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p -tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2, 6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc., alicyclic hydrocarbon group Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) Examples include aryl-cycloalkyl groups such as phenylcyclohexyl groups. R a2’ and R a3’ They bond with each other and together with the carbon atoms and X they bond to, complex When forming a ring, -C(R a1’ )(Ra2’ )-XR a3’ The following rings are examples: * indicates a bonding site. TIFF0007927934000026.tif18130R a1’ and R a2’ Preferably, at least one of them is a hydrogen atom. na' is preferably 0.

[0034] The following are examples of base (1): In equation (1), R a1 , R a2 and R a3 is an alkyl group, ma=0, and n A group where a=1. A tert-butoxycarbonyl group is preferred as this group. In equation (1), R a1 , R a2 However, together with the carbon atoms to which these bond, adamant Forms a chill group, R a3 A group that is an alkyl group, with ma=0 and na=1. In equation (1), R a1 and R a2 Each of them is an alkyl group independently, and R a3 Adama A methyl group with ma=0 and na=1. The following are specific examples of group (1). * indicates a bonding site. TIFF0007927934000027.tif171163

[0035] The following are specific examples of group (2). * indicates a bonding site. TIFF0007927934000028.tif68162

[0036] The monomer (a1) preferably has an acid-unstable group and an ethylenically unsaturated bond. Mer, more preferably a (meth)acrylic monomer having an acid-unstable group.

[0037] Among (meth)acrylic monomers having an acid-unstable group, preferably those having 5 to 20 carbon atoms. Examples include those having alicyclic hydrocarbon groups. A resin (A) having structural units derived from monomer (a1) is used in the resist composition. This allows for an improvement in the resolution of the resist pattern.

[0038] As a structural unit derived from a (meth)acrylic monomer having group (1), formula (a1- A structural unit represented by (0) (hereinafter sometimes referred to as structural unit (a1-0)), formula (a1 A structural unit represented by -1) (hereinafter sometimes referred to as structural unit (a1-1)) or formula ( The structural units represented by a1-2) (hereinafter sometimes referred to as structural units (a1-2)) are listed below. Resin (A) is composed of structural units (a1-1) and structural units (a1-2). It includes at least one selected from the group. Preferably, it includes structural units (a1-1) and components These are at least two structural units selected from the group consisting of building units (a1-2). It may be used alone or in combination of two or more types. Resin (A) is a structural unit (a1-1 ) and structural units (a1-2) - at least one selected from the group and further structural units (a1-0) may be included. TIFF0007927934000029.tif44143[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 - CO-O- represents a bond, k1 is an integer from 1 to 7, and * is the bonding site with -CO-. represent. R a01, R a4 and R a5 These are, independently, a hydrogen atom, a halogen atom, or a halogen. This represents an alkyl group having 1 to 6 carbon atoms, which may contain atoms. R a02 , R a03 and R a04 These are, independently, alkyl groups with 1 to 8 carbon atoms and alkyl groups with 3 to 8 carbon atoms. 18 alicyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof It represents the basis. R a6 and R a7 These are, independently, alkyl groups with 1 to 8 carbon atoms and axyl groups with 2 to 8 carbon atoms. Lukenyl group, alicyclic hydrocarbon group having 3 to 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms or This represents the group formed by combining these elements. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

[0039] R a01 , R a4 and R a5 Preferably, is a hydrogen atom or a methyl group, and more preferably It is a methyl group. L a01 , L a1 and L a2 Preferably, an oxygen atom or *-O-(CH2) k01 -C OO- (where k01 is preferably an integer from 1 to 4, more preferably It is 1, more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 Alkyl groups, alkenyl groups, alicyclic groups in Hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these include R of group (1).a1 , R a2 and R a3 The same groups as those listed above can be cited. R a02 , R a03 , and R a04 The alkyl group in this case is preferably an alkyl group having 1 to 6 carbon atoms. It is a group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. ru. R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. More preferably, a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, and further Preferably, it is an ethyl group, an isopropyl group, or a t-butyl group. R a6 and R a7 The alkenyl group in is preferably an alkenyl group having 2 to 6 carbon atoms. Yes, more preferably an ethenyl group, propenyl group, isopropenyl group or butenyl group. ru. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the alicyclic hydrocarbon group is preferably The range is 5 to 12, and more preferably 5 to 10. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the aromatic hydrocarbon group is preferably The range is 6 to 12, and more precisely, 6 to 10. Groups that combine alkyl groups and alicyclic hydrocarbon groups are formed by combining these alkyl groups and alicyclic hydrocarbon groups. It is preferable that the total number of carbon atoms in the combined group is 18 or less. Groups formed by combining alkyl groups and aromatic hydrocarbon groups are composed of these alkyl groups and aromatic hydrocarbon groups. It is preferable that the total number of carbon atoms in the combined group is 18 or less. R a02 and R a03 Preferably, an alkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms. A hydrocarbon group, more preferably a methyl group, an ethyl group, a phenyl group, or a naphthyl group. ru. R a04 Preferably, an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon having 5 to 12 carbon atoms. The group is a methyl group, more preferably an ethyl group, a cyclohexyl group, or an adamantyl group. be. R a6 and R a7 Each is independently preferably an alkyl group having 1 to 6 carbon atoms, 2-6 alkenyl groups or 6-12 aromatic hydrocarbon groups, more preferably Tyl group, ethyl group, isopropyl group, t-butyl group, ethenyl group, phenyl group or naphthyl group It is a group, and more preferably an ethyl group, isopropyl group, t-butyl group, ethenyl group or It is a phenyl group. m1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0040] Examples of structural units (a1-0) are given by equations (a1-0-1) to (a1-0-18). A structural unit represented by one of the following and R in the structural unit (a1-0) a01 This corresponds to A structure in which the til group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. The manufacturing units are listed, as in equations (a1-0-1) to (a1-0-10) and (a1-0-13). A structural unit represented by any of the formulas (a1-0-14) is preferred. TIFF0007927934000030.tif98165

[0041] As for the structural unit (a1-1), for example, as described in Japanese Patent Publication No. 2010-204646 Examples of structural units derived from monomers include those from formula (a1-1-1) to formula (a1 -1-7) Structural units represented by any of the above and R in structural units (a1-1) a4 ni A structural unit in which the corresponding methyl group is replaced by a hydrogen atom is preferred, and formulas (a1-1-1) to formulas (a1-1-1) are preferred. A structural unit represented by any of (a1-1-4) is more preferable. TIFF0007927934000031.tif41168

[0042] The structural unit (a1-2) is any of the formulas (a1-2-1) to (a1-2-12). The structural unit represented by and the R in the structural unit (a1-2) a5 The methyl group corresponding to water Examples of structural units that are replaced by elementary atoms, halogen atoms, haloalkyl groups, or other alkyl groups include Equations (a1-2-2), (a1-2-5), (a1-2-6), and (a1- 2-10) A structural unit represented by any of the formulas (a1-2-12) is preferred. TIFF0007927934000032.tif75155

[0043] If resin (A) contains structural unit (a1-0), its content is the total structural unit of resin (A). For each position, it is usually 5-80 mol%, preferably 5-75 mol%, and more preferably The percentage is between 10 and 70 mol%. If resin (A) contains structural unit (a1-1) and / or structural unit (a1-2), The total content of these is typically 10 to 90 mol% relative to the total structural units of resin (A), and is preferable. More preferably 15-85 mol%, more preferably 20-80 mol%, and even more preferably More preferably, it is 20-75 mol%, and more preferably 20-70 mol%.

[0044] A structural unit having a base (2) in structural unit (a1) is represented by formula (a1-4). Examples of structural units (hereinafter sometimes referred to as "structural units (a1-4)") include the following. TIFF0007927934000033.tif4564[In formula (a1-4), R a32 This is a hydrogen atom, a halogen atom, or a carbon-1 atom which may have a halogen atom. Represents alkyl groups up to 6. R a33 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxyalkyl group having 2 to 12 carbon atoms Lucoxy group, C2-C4 alkylcarbonyl group, C2-C4 alkylcarbonyl This represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a30 is a single bond or * -X a31 -( A a32 -X a32 ) nc - represents -R a32 they combine This represents the bonding site with the carbon atom. A a32 This represents an alkanediyl group with 1 to 6 carbon atoms. X a31 and X a32 These represent -O-, -CO-O-, or -O-CO- independently. nc represents 0 or 1. la represents an integer from 0 to 4. If la is an integer greater than or equal to 2, Number R a33 They may be the same or different from each other. Ra34 and R a35 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R a36 R represents a hydrocarbon group with 1 to 20 carbon atoms. a35 and R a36 they combine with each other and Together with the -CO- to which they bond, they form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the carbonized water The -CH2- contained in the elementary group and the divalent hydrocarbon group is replaced by -O- or -S- That's good too.

[0045] R a32 and R a33 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. These are some examples. R a32 C1-C6 alkyl groups that may have a halogen atom include: Trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, pe fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, Tyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples include pentyl groups, pentyl groups, hexyl groups, and perfluorohexyl groups. R a32 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and the hydrogen atom, methyl group or An ethyl group is more preferable, and a hydrogen atom or a methyl group is even more preferable. R a33 The alkyl groups in this context are methyl, ethyl, propyl, and isopropyl groups. Examples include the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. It is possible. R a33 The alkoxy groups in this context include methoxy, ethoxy, propoxy, and iso Propoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyl oxy Examples include the hydroxyl group and the hexyloxy group. Alkoxy groups are alkoxy groups with 1 to 4 carbon atoms. Preferably, a methoxy group or an ethoxy group is preferred, and a methoxy group is even more preferred. R a33 Examples of alkoxyalkyl groups in this context include methoxymethyl group and ethoxyethyl group. , propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxy Examples include methyl groups and tert-butoxymethyl groups. Alkoxyalkyl groups have a number of carbon atoms. 2 to 8 alkoxyalkyl groups are preferred, and methoxymethyl or ethoxyethyl groups are preferred. A methoxymethyl group is more preferable, and a methoxymethyl group is even more preferable. R a33 Examples of alkoxyalkoxy groups in this context include methoxymethoxy groups and methoxyethyl groups. Xy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isoprop Xymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, tert-butoxy A cymethoxy group is one example. Alkoxyalkoxy groups are alkoxyal groups with 2 to 8 carbon atoms. A coxy group is preferred, and a methoxyethoxy group or an ethoxyethoxy group is more preferred. R a33 The alkylcarbonyl groups in this include acetyl, propionyl, and butyric groups. Examples include lyl groups. Alkyl carbonyl groups are alkyl carbonyl groups having 2 to 3 carbon atoms. A is preferred, and an acetyl group is more preferred. R a33 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups and propionyl groups. Examples include the oxy group and the butyryloxy group. The alkylcarbonyloxy group has a number of carbon atoms. Two to three alkylcarbonyloxy groups are preferred, and acetyloxy groups are more preferred. R a33 This includes halogen atoms, hydroxyl groups, C1-C4 alkyl groups, and C1-C4 An alkoxy group or an alkoxyalkoxy group having 2 to 8 carbon atoms is preferred, along with a fluorine atom and iodine. Elementary atom, hydroxyl group, methyl group, methoxy group, ethoxy group, ethoxyethoxy group or ethoxyethoxy group A toxicmethoxy group is more preferred, along with a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, A methoxy group or an ethoxyethoxy group is even more preferred.

[0046] *-X a31 -( A a32 -X a32 ) nc - for example, *-O-, *-CO-O-, *-OC O-, *-CO-OA a32 -CO-O-, *-O-CO-A a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO-, These include *-CO-O- and *-CO-OA. a32 -CO-O- or *- OA a32 -CO-O- is preferred.

[0047] The above-mentioned alkanediyl groups include methylene group, ethylene group, and propane-1,3-diyl yl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group Iyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane -1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group Examples include the 2-methylbutane-1,4-diyl group and the 2-methylbutane-1,4-diyl group. A a32 It is preferable that this is a methylene group or an ethylene group.

[0048] A a30 These are single bonds, *-CO-O- or *-CO-OA a32 Being a CO-O Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. More preferably, the bond is a single bond or even more preferably *-CO-O-.

[0049] la is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. R a34 , R a35 and R a36 Examples of hydrocarbon groups in this context include alkyl groups and alicyclic hydrocarbon groups. Examples include aromatic hydrocarbon groups and groups formed by combining these. Alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples include syl groups, heptyl groups, and octyl groups. The alicyclic hydrocarbon group may be monocyclic or polycyclic. Monocyclic alicyclic hydrocarbon group Examples include cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, and cyclooctyl groups. Examples of cycloalkyl groups include decahydrona. Phthyl groups, adamantyl groups, norbornyl groups, and the following groups (* indicates a bonding site), etc. It can be listed. TIFF0007927934000034.tif10151 Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) Cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbol Alkylcycloalkyl groups such as ylethyl groups or cycloalkylalkyl groups), benzyl Aralkyl groups such as p-methylphenyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p -tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2, 6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc., alicyclic hydrocarbon group Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) Examples include aryl-cycloalkyl groups such as phenylcyclohexyl groups, etc. , R a36 Examples include alkyl groups having 1 to 18 carbon atoms, and alicyclic hydrocarbon groups having 3 to 18 carbon atoms. Aromatic hydrocarbon groups having 6 to 18 carbon atoms, or groups formed by combining these. It can be listed.

[0050] R a34 Preferably, it is a hydrogen atom. R a35 Preferably, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a C3 to 12 carbon atom. It is an alicyclic hydrocarbon group, more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, or a C3 to 18 carbon atom Alicyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof The group formed is more preferably an alkyl group having 1 to 18 carbon atoms, or a group having 3 to 1 carbon atoms. It is an 8-cell alicyclic hydrocarbon group or an aralkyl group having 7 to 18 carbon atoms. a36 Alki in The rico group and alicyclic hydrocarbon group are preferably unsubstituted.a36 Aromatic carbonization in The hydrogen group is preferably an aromatic ring having an aryloxy group with 6 to 10 carbon atoms. -OC(R) in structural units (a1-4) a34 )(R a35 )-OR a36 is an acid (for example) It is eliminated upon contact with p-toluenesulfonic acid, forming a hydroxyl group. -OC(R a34 )(R a35 )-OR a36 It bonds to the ortho- or para-position of the benzene ring. It is preferable that the bond is formed at the p-position, and more preferably that it is formed at the p-position.

[0051] As for structural units (a1-4), for example, see Japanese Patent Publication No. 2010-204646. Examples include monomer-derived structural units. Preferably, formulas (a1-4-1) to (a1 -4-18) Structural units and R a32 The hydrogen atom corresponding to the halogen Examples include atoms, haloalkyl groups, or structural units substituted with alkyl groups, and more preferably... These are equations (a1-4-1) to (a1-4-5), equation (a1-4-10), and equation (a1-4- 13) Examples of structural units can be found in equations (a1-4-14), respectively. TIFF0007927934000035.tif100166

[0052] If resin (A) contains structural units (a1-4), the content of these units is the total structural content of resin (A). The percentage of the total units is preferably 3 to 80 mol%, and preferably 5 to 75 mol%. More preferably, 7 to 70 mol%, and even more preferably 7 to 65 mol%. It is even more preferable that the amount is 10 to 60 mol%, and is particularly preferable.

[0053] As structural units derived from (meth)acrylic monomers having group (2), formula (a1 Structural units represented by -5) (hereinafter sometimes referred to as "structural units (a1-5)") are also mentioned. It can be done. TIFF0007927934000036.tif4558 formula (a1-5), R a8 This may have a halogen atom, or it may have a C1-C6 alkyl group, a hydrogen atom, or a halogen atom. It represents a chlorogenic atom. Z a1 This is a single bond or *-(CH2) h3 -CO-L 54 - represents one of 1-4. Represents an integer of L, where * is L 51 This represents the connection point. L 51 , L 52 , L 53 and L 54 These represent either -O- or -S- independently. s1 represents an integer between 1 and 3. s1' represents an integer between 0 and 3.

