Photosensitive composition, photosensitive film, lower layer film, method for producing structure having phase-separated structure, and compound

Abstract

To provide a photosensitive composition which can change the polarity of a film surface by exposure even under low exposure dose and low post-baking temperature conditions, a photosensitive film, a lower layer film, a method for producing a structure having a phase-separated structure, and a compound.SOLUTION: A photosensitive composition includes an acid-degradable compound (A) and a photoacid generating agent (B), where the acid-degradable compound (A) is one or more compounds represented by any of formulae (A1) to (A4) below: Ra1-(-CH2-CRa2Ra3-)n-Ra4-O-(-CO-Ra5-CO-)-O-Ra6-Ra7 (A1), Ra1-(-CH2-CRa2Ra3-)n-Ra4-O-(-CO-Ra5-O-)-CO-Ra6-Ra7 (A2), Ra1-(-CH2-CRa2Ra3-)n-Ra4-CO-(-O-Ra5-CO-)-O-Ra6-Ra7 (A3), and Ra1-(-CH2-CRa2Ra3-)n-Ra4-CO-(-O-Ra5-O-)-CO-Ra6-Ra7 (A4).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition, a photosensitive film, an underlayer film, a method for producing a structure having a phase-separated structure, and a compound. [Background technology]

[0002] In recent years, with the further miniaturization of large-scale integrated circuits (LSIs), there is a demand for technology to process even more delicate structures. In response to such demands, development is underway of a technology for forming finer patterns by utilizing a phase-separated structure formed by the self-assembly of a block copolymer in which mutually incompatible blocks are bonded.

[0003] The block copolymer undergoes phase separation in microscopic regions due to repulsion between mutually incompatible blocks, and forms a structure with a regular periodic structure by heat treatment, etc. Specific examples of this periodic structure include cylinders (columnar), lamellae (plates), and spheres.

[0004] To utilize the phase-separated structure of block copolymers, it is essential to form the self-assembled nanostructures formed by microphase separation only in specific regions and align them in the desired direction. To achieve this positional and orientation control, processes such as graphoepitaxy, which uses guide patterns to control the phase separation pattern, and chemical epitaxy, which controls the phase separation pattern by changing the chemical state of the substrate, have been proposed.

[0005] For example, Patent Document 1 discloses that the surface polarity can be lithographically changed to control the phase separation pattern by using an underlayer containing an acid-sensitive copolymer having an acid-decomposable group, an attachment group, and a functional group, and a photoacid generator. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2018-139007 Summary of the Invention [Problem to be solved by the invention]

[0007] In the invention described in Patent Document 1, the acid generated from a photoacid generator upon exposure decomposes the acid-decomposable groups in the side chains of the copolymer to form polar domains. However, this invention has the problem of requiring a high exposure dose and post-baking temperature.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive composition, a photosensitive film, an underlayer film, a method for producing a structure containing a phase-separated structure, and a compound that can change the polarity of a film surface by exposure even under conditions of a low exposure dose and a low post-bake temperature. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved by using a photosensitive composition containing a specific acid-decomposable compound (A) and a photoacid generator (B), thereby completing the present invention. Specifically, the present invention provides the following.

[0010] A first aspect of the present invention is a composition comprising an acid-decomposable compound (A) and a photoacid generator (B), In the photosensitive composition, the acid-decomposable compound (A) is one or more compounds represented by any one of the following formulae (A1) to (A4). R a1 -(-CH2-CR a2 R a3 -) n -R a4 -O-(-CO-R a5 -CO-)-OR a6 -R a7 ···(A1) R a1 -(-CH2-CR a2 R a3 -) n -Ra4 -O-(-CO-R a5 -O-)-CO-R a6 -R a7 ···(A2) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -CO-)-OR a6 -R a7 ···(A3) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -O-)-CO-R a6 -R a7 ···(A4) (In formulas (A1) to (A4), R a1 is an alkyl group, and R a2 is a hydrogen atom or an alkyl group, and R a3 is an aromatic group which may have a substituent, and R a4 is an alkylene group, and R a5 is a residue obtained by removing a terminal carboxyl group or a terminal hydroxyl group from a linear aliphatic polyester, and R a6 is an alkylene group, and R a7 is a hydroxy group, a carboxy group, a phosphate group, a mercapto group, or an amino group, and n is -CH2-CR a2 R a3 - is the number of repeating structural units represented by the formula (1), and is an integer of 2 or more.