[0054] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of C1-C6 alkyl groups that may have a halogen atom include methyl and ethyl groups. Group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluorine Examples include methyl and trifluoromethyl groups. In equation (a1-5), R a8 This is a hydrogen atom, a methyl group, or a trifluoromethyl group preferable. L 51 An oxygen atom is preferred. L 52 and L 53 Preferably, one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably an integer between 0 and 2. Z a1 A single bond or *-CH2-CO-O- is preferred.

[0055] Examples of structural units (a1-5) are described in Japanese Patent Publication No. 2010-61117. Examples of monomer-derived structural units include those from formula (a1-5-1) to formula (a1-5- 4) The structural units represented by formula (a1-5-1) or formula (a1-5-2 A structural unit represented by ) is more preferable. TIFF0007927934000037.tif33133

[0056] If resin (A) contains structural units (a1-5), the percentage of these units is the total structural content of resin (A). The amount is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and 5 to 40 mol% relative to the unit. A % of 10% is more preferable, and 5 to 30 mol% is even more preferable.

[0057] In addition, the following structural units (a1) can also be listed. TIFF0007927934000038.tif31162

[0058] When resin (A) contains structural units such as (a1-3-1) to (a1-3-7) above The content is preferably 10 to 95 mol% relative to the total structural units of resin (A), and 15 ~90 mol% is more preferred, 20~85 mol% is even more preferred, and 20~70 mol% is More preferably, 20 to 60 mol% is particularly preferred.

[0059] In addition, the following structural units (a1) can also be listed. TIFF0007927934000039.tif4994 When resin (A) contains structural units such as (a1-6-1) to (a1-6-3) above. The content is preferably 10 to 60 mol% relative to the total structural units of resin (A), and 15 ~55 mol% is more preferred, 20~50 mol% is even more preferred, and 20~45 mol% is More preferably, 20 to 40 mol% is particularly preferred.

[0060] <Structural unit (s)> A structural unit (s) is a monomer that does not have an acid-unstable group (hereinafter referred to as "monomer (s)"). It is derived from (there is a combination). The monomer that derives the structural unit (s) is an acid-resistant monomer known in the field of resists. Monomers without a stable group can be used. The structural unit (s) preferably has a hydroxyl group or a lactone ring. A structural unit having a xyl group and not having an acid-unstable group (hereinafter referred to as "structural unit (a2)") A structural unit having a lactone ring and / or not having an acid-unstable group (hereinafter referred to as "structural unit") If a resin having a "production unit (a3)" is used in the resist composition of the present invention, This improves the resolution of the resist pattern and its adhesion to the substrate.

[0061] <Structural Unit (a2)> The hydroxyl group in structural unit (a2) can be an alcoholic hydroxyl group or a phenolic group. A hydroxyl group may also be used. When manufacturing a resist pattern from the resist composition of the present invention, KrF is used as the exposure light source. High-energy beams such as excimer lasers (248 nm), electron beams, or EUV (ultra-ultraviolet light) are used. If present, the structural unit (a2) is a structural unit having a phenolic hydroxyl group ( a2) is preferred, and it is even more preferable to use the structural unit (a2-A) described later. When using an ArF excimer laser (193 nm), the structural unit (a2) is A A structural unit (a2) having a hydroxyl group is preferred, and the structural unit (a2) described later is -1) is more preferable. The structural unit (a2) contains one type alone. It is acceptable to include two or more types.

[0062] Structural units having a phenolic hydroxyl group in structural unit (a2) include those of formula (a Examples of structural units represented by 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") include It is possible. TIFF0007927934000040.tif4653[In formula (a2-A), R a50 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents the alkyl group. R a51 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxyalkyl group having 2 to 12 carbon atoms Lucoxy group, C2-C4 alkylcarbonyl group, C2-C4 alkylcarbonyl This represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 -( A a52 -X a52 ) nb - represents -R a50 they combine This indicates the bonding position with the carbon atom. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent -O-, -CO-O-, or -O-CO- independently. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, Number R a51They may be the same or different from each other.

[0063] R a50 and R a51 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. These are some examples. R a50 C1-C6 alkyl groups that may have a halogen atom include: Trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, pe fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, Tyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples include pentyl groups, pentyl groups, hexyl groups, and perfluorohexyl groups. R a50 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and the hydrogen atom, methyl group or An ethyl group is more preferable, and a hydrogen atom or a methyl group is even more preferable. R a51 The alkyl groups in this context are methyl, ethyl, propyl, and isopropyl groups. Examples include the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and may have a methyl group or an ethyl group. More preferably, a methyl group is even more preferred. R a51 The alkoxy groups in this context include methoxy, ethoxy, propoxy, and iso Examples include propoxy groups, butoxy groups, sec-butoxy groups, and tert-butoxy groups. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and is either a methoxy group or an ethoxy group. More preferably, a methoxy group is even more preferred. R a51 Examples of alkoxyalkyl groups in this context include methoxymethyl group and ethoxyethyl group. , propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxy Examples include methyl groups and tert-butoxymethyl groups. Alkoxyalkyl groups have a number of carbon atoms. 2 to 8 alkoxyalkyl groups are preferred, and methoxymethyl or ethoxyethyl groups are preferred. A methoxymethyl group is more preferable, and a methoxymethyl group is even more preferable. R a51 Examples of alkoxyalkoxy groups in this context include methoxymethoxy groups and methoxyethyl groups. Xy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isoprop Xymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, tert-butoxy A cymethoxy group is one example. Alkoxyalkoxy groups are alkoxyal groups with 2 to 8 carbon atoms. A coxy group is preferred, and a methoxyethoxy group or an ethoxyethoxy group is more preferred. R a51 The alkylcarbonyl groups in this include acetyl, propionyl, and butyric groups. Examples include lyl groups. Alkyl carbonyl groups are alkyl carbonyl groups having 2 to 3 carbon atoms. A is preferred, and an acetyl group is more preferred. R a51 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups and propionyl groups. Examples include the oxy group and the butyryloxy group. The alkylcarbonyloxy group has a number of carbon atoms. Two to three alkylcarbonyloxy groups are preferred, and acetyloxy groups are more preferred. R a51 This includes halogen atoms, hydroxyl groups, C1-C4 alkyl groups, and C1-C4 An alkoxy group or an alkoxyalkoxy group having 2 to 8 carbon atoms is preferred, along with a fluorine atom and iodine. Elementary atom, hydroxyl group, methyl group, methoxy group, ethoxy group, ethoxyethoxy group or ethoxyethoxy group A toxicmethoxy group is more preferred, along with a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, A methoxy group or an ethoxyethoxy group is even more preferred.

[0064] *-X a51 -( A a52 -X a52 ) nb - for example, *-O-, *-CO-O-, *-OC O-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO-, These include *-CO-O- and *-CO-OA. a52 -CO-O- or *- OA a52 -CO-O- is preferred.

[0065] Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and Examples include 2-methylbutane-1,4-diyl groups. A a52 It is preferable that this is a methylene group or an ethylene group.

[0066] A a50 These are single bonds, *-CO-O- or *-CO-OA a52 Being a CO-O Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. More preferably, the bond is a single bond or even more preferably *-CO-O-.

[0067] mb is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. The hydroxyl group is preferably bonded to the ortho- or para-position of the benzene ring, and at the para-position It is more preferable for them to combine.

[0068] As for the structural unit (a2-A), see Japanese Patent Publication No. 2010-204634, Japanese Patent Publication No. 2012- Examples include monomer-derived structural units described in Publication No. 12577. The structural unit (a2-A) is represented by equations (a2-2-1) to (a2-2-16). In the structural units and the structural units represented by formulas (a2-2-1) to (a2-2-16) R in structural unit (a2-A) a50 The methyl group corresponding to a hydrogen atom, halogen atom Examples include structural units that are replaced by haloalkyl groups or other alkyl groups. Structural unit ( a2-A) is a structural unit represented by formula (a2-2-1), and is represented by formula (a2-2-3) Structural units, structural units represented by formula (a2-2-6), structures represented by formula (a2-2-8) Units, structural units represented by formulas (a2-2-12) to (a2-2-14), and formulas (a2- 2-1) Structural units represented by formula (a2-2-3), Structural units represented by formula (a2-2- 6) Structural units represented by formula (a2-2-8), structural units represented by formula (a2-2-12 In the structural unit represented by equation (a2-2-14), in structural unit (a2-A) R a50 Preferably, the structural unit is one in which the corresponding methyl group is replaced by a hydrogen atom. Structural units represented by formula (a2-2-3), structural units represented by formula (a2-2-8), formula ( a2-2-12) ~ Structural units represented by formula (a2-2-14) and formula (a2-2-3) The structural units represented, the structural units represented by formula (a2-2-8), formula (a2-2-12) to formula In the structural unit represented by (a2-2-14), R in structural unit (a2-A) a5 0 It is more preferable that the corresponding methyl group is replaced by a hydrogen atom in the structural unit, and the formula In the structural units represented by (a2-2-8) and the structural units represented by formula (a2-2-8) And, R in the structural unit (a2-A) a50 The corresponding methyl group is replaced by a hydrogen atom. It is even more preferable that the structural unit is a [specific structural unit]. TIFF0007927934000041.tif63169

[0069] Content of structural unit (a2-A) when structural unit (a2-A) is present in resin (A) This is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, relative to the total structural units. It is mol%, more preferably 15-65 mol%, and even more preferably 20- It is 65 mol%. Structural unit (a2-A) is polymerized using structural unit (a1-4), for example, and then p-Tol It can be incorporated into resin (A) by treating it with an acid such as ene sulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0070] Structural units having an alcoholic hydroxyl group in structural unit (a2) include those with the formula ( The structural unit represented by a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") It can be listed. TIFF0007927934000042.tif4562 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 -CO-O- represents, k2 represents an integer between 1 and 7. * represents the associative position with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 Each of these independently represents a hydrogen atom, a methyl group, or a hydroxyl group. o1 represents an integer between 0 and 10.

[0071] In equation (a2-1), L a3 Preferably, -O-, -O-(CH2) f1 -CO-O- (where f1 represents any integer from 1 to 4), and more preferably -O-. R a14 The group is preferably a methyl group. R a15 Preferably, it is a hydrogen atom. R a16 This is preferably a hydrogen atom or a hydroxyl group. o1 is preferably an integer between 0 and 3, more preferably 0 or 1.

[0072] As for the structural unit (a2-1), for example, see Japanese Patent Publication No. 2010-204646. Examples of structural units derived from monomers are given by equations (a2-1-1) to (a2-1-6). A structural unit represented by any of the following formulas is preferred, from formula (a2-1-1) to formula (a2-1-4) A structural unit represented by either formula (a2-1-1) or formula (a2-1- The structural unit represented in 3) is even more preferable. TIFF0007927934000043.tif47132

[0073] If resin (A) contains structural units (a2-1), the content of these units is the total structural unit content of resin (A). For each position, it is usually 1 to 45 mol%, preferably 1 to 40 mol%, and more preferably The amount is 1 to 35 mol%, more preferably 1 to 20 mol%, and even more preferably The percentage is between 1 and 10 mol%.

[0074] <Structural unit (a3)> The lactone rings of structural unit (a3) ​​are a β-propiolactone ring and a γ-butyrolactone ring. It can be a monocyclic ring such as a δ-valerolactone ring, and the contraction of a monocyclic lactone ring with other rings. A ring compound is also acceptable. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or γ - A bridged ring containing a butyrolactone ring structure (e.g., a structural unit represented by the following formula (a3-2)) These are some examples.

[0075] The structural unit (a3) ​​is preferably formula (a3-1), formula (a3-2), formula (a3-3) Alternatively, it is a structural unit represented by formula (a3-4). These may be contained individually. It may contain two or more types. TIFF0007927934000044.tif52164[In formulas (a3-1), (a3-2), (a3-3), and (a3-4), L a4 , L a5 and L a6 These are, independently, -O- or *-O-(CH2) k3 -C This represents a base represented by OO-(where k3 is an integer from 1 to 7). L a7 is -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- represents vinegar. L a8 and L a9 Each of these independently represents an alkanediyl group with 1 to 6 carbon atoms. * indicates the bonding position with the carbonyl group. R a18 , R a19 and R a20 Each of these independently represents either a hydrogen atom or a methyl group. R a24 This includes an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom, or represents a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 This represents an aliphatic hydrocarbon group with 1 to 4 carbon atoms. R a22 , R a23 and R a25 Each of these independently comprises a carboxyl group, a cyano group, or a carbon Represents aliphatic hydrocarbon groups with prime numbers 1 through 4. p1 represents an integer between 0 and 5. q1 represents an integer between 0 and 3. r1 represents an integer between 0 and 3. w1 represents an integer between 0 and 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 They may be the same or different from each other.

[0076] R a21 , R a22 , R a23 and R a25 As for aliphatic hydrocarbon groups in this context, methyl ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and ter Examples include alkyl groups such as t-butyl groups. R a24 The halogen atoms in this include fluorine, chlorine, bromine, and iodine. Atoms are one example. R a24 The alkyl groups in this context include methyl, ethyl, propyl, and isopropyl groups. butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Examples include alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups. Alternatively, an ethyl group may be used. R a24 Examples of alkyl groups having a halogen atom include the trifluoromethyl group. Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perf Perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Lufluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl Examples include the 14-3 group and the triiodomethyl group.

[0077] L a8 and L a9 Examples of alkanediyl groups in this context include methylene groups, ethylene groups, and pro groups. Pan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, tan-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pen Examples include tan-1,4-diyl groups and 2-methylbutane-1,4-diyl groups.

[0078] In equations (a3-1) to (a3-3), L a4 ~L a6Each is independently preferred Alternatively, -O- or *-O-(CH2) k3 In -CO-O-, k3 is one of 1 to 4. The base is an integer, more preferably -O- and *-O-CH2-CO-O-, even more preferably It is an oxygen atom. R a18 ~R a21 The group is preferably a methyl group. R a22 and R a23 Each of these is independently preferably a carboxyl group, a cyano group, or a melanin group. It is a chill group. p1, q1, and r1 are each independently, preferably integers between 0 and 2. More preferably, it is 0 or 1.

[0079] In equation (a3-4), R a24 Preferably, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is a group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a group of the same type. It is either a hydrogen atom or a methyl group. R a25 The group is preferably a carboxyl group, a cyano group, or a methyl group. L a7 Preferably -O- or *-OL a8 -CO-O- and, far It is -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. w1 is preferably an integer between 0 and 2, and more preferably 0 or 1. In particular, formula (a3-4)' is preferred over formula (a3-4). TIFF0007927934000045.tif3849 (in the formula, R a24 , L a7 (This expresses the same meaning as above.)

[0080] The structural unit (a3) ​​is the monomer described in Japanese Patent Publication No. 2010-204646. , monomers described in Japanese Patent Publication No. 2000-122294, Japanese Patent Publication No. 2012-41274 Examples of structural units derived from monomers described in the publication are listed below. Structural unit (a3) ​​is , formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , equation (a3-3-1), equation (a3-3-2), and equation (a3-4-1) ~ equation (a3-4-1 2) A structural unit represented by any of the above, and in the said structural unit, formula (a3-1) to formula ( R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to water Structural units that are replaced by elementary atoms are preferred.

[0081] TIFF0007927934000046.tif116165

[0082] If resin (A) contains structural units (a3), the total content of these units is the total structural unit content of resin (A). The amount is usually 5-70 mol%, preferably 10-65 mol%, and more preferably More specifically, it is between 10 and 60 mol%. Also, structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structure The content of units (a3-4) is 5 to 60 units relative to the total structural units of resin (A), respectively. % is preferred, 5 to 50 mol% is more preferred, and 10 to 50 mol% is even more preferred.

[0083] <Structural Unit (a4)> The following are examples of structural units (a4): TIFF0007927934000047.tif2862[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42This represents a saturated hydrocarbon group having a halogen atom with 1 to 24 carbon atoms, and the saturated hydrocarbon water The -CH2- group in the element may be replaced by -O- or -CO-. R 42 The saturated hydrocarbon groups represented by these terms include chain-type saturated hydrocarbon groups and monocyclic or polycyclic alicyclic saturated hydrocarbon groups. Examples include hydrocarbon groups, and groups formed by combining these.

[0084] Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, and pentyl groups. Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, Examples include xadecyl groups, heptadecyl groups, and octadecyl groups. Examples of monocyclic or polycyclic alicyclic saturated hydrocarbon groups include cyclopentyl groups and cyclohexyl groups. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic lipids such as adamantyl groups, norbornyl groups, and the following groups (* indicates the binding site). Examples include cyclic saturated hydrocarbon groups. TIFF0007927934000048.tif10146 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic saturated hydrocarbon groups include -Alkanediyl group-alicyclic saturated hydrocarbon group, -Alkanediyl group-alkyl Examples include AL groups, -alkanediyl groups, -alicyclic saturated hydrocarbon groups, -alkyl groups, etc.

[0085] The structural unit (a4) is the structural unit represented by formula (a4-0) and the structural unit represented by formula (a4-1). Examples include structural units and structural units represented by formula (a4-4). TIFF0007927934000049.tif4551[In formula (a4-0), R 54represents a hydrogen atom or a methyl group. L 4a This represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a This is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. This represents a luorocycloalkanediyl group. R 64 This represents a hydrogen atom or a fluorine atom.

[0086] L 4a The alkanediyl groups in this include methylene group, ethylene group, propane-1, Linear alkanediyl groups such as 3-diyl groups and butane-1,4-diyl groups, ethane-1,1 -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylprop Branched alkanes such as pan-1,3-diyl groups and 2-methylpropane-1,2-diyl groups A diyl group is one example.

[0087] L 3a In this context, perfluoroalkanediyl groups include difluoromethylene groups and per Fluoroethylene group, perfluoroethylfluoromethylene group, perfluoropropane- 1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane- 2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2, 2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5 -diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3,3 -diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2 -diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4 -diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8 -diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3 Examples include diyl groups and perfluorooctane-4,4-diyl groups. L 3a As for the perfluorocycloalkanediyl group in this context, perfluorocyclo xandiyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl Examples include yl groups and perfluoroadamantanediyl groups.

[0088] L 4a The is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond. The bond is a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably Alternatively, it is a perfluoroalkanediyl group with 1 to 3 carbon atoms.

[0089] The structural units (a4-0) include the structural units shown below and the structural units within the following structural units ( a4-0) R 54 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. JPEG0007927934000050.jpg95166

[0090] TIFF0007927934000051.tif4866[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 This represents a saturated hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. The -CH2- group in the hydrocarbon group may be replaced by -O- or -CO-. A a41This is an alkanediyl group having 1 to 6 carbon atoms, which may have substituents, or a compound of formula (ag 1) represents the base. However, A a41 and R a42 At least one of them is a substitution It has a halogen atom (preferably a fluorine atom) as a base. TIFF0007927934000052.tif1488 [In formula (a-g1), s represents either 0 or 1. A a42 and A a44 Each of these is independently a divalent carbon atom having 1 to 5 carbon atoms, which may have substituents. This represents a saturated hydrocarbon group. A a43 This is a divalent saturated hydrocarbon group having 1 to 5 carbon atoms, which may have single bonds or substituents. It represents. X a41 and X a42 These are, independently, -O-, -CO-, -CO-O-, or -O-CO - represents However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates a binding site, and the * on the right is -O-CO-R a42 This is the junction site.

[0091] R a42 The saturated hydrocarbon groups in this context include chain-like hydrocarbon groups and monocyclic or polycyclic saturated alicyclic groups. Examples include hydrocarbon groups and groups formed by combining them.

[0092] Chain hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa Examples include decyl groups, heptadecyl groups, and octadecyl groups. Examples of monocyclic or polycyclic saturated alicyclic hydrocarbon groups include cyclopentyl groups and cyclohexyl groups. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic lipids such as adamantyl groups, norbornyl groups, and the following groups (* indicates the binding site). Examples include cyclic hydrocarbon groups. TIFF0007927934000053.tif10160 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more saturated alicyclic hydrocarbon groups include -alkanediyl group-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkyl Examples include -alkanediyl groups, -saturated alicyclic hydrocarbon groups, -alkyl groups, etc.

[0093] R a42 The substituents it possesses include halogen atoms and groups represented by formula (a-g3). At least one selected from the group consisting of the group is given. As for halogen atoms, Examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and preferably fluorine atoms. . TIFF0007927934000054.tif855[In formula (a-g3), X a43 * represents an oxygen atom, a carbonyl group, *-O-CO-, or *-CO-O-. A a45 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. * is R a42 This represents the connection point with [the other element]. However, R a42 -X a43 -A a45 In R a42 If it does not have a halogen atom, then A a4 5This represents a saturated hydrocarbon group having 1 to 17 carbon atoms and containing at least one halogen atom.

[0094] A a45 The saturated hydrocarbon groups in this context include methyl, ethyl, propyl, and butyl groups. pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentade Alkyl groups such as syl, hexadecyl, heptadecyl, and octadecyl groups; Monocyclic groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups Alicyclic hydrocarbon groups; as well as decahydronaphthyl groups, adamantyl groups, norbornyl groups and Examples include polycyclic alicyclic hydrocarbon groups such as the following groups (* indicates a bonding site). TIFF0007927934000055.tif10160 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic hydrocarbon groups include -Alkanediyl group-alicyclic hydrocarbon group, -Alkanediyl group-alkyl group, -Al Examples include candiyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0095] R a42 The halogen atom is preferably a saturated hydrocarbon group which may have a halogen atom. Alkyl groups having and / or saturated hydrocarbon groups having a group represented by formula (a-g3) are suitable. It is preferable. R a42 If it is a saturated hydrocarbon group having a halogen atom, it preferably has a fluorine atom. A saturated hydrocarbon group, more preferably a perfluoroalkyl group or perfluoroalkyl group. It is a chloroalkyl group, and more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. The perfluoromethyl group, perfluoroethyl group, and perfluoropropyl group are examples of perfluoropropyl groups. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro Examples include oroheptyl groups and perfluorooctyl groups. Examples of the 'l' group include the perfluorocyclohexyl group. R a42 However, if it is a saturated hydrocarbon group having a group represented by formula (a-g3), then formula (a- Including the number of carbon atoms in the group represented by g3), R a42 The total number of carbon atoms should preferably be 15 or less. Furthermore, 12 or less is more preferable. When the group represented by formula (a-g3) is used as a substituent, The number should preferably be one.

[0096] R a42 If is a saturated hydrocarbon group having a group represented by formula (a-g3), then R a42 is, More preferably, the group is represented by the formula (a-g2). TIFF0007927934000056.tif871[In formula (a-g2), A a46 This comprises a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, which may have a halogen atom. represent. X a44 This represents **-O-CO- or **-CO-O- (where ** is A a46 The connection site represent.). A a47 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. However, A a46 , A a47 and X a44 The total number of carbon atoms is 18 or less, A a46 and A a47 of Of these, at least one has at least one halogen atom. * indicates a bonding site with a carbonyl group.

[0097] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3. A a47 The number of carbon atoms in the saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 12, A a 47 A cyclohexyl group or an adamantyl group is more preferable.

[0098] The preferred structure of the group represented by formula (a-g2) is as follows (* represents a carbonyl group) (This is the junction site.) TIFF0007927934000057.tif14160

[0099] A a41 The alkanediyl groups in this include methylene group, ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 Linear alkanediyl groups such as ,6-diyl groups; propane-1,2-diyl groups, butane-1 ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- Examples include branched alkanediyl groups such as diyl groups and 2-methylbutane-1,4-diyl groups. ru. A a41 The substituents in the alkanediyl group represented by are a hydroxyl group and a carbon 1- Examples include 6 alkoxy groups. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a carbon number The group is an alkanediyl group of type 2 to 4, and more preferably an ethylene group.

[0100] A in the group represented by formula (a-g1) a42 , A a43 and A a44Divalent saturated carbonized water The elemental groups include linear or branched alkanediyl groups and monocyclic divalent alicyclic saturated hydrocarbon groups. , and formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group. Examples include divalent saturated hydrocarbon groups. Specifically, methylene groups, ethylene groups, and p Ropan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2- Examples include methylpropane-1,2-diyl groups. A a42 , A a43 and A a44 The substituents of the divalent saturated hydrocarbon group represented by are hydroxyl groups. Examples include alkoxy groups having 1 to 6 carbon atoms. s is preferably 0.

[0101] In the group represented by formula (a-g1), X a42 -O-, -CO-, -CO-O- or The following are examples of groups that are -O-CO-. In the following examples, * and ** represents a binding site, and ** is -O-CO-R a42 This is the junction site. TIFF0007927934000058.tif46140

[0102] The structural units represented by formula (a4-1) are the structural units shown below and the structural units shown below. R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to this is placed on a hydrogen atom. Examples of replaced structural units include: TIFF0007927934000059.tif92135

[0103] TIFF0007927934000060.tif132150

[0104] The structural units represented by formula (a4-1) are the structural units represented by formula (a4-2) and Examples of structural units are given by formula (a4-3). TIFF0007927934000061.tif4256[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 This represents an alkanediyl group having 1 to 6 carbon atoms, and the -C contained in the alkanediyl group H2- may be replaced by -O- or -CO-. R f6 This represents a saturated hydrocarbon group having 1 to 20 fluorine atoms. However, L 44 and R f6 The upper limit for the total number of carbon atoms is 21.

[0105] L 44 The alkanediyl group with 1 to 6 carbon atoms is A a41 Similar to the examples given above, It can be done. R f6 The saturated hydrocarbon group is R 42 Similar to the examples given earlier, the same types of bases can be cited. L 44 In this context, an alkanediyl group having 2 to 4 carbon atoms is preferred. An ethylene group is more preferable.

[0106] Examples of structural units represented by formula (a4-2) include formulas (a4-1-1) to (a4 The structural units represented in (a4-2) are as follows: R f5 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It can be cited as a structural unit.

[0107] TIFF0007927934000062.tif5671[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 This represents an alkanediyl group with 1 to 6 carbon atoms. A f13 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, which may contain a fluorine atom. vinegar. X f12 This represents *-O-CO- or *-CO-O- (* is A f13 This represents the connection point. ). A f14 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a fluorine atom. However, A f13 and A f14 At least one of them has a fluorine atom, L 5 , A f13 and A f14 The upper limit for the total number of carbon atoms is 20.

[0108] L 5 The alkanediyl group in A is a41 The same as the example with the alkanediyl group. The basis for this can be cited.

[0109] A f13 A preferred divalent saturated hydrocarbon group which may have a fluorine atom is A divalent chain-type saturated hydrocarbon group which may have a fluorine atom and a fluorine atom A divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkanedi It is a lu group. Examples of divalent chain-type saturated hydrocarbon groups that may contain a fluorine atom include methylene groups and ethyl acetate groups. Alkanediyl groups such as len group, propanediyl group, butanediyl group and pentanediyl group ; Difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, Perfluoroalkanes such as the fluorobutanediyl group and the perfluoropentanediyl group. Examples include diyl groups. Divalent alicyclic saturated hydrocarbon groups, which may contain a fluorine atom, are monocyclic and polycyclic. A slight misalignment is also acceptable. Examples of monocyclic groups include cyclohexanediyl groups and perfluorocyclodiyl groups. Examples include the xandiyl group. Polycyclic groups include the adamantanediyl group and norbol. Examples include the nandiyl group and the perfluoroadamantanediyl group.

[0110] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42 in Similar groups to those exemplified can be cited. Among them, the trifluoromethyl group and the difluoromethyl group are particularly noteworthy. Tyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3, 3,3-Pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2, 2,3,3,4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group , perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and per Fluoroctyl groups and other alkyl fluorides, cyclopropylmethyl groups, cyclopropyl groups Cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group Xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbol Nyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl A methyl group is preferred.

[0111] In equation (a4-3), L 5 An ethylene group is preferred. A f13 The divalent saturated hydrocarbon group is a divalent chain-type saturated hydrocarbon group having 1 to 6 carbon atoms and carbon A group containing a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms is preferred, and a divalent chain having 2 to 3 carbon atoms is preferred. A saturated hydrocarbon group is even more preferred. A f14 The saturated hydrocarbon group is a chain-type saturated hydrocarbon group having 3 to 12 carbon atoms and a group having 3 to 12 carbon atoms. Groups containing alicyclic saturated hydrocarbon groups are preferred, and chain-type saturated hydrocarbon groups having 3 to 10 carbon atoms and Groups containing alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms are even more preferred. Among them, A f14 teeth Preferably, the group contains an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably, Cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group and It is a damantyl group.

[0112] Examples of structural units represented by equation (a4-3) include equation (a4-1'-1) ~ equation (a The structural units represented in 4-1'-11) are listed below. Keru R f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also shown in formula (a4-3). It can be cited as a structural unit.

[0113] Another example of a structural unit (a4) is the structural unit represented by formula (a4-4). TIFF0007927934000063.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is, -(CH2) j1 -,-(CH2) j2 -O-(CH2) j3- or - (CH2) j4 - CO-O-(CH2) j5 - represents j1 through j5 each independently represent an integer from 1 to 6. R f22 This represents a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom.

[0114] R f22 The saturated hydrocarbon group is R a42 Examples include saturated hydrocarbon groups similar to those represented by the symbol. R f22 This refers to an alkyl group having 1 to 10 carbon atoms that contains a fluorine atom, or a carbon atom containing a fluorine atom. A cycloaliphatic saturated hydrocarbon group having 1 to 10 prime atoms is preferred, and a group having 1 to 10 carbon atoms and a fluorine atom is preferred. Alkyl alkyl groups are more preferred, and C1-C6 alkyl groups having a fluorine atom are even more preferred. It's nice.

[0115] In equation (a4-4), A f21 As for, -(CH2) j1 - is preferred, ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0116] Examples of structural units represented by formula (a4-4) include the following structural units and the following formula In the structural unit shown, R in structural unit (a4-4) f21 The methyl group corresponding to One example is a structural unit in which a hydrogen atom has been replaced. JPEG0007927934000064.jpg87160

[0117] If resin (A) has structural units (a4), the content of these units is the total structural unit content of resin (A). A percentage of the position is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and 3 to 10 mol%. A percentage is even more preferable.

[0118] <Structural Unit (a5)> The non-leaved hydrocarbon groups possessed by structural unit (a5) include linear, branched, or cyclic hydrocarbons. Groups having a group are examples. In particular, structural unit (a5) has an alicyclic hydrocarbon group. The base is preferable. Examples of structural units (a5) include the structural unit represented by formula (a5-1). . TIFF0007927934000065.tif3555[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 This represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in this alicyclic hydrocarbon group The elementary atoms may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- group contained in may be replaced by -O- or -CO-.