[0011] A second aspect of the present invention is a composition comprising an acid-decomposable compound (A) and a photoacid generator (B), The photosensitive film is one in which the acid-decomposable compound (A) is one or more compounds represented by any one of the following formulas (A1) to (A4). R a1 -(-CH2-CR a2 R a3 -) n -R a4 -O-(-CO-Ra5 -CO-)-OR a6 -R a7 ···(A1) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -O-(-CO-R a5 -O-)-CO-R a6 -R a7 ···(A2) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -CO-)-OR a6 -R a7 ···(A3) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -O-)-CO-R a6 -R a7 ···(A4) (In formulas (A1) to (A4), R a1 is an alkyl group, and R a2 is a hydrogen atom or an alkyl group, and R a3 is an aromatic group which may have a substituent, and R a4 is an alkylene group, and R a5 is a residue obtained by removing a terminal carboxyl group or a terminal hydroxyl group from a linear aliphatic polyester, and R a6 is an alkylene group, and R a7 is a hydroxy group, a carboxy group, a phosphate group, a mercapto group, or an amino group, and n is -CH2-CR a2 R a3 - is the number of repeating structural units represented by the formula (1), and is an integer of 2 or more.

[0012] A third aspect of the present invention is an underlayer membrane used as a template for phase separating a block copolymer, comprising: the underlayer film is formed by position-selectively exposing the photosensitive film according to the second embodiment; The underlayer film has exposed and unexposed regions that differ in hydrophilicity.

[0013] A fourth aspect of the present invention is a method for forming an underlayer film according to the third aspect on a substrate; forming an upper layer film containing a block copolymer on the lower layer film; and phase-separating the block copolymer in the upper layer film.

[0014] A fifth aspect of the present invention is a compound represented by any one of the following formulas (A1) to (A4). R a1 -(-CH2-CR a2 R a3 -) n -R a4 -O-(-CO-R a5 -CO-)-OR a6 -R a7 ···(A1) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -O-(-CO-R a5 -O-)-CO-R a6 -R a7 ···(A2) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -CO-)-OR a6 -R a7 ···(A3) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -O-)-CO-R a6 -R a7 ···(A4) (In formulas (A1) to (A4), R a1 is an alkyl group, and R a2 is a hydrogen atom or an alkyl group, and R a3 is an aromatic group which may have a substituent, and R a4 is an alkylene group, and R a5 is a residue obtained by removing a terminal carboxyl group or a terminal hydroxyl group from a linear aliphatic polyester, and R a6 is an alkylene group, and R a7 is a hydroxy group, a carboxy group, a phosphate group, a mercapto group, or an amino group, and n is -CH2-CR a2 R a3 - is the number of repeating structural units represented by the formula (1), and is an integer of 2 or more. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a photosensitive composition, a photosensitive film, an underlayer film, a method for producing a structure containing a phase-separated structure, and a compound, which are capable of changing the polarity of a film surface by exposure even under conditions of a low exposure dose and a low post-bake temperature. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 2 is a schematic process diagram illustrating an embodiment of step (i). DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments and can be practiced with appropriate modifications within the scope of the object of the present invention.

[0018] ≪Photosensitive composition≫ The photosensitive composition contains an acid-decomposable compound (A) and a photoacid generator (B). The acid-decomposable compound (A) is one or more compounds represented by any one of the following formulae (A1) to (A4). R a1 -(-CH2-CR a2 Ra3 -) n -R a4 -O-(-CO-R a5 -CO-)-OR a6 -R a7 ···(A1) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -O-(-CO-R a5 -O-)-CO-R a6 -R a7 ···(A2) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -CO-)-OR a6 -R a7 ···(A3) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -O-)-CO-R a6 -R a7 ···(A4) (In formulas (A1) to (A4), R a1 is an alkyl group, and R a2 is a hydrogen atom or an alkyl group, and R a3 is an aromatic group which may have a substituent, and R a4 is an alkylene group, and R a5 is a residue obtained by removing a terminal carboxyl group or a terminal hydroxyl group from a linear aliphatic polyester, and R a6 is an alkylene group, and R a7 is a hydroxy group, a carboxy group, a phosphate group, a mercapto group, or an amino group, and n is -CH2-CR a2 R a3 - is the number of repeating structural units represented by the formula (1), and is an integer of 2 or more.

[0019] Below, R a5The residue obtained by removing the terminal carboxyl group or hydroxyl group from the linear aliphatic polyester is also referred to as a "polyester residue."

[0020] By applying the photosensitive composition to a substrate to form a photosensitive film, the acid-decomposable compound (A) a7 is fixed to the substrate via the functional group R a1 -(-CH2-CR a2 R a3 -) n When the photosensitive film is exposed to light, the acid generated from the photoacid generator (B) reacts with the R a5 The ester bonds in the polyester residues and the ester bonds adjacent to the polyester residues are hydrolyzed, resulting in the appearance of highly polar linear aliphatic polyesters on the film surface. Therefore, by position-selectively exposing the photosensitive film, it is possible to form a pattern in which the polarity of the film surface differs between the exposed and unexposed regions. Since the acid-decomposable compound (A) has many ester bonds in the polymer main chain, it is believed that the polarity of the film surface can be changed by exposure even under conditions of low exposure dose and low post-bake temperature.

[0021] <Acid decomposable compound (A)> The photosensitive composition contains an acid-decomposable compound (A). The acid-decomposable compound (A) is one or more compounds represented by any one of formulas (A1) to (A4). Among these, the compound represented by formula (A2) is preferred.

[0022] In formula (A1) to formula (A4), n R a2 , and n R a3 may be the same or different. The acid-decomposable compound (A) may contain only compounds having the same polyester residue, or may contain two or more compounds having different polyester residues.

[0023] R a1The number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 5 or less. R a1 Examples of the alkyl group as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0024] R a2 The alkyl group preferably has 1 or more and 10 or less carbon atoms, more preferably 1 or more and 5 or less carbon atoms. R a2 As the alkyl group, R a1 Examples of the alkyl group include the same groups as those of the alkyl group. R a2 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group.

[0025] R a3 The aromatic group which may have a substituent as the aromatic group may be an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, but is preferably an aromatic hydrocarbon group which may have a substituent, and more preferably an aromatic hydrocarbon group.

[0026] The type of aromatic hydrocarbon group is not particularly limited as long as the desired effect is not impaired. The aromatic hydrocarbon group may be a monocyclic aromatic group, a group formed by condensing two or more aromatic hydrocarbon groups, or a group formed by bonding two or more aromatic hydrocarbon groups via a single bond. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group. Among these, a phenyl group is preferred.

[0027] The type of aromatic heterocyclic group is not particularly limited as long as the desired effect is not impaired.The aromatic heterocyclic group may be a monocyclic group or a polycyclic group.Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzimidazolyl group.

[0028] Examples of the substituent that the aromatic group may have include an alkyl group which may have an oxygen atom and / or a silicon atom, a hydroxy group, a nitro group, a halogen atom, an acetoxy group, etc. Among these, an alkyl group which may have an oxygen atom and / or a silicon atom is preferred.

[0029] The alkyl group which may have an oxygen atom and / or a silicon atom is preferably an alkyl group which may be interrupted by an oxygen atom and which may be substituted with an alkylsilyl group, specifically, an alkyl group, an alkylsilyl group, an alkylsilylalkyl group, an alkylsilyloxy group, an alkylsilyloxyalkyl group, an alkoxy group, etc.

[0030] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

[0031] The alkylsilyl group is preferably a trialkylsilyl group, and specific examples thereof include a trimethylsilyl group. The alkylsilylalkyl group is preferably a trialkylsilylalkyl group, and specific examples thereof include a trimethylsilylmethyl group, a 2-trimethylsilylethyl group, and a 3-trimethylsilyl-n-propyl group. The alkylsilyloxy group is preferably a trialkylsilyloxy group, and specific examples thereof include a trimethylsilyloxy group. The alkylsilyloxyalkyl group is preferably a trialkylsilyloxyalkyl group, and specific examples thereof include a trimethylsilyloxymethyl group, a 2-trimethylsilyloxyethyl group, and a 3-trimethylsilyloxy-n-propyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0032] The total number of carbon atoms in the alkyl group, which may be interrupted by oxygen atoms and may be substituted with an alkylsilyl group, is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, even more preferably 1 or more and 3 or less, and particularly preferably 1 or 2.

[0033] The number of substituents that the aromatic group has is preferably an integer of 0 or more and 3 or less, more preferably 0 or 1, and even more preferably 0.

[0034] n is preferably 2 or more and 200 or less, more preferably 10 or more and 150 or less, and even more preferably 30 or more and 100 or less.

[0035] R a4 The alkylene group as the alkylene group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 5 or less carbon atoms. R a4 The alkylene group as may be linear or branched, but is preferably linear. R a4 Examples of the alkylene group include a methylene group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group.