[0119] R 52 The alicyclic hydrocarbon group in this can be either monocyclic or polycyclic. Examples of alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, and cyclopene. Examples include chill groups and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include, for example, Examples include adamantyl groups and norbornyl groups. Aliphatic hydrocarbon groups with 1 to 8 carbon atoms include, for example, methyl, ethyl, propyl, and iso groups. Propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl Examples include alkyl groups such as the octyl group and the 2-ethylhexyl group. Examples of alicyclic hydrocarbon groups with substituents include the 3-methyladamantyl group. ru. R52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably k is an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0120] L 55 In this context, divalent saturated hydrocarbon groups include divalent chain saturated hydrocarbon groups and divalent lipids. Examples include cyclic saturated hydrocarbon groups, preferably divalent chain saturated hydrocarbon groups. Examples of divalent chain-type saturated hydrocarbon groups include methylene groups, ethylene groups, and propanedi groups. Examples include alkanediyl groups such as the yl group, butanediyl group, and pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of saturated hydrocarbon groups include cyclopentanediyl groups and cyclohexanediyl groups. Examples include the roalkanediyl group. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include ada Examples include mantanediyl groups and norbornanediyl groups.

[0121] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by can be replaced with -O- or -CO-. Examples of the replaced groups include those represented by formulas (L1-1) to (L1-4). In the following formula, * and ** represent bonding sites, respectively, with * representing the bonding site with the oxygen atom. TIFF0007927934000066.tif18164 formula (L1-1), X x1 This represents *-O-CO- or *-CO-O- (* is L x1 (This represents the connection point with [another element].) . L x1 This represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, Lx1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 17 carbon atoms. L x4 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. L x6 and L x7 Each of these independently consists of a single bond or a divalent aliphatic saturated carbon with 1 to 14 carbon atoms. It represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 This represents a divalent alicyclic saturated hydrocarbon group with 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0122] L x1 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x2 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a single bond. L x3 Preferably, it is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. Lx4 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x6 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably The group is either a methylene group or an ethylene group. L x7 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. L x9 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. W x1 Preferably, a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably It is either a cyclohexanediyl group or an adamantanediyl group.

[0123] Examples of groups represented by formula (L1-1) include the divalent groups shown below. TIFF0007927934000067.tif53135

[0124] Examples of groups represented by formula (L1-2) include the divalent groups shown below. TIFF0007927934000068.tif23130

[0125] Examples of groups represented by formula (L1-3) include the divalent groups shown below. TIFF0007927934000069.tif15145

[0126] Examples of groups represented by formula (L1-4) include the divalent groups shown below. TIFF0007927934000070.tif26114

[0127] L 55 Preferably, it is a single bond or a group represented by formula (L1-1).

[0128] Structural units (a5-1) include the structural units shown below and the structural units within the following structural units ( a5-1) R 51 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007927934000071.tif77158

[0129] TIFF0007927934000072.tif39159 If resin (A) has structural units (a5), the content of these units is the total structural unit content of resin (A). A value of 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 3 to 15 mol% is preferred. A percentage is even more preferable.

[0130] <Structural Unit (II)> Resin (A) further decomposes upon exposure to generate acid, resulting in structural units (hereinafter referred to as "structural units") It may contain (II) (in some cases). Structural unit (II) may be specifically Examples include the structural unit described in Japanese Patent Publication No. 2016-79235, with a sulfonate side chain. A structural unit having a carboxylate group or a side chain with an organic cation, or a sulfonate group. It is preferable that the structural unit has an o group and an organic anion.

[0131] Structural units having a sulfonate group or carboxylate group and an organic cation in the side chain It is preferable that the structural unit is represented by formula (II-2-A'). TIFF0007927934000073.tif3189 [In formula (II-2-A'), X III3 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group contains The -CH2- that is present may be replaced by -O-, -S-, or -CO-, and the saturated coal The hydrogen atoms contained in the hydrogen group are halogen atoms, and the number of carbon atoms that may contain halogen atoms. It may be replaced by alkyl groups or hydroxyl groups numbered 1 to 6. A x1 This represents an alkanediyl group having 1 to 8 carbon atoms, and the water contained in the alkanediyl group The elementary atoms may be substituted with fluorine atoms or perfluoroalkyl groups having 1 to 6 carbon atoms. stomach. RA - This represents a sulfonate group or a carboxylate group. R III3 This is a hydrogen atom, a halogen atom, or a C1 atom which may have a halogen atom. Represents alkyl groups up to 6. ZA + This represents an organic cation.

[0132] R III3 The halogen atoms represented include fluorine, chlorine, bromine, and yo Examples include porcini atoms. R III3 A C1-C6 alkyl group which may have a halogen atom represented by So, R a8 A C1-C6 alkyl group which may have a halogen atom represented by the same Some examples include the following. A x1 Examples of alkanediyl groups with 1 to 8 carbon atoms, represented by the methylene group and the ethylene group, are available. , propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl Group, hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group yl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl Examples include the 1,4-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. ru. A x1 Examples of perfluoroalkyl groups having 1 to 6 carbon atoms that may be substituted include tri Fluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroiso Propyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl Examples include tyl groups, perfluoropentyl groups, and perfluorohexyl groups.

[0133] X III3 Divalent saturated hydrocarbon groups having 1 to 18 carbon atoms, as represented by , can be linear or branched. Examples include alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these These can be combined in any way. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, do Linear alkanediyl groups such as decane-1,12-diyl groups; butane-1,3-diyl groups, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pen Branched alkanedi such as tan-1,4-diyl group and 2-methylbutane-1,4-diyl group cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclo Cycloalkanes such as xane-1,4-diyl groups and cyclooctane-1,5-diyl groups Divalent monocyclic or alicyclic saturated hydrocarbon groups such as the 1,4-diyl group; norbornane-1,4-diyl group, Lunan-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6- Examples include divalent polycyclic and alicyclic saturated hydrocarbon groups such as diyl groups.

[0134] The -CH2- group in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. Examples include the divalent groups represented by equations (X1) to (X53). However, Furthermore, the -CH2- group contained in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. The number of carbon atoms in each preceding element is 17 or less. In the following formula, * and ** represent bonding sites. * is A x1 This represents the connection point. TIFF0007927934000074.tif145161

[0135] X 3 This represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 This represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. X 6 This represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7 This represents a trivalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 8 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms.

[0136] ZA + Examples of organic cations represented include organic onium cations and organic sulfonium cations. Thione, organic iodonium cation, organic ammonium cation, benzothiazolium cation Examples include thione and organic phosphonium cations. Among these, organic sulfonium Mucations and organiciodonium cations are preferred, and arylsulfonium cations are More preferable. Specifically, it can be expressed by any of the above formulas (b2-1) to (b2-4). The cation (hereinafter, depending on the formula number, it may be referred to as "cation (b2-1)," etc.) These are some examples.

[0137] The structural unit represented by formula (II-2-A') is the structural unit represented by formula (II-2-A) It is preferable that this be the case. JPEG0007927934000075.jpg37109 [In formula (II-2-A), R III3 , X III3 and ZA + This expresses the same meaning as above. z represents an integer between 0 and 6. R III2 and R III4 Each of these is independently a hydrogen atom, a fluorine atom, or a carbon atom with 1 carbon atom. Represents a perfluoroalkyl group of ~6, and when z is 2 or greater, multiple R III2 and R II I4 They may be the same or different from each other. Q a and Q b Each is independently a fluorine atom or a perfluoroal with 1 to 6 carbon atoms. [Represents the kill group.]

[0138] R III2 , R III4 Q a and Q b Perfluoroalkyl compounds with 1 to 6 carbon atoms, represented by As for the group Q, see the aforementioned Q b1 This is the same as a perfluoroalkyl group with 1 to 6 carbon atoms, as represented by This is one example.

[0139] The structural unit represented by formula (II-2-A) is the same as the structural unit represented by formula (II-2-A-1). It is preferable that it be in that position. TIFF0007927934000076.tif5576 [In formula (II-2-A-1), R III2 , R III3 , R III4 Q a Q b , z and ZA + This has the same meaning as above. represent. R III5 This represents a saturated hydrocarbon group with 1 to 12 carbon atoms. X I2 This represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and contains -CH2- may be replaced with -O-, -S-, or -CO- in the saturated carbonized water. The hydrogen atoms in the elementary group may be substituted with halogen atoms or hydroxyl groups.

[0140] R III5 Examples of saturated hydrocarbon groups having 1 to 12 carbon atoms include the methyl group and the ethyl group. propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pe Nthyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and Examples include linear or branched alkyl groups such as dodecyl groups. X I2 As a divalent saturated hydrocarbon group represented by , X III3 Divalent saturated carbon represented by Examples include those similar to hydrogenated groups.

[0141] The structural unit represented by formula (II-2-A-1) is represented by formula (II-2-A-2). A structural unit that can be made into a structure is preferable. TIFF0007927934000077.tif5287 [In formula (II-2-A-2), R III3 , RIII5 and ZA + This expresses the same meaning as above. m and nA each independently represent either 1 or 2.

[0142] Examples of structural units represented by formula (II-2-A') include the following structural unit, R III3 The group equivalent to the methyl group is a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a halogen A C1-C6 alkyl group that may have a C1 atom (for example, a trifluoromethyl group, etc.) Structural units that have been replaced by ) etc. and structural units described in International Publication No. 2012 / 050015 It can be listed. ZA + This represents an organic cation. TIFF0007927934000078.tif86163

[0143] A structural unit having a sulfonio group and an organic anion in its side chain is represented by formula (II-1-1). It is preferable that the structural unit is such that it can be formed. JPEG0007927934000079.jpg3381 [In formula (II-1-1), A II1 This represents a single bond or a divalent linking group. R II1 This represents a divalent aromatic hydrocarbon group with 6 to 18 carbon atoms. R II2 and R II3 Each of these independently represents a hydrocarbon group with 1 to 18 carbon atoms, and R II2 and R II3 They bond to each other, forming a ring with the sulfur atoms to which they are bonded. That's fine. R II4 This is a hydrogen atom, a halogen atom, or a C1-C2 atom which may have a halogen atom. This represents an alkyl group of 6. A - This represents an organic anion. R II1As a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, the phenylene group is an example. Examples include naphthylene groups, etc. R II2 and R II3 Examples of hydrocarbon groups represented include alkyl groups and alicyclic hydrocarbon groups. Examples include aromatic hydrocarbon groups and groups formed by combining them. Examples of alkyl groups and alicyclic hydrocarbon groups are the same as those described above. Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. , aralkyl groups such as benzyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl Nyl group, p-tert-butylphenyl group, tolyl group, xylyl group, coumenyl group, mesityl (e.g., 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group), alicyclic carbon Aromatic hydrocarbon groups having a hydrogenated group (p-cyclohexylphenyl group, p-adamantyl group) Examples include phenyl groups, phenylcyclohexyl groups, and other aryl-cycloalkyl groups. It can be done. R II4 The halogen atoms represented include fluorine, chlorine, bromine, and iodine. Examples include elementary atoms. R II4 A C1-C6 alkyl group which may have a halogen atom represented by R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by Some examples can be listed. A II1 Examples of divalent linking groups represented by include divalent saturated carbons with 1 to 18 carbon atoms. A hydrogen group is one example, and the -CH2- contained in the divalent saturated hydrocarbon group is -O-, -S- or It may be replaced with -CO-. Specifically, X III3 Represented by 1 to 1 carbon atoms Examples include the same divalent saturated hydrocarbon group as in 8.

[0144] The structural units containing cations in formula (II-1-1) are the structural units represented below, R II4 The group corresponding to the methyl group is a hydrogen atom, a halogen atom (for example, a fluorine atom) or A C1-C6 alkyl group which may have a halogen atom (for example, trifluoromethyl Examples include structural units that have been replaced by groups such as the 'L' group. TIFF0007927934000080.tif85130

[0145] A - Examples of organic anions represented by this include sulfonic acid anions and sulfonylimido anions. Examples include sulfonylmethide anions and carboxylic acid anions. - It is represented The organic anion is preferably a sulfonate anion, and as for the sulfonate anion, see the above. Examples similar to the anion represented by formula (B1) are given.

[0146] A - Examples of sulfonylimid anions represented by the formula include the following: TIFF0007927934000081.tif36136

[0147] Examples of sulfonylmethide anions include the following: TIFF0007927934000082.tif29123

[0148] Examples of carboxylic acid anions include the following: TIFF0007927934000083.tif51152

[0149] Examples of structural units represented by formula (II-1-1) include the following structural units. It is possible. JPEG0007927934000084.jpg88149

[0150] When resin (A) contains structural unit (II), the content of structural unit (II) is: The amount is preferably 1 to 20 mol%, and more preferably 2 to 1 mol%, relative to the total structural units of fat (A). The percentage is 15 mol%, and more preferably 3 to 10 mol%.

[0151] Resin (A) may have structural units other than those described above, and such structural units In terms of rank, well-known structural units in this field can be cited.

[0152] The resin (A) preferably has structural units (a1) (however, structural units (a1-1) and structure It includes at least one selected from the group consisting of units (a1-2), and structural units (s) and The resin consists of the above, that is, a copolymer of monomer (a1) and monomer (s). The structural unit (a1) is preferably a structural unit (a1-1) and a structural unit (a1-2) It consists of at least two species selected from the group. The structural unit (s) is preferably from the group consisting of structural unit (a2) and structural unit (a3). It is at least one selected. The structural unit (a2) is preferably represented by formula (a2-1). It is a structural unit represented by formula (a2-A). The structural unit (a3) ​​is preferred Alternatively, structural units represented by formula (a3-1), structural units represented by formula (a3-2), and formula ( It is at least one selected from the group consisting of structural units represented in a3-4).

[0153] Each structural unit constituting resin (A) may be used individually or in combination of two or more types. Furthermore, using monomers that derive these structural units, known polymerization methods (e.g., radical polymerization) can be used. Therefore, it can be manufactured. The content of each structural unit in resin (A) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,5 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 (less than 15,000, more preferably less than 15,000). In this specification, weight average fraction The amount of molecules was determined by gel permeation chromatography under the conditions described in the examples. That is the case.

[0154] <Resins other than resin (A)> The resist composition of the present invention may contain resins other than resin (A). Examples of resins other than resin (A) include structural unit (a4) or structural unit (a5). Examples include resins (hereinafter sometimes referred to as resin(X)).

[0155] Among the resins (X), resins containing structural units (a4) are preferred. In resin (X), the content of structural unit (a4) is equal to the sum of all structural units in resin (X). In contrast, it is preferable that the amount be 30 mol% or more, and more preferably 40 mol% or more. Furthermore, it is even more preferable that the amount be 45 mol% or more. The structural units that resin (X) may further possess include structural unit (a2) and structural unit (a3) and other structural units derived from known monomers are examples. Among them, resin ( X) is preferably a resin consisting only of structural unit (a4) and / or structural unit (a5). It is more preferable that the resin consists solely of structural units (a4). Each structural unit constituting the resin (X) may be used individually or in combination of two or more types. These monomers that induce structural units can be used in known polymerization methods (e.g., radical polymerization). Therefore, it can be manufactured. The content of each structural unit in resin (X) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000). The value is 0 or greater, and 80,000 or less (more preferably 60,000 or less). The method for measuring the weight-average molecular weight is the same as in the case of resin (A). If the resist composition contains resin (X), its content is as follows: per 100 parts by mass of resin (A) Preferably, it is 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further Preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 1 The layer is preferably 1 to 8 parts by mass.

[0156] The content of resin (A) in the resist composition is 8 in relation to the solid content of the resist composition. Preferably, it is 0% by mass or more and 99% by mass or less, and preferably 90% by mass or more and 99% by mass or less. It is preferable. Also, if it contains resins other than resin (A), then resin (A) and resins other than resin (A) The total content of the resin is 80% by mass or more and 99% by mass or less relative to the solid content of the resist composition. The resist composition is preferably as follows: The solid content of a substance and the resin content thereto are determined by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as fluoroscopy.

[0157] <Acid Generator (B)> The acid generator (B) may be either nonionic or ionic. As herbal preparations, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate ester) are used. Sulfonate, oximesulfonate, N-sulfonyloxiimide, sulfonyloxyke Ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, keto Examples include sulfones, sulfonyl diazomethanes, etc. Ionic acid generators include onions. Onium salts containing um cations (e.g., diazonium salts, phosphonium salts, sulfonium salts) Typical examples include salts (iodonium salts). An anion of anium salts is aniodonium sulfonate. Examples include sulfonylimide anions, sulfonylmethide anions, and others.

[0158] As for the acid generating agent (B), see Japanese Patent Publication No. 63-26653, Japanese Patent Publication No. 55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 Japanese Patent Publication No. 62-153853, Japanese Patent Publication No. 63-146029, U.S. Patent No. 3,779, Patent No. 778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate acid when exposed to radiation, as described in publications No. 126, 712, etc., can be used. Compounds manufactured by known methods may also be used. The acid generator (B) may consist of two or more types. They may be used in combination.

[0159] The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a fluorine-containing acid generator of formula (B1). This is a salt represented by (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007927934000085.tif2961[In formula (B1), Q b1 and Q b2Each of these independently contains a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. It represents the 'L' group. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and contains The -CH2- group may be replaced by -O- or -CO-, and the divalent saturated carbon The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms or hydroxyl groups. Y is a methyl group which may have substituents or a C3-C2 group which may have substituents 4 represents an alicyclic hydrocarbon group, and the -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced with SO2- or -CO-. Z1 + This represents an organic cation.

[0160] Q b1 and Q b2 The perfluoroalkyl group represented by is a trifluoromethyl group, perfluoro Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro Butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perflu Examples include the olopentyl group and the perfluorohexyl group. Q b1 and Q b2 Each of these independently consists of a fluorine atom or a trifluoromethyl group. Preferably, both are fluorine atoms, and more preferably, both are fluorine atoms.

[0161] L b1 Examples of divalent saturated hydrocarbon groups in this context include linear alkanediyl groups and branched alkanediyl groups. Examples include dipropyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these groups It may also be a group formed by combining two or more of these types. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- Linear alkanediyl groups such as diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as n-1,4-diyl group and cyclooctane-1,5-diyl group A monocyclic, divalent, alicyclic saturated hydrocarbon group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic saturated carbon such as 1,5-diyl group and adamantane-2,6-diyl group Examples include hydrogen groups.

[0162] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by -O- or -CO- The substituted base can be represented, for example, by any of the following equations: (b1-1) to (b1-3). The bases are listed. Furthermore, the bases represented by formulas (b1-1) to (b1-3) and their specific examples are In the example bases represented by formulas (b1-4) to (b1-11), * and ** are bonding parts. The position is indicated, and * represents the connection site with -Y.

[0163] TIFF0007927934000086.tif26117 [In formula (b1-1), L b2 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms. L b3 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms. L b5 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups. L b7 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0164] In the groups represented by formulas (b1-1) to (b1-3), the saturated hydrocarbon group is included. If -CH2- is replaced by -O- or -CO-, the number of carbon atoms before replacement is... This is the number of carbon atoms in the hydrocarbon group. As for divalent saturated hydrocarbon groups, L b1 Examples include divalent saturated hydrocarbon groups. ru. L b2 The bond is preferably a single bond. L b3 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 Preferably, the divalent saturated hydrocarbon group has 1 to 8 carbon atoms, and the divalent saturated hydrocarbon water The hydrogen atoms in the elementary group may be substituted with fluorine atoms. L b5 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 The saturated hydrocarbon group is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms. L b7 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. The -CH2- contained in the divalent saturated hydrocarbon group is replaced by -O- or -CO-. That's good too.

[0165] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by -O- or -CO- The replaced group is preferably the group represented by formula (b1-1) or formula (b1-3). The base represented by equation (b1-1) is shown in equations (b1-4) to (b1-8), respectively. The basis for this is listed below. TIFF0007927934000087.tif48120[In formula (b1-4), L b8 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups. In formula (b1-5), L b9 This represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and contains The -CH2- group may be replaced by -O- or -CO-. L b10 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b12 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b11 and L b12The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 This represents a divalent saturated hydrocarbon group with 1 to 19 carbon atoms. L b14 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. L b15 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and this divalent saturated hydrocarbon group The -CH2- group may be replaced by -O- or -CO-. L b17 This represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. L b18 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b16 ~L b18 The total number of carbon atoms is 19 or less. L b8 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 This is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 Preferably, it is a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0166] The base represented by equation (b1-3) is given by equations (b1-9) to (b1-11), respectively. The bases that can be represented are listed below. TIFF0007927934000088.tif22140[In formula (b1-9), L b19 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b20 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b22 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b25 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b26 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0167] Furthermore, between the group represented by formula (b1-9) and the group represented by formula (b1-11), When a hydrogen atom in a hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before replacement is defined as the number of carbon atoms in the saturated hydrocarbon group. Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, and b thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group These are some examples.

[0168] The following are examples of bases represented by formula (b1-4): TIFF0007927934000089.tif17150

[0169] The following are examples of bases represented by formula (b1-5): TIFF0007927934000090.tif72149

[0170] The following are examples of bases represented by formula (b1-6): TIFF0007927934000091.tif30150

[0171] The following are examples of bases represented by formula (b1-7): TIFF0007927934000092.tif64150

[0172] The following are examples of bases represented by formula (b1-8): TIFF0007927934000093.tif23150

[0173] The following are examples of bases represented by formula (b1-2): TIFF0007927934000094.tif31161

[0174] The following are examples of bases represented by formula (b1-9): TIFF0007927934000095.tif44137

[0175] The following are examples of bases represented by formula (b1-10): TIFF0007927934000096.tif89157 (* and ** represent binding sites, with * representing the binding site with Y.)

[0176] The following are examples of bases represented by formula (b1-11): TIFF0007927934000097.tif82158

[0177] Examples of alicyclic hydrocarbon groups represented by Y include formulas (Y1) to (Y11), formula (Y36) to (Y36). Examples of groups represented by formula (Y38) include those shown. The -CH2- group in the alicyclic hydrocarbon group represented by Y is either -O-, -SO2-, or -CO When replaced by -, the number of replacements may be one or two or more. Such a base is Examples of groups include those represented by equations (Y12) to (Y35) and (Y39) to (Y43). . The alicyclic hydrocarbon group represented by TIFF0007927934000098.tif84165Y is preferably formula (Y1) to formula (Y20), formula ( Y26), equation (Y27), equation (Y30), equation (Y31), equation (Y39) to equation (Y43) A group represented by any of the following, more preferably by formula (Y11), formula (Y15), or formula (Y16) ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39) A group represented by formula (Y40), formula (Y42), or formula (Y43), more preferably Alternatively, see equation (Y11), equation (Y15), equation (Y20), equation (Y26), equation (Y27), equation ( Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42), or formula (Y43) It is a base represented by . The alicyclic hydrocarbon group represented by Y is given by formulas (Y28) to (Y35), (Y39) to (Y 40) If it is a spiro ring containing an oxygen atom, such as formula (Y42) or formula (Y43), 2 The alkanediyl group between the oxygen atoms preferably has one or more fluorine atoms. Furthermore, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom It is preferable that the fluorine atom is not substituted.

[0178] The substituents of the methyl group represented by Y include halogen atoms, hydroxyl groups, and groups with 3 to 1 carbon atoms. 6 alicyclic hydrocarbon groups, C6-C18 aromatic hydrocarbon groups, glycidyloxy groups, -( CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 teeth, Alkyl groups with 1 to 16 carbon atoms, alicyclic hydrocarbon groups with 3 to 16 carbon atoms, and aromatic groups with 6 to 18 carbon atoms. This represents a fragrant hydrocarbon group or a group formed by combining these groups, and the alkyl group and the alicyclic hydrocarbon. The -CH2- group may be replaced by -O-, -SO2-, or -CO-. The hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are It may be replaced by a droxy group or a fluorine atom. ja is an integer from 0 to 4. Examples include: ) which represent... The substituents of the alicyclic hydrocarbon group represented by Y include halogen atoms, hydroxyl groups, and hydroxyl groups. A C1-C16 alkyl group which may be substituted with a roxy group (the alkyl group contains -CH2- may be replaced by -O- or -CO-. ), lipids with 3 to 16 carbon atoms. Cyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, aralkyl groups with 7 to 21 carbon atoms, Glycidyloxy group, -(CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO -R b1 group (in the formula, R b1 This refers to alkyl groups with 1 to 16 carbon atoms and alicyclic carbonized water with 3 to 16 carbon atoms. The alkyl group represents an elemental group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. The -CH2- contained in the alicyclic hydrocarbon group and the alicyclic hydrocarbon group is -O-, -SO2-, or -CO- The alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group The hydrogen atoms contained in may be replaced by hydroxyl groups or fluorine atoms. Examples include: , representing an integer between 0 and 4.

[0179] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alicyclic hydrocarbon groups include cyclopentyl groups, cyclohexyl groups, and methyl cyclohexyl groups. Chlohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, no Examples include the rubornyl group and the adamantyl group. Alicyclic hydrocarbon groups are chain hydrocarbon groups. They may also contain, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. be. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, and biphenyl groups. Examples include aryl groups such as nyl groups and phenanthryl groups. Aromatic hydrocarbon groups are chain carbon It may have a hydrogenated group or an alicyclic hydrocarbon group, and a chain hydrocarbon group having 1 to 18 carbon atoms. Aromatic hydrocarbon groups (tolyl group, xylyl group, cumenyl group, mesityl group, p-methyl) Phenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethyl Alicyclic carbons (such as 2-methyl-6-ethylphenyl groups and 2-methyl-6-ethylphenyl groups), and carbon atoms with 3 to 18 carbon atoms. Aromatic hydrocarbon groups having a hydrogenated group (p-adamantylphenyl group, p-cyclohexyl Examples include phenyl groups, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14. Furthermore, it is 6 to 10. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, and b Tyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group Examples include the following. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 It is ~6, and more preferably 1~4. Alkyl groups substituted with hydroxyl groups include hydroxymethyl groups and hydroxy Examples include hydroxyalkyl groups such as ethyl groups. Examples of aralkyl groups include benzyl group, phenethyl group, phenylpropyl group, and naphthyl group. Examples include tyl groups and naphthylethyl groups. The -CH2- group in the alkyl group is replaced by -O-, -SO2-, or -CO-, etc. The groups include alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, and alkyl groups. Examples include carbonyloxy groups or groups that combine these. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 12. Yes, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkoxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups. Examples include alkoxycarbonyl groups and butoxycarbonyl groups. The number of carbon atoms in the alkoxycarbonyl group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. Examples include the following. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, and more preferably The value is between 2 and 6, and more preferably between 2 and 4. Examples of alkylcarbonyloxy groups include acetyloxy groups and propionyloxy groups. Examples include the cy group and the butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4.

[0180] Examples of combined groups include groups that combine an alkoxy group and an alkyl group, and A group combining a lucoxy group and an alkoxy group, or a group combining an alkoxy group and an alkylcarbonyl group. Groups combining these, groups combining an alkoxy group and an alkylcarbonyloxy group, etc. It can be listed. Examples of groups combining an alkoxy group and an alkyl group include the methoxymethyl group. Alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, and ethoxymethyl group For example, the number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, and more preferably k is 2 to 6, and more preferably 2 to 4. Groups that combine alkoxy groups include methoxymethoxy groups and metoxy groups. Alkoxyalkoxy groups such as xyethoxy group, ethoxymethoxy group, and ethoxyethoxy group Examples include the following. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, and more Preferably, it is 2 to 6, and more preferably 2 to 4. Examples of groups combining an alkoxy group and an alkylcarbonyl group include methoxyacetyl. Alco groups such as methoxypropionyl group, ethoxyacetyl group, and ethoxypropionyl group Examples include xyalkylcarbonyl groups. The number of carbon atoms in an alkoxyalkylcarbonyl group is... Preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. be. Groups that combine an alkoxy group and an alkylcarbonyloxy group include methoxya Cetyloxy group, Methoxypropionyloxy group, Ethoxyacetyloxy group, Ethoxy Examples include alkoxyalkylcarbonyloxy groups such as propionyloxy groups. The number of carbon atoms in the coxyalkylcarbonyloxy group is preferably 3 to 13, and more preferably k is between 3 and 7, and more preferably between 3 and 5. The -CH2- group in the alicyclic hydrocarbon group is replaced by -O-, -SO2-, or -CO-, etc. The basis for the division is expressed by equations (Y12) to (Y35) and (Y39) to (Y43). Examples include the bases.

[0181] The following are examples of Y: TIFF0007927934000099.tif160165

[0182] Y is preferably a cycloaliphatic hydrocarbon group having 3 to 24 carbon atoms, which may have substituents. More preferably, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, which may have substituents. More preferably, it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may have substituents. More preferably, the adamantyl group may have substituents, and the alicyclic hydrocarbon The -CH2- group constituting the group or adamantyl group is replaced with -CO-, -SO2-, or -CO-. It may be replaced. Specifically, Y is preferably an adamantyl group, hydroxyadamantine A group represented by a dol group, an oxoadamantyl group, or formulas (Y42), (Y100) to (Y114) It is a base.

[0183] The anions in the salt represented by formula (B1) are given by formula (B1-A-1) ~ formula (B1- Anions represented by A-59) (hereinafter referred to as "anion (B1-A-1)" etc. depending on the formula number) In some cases, this is preferable, and formulas (B1-A-1) to (B1-A-4), formula (B1 -A-9), Formula (B1-A-10), Formula (B1-A-24) ~ Formula (B1-A-33), Formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-5 An anion represented by any of 9) is more preferred. TIFF0007927934000100.tif154162

[0184] TIFF0007927934000101.tif65159

[0185] TIFF0007927934000102.tif101154

[0186] TIFF0007927934000103.tif128162

[0187] TIFF0007927934000104.tif50138

[0188] TIFF0007927934000105.tif85165

[0189] TIFF0007927934000106.tif100160

[0190] Here R i2 ~R i7 These are, independently of each other, for example, alkyl groups having 1 to 4 carbon atoms, preferably The group is either a methyl group or an ethyl group. i8 For example, a chain-like hydrocarbon group having 1 to 12 carbon atoms. Preferably, alkyl groups having 1 to 4 carbon atoms, alicyclic hydrocarbon groups having 5 to 12 carbon atoms, or these. A group formed by combining these, more preferably a methyl group, an ethyl group, or a cyclohex group. It is either an adamantyl group or an adamantyl group. A41 These are single bonds or alkanediyl compounds with 1 to 4 carbon atoms. It is the basis. Q b1 and Q b2 This expresses the same meaning as above. Specifically, the anion in the salt represented by formula (B1) is as shown in Japanese Patent Publication No. 2010-20. Anions listed in Public Gazette No. 4646 are examples.

[0191] Preferably, the anion in the salt represented by formula (B1) is formula (B1a-1) ~ formula ( The anions represented by B1a-38 are listed below. TIFF0007927934000107.tif208160

[0192] TIFF0007927934000108.tif168155

[0193] In particular, equations (B1a-1) to (B1a-3) and equations (B1a-7) to (B1a- 16), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a- An anion represented by any of 38) is preferred.