[0036] R a5The polyester residue as the above is a residue obtained by removing a terminal carboxy group or hydroxy group from a linear aliphatic polyester. The linear aliphatic polyester may be a homopolyester or a copolyester. A copolyester is composed of two or more different types of linear aliphatic polyester blocks. The two or more different types of linear aliphatic polyester blocks may be multiple types of homopolyester blocks, multiple types of copolyester blocks, or a combination of one or more types of homopolyester blocks and one or more types of copolyester blocks.

[0037] R a5 Examples of the linear aliphatic polyester that provides the polyester residue as the above include polycondensates of aliphatic hydroxycarboxylic acids, ring-opening polymers of lactones, and polycondensates of aliphatic dicarboxylic acids and aliphatic diols. Among these, polycondensates of aliphatic hydroxycarboxylic acids and ring-opening polymers of lactones are preferred.

[0038] The aliphatic hydroxycarboxylic acid preferably has 2 or more and 20 or less carbon atoms, more preferably 2 or more and 10 or less carbon atoms, and even more preferably 2 or more and 5 or less carbon atoms. As the polycondensation product of an aliphatic hydroxycarboxylic acid, a polycondensation product of a compound having one hydroxy group and one carboxy group is preferred, and polylactic acid, polyglycolic acid, and polyhydroxybutyric acid are more preferred.

[0039] The lactone preferably has 2 or more and 20 or less carbon atoms, more preferably 3 or more and 10 or less carbon atoms, and even more preferably 4 or more and 8 or less carbon atoms. As the ring-opening polymer of lactone, a ring-opening polymer of aliphatic lactone is preferred, and polycaprolactone, polybutyrolactone, and polyvalerolactone are more preferred.

[0040] R a5 The number of ester bonds contained in the residue as is preferably 2 or more and 200 or less, more preferably 4 or more and 150 or less, and even more preferably 6 or more and 100 or less, in terms of easily achieving the desired effect.

[0041] R a6 The alkylene group as the alkylene group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 5 or less carbon atoms. R a6 The alkylene group as may be linear or branched, but is preferably linear. R a6 As the alkylene group, R a4 Examples of the alkylene group include the same groups as the alkylene group.

[0042] R a7 As the alkyl group, a hydroxy group and a carboxy group are preferred, and a carboxy group is more preferred.

[0043] The number average molecular weight of the compound represented by any one of formulas (A1) to (A4) is preferably 1,000 or more and 100,000 or less, more preferably 3,000 or more and 75,000 or less, and even more preferably 5,000 or more and 50,000 or less, in order to easily obtain the desired effects. The dispersity (weight average molecular weight / number average molecular weight) of the compound represented by any one of Formulas (A1) to (A4) is not particularly limited, but is preferably 1.0 or more and 1.5 or less, more preferably 1.0 or more and 1.4 or less, and even more preferably 1.0 or more and 1.3 or less. In this specification, the number average molecular weight and weight average molecular weight refer to the number average molecular weight and weight average molecular weight calculated in terms of standard polystyrene as determined by size exclusion chromatography (SEC) measurement.

[0044] The method for producing the compound represented by any one of formulas (A1) to (A4) is not particularly limited. For example, the compound represented by formula (A2) can be produced by the following method. First, compounds represented by the following formulae (A1a) to (A4a) are reacted with monomers such as aliphatic hydroxycarboxylic acids, dimeric cyclic esters of aliphatic hydroxycarboxylic acids, lactones, aliphatic dicarboxylic acids, and aliphatic diols to obtain compounds represented by the following formulae (A1b) to (A4b). In addition, the compounds represented by formulae (A1b) to (A4b) can also be obtained by condensing the compounds represented by formulae (A1a) to (A4a) with a linear aliphatic polyester in a conventional manner.

[0045] The compounds represented by the following formula (A1b) or formula (A3b) have a carboxyalkyl terminal group and can therefore be used as the compounds represented by formula (A1) or formula (A3), respectively. The compounds represented by the following formula (A2b) or formula (A4b) have a hydroxyalkyl terminal group and can therefore be used as the compounds represented by formula (A2) or formula (A4), respectively.

[0046] R a7 is a carboxy group, for example, a compound represented by formula (A2) or (A4) can be obtained by reacting a compound represented by formula (A2b) or formula (A4b) with an anhydride of an aliphatic dicarboxylic acid such as succinic anhydride.

[0047] R a7 is a hydroxy group, for example, a compound represented by formula (A1b) or formula (A3b) can be condensed with an aliphatic diol such as ethylene glycol to obtain a compound represented by formula (A1) or formula (A3).

[0048] Also, R a7 is a carboxy group, for example, the compounds represented by formula (A1b) to formula (A4b) can be reacted with Hal-R a6 -CO-OR a8 The compound represented by the formula (I) is etherified or esterified in a conventional manner, and then deprotected to give R a8By removing R, the compounds represented by formula (A1) to formula (A4) can be obtained. In the above formulas, Hal is a halogen atom such as a chlorine atom or a bromine atom. a6 is R in formulas (A1) to (A4). a6 Similar to R a8 is a tertiary alkyl group such as a tert-butyl group.

[0049] R a7 is a hydroxy group, a phosphate group, a mercapto group, or an amino group, the compounds represented by formula (A1b) to formula (A4b) can be treated with Hal-R a6 -R a7 The compounds represented by the formulae (A1) to (A4) can be obtained by etherifying or esterifying the compounds represented by the formulae (A1) to (A4) in accordance with a conventional method.

[0050] Hereinafter, R in formulas (A1a) to (A4a) and formulas (A1b) to (A4b) a1 ~R a5 , and n are as explained in formulas (A1) to (A4). R a1 -(-CH2-CR a2 R a3 -) n -R a4 -OH···(A1a) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -OH···(A2a) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -COOH···(A3a) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -COOH···(A4a) R a1 -(-CH2-CR a2 R a3 -) n-R a4 -O-(-CO-R a5 -CO-)-OH···(A1b) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -O-(-CO-R a5 -O-)-H···(A2b) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -CO-)-OH···(A3b) R a1 -(-CH2-CR a2 R a3 -) n -R a4 -CO-(-OR a5 -O-)-H···(A4b)

[0051] <Photoacid generator (B)> The photosensitive composition contains a photoacid generator (B). The photoacid generator (B) is not particularly limited as long as it is a compound that generates an acid directly or indirectly when exposed to light. Examples of the photoacid generator (B) include the first to fifth photoacid generators described below.

[0052] (First Photoacid Generator) The first photoacid generator includes a compound represented by the following formula (b1).

[0053] [ka]

[0054] In the above formula (b1), X 1b represents a sulfur atom or iodine atom with a valence of g, where g is 1 or 2. h is the number of repeating units of the structure in parentheses and is an integer of 0 or more. R 1b is X 1band represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, and R 1b R may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen. 1b The number of is g+h(g-1)+1, and R 1b may be the same or different from each other. 1b are directly connected to each other, or -O-, -S-, -SO-, -SO2-, -NH-, -NR 2b -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group; 1b may form a ring structure containing R 2b is an alkyl group having from 1 to 5 but not less than 1 carbon atom, or an aryl group having from 6 to 10 but not more than 1 carbon atom.

[0055] X 2b is a structure represented by the following formula (b2).

[0056] [ka]

[0057] In the above formula (b2), X 4b represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms; X 4bX may be substituted with at least one selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, hydroxy, cyano, nitro, and halogen. 5b -O-, -S-, -SO-, -SO2-, -NH-, -NR 2b represents -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group. h represents the number of repeating units of the structure in parentheses. h+1 X 4b and h X's 5b may be the same or different. 2b is the same as defined above.

[0058] X 3b- is a counter ion of the onium, and examples thereof include a fluorinated alkylfluorophosphate anion represented by the following formula (b9), (b13), (b14), or (b17), or a borate anion represented by the following formula (b18).

[0059] [ka]

[0060] In the above formula (b9), R 20b are groups represented by the following formulae (b10), (b11), and (b12).

[0061] [ka]

[0062] In the formula (b10), x represents an integer of 1 or more and 4 or less. In the formula (b11), R 21b represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, or a linear or branched alkoxy group having from 1 to 6 carbon atoms, and y represents an integer of from 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

[0063] [ka]

[0064] In the above formulas (b13) and (b14), X b represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms. b , Z b each independently represents a linear or branched alkyl group in which at least one hydrogen atom has been substituted with a fluorine atom, and the alkyl group has 1 or more and 10 or less carbon atoms, preferably 1 or more and 7 or less, and more preferably 1 or more and 3 or less carbon atoms.

[0065] X b The number of carbon atoms in the alkylene group, or Y b , Z b The smaller the number of carbon atoms in the alkyl group, the better the solubility in organic solvents, and therefore the more preferable.

[0066] Also, X b or an alkylene group of Y b , Z b In the alkyl group, the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The proportion of fluorine atoms in the alkylene group or alkyl group, i.e., the fluorination rate, is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably a perfluoroalkylene group or perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

[0067] [ka]

[0068] In the above formula (b17), R 3brepresents an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms. j represents the number of R groups, and is an integer of 1 to 5. 3b may be the same or different.