[0194] Z1 + Examples of organic cations include organic onium cations and organic sulfonium cations. Organic iodium cation, organic ammonium cation, benzothiazolium cation and Examples include organic phosphonium cations. Among these, organic sulfonium cationic cations are particularly noteworthy. N and organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) ( Below, depending on the formula number, it may be referred to as "cation (b2-1)," etc. ) is an example. In formulas (b2-1) to (b2-4) of TIFF0007927934000109.tif46167, R b4 ~R b6 These are, independently, chain hydrocarbon groups with 1 to 30 carbon atoms and groups with 3 to 36 carbon atoms. This term represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and is contained in the chain-like hydrocarbon group. The hydrogen atoms present are found in hydroxyl groups, alkoxy groups with 1 to 12 carbon atoms, and lipid groups with 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms and aliphatic hydrocarbon groups with 1 to 18 carbon atoms. They may also be substituted with an alkylcarbonyl group or glycidyloxy group having 2 to 4 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group are halogen atoms, hydroxyl groups, and C1- 18 aliphatic hydrocarbon groups, C1-C12 alkyl fluorides, or C1-C12 It may be substituted with a coxy group. R b4 and R b5 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. Even if the -CH2- contained in the ring is replaced by -O-, -S-, or -CO- good. R b7 and R b8 These are, independently, a halogen atom, a hydroxyl group, and a lipid with 1 to 12 carbon atoms. This represents a fatty hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer between 0 and 5. When m2 is 2 or more, multiple R b7 They may be the same or different, and when n2 is 2 or more, multiple Number R b8 They may be the same or different. R b9 and R b10 Each of these is independently a chain-like hydrocarbon group having 1 to 36 carbon atoms or a group having 3 to 3 carbon atoms. It represents 36 alicyclic hydrocarbon groups. R b9 and R b10 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. It may be done, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. That's good too. R b11 This consists of a hydrogen atom, a chain hydrocarbon group with 1 to 36 carbon atoms, and an alicyclic carbon group with 3 to 36 carbon atoms. This represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 This refers to a chain-type hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or This represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in this chain-like hydrocarbon group are carbon It may be substituted with an aromatic hydrocarbon group having prime numbers 6 to 18, and the aromatic hydrocarbon group contains The hydrogen atom is a carbon-1 to carbon-12 alkoxy group or a carbon-1 to carbon-12 alkyl carbonyl group. It may be substituted with an oxy group. R b11 and R b12 These molecules bond to each other, forming a ring including the -CH-CO- groups to which they are joined. It is also possible that the -CH2- contained in the ring is replaced by -O-, -S-, or -CO-. That's fine. R b13 ~R b18 These are, independently, a halogen atom, a hydroxyl group, and a lipid with 1 to 12 carbon atoms. This represents a fatty hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. L b31 This represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer between 0 and 5. q2 and r2 each independently represent an integer between 0 and 4. u2 represents either 0 or 1. When o2 is 2 or more, multiple R b13 They are the same or different, and when p2 is 2 or more, multiple R b14 They are the same or different, and when q2 is 2 or more, multiple R b15 They are the same or different, r2 When there are 2 or more R b16 They are the same or different, and when s2 is 2 or more, multiple R b17 teeth If the same or different, and t2 is 2 or more, multiple R b18 They are either the same or different.

[0195] Aliphatic hydrocarbon groups refer to both chain-type hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, and butyl groups. Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and Examples include alkyl groups with a 2-ethylhexyl group. In particular, R b9 ~R b12 The chain-like hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and monocyclic alicyclic carbon Examples of hydrogen groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of cycloalkyl groups include cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of polycyclic alicyclic hydrocarbon groups include the decahydronaphthyl group and the adamantyl group. Examples include norbornyl groups and the following groups. TIFF0007927934000110.tif11158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably These have 4 to 12 carbon atoms.

[0196] As an example of an alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, methylcyclohex xyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyl Ruadamantan-2-yl group, 2-isopropyladamantan-2-yl group, methyl nor Examples include bornyl groups and isobornyl groups. Hydrogen atoms are substituted with aliphatic hydrocarbon groups. In alicyclic hydrocarbon groups, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferable. The number is 20 or less. A fluoride alkyl group refers to an alkyl group having 1 to 12 carbon atoms and containing a fluorine atom. Examples include oromethyl groups, difluoromethyl groups, trifluoromethyl groups, and perfluorobutyl groups. The number of carbon atoms in the alkyl fluoride is preferably 1 to 9, and more preferably 1 to It is 6, and more preferably 1 to 4.

[0197] Aromatic hydrocarbon groups include phenyl, biphenyl, naphthyl, and phenanthryl groups. Examples include aryl groups. Aromatic hydrocarbon groups include chain hydrocarbon groups or alicyclic hydrocarbon groups. It may have an elementary group, and an aromatic hydrocarbon group having a chain-like hydrocarbon group (tolyl group, xyl t-butylphenyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl (e.g., 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group) and alicyclic carbon Aromatic hydrocarbon groups having a hydrogenated group (p-cyclohexylphenyl group, p-adamantyl group) Examples include phenyl groups, etc. Furthermore, if the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, Chain-type hydrocarbon groups with 1 to 18 prime numbers and alicyclic hydrocarbon groups with 3 to 18 carbon atoms are preferred. As an aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group, p-methoxyphenyl Examples include the 'L' group. Examples of chain hydrocarbon groups in which hydrogen atoms are substituted with aromatic hydrocarbon groups include the benzyl group and the ferrous hydrocarbon group. Netyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. An example is the aralkyl group.

[0198] Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups, etc. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. It is possible. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkylcarbonyloxy groups include methylcarbonyloxy group and ethylcarbonyl Oxy group, propyl carbonyloxy group, isopropyl carbonyloxy group, butylcarbon Bonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy C group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples include oxy groups and 2-ethylhexylcarbonyloxy groups.

[0199] R b4 and R b5 The ring formed when these atoms bond to each other and together with the sulfur atom they bond to is The rings may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may have 3 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Furthermore, the ring containing the sulfur atom can be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. For example, the following ring can be cited. * indicates a bonding site. TIFF0007927934000111.tif23143

[0200] R b9 and R b10 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothi Examples include the ophenium ring, thian-1-ium ring, and 1,4-oxatian-4-ium ring. It can be done. R b11 and R b12 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring Examples include oxonorbornane rings and oxoadamantane rings.

[0201] Among cations (b2-1) to (b2-4), preferably cation (b2 -1) The following cations can be considered as cations (b2-1): TIFF0007927934000112.tif80158

[0202] TIFF0007927934000113.tif110165

[0203] The following cations can be considered as cations (b2-2): TIFF0007927934000114.tif18150

[0204] The following cations can be considered as cations (b2-3): TIFF0007927934000115.tif26140

[0205] The following cations can be considered as cations (b2-4): TIFF0007927934000116.tif127165

[0206] The acid generator (B) is a combination of the anion and the organic cation described above, and these are They can be combined in any way. The acid generator (B) is preferably of formula (B1a-1)~ Formula (B1a-3), Formula (B1a-7) ~ Formula (B1a-16), Formula (B1a-18), Formula ( Anio expressed by any of the following equations (B1a-19), (B1a-22) to (B1a-38) A combination of cation (b2-1), cation (b2-3), or cation (b2-4) The voice can be raised.

[0207] The acid generator (B) is preferably represented by formulas (B1-1) to (B1-56), respectively. Examples include those that are used. Among them, those containing arylsulfonium cations are preferred. Formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B 1-31) The form represented by formula (B1-56) is particularly preferred. TIFF0007927934000117.tif87150

[0208] TIFF0007927934000118.tif145158

[0209] TIFF0007927934000119.tif92153

[0210] TIFF0007927934000120.tif127143

[0211] TIFF0007927934000121.tif62163

[0212] TIFF0007927934000122.tif92158

[0213] In the resist composition of the present invention, the content of the acid generator is as follows: Preferably 1 to 45 parts by mass, more preferably 3 to 4 parts by mass, relative to the volume. The amount is 0 parts by mass or less, more preferably 10 parts by mass or more and 40 parts by mass or less.

[0214] <Solvent (E)> The solvent (E) content is typically 90% by mass or more and 99.9% by mass or less in the resist composition. Yes, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of solvent (E) is 99% by mass or less. The content of solvent (E) is determined, for example, by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as chromatography. The solvent (E) includes ethyl cellosolve acetate, methyl cellosolve acetate, and Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, vinegar Esters such as butyl acid, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl Ketones such as lucetone, 2-heptanone, and cyclohexanone; γ-butyrolactone, etc. Examples include cyclic esters; etc. One of the solvents (E) may be used alone. You may use two or more types.

[0215] <Quencher (C)> Quencher (C) is generated from a basic nitrogen-containing organic compound and an acid generator (B). Examples include salts that produce acids with weaker acidity than the acid that produces the quencher. If (C) is included, the amount of quencher (C) is based on the solid content of the resist composition. Preferably, it is about 0.01 to 15% by mass, and about 0.01 to 10% by mass. It is more preferable that it be about 0.01 to 5% by mass, and even more preferable that it be about 0.01 It is even more preferable that the amount be around 3% by mass. Basic nitrogen-containing organic compounds include amines and ammonium salts. Examples include aliphatic amines and aromatic amines. Aliphatic amines include primary amines. Examples include amines, secondary amines, and tertiary amines. Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, and diisopropylamine. Ruaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine Octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine mine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, methyldinonylamine, methylddecylamine, ethyl dibuty Luamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine Ethyl dioctylamine, ethyl dinonylamine, ethyl didecylamine, dicyclo Xylmethylamine, Tris[2-(2-methoxyethoxy)ethyl]amine, Triiso Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine Mine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmeth , 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridazole 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl (Lu)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disul fide, 2,2'-dipyridylamine, 2,2'-dipicolyamine, bipyridine, etc. can be mentioned , preferably diisopropylaniline, more preferably 2,6-diiso propylaniline is mentioned. Examples of ammonium salts include tetramethylammonium hydroxide, tetraisopropyla mmonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrime thylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammo nium hydroxide, tetra-n-butylammonium salicylate, choline, etc. are mentioned .

[0216] The acidity of a salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is represented by the acid dissociation constant (pKa). For salts that generate an acid weaker in acidity than the acid generated from the acid generator (B) , the acid dissociation constant of the acid generated from the salt is generally a salt satisfying -3 < pKa, preferably it is a salt satisfying -1 < pKa < 7, more preferably a salt satisfying 0 < pKa < 5. As salts that generate an acid weaker in acidity than the acid generated from the acid generator (B), those represented by the following formula , salts represented by formula (D) described in Japanese Patent Application Laid-Open No. 2015-147926 (hereinafter referred to as " weak acid inner salt (D)" in some cases), and Japanese Patent Application Laid-Open No. 2012-229206 , Japanese Patent Application Laid-Open No. 2012-6908, Japanese Patent Application Laid-Open No. 2012-72109, Japanese Patent Application Laid-Open No. 2011-3 Examples include the salts described in Japanese Patent Publication No. 9502 and Japanese Patent Application Publication No. 2011-191745. Preferably This produces a salt (carb) that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B). It is a salt having an acid anion, and more preferably, a weak acid intramolecular salt (D). TIFF0007927934000123.tif89165

[0217] Examples of intramolecular salts (D) of weak acids include the following salts: TIFF0007927934000124.tif72165

[0218] <Other ingredients> The resist composition of the present invention may optionally include components other than those described above (hereinafter referred to as "other components"). It may be referred to as "F (F)". It may contain other components (F) in particular. There are no known additives in the resist field, such as sensitizers, dissolution inhibitors, surfactants, and stabilizers. Agents, dyes, etc. can be used.

[0219] <Preparation of resist composition> The resist composition of the present invention comprises a salt (I), a resin (A), an acid generator (B), and necessary Depending on the resin used, a resin other than resin (A), solvent (E), quencher (C), and its It can be prepared by mixing with other components (F). The mixing order is arbitrary, and in particular It is not limited to this. The mixing temperature can range from 10 to 40°C, depending on the type of resin, etc. An appropriate temperature can be selected depending on the solubility in solvents (E), etc. The mixing time is Depending on the mixing temperature, you can choose an appropriate time from 0.5 to 24 hours. There are no particular restrictions on the mixing method, and stirring and mixing can be used. After mixing each component, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable to do so.

[0220] <Method for manufacturing resist patterns> The method for manufacturing a resist pattern of the present invention is: (1) A step of applying the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) Includes a step of developing the composition layer after heating. To coat the resist composition onto the substrate, a commonly used device such as a spin coater is used. Therefore, it can be done. Examples of substrates include inorganic substrates such as silicon wafers. Before applying the Dist composition, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate. It's fine if you do that. By drying the applied composition, the solvent is removed and a composition layer is formed. Drying is performed. For example, evaporating a solvent using a heating device such as a hot plate (so-called private heating) This is done by (k) or by using a vacuum device. The heating temperature is 50-200°C. It is preferable that the heating time be 10 to 180 seconds. Also, vacuum drying The pressure used during this process is 1 to 1.0 × 10 5 It is preferable that the pressure be around Pa. The resulting composition layer is typically exposed using an exposure machine. The exposure machine is an immersion exposure machine. This is also good. As exposure light sources, KrF excimer laser (wavelength 248nm), ArF excimer Ultraviolet lasers such as lasers (wavelength 193nm) and F2 excimer lasers (wavelength 157nm) Laser light is emitted from solid-state laser sources (such as YAG or semiconductor lasers). These devices emit high-harmonic laser light in the far-ultraviolet or vacuum-ultraviolet region by wavelength conversion, such as electron beams and ultra-high-frequency lasers. Various methods can be used, such as those that irradiate with ultraviolet light (EUV). In some cases, the act of irradiating with these radiations is collectively referred to as "exposure." Typically, exposure is performed through a mask corresponding to the desired pattern. The exposure light source is electron In the case of lines, exposure may be performed by direct drawing without using a mask. The composition layer after exposure is heat-treated to promote the deprotection reaction at the acid-unstable groups. Perform a loose post-exposure bake. The heating temperature is usually around 50-200°C, or as preferred. The temperature is approximately 70-150°C. The heated composition layer is typically developed using a developing device and a developing solution. Examples include the dipping method, paddle method, spray method, and dynamic dispensing method. The development temperature is preferably, for example, 5 to 60°C, and the development time is, for example, 5 It is preferable that the developing time is ~300 seconds. By selecting the type of developer as follows: Positive-type resist patterns or negative-type resist patterns can be manufactured. When producing a positive-type resist pattern from the resist composition of the present invention, the developer is used as follows: An alkaline developer is used. The alkaline developer is a type of alkaline water used in this field. Any solution will do. For example, tetramethylammonium hydroxide or (2-hydroxy Examples include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). Alkaline developers may contain surfactants. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is washed away. It is preferable to remove it. When manufacturing a negative-type resist pattern from the resist composition of the present invention, the developer is used as A developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used. Organic solvents contained in organic developers include ketosols such as 2-hexanone and 2-heptanone. Solvents; glycol ethers such as propylene glycol monomethyl ether acetate Sterling solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. Glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole Examples include aromatic hydrocarbon solvents such as the like. In organic developer solutions, the content of organic solvents is preferably 90% by mass or more and 100% by mass or less. It is more preferable that the concentration be 95% by mass or more and 100% by mass or less, and that it be substantially composed of only organic solvents. It is preferable. Among organic developers, those containing butyl acetate and / or 2-heptanone are Preferred. The total content of butyl acetate and 2-heptanone in the organic developer is 50% by mass. Preferably, the amount is 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the composition consists solely of butyl acetate and / or 2-heptanone. Organic developers may contain surfactants. Also, organic developers may contain trace amounts of surfactants. It may contain moisture. During development, by substituting a different type of solvent than the organic developer, development can be stopped. That's good too. It is preferable to wash the resist pattern with a rinsing solution after development. The rinsing solution can be: There are no particular restrictions as long as it does not dissolve the resist pattern, including general organic solvents. A liquid can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove any remaining rinse solution from the substrate and patterns.