[0069] [ka]

[0070] In the above formula (b18), R 4b ~R 7b each independently represents a fluorine atom or a phenyl group, and some or all of the hydrogen atoms of the phenyl group may be substituted with at least one selected from the group consisting of a fluorine atom and a trifluoromethyl group.

[0071] Examples of the onium ion in the compound represented by the formula (b1) include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis (4-Fluorophenyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenyl sulfonium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, octadecylmethylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, or 4-isobutylphenyl(p-tolyl)iodonium.

[0072] In the fluorinated alkylfluorophosphate anion represented by the above formula (b17), R 3brepresents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The proportion of hydrogen atoms in the alkyl group substituted with fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. If the fluorine atom substitution rate is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by formula (b1) will be reduced.

[0073] Particularly preferred R 3b is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%, and specific examples include CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C. 3b The number j is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

[0074] A specific example of a preferred fluorinated alkyl fluorophosphate anion is [(CF3CF2)2PF4] - , [(CF3CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [(CF3CF2CF2)2PF4] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - , [(CF3CF2CF2CF2)2PF4] - , or [(CF3CF2CF2)3PF3] - Among these, [(CF3CF2)3PF3]- , [(CF3CF2CF2)3PF3] - , [((CF3)2CF)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CFCF2)3PF3] - , or [((CF3)2CFCF2)2PF4] - is particularly preferred.

[0075] A preferred example of the borate anion represented by the formula (b18) is tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ), tetrakis[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - ), difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ), trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - ), tetrakis(difluorophenyl)borate ([B(C6H3F2)4] - Among these, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ) is particularly preferred.

[0076] (Second Photoacid Generator) Examples of the second photoacid generator include 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furyl)ethenyl]-s-triazine, and 2,4-bis (Trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)ethenyl]-s-triazine phenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine azine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,Examples of halogen-containing triazine compounds include 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, and tris(2,3-dibromopropyl)-1,3,5-triazine, as well as halogen-containing triazine compounds represented by the following formula (b3), such as tris(2,3-dibromopropyl)isocyanurate.

[0077] [ka]

[0078] In the above formula (b3), R 9b , R 10b , R 11b each independently represents a halogenated alkyl group.

[0079] (Third Photoacid Generator) Examples of the third photoacid generator include α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and compounds represented by the following formula (b4) containing an oxime sulfonate group.

[0080] [ka]

[0081] In the above formula (b4), R 12b represents a monovalent, divalent, or trivalent organic group; R 13brepresents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group, and n represents the number of repeating units of the structure in the parentheses.

[0082] In the above formula (b4), examples of the aromatic group include aryl groups such as phenyl and naphthyl groups, and heteroaryl groups such as furyl and thienyl groups. These may have one or more suitable substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, and nitro groups. In addition, R 13b is particularly preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group. 12b is an aromatic group, and R 13b is an alkyl group having 1 to 4 carbon atoms.

[0083] The photoacid generator represented by the above formula (b4) is, when n=1, R 12b is a phenyl group, a methylphenyl group, or a methoxyphenyl group, and R 13b is a methyl group, specifically α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](o-tolyl)acetonitrile, etc. When n=2, specific examples of the photoacid generator represented by the above formula (b4) include photoacid generators represented by the following formula:

[0084] [ka]

[0085] (Fourth Photoacid Generator) Examples of the fourth photoacid generator include bissulfonyldiazomethanes such as bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, and dinitrobenzyl carbonate; sulfonic acid esters such as pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, and N-methylsulfonyloxyphthalimide; and N-(trifluoromethylsulfonyloxy)phthalimide. (l) Trifluoromethanesulfonic acid esters such as phthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, and N-(trifluoromethylsulfonyloxy)-4-butyl-1,8-naphthalimide; onium salts such as diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, and (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; benzoin tosylates such as benzoin tosylate and α-methylbenzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, and benzyl carbonate.

[0086] (5th Photoacid Generator) The fifth photoacid generator includes a compound (B0) represented by the following formula (b0) (hereinafter also referred to as "component (B0)").

[0087] [ka] [In the formula, Ar represents an aromatic ring. Rf 0 represents a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 0 represents a divalent linking group containing -C(=O)-O-, -OC(=O)- or -OS(=O)2-. 0 represents a cyclic group. 0 represents an organic group. n01 is an integer of 1 or more as long as the valence allows. n02 is an integer of 0 or more as long as the valence allows. However, L 0 -Yb 0 -OC(=O)-Yb 0 If Yb 0 is an alicyclic group which may have a substituent, a fused cyclic group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent, and in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. 0 may be the same or different. When n02 is 2 or more, multiple Rb 0 may be the same or different, m is an integer of 1 or more, and M m+ represents a cation with a valence of m.]

[0088] {anion part} In the formula (b0), the aromatic ring in Ar is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include, but are not limited to, pyridine rings, thiophene rings, and furan rings.

[0089] The aromatic ring in Ar is preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

[0090] In the formula (b0), Rf 0 The fluorinated alkyl group having from 1 to 5 carbon atoms in the formula (I) is a group in which some or all of the hydrogen atoms of an alkyl group having from 1 to 5 carbon atoms have been substituted with fluorine atoms. The fluorinated alkyl group may be linear or branched, but is preferably linear. Rf 0 The linear fluorinated alkyl group in Rf preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms, and even more preferably 1 carbon atom. 0 The branched fluorinated alkyl group in the formula (I) preferably has 3 or 4 carbon atoms, and more preferably has 3 carbon atoms. Rf 0 In terms of acid strength, the fluorinated alkyl group having 1 to 5 carbon atoms is preferably a perfluoroalkyl group, more preferably a trifluoromethyl group.

[0091] Rf 0 From the viewpoint of acid strength, is preferably a fluorine atom or a trifluoromethyl group, more preferably a fluorine atom.

[0092] In the formula (b0), Rb 0 The organic group in the formula (I) is a hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an aliphatic hydrocarbon group.

[0093] Rb 0 The aliphatic hydrocarbon group in Rb preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. 0 The aliphatic hydrocarbon group in Rb may be saturated or unsaturated, but is preferably saturated. 0 The aliphatic hydrocarbon group in is preferably a linear or branched alkyl group.

[0094] Rb 0 The linear alkyl group in Rb preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms, and even more preferably 1 carbon atom. 0 The branched alkyl group in the formula (I) preferably has 3 or 4 carbon atoms, and more preferably 3 carbon atoms. Rb 0 The organic group in is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and further preferably an ethyl group or a methyl group.

[0095] In the formula (b0), n01 is an integer of 1 or more as far as the atomic valence allows. n01 is preferably 1 or more and 4 or less, more preferably 2 or more and 4 or less, even more preferably 3 or 4, and particularly preferably 4.

[0096] In the formula (b0), n02 is, as far as the valence allows, an integer of 0 or more. n02 is preferably 0 or more and 3 or less, more preferably 0 or more and 2 or less, even more preferably 0 or 1, and particularly preferably 0.

[0097] In the above formula (b0), L 0 Examples of the divalent linking group in L include -C(=O)-O-, -OC(=O)-, and -OS(=O)2-, as well as combinations of one or more of these with an alkylene group. 0 When the divalent linking group in is -C(=O)-O-, -OC(=O)-, or -OS(=O)2-, L 0-Yb 0 is -C(=O)-O-Yb 0 , -OC(=O)-Yb 0 , or -OS(=O)2-Yb 0 is. L 0 is a combination of one or more of -C(=O)-O-, -OC(=O)-, and -OS(=O)2- with an alkylene group, the alkylene group may be linear or branched.

[0098] L 0 Examples of the divalent linking group in the formula (L0-1) include linking groups represented by the following general formula (L0-1).

[0099] [ka] [In the formula, Lb 01 and Lb 02 each independently represents a single bond or an alkylene group having 1 to 5 carbon atoms; L 01 represents -C(=O)-O-, -OC(=O)-, or -OS(=O)2-; n03 represents an integer of 1 or more and 3 or less. However, when n03 is 2 or 3, Lb 01 When n03 is 2 or 3, multiple Lb 01 may be the same or different. When n03 is 2 or more, multiple L 01 may be the same or different. * represents a bond bonded to Ar in the formula (b0), and ** represents a bond bonded to Yb in the formula (b0). 0 is a bond that bonds to .]

[0100] In the above formula (L0-1), Lb 01 and Lb 02 The alkylene group having 1 to 5 carbon atoms in the formula (Lb) may be linear or branched, but is preferably linear. 01 and Lb 02 The linear alkylene group in Lb preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms. 01 and Lb 02The branched alkylene group in the formula (I) preferably has 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms.

[0101] In the formula (L0-1), n03 is preferably 1 or 2, and more preferably 1.

[0102] L 0 Examples of the divalent linking group in the formula (L01-1) include linking groups represented by the following general formulae (L01-1) to (L01-3).