[0221] <Application> The resist composition of the present invention is a resist composition for KrF excimer laser exposure, and ArF Resist compositions for Kishima laser exposure, resist compositions for electron beam (EB) exposure, or EU Resist compositions for V exposure, particularly resist compositions for electron beam (EB) exposure or EUV exposure It is suitable as a resist composition for use and is useful for semiconductor microfabrication. [Examples]

[0222] The present invention will be described in more detail with reference to examples. In the examples, the content or amount used is expressed Unless otherwise specified, "%" and "parts" refer to mass. The weight-average molecular weight was determined by gel permeation chromatography under the following conditions. It is a value. Equipment: HLC-8120GPC model (manufactured by Tosoh Corporation) Column: TSKgel Multipore H XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

[0223] Furthermore, the structure of the compound was determined by mass spectrometry (LC: Agilent 1100, MASS: A This was confirmed by measuring molecular ion peaks using a Gilent LC / MSD (LC / MSD) system. In the following examples, the value of this molecular ion peak is indicated by "MASS".

[0224] Synthesis Example 1: Synthesis of the compound represented by formula (I-1) TIFF0007927934000125.tif34134 5 parts of the compound represented by formula (I-1-a), 230 parts of ethyl acetate, and formula (I-1-b) 12.88 parts of the compound shown were mixed, stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture, add 23.48 parts of diisopropylethylamine dropwise, then heat up to 70°C. The mixture was heated to 70°C and stirred for 2 hours, then cooled to 23°C. The resulting mixture was then subjected to ion exchange. Add 120 parts of replacement water, stir at 23°C for 30 minutes, and separate to obtain the organic layer. Add 120 parts of a 5% oxalic acid aqueous solution to the prepared organic layer, stir at 23°C for 30 minutes, and then separate the liquids. This yielded an organic layer. To the obtained organic layer, 120 parts of deionized water were added and incubated at 23°C for 3 minutes. The organic layer was obtained by stirring for 0 minutes and then separating the liquid. This washing procedure was repeated 5 times. The organic layer is concentrated, and the concentrated mass is stored in a column (silica gel 60N (spherical, neutral) 100-210). μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) take a portion. This yielded 7.24 parts of the compound represented by formula (I-1). MASS (mass spectrometry):227.1[M+H] +

[0225] Synthesis Example 2: Synthesis of the compound represented by formula (I-5) TIFF0007927934000126.tif36138 8 parts of the compound represented by formula (I-5-a), 100 parts of ethyl acetate and formula (I-1-b) 15.72 parts of the compound shown were mixed, stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture, add 10.59 parts of diisopropylethylamine dropwise, then heat up to 70°C. The mixture was heated, stirred at 70°C for 4 hours, and then cooled to 23°C. The resulting mixture was then subjected to ion exchange. Add 100 parts of replacement water, stir at 23°C for 30 minutes, and separate the liquid to obtain the organic layer. Add 50 parts of a 5% oxalic acid aqueous solution to the prepared organic layer, stir at 23°C for 30 minutes, and then separate the liquid and liquid layers. An organic layer was obtained by this process. 50 parts of deionized water were added to the obtained organic layer and incubated at 23°C for 30 minutes. The organic layer was obtained by stirring and then separating the liquid. This washing procedure was repeated five times. The cell layer is concentrated, and the concentrated mass is placed in a column (silica gel 60N (spherical, neutral) 100-210 μm). (Manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to be taken separately. From this, 7.15 parts of the compound represented by formula (I-5) were obtained. MASS (mass spectrometry):527.1[M+H] +

[0226] Synthesis Example 3: Synthesis of the compound represented by formula (I-9) TIFF0007927934000127.tif30147 6.50 parts of the compound represented by formula (I-9-a), 160 parts of ethyl acetate and formula (I-1- Mix 15.19 parts of the compound represented in (b), stir at 23°C for 30 minutes, and then cool to 5°C. Then, 18.05 parts of diisopropylethylamine were added dropwise to the resulting mixture, and then 70 The mixture was heated to 70°C, stirred for 4 hours, and then cooled to 23°C. Add 160 parts of decontaminated water, stir at 23°C for 30 minutes, and separate to obtain an organic layer. Add 80 parts of a 5% oxalic acid aqueous solution to the obtained organic layer, stir at 23°C for 30 minutes, and separate the liquid-liquid. An organic layer was obtained by this process. 80 parts of deionized water were added to the obtained organic layer and heated at 23°C. The organic layer was obtained by stirring for 30 minutes and then separating the liquid. This washing procedure was repeated five times. The prepared organic layer was concentrated, and the concentrated mass was stored in a column (silica gel 60N (spherical, neutral) 100-21 0 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) take a portion. As a result, 5.80 parts of the compound represented by formula (I-9) were obtained. MASS (mass spectrometry):319.2[M+H] +

[0227] Synthesis Example 4: Synthesis of the compound represented by formula (I-39) TIFF0007927934000128.tif39123 5.00 parts of the compound represented by formula (I-39-a), and the compound represented by formula (I-39-c) Mix 0.008 parts of the substance and 50 parts of toluene, stir at 23°C for 30 minutes, then at 100°C. The temperature was raised. Compound 6, represented by formula (I-39-b), was added to the resulting mixed solution at 100°C. 0.19 parts were added dropwise, stirred at 110°C for 2 hours, and then cooled to 23°C. The resulting mixture Add 25 parts ethyl acetate and 30 parts deionized water, stir at 23°C for 30 minutes, then The organic layer was separated by saturation. 30 parts of deionized water were added to the recovered organic layer and incubated at 23°C. After stirring for 30 minutes, the organic layer was separated and removed. This washing procedure was repeated three times. By concentrating the resulting organic layer, 5.85 parts of the compound represented by formula (I-39) were obtained. . MASS (mass spectrometry): 167.1[M+H] +

[0228] Synthesis Example 5: Synthesis of the compound represented by formula (I-37) TIFF0007927934000129.tif35136 20 parts of compound represented by formula (I-37-a), 2 parts of compound represented by formula (I-39-c) Mix 0.28 parts, 100 parts ethyl acetate, and 14 parts tetrahydrofuran, and bake at 23°C for 30 minutes. After stirring, the mixture was cooled to 10°C. The resulting mixed solution was then treated with formula (I-37-b) at 10°C. 6.55 parts of the compound represented by ) were added dropwise, the temperature was raised to 23°C, and the mixture was stirred at 23°C for 2 hours. Add 70 parts of deionized water to the mixture and stir at 23°C for 30 minutes, then separate the liquid and extract the liquid. The organic layer was removed. This washing operation was repeated five times. The resulting organic layer was concentrated into a concentrated mass. The column (silica gel 60N (spherical, neutral) 100-210μm; manufactured by Kanto Chemical Co., Ltd.) Opening solvent: n-heptane / ethyl acetate = 10 / 1) By fractionation, formula (I-37) 8.75 parts of the compound were obtained. MASS (mass spectrometry): 183.1[M+H] +

[0229] Synthesis Example 6: Synthesis of the compound represented by formula (I-4) TIFF0007927934000130.tif32123 5 parts of the compound represented by formula (I-1-a), 230 parts of ethyl acetate, and formula (I-1-b) 4.29 parts of the compound shown were mixed, stirred at 23°C for 30 minutes, and then cooled to 5°C. After adding 5.86 parts of diisopropylethylamine dropwise to the mixture, the temperature was raised to 70°C. The mixture was stirred at 70°C for 2 hours, then cooled to 23°C. Deionized water was added to the resulting mixture. 120 parts were added, stirred at 23°C for 30 minutes, and the organic layer was obtained by liquid-liquid separation. Add 120 parts of a 5% oxalic acid aqueous solution to the organic layer, stir at 23°C for 30 minutes, and then separate the liquids. An organic layer was obtained by this process. 120 parts of deionized water were added to the obtained organic layer and incubated at 23°C for 30 minutes. The organic layer was obtained by stirring and then separating the liquid. This washing procedure was repeated five times. The cell layer is concentrated, and the concentrated mass is placed in a column (silica gel 60N (spherical, neutral) 100-210 μm). (Manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to be taken separately. From this, 2.44 parts of the compound represented by formula (I-4) were obtained. MASS (mass spectrometry): 169.1[M+H] +

[0230] Synthesis Example 7: Synthesis of the compound represented by formula (I-41) TIFF0007927934000131.tif32134 5 parts of the compound represented by formula (I-41-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 3.92 parts of the compound represented by formula (I-1-b) dropwise to the mixture, ferment at 23°C for 18 hours. Stirring was continued. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. An organic layer was obtained by liquid-liquid separation. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. The washing operation was performed five times. The resulting organic layer was concentrated, and the concentrated mass was placed in a column (silica gel 6 0N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / By separating ethyl acetate (10 / 1), compound 3.08, represented by formula (I-41), is obtained. I got a part. MASS (mass spectrometry):478.9[M+H] +

[0231] Synthesis Example 8: Synthesis of the compound represented by formula (I-45) TIFF0007927934000132.tif33117 5 parts of the compound represented by formula (I-45-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 12.32 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. To the mixture, 6.01 parts of the compound represented by formula (I-1-b) were added dropwise, and then the mixture was incubated at 23°C for 18 minutes. The mixture was stirred for a certain amount of time. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. The organic layer was then separated to obtain an organic layer. To the obtained organic layer, 16 parts of a 5% oxalic acid aqueous solution were added. The organic layer was then stirred at 23°C for 30 minutes and separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. This washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mass was placed on a column (silica gel). 60N (spherical, neutral), 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane By fractionating ethyl acetate (10 / 1), compound 3.8, represented by formula (I-45), is obtained. I got four parts. MASS (mass spectrometry):353.0[M+H] +

[0232] Synthesis Example 9: Synthesis of the compound represented by formula (I-55) TIFF0007927934000133.tif28147 10 parts of the compound represented by formula (I-55-a), 75 parts of ethyl acetate and diisopropyl acetate Mix 26.85 parts of thylamine, stir at 23°C for 30 minutes, and then cool to 5°C. To the mixture, 15.11 parts of the compound represented by formula (I-1-b) were added dropwise, and then the mixture was left at 23°C. The mixture was heated and stirred at 23°C for 18 hours. 75 parts of deionized water were added to the resulting mixture. The organic layer was obtained by stirring at 23°C for 30 minutes and then separating the liquid. 5% chlorine was added to the resulting organic layer. Add 30 parts of an aqueous solution of oxalic acid, stir at 23°C for 30 minutes, and separate the solution to obtain an organic layer. Add 40 parts of deionized water to the resulting organic layer, stir at 23°C for 30 minutes, and then separate the liquid and water. An organic layer was obtained by this process. This washing operation was repeated five times. The obtained organic layer was concentrated, and concentrated milk The column (silica gel 60N (spherical, neutral) 100-210μm; manufactured by Kanto Chemical Co., Ltd.) Developing solvent: n-heptane / ethyl acetate = 10 / 1) By fractionation, formula (I-55) 12.32 parts of the compound represented by [formula] were obtained. MASS (mass spectrometry):367.1[M+H] +

[0233] Synthesis Example 10: Synthesis of the compound represented by formula (I-60) TIFF0007927934000134.tif63160 10 parts of compound represented by formula (I-60-a), 0 parts of compound represented by formula (I-39-c) Mix 0.55 parts, 100 parts ethyl acetate, and 10 parts tetrahydrofuran, and bake at 23°C for 30 minutes. After stirring, the mixture was cooled to 10°C. The resulting mixed solution was then treated with formula (I-60-b) at 10°C. 2.76 parts of the compound represented by ) were added, the temperature was raised to 23°C, and the mixture was stirred at 23°C for 2 hours. Add 70 parts of deionized water to the mixture and stir at 23°C for 30 minutes, then separate the liquid and extract the liquid. The organic layer was removed. This washing operation was repeated five times. The resulting organic layer was concentrated into a concentrated mass. The column (silica gel 60N (spherical, neutral) 100-210μm; manufactured by Kanto Chemical Co., Ltd.) Opening solvent: n-heptane / ethyl acetate = 10 / 1) By fractionation, formula (I-60) 9.15 parts of the compound were obtained. MASS (mass spectrometry):481.3[M+H] +

[0234] Synthesis Example 11: Synthesis of the compound represented by formula (I-65) TIFF0007927934000135.tif35133 5 parts of the compound represented by formula (I-65-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 3.92 parts of the compound represented by formula (I-1-b) dropwise to the mixture, ferment at 23°C for 18 hours. Stirring was continued. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. An organic layer was obtained by liquid-liquid separation. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. The washing operation was performed five times. The resulting organic layer was concentrated, and the concentrated mass was placed in a column (silica gel 6 0N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / By fractionating ethyl acetate (10 / 1), compound 2.48, represented by formula (I-65), is obtained. I got a part. MASS (mass spectrometry):478.9[M+H] +

[0235] Synthesis Example 12: Synthesis of the compound represented by formula (I-71) TIFF0007927934000136.tif36122 5 parts of the compound represented by formula (I-65-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 1.86 parts of the compound represented by formula (I-1-b) dropwise to the mixture, ferment at 23°C for 18 hours. Stirring was continued. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. An organic layer was obtained by liquid-liquid separation. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. The washing operation was performed five times. The resulting organic layer was concentrated, and the concentrated mass was placed in a column (silica gel 6 0N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / By separating ethyl acetate (10 / 1), compound 3.44, represented by formula (I-71), is obtained. I got a part. MASS (mass spectrometry):420.9[M+H] +

[0236] Synthesis Example 13: Synthesis of the compound represented by formula (I-75) TIFF0007927934000137.tif34130 5 parts of the compound represented by formula (I-41-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 5.00 parts of the compound represented by formula (I-75-b) to the mixture, bake at 23°C for 18 minutes. The mixture was stirred for a certain amount of time. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. The organic layer was then separated to obtain an organic layer. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was then stirred at 23°C for 30 minutes and separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. This washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mass was placed on a column (silica gel). 60N (spherical, neutral), 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane By fractionating ethyl acetate (10 / 1), compound 3.4, represented by formula (I-75), is obtained. I got four parts. MASS (mass spectrometry):531.0[M+H] +

[0237] Synthesis Example 14: Synthesis of the compound represented by formula (I-76) TIFF0007927934000138.tif34130 5 parts of the compound represented by formula (I-65-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 5.00 parts of the compound represented by formula (I-75-b) to the mixture, bake at 23°C for 18 minutes. The mixture was stirred for a certain amount of time. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. The organic layer was then separated to obtain an organic layer. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was then stirred at 23°C for 30 minutes and separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. This washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mass was placed on a column (silica gel). 60N (spherical, neutral), 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane By fractionating ethyl acetate (10 / 1), compound 2.1, represented by formula (I-76), is obtained. I got 6 copies. MASS (mass spectrometry):531.0[M+H] +

[0238] Synthesis Example 15: Synthesis of the compound represented by formula (I-79) TIFF0007927934000139.tif33122 5 parts of the compound represented by formula (I-41-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 2.38 parts of the compound represented by formula (I-75-b) to the mixture, bake at 23°C for 18 minutes. The mixture was stirred for a certain amount of time. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. The organic layer was then separated to obtain an organic layer. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was then stirred at 23°C for 30 minutes and separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. This washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mass was placed on a column (silica gel). 60N (spherical, neutral), 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane By taking a fraction of ethyl acetate (10 / 1), compound 1.6 represented by formula (I-79) is obtained. I obtained 8 copies. MASS (mass spectrometry):446.9[M+H] +

[0239] Synthesis Example 16: Synthesis of the compound represented by formula (I-80) TIFF0007927934000140.tif35122 5 parts of the compound represented by formula (I-65-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 2.38 parts of the compound represented by formula (I-75-b) to the mixture, bake at 23°C for 18 minutes. The mixture was stirred for a certain amount of time. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. The organic layer was then separated to obtain an organic layer. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was then stirred at 23°C for 30 minutes and separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. This washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mass was placed on a column (silica gel). 60N (spherical, neutral), 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane By fractionating ethyl acetate (10 / 1), compound 3.8, represented by formula (I-80), is obtained. I got 9 copies. MASS (mass spectrometry):446.9[M+H] +