[0103] [ka] [In the formula, Lb 011 ~Lb 031 Lb each independently represents a single bond or an alkylene group having 1 to 5 carbon atoms. 012 ~Lb 032 each independently represents a single bond or a divalent linking group. nb01 to nb03 each independently represents an integer of 1 or more and 3 or less. However, when nb01 to nb03 are 2 or 3, Lb 011 ~Lb 031 When nb01 is 2 or 3, multiple Lb 011 may be the same or different. When nb02 is 2 or 3, multiple Lb 021 may be the same or different. When nb03 is 2 or 3, multiple Lb 031 may be the same or different. * represents a bond bonded to Ar in the general formula (b0), and ** represents a bond bonded to Yb in the general formula (b0). 0 represents a bond to the atom.]

[0104] In the formulae (L01-1) to (L01-3), Lb 011 ~Lb 031 The alkylene group having 1 to 5 carbon atoms in the formula (L0-1) is Lb 01 The same can be mentioned. In the formulae (L01-1) to (L01-3), Lb 012 ~Lb 032Examples of the divalent linking group in the formula (L0-1) include alkylene groups having 1 to 5 carbon atoms which may have -C(=O)-O-, -OC(=O)-, or -OS(=O)2-. Examples of the alkylene group having 1 to 5 carbon atoms include Lb 01 The same can be mentioned. In the formulae (L01-1) to (L01-3), nb01 to nb03 are preferably 1 or 2, and more preferably 1.

[0105] L in the formula (b0) 0 Examples of the group include groups represented by any of the following general formulae (L0-1-1) to (L0-1-5).

[0106] [ka] [In the formula, Vb 01 and Vb 02 each independently represents a single bond or an alkylene group having 1 to 5 carbon atoms. 03 represents an alkylene group having 1 to 5 carbon atoms. * represents a bond bonded to Ar in the formula (b0), and ** represents a bond bonded to Yb in the formula (b0). 0 is a bond that bonds to .]

[0107] In the above formulas (L0-1-1) to (L0-1-5), Vb 01 and Vb 02 The alkylene group having 1 to 5 carbon atoms in the formula (Vb) may be linear or branched, but is preferably linear. 01 and Vb 02 The linear alkylene group in Vb preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms. 01 and Vb 02 The branched alkylene group in the formula (I) preferably has 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms.

[0108] ≪Yb 0 About≫ L 0 -Yb 0-OC(=O)-Yb 0 If not: L 0 -Yb 0 -OC(=O)-Yb 0 otherwise, Yb 0 is a cyclic group. Yb 0 The cyclic group in (I) is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably saturated.

[0109] Yb 0 The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. Yb 0 Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Yb 0 Specific examples of the aromatic hydrocarbon group in the above include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.

[0110] Yb 0 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 or more and 20 or less carbon atoms, and more preferably has 3 or more and 12 or less carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkane is preferably a polycycloalkane having a bridged ring polycyclic skeleton, such as adamantane, norbornane, isobornane, bornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a fused ring polycyclic skeleton, such as a cyclic group having a steroid skeleton.

[0111] Yb 0 The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, further preferably an adamantyl group, a norbornyl group, or a bornyl group, and particularly preferably an adamantyl group.

[0112] The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has from 1 to 10 carbon atoms, more preferably from 1 to 6, even more preferably from 1 to 4, and most preferably from 1 to 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specific examples thereof include a methylene group [-CH-], an ethylene group [-(CH)-], a trimethylene group [-(CH)-], a tetramethylene group [-(CH)-], and a pentamethylene group [-(CH)-]. The branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0113] Also, Yb 0 The cyclic hydrocarbon group in may contain a heteroatom, such as a heterocycle. Specific examples include lactone-containing cyclic groups represented by the following general formulae (a2-r-1) to (a2-r-7), -SO2- containing cyclic groups represented by the following general formulae (b5-r-1) to (b5-r-4), and heterocyclic groups represented by the following chemical formulae (r-hr-1) to (r-hr-16). In the formula, * represents L in formula (b0). 0 represents a bond bonded to In this specification, the term "lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -OC(=O)- in its ring skeleton. The lactone ring is counted as the first ring, and when there is only a lactone ring, it is called a monocyclic group. When there is further ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

[0114] [ka] [In the formula, Ra' 21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group; R" is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group; A" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom, or a sulfur atom; n' is an integer of 0 to 2, and m' is 0 or 1. * represents a bond (the same applies hereinafter).

[0115] [ka] [In the formula, Rb' 51 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, or an -SO2- containing cyclic group; B" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom; and n' is an integer of 0 to 2. * represents a bond.]

[0116] [ka]

[0117] In