[0240] Synthesis Example 17: Synthesis of the compound represented by formula (IX-1) TIFF0007927934000141.tif26116 25.7 parts of the compound represented by formula (IX-1-a), 120 parts of acetone and triethyl 48.58 parts of min were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. The resulting mixture After adding 36.91 parts of the compound represented by formula (IX-1-b) to the mixture, the temperature is raised to 23°C. The mixture was heated and stirred at 23°C for 6 hours. To the resulting mixture, tert-butyl methyl ether 1 Add 20 parts and 80 parts of deionized water, stir at 23°C for 30 minutes, and separate the liquids to obtain An organic layer was obtained. 60 parts of saturated ammonium chloride aqueous solution were added to the obtained organic layer, and it was incubated at 23°C for 3 minutes. The organic layer was stirred for 0 minutes and then separated to obtain an organic layer. 60% deionized water was added to the obtained organic layer. The mixture was added, stirred at 23°C for 30 minutes, and then separated to obtain an organic layer. This was followed by the washing procedure. This was repeated 5 times. The resulting organic layer was concentrated, and the concentrated mass was placed on a column (silica gel 60N (spherical, (Neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 5 / 1) By fractionation, 27.18 parts of the compound represented by formula (IX-1) were obtained. MASS (mass spectrometry):207.1[M+H] +

[0241] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. These are referred to as "monomers (a1-1-3)" etc., according to their formula numbers. TIFF0007927934000142.tif48154

[0242] Synthesis Example 18 [Synthesis of Resin A1] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( Using a2-1-3), monomer (a3-4-2) and monomer (a1-4-2), Molar ratio [Monomer (a1-1-3):Monomer (a1-2-6):Monomer (a2-1- 3): Monomer (a3-4-2): Monomer (a1-4-2) is in a ratio of 20:35:3:1 Mix in a ratio of 5:27, and further, add the total amount of all monomers to this monomer mixture. Methyl isobutyl ketone was mixed in an amount 1.5 times its mass relative to the mass. As initiators, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) Add 1.2 mol% and 3.6 mol% of the total monomer amount, respectively, and then It was heated at 73°C for approximately 5 hours. After that, the polymerization reaction solution was mixed with a certain amount of monomer relative to the total mass of the monomers. Add 2.0 times the mass of p-toluenesulfonic acid aqueous solution (2.5% by weight) and stir for 12 hours. Afterward, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and then filtered. By recovering the material, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 Resin A1 is produced with a yield of 63% It was obtained as follows. This resin A1 has the following structural units. TIFF0007927934000143.tif38153

[0243] Synthesis Example 19 [Synthesis of Resin A2] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( Using monomers a2-1-3), a3-4-2, and a1-4-13, Molar ratio [monomer(a1-1-3):monomer(a1-2-6):monomer(a2-1 -3): Monomer (a3-4-2): Monomer (a1-4-13)] is 20:35:3 Mix them in a ratio of 15:27, and then add all the monomers to this monomer mixture. Methyl isobutyl ketone was mixed in an amount equal to 1.5 times the total mass. The resulting mixture In addition, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) are used as initiators. Tolyl was added at concentrations of 1.2 mol% and 3.6 mol% relative to the total amount of monomer, and The mixture was heated at 73°C for approximately 5 hours. After that, the polymerization reaction solution was mixed with a total amount of monomers relative to the total mass. Then, add 2.0 times the mass of p-toluenesulfonic acid aqueous solution (2.5% by weight) and stir for 12 hours. After mixing, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin. By filtering and recovering the material, the weight-average molecular weight is approximately 5.1 × 10⁻⁶. 3 The resin A2 is produced in a yield of 6 It was obtained at a concentration of 1%. This resin A2 has the following structural units. TIFF0007927934000144.tif38153

[0244] Synthesis Example 20 [Synthesis of Resin A3] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer ( Using a3-4-2) and monomer (a1-4-2), the molar ratio [monomer (a1-2 -6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (a1-4- 2) Mix the monomers in a ratio of 53:3:12:32, and further mix this monomer mixture The substance is mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all monomers. The resulting mixture was then mixed with azobisisobutyronitrile and azobis(2,4) as initiators. (dimethylvaleronitrile) is added at 1.2 mol% and 3.6 mol% respectively relative to the total amount of monomer. The mixture was added in ol% and heated at 73°C for approximately 5 hours. Afterward, the polymerization reaction solution was mixed with the total monomer. A p-toluenesulfonic acid aqueous solution (2.5% by weight) in an amount equal to 2.0 times the total mass of the total amount. After adding the mixture and stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the resin and then filtering and recovering it, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 dea Resin A3 was obtained with a yield of 88%. This resin A3 has the following structural units. TIFF0007927934000145.tif38128

[0245] Synthesis Example 21 [Synthesis of Resin A4] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer ( Using a3-4-2) and monomer (a1-4-13), the molar ratio [monomer (a1- 2-6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (a1-4 Mix the monomers in the ratio of -13) to 53:3:12:32, and further, this monomer To the mixture, add methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all monomers. Combined. To the resulting mixture, azobisisobutyronitrile and azobis(2) were added as initiators. ,4-dimethylvaleronitrile) is added at 1.2 mol% and 3 mol% respectively relative to the total amount of monomer. 6 mol% was added, and these were heated at 73°C for approximately 5 hours. After that, the entire monopolymer was added to the polymerization reaction solution. A p-toluenesulfonic acid aqueous solution (2.5 by weight) is added in an amount equal to 2.0 times the total mass of the amount of Mer. %) was added, stirred for 12 hours, and then separated. The recovered organic layer contained a large amount of n-heptane. By pouring it into the solution and allowing the resin to precipitate, then filtering and recovering it, the weight-average molecular weight is approximately 5.1 × 10⁻⁶. 3 Resin A4 was obtained in a yield of 79%. This resin A4 has the following structural units: ru. TIFF0007927934000146.tif38128

[0246] Synthesis Example 22 [Synthesis of Resin AX1] 100 parts of polyvinylphenol (VP-15000; manufactured by Nippon Soda Co., Ltd.), methyliso 400 parts of butyl ketone and 0.004 parts of p-toluenesulfonic acid dihydrate were added, The mixed solution was concentrated until the total volume was 273 parts. Ethyl vinyl ether was added to the concentrated resin solution. Add 8.01 parts dropwise and stir for 2.5 hours to allow the reaction to proceed. Then, add ions to this reaction solution. 58.2 parts of replacement water and 0.005 parts of triethylamine were added and the mixture was stirred and separated. Then, 60 parts of deionized water were added to the organic layer and the separation process was repeated four times. The organic layer after washing. By concentrating it, the weight-average molecular weight becomes approximately 1.6 × 10⁻⁶. 4 The resin AX1 yielded 8 The result was obtained at 8%. The introduction rate of ethoxyethyl groups to the total structural units of resin AX1 was 30.1 moles. It was %. Resin AX1 has the following structural units. TIFF0007927934000147.tif37108

[0247] <Preparation of the resist composition> As shown in Table 1, the following components were mixed, and the resulting mixture contained fluorine with a pore size of 0.2 μm. The resist composition was prepared by filtering through a resin filter. [Table 1] TIFF0007927934000149.tif67162

[0248] <Resin> A1, A2, A3, A4, AX1: Resin A1, Resin A2, Resin A3, Resin A4, Resin A X1 <Acid Generator> B1-43: Salt represented by formula (B1-43) (Implementation of Japanese Patent Publication No. 2016-47815) (Synthesized according to the example) TIFF0007927934000150.tif4381<Compound (I)> I-1: Compound represented by formula (I-1) I-4: Compound represented by formula (I-4) I-5: Compound represented by formula (I-5) I-9: Compound represented by formula (I-9) I-37: Compound represented by formula (I-37) I-39: Compound represented by formula (I-39) I-41: Compound represented by formula (I-41) I-45: Compound represented by formula (I-45) I-55: Compound represented by formula (I-55) I-60: Compound represented by formula (I-60) I-65: Compound represented by formula (I-65) I-71: Compound represented by formula (I-71) I-75: Compound represented by formula (I-75) I-76: Compound represented by formula (I-76) I-79: Compound represented by formula (I-79) I-80: Compound represented by formula (I-80) IX-1: Compound represented by formula (IX-1) <Quencher (C)> C1: Synthesized by the method described in Japanese Patent Publication No. 2011-39502 TIFF0007927934000151.tif4347<solvent> Propylene glycol monomethyl ether acetate, 400 units Propylene glycol monomethyl ether, 100 parts γ-Butyrolactone 5 parts

[0249] (Electron beam exposure evaluation of resist composition: butyl acetate development) A 6-inch silicon wafer is subjected to hexamethyldisilaza on a direct hot plate. The silicon wafer was treated at 90°C for 60 seconds using a solvent. The resist composition was then applied to this silicon wafer. The layer was spin-coated to a thickness of 0.04 μm. Then, direct hot plated... On the grid, the composition layer was formed by pre-baking for 60 seconds at the temperature shown in the "PB" column of Table 1. On the composition layer formed on the surface, an electron beam lithography machine [Hitachi Ltd.'s "HL-800D"] was used. Using 50 keV, the exposure level is changed in steps to create a line and space pattern. I drew it directly. After exposure, post-exposure is performed on a hot plate at the temperature shown in the "PEB" column of Table 1 for 60 seconds. Jar baking was performed. Next, the composition layer on this silicon wafer was treated with acetic acid as the developer. Using butyl (manufactured by Tokyo Chemical Industry Co., Ltd.), dynamic dispensing was performed at 23°C for 20 seconds. A resist pattern was obtained by developing the material according to the specified method. The obtained resist pattern (line and space pattern) is observed using a scanning electron microscope. I guess the line width and space width of the 60nm line and space pattern are in a 1:1 ratio. The exposure level was defined as the effective sensitivity.

[0250] Line Edge Roughness Evaluation (LER): Sidewall of a resist pattern manufactured with effective sensitivity. The amplitude of surface irregularities was measured using a scanning electron microscope to determine the line edge roughness. The results are shown in Table 2. [Table 2] TIFF0007927934000153.tif62143 [Industrial applicability]

[0251] The resist composition of the present invention has a line edge roughness (LE) of the resulting resist pattern. Because it has excellent R) properties, it is suitable for microfabrication of semiconductors and is extremely useful in industry.

Claims

1. The compound represented by formula (I), A resin having a primary acid-unstable group, A resist composition comprising an acid generator containing a salt comprising a sulfonate anion and an organic sulfonium cation or an organic iodonium cation, A resist composition comprising a resin having the first acid-unstable group, at least one selected from the group consisting of structural units represented by formula (a1-1) and structural units represented by formula (a1-2), a structural unit represented by formula (a2-A), and a structural unit represented by formula (a3-4). [In formula (I), L 1 This represents an alkanediyl group having 1 to 6 carbon atoms, which may have a single bond or substituents. R １ This represents a secondary acid-unstable group. R ２ represents *-L １ -OH, *-L １ -O-R １ , *-X １ -Ph-L １ -OH or *-X １ -Ph-L １ -O-R １ , and * represents a binding site to the benzene ring. R １ and R ２ may together form a group having an acetal ring structure. X 1 These are single bonds, alkanediyl groups with 1 to 6 carbon atoms, -O-, -S-, -SO-, or -SO ２ It represents -. Ph represents a phenylene group which may have substituents. m2 represents an integer from 0 to 3, and when m2 is 1 or greater, multiple L １ and multiple R １ Each of them may be the same or different from each other, and when m2 is 2 or more, multiple R ２ They may be identical or different from one another. R ３ This represents a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, and the alkyl group contains -CH 2 The dash may be replaced by -O- or -CO-. m3 represents an integer from 0 to 5, and when m3 is 2 or greater, multiple R ３ They may be the same or different from each other, provided that 0 ≤ m² + m³ ≤ 5. [In formulas (a1-1) and (a1-2), L a1 and L a2 These are, independently, -O- or *-O- (CH ２ ) k1 This represents -CO-O-, where k1 is an integer from 1 to 7, and * represents the bonding site with -CO-. R a4 and R a5 Each of these independently represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. R a6 and R a7 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group that is a combination of these. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3. [In formula (a3-4), L ａ７ は、-O-、*-O-L ａ８ -O-、*--L ａ８ -C-O-、*-O-� ａ８ -C---L ａ９ ------*-O-L ａ８ -O-C-L ａ９ -O- represents。 L ａ８ and L ａ９ Each of these independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding position with the carbonyl group. R ａ２４ This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom. R ａ２５ This represents a carboxyl group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. w1 represents an integer between 0 and 8. When w1 is 2 or greater, multiple R ａ２５ They may be the same or different from each other. [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a51 represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 represents a single bond or *-X a51-(A a52-X a52)nb-, where * represents the bonding site with the carbon atom to which -R a50 is bonded. A a52 represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 each independently represent -O-, -CO-O-, or -O-CO-. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, multiple R a51s may be identical or different from one another.

2. L １ The resist composition according to claim 1, wherein the group is an alkanediyl group having 1 to 4 carbon atoms, which may have a single bond or a halogen atom.

3. R １ The resist composition according to claim 1 or 2, wherein the group is represented by formula (1a) or formula (2a). [In formula (1a), R aa1 , R aa2 and R aa3 Each independently represents an alkyl group having 1 to 8 carbon atoms which may have substituents, an alkenyl group having 2 to 8 carbon atoms which may have substituents, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have substituents, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have substituents, or R aa1 and R aa2 These atoms bond with each other to form alicyclic hydrocarbon groups with 3 to 20 carbon atoms, along with the carbon atoms to which they bond. naa represents 0 or 1. * indicates a connection site. [In formula (2a), R aa1’ and R aa2’ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ They combine with each other and they combine -C-X ａ - Together with the hydrocarbon group, it forms a heterocyclic group having 3 to 20 carbon atoms, and the -CH contained in the hydrocarbon group and the heterocyclic group ２ The dash (-) may be replaced with -O- or -S-. X a This represents an oxygen atom or a sulfur atom. * indicates a connection site.

4. R １ This is the base represented by formula (2a), R aa2’ and R aa3’ They combine with each other and they combine -C-X ａ The resist composition according to claim 3, which forms a heterocyclic group having 3 to 20 carbon atoms together with -.

5. m2 is 1 or 2, at least one R ２ is, *-L １ A resist composition according to any one of claims 1 to 4, wherein the resist is -OH.

6. m2 is 1 or 2, at least one R ２ is, *-L １ -O-R １ The resist composition according to any one of claims 1 to 4.

7. m2 is 1 or 2, at least one R ２ is, *-X １ -Ph-L １ -O-R １ The resist composition according to any one of claims 1 to 4.

8. m3 is 1 or 2, R ３ The resist composition according to any one of claims 1 to 7, wherein the atom is a halogen atom.

9. The resist composition according to any one of claims 1 to 8, wherein the acid generator is an acid generator represented by formula (B1). [In formula (B1), Q ｂ１ and Q ｂ２ Each of these independently represents either a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L ｂ１ This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH contained in this divalent saturated hydrocarbon group is ２ The - may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group. Y represents a cyclic hydrocarbon group having 3 to 24 carbon atoms, which may have substituents, and the cyclic hydrocarbon group contains -CH ２ - is -O-, -SO ２ It may be replaced with - or -CO-. Z ＋ This represents an organic cation.

10. The resist composition according to any one of claims 1 to 9, further comprising a salt that generates an acid with a lower acidity than the acid generated from the acid generator.

11. (1) A step of applying the resist composition according to any one of claims 1 to 10 onto a substrate, (2) A step of drying the coated composition to form a composition layer, (3) Exposure step of the composition layer, (4) A step of heating the composition layer after exposure, (5) A step of developing the composition layer after heating, A method for manufacturing a resist pattern that includes [the specified element].

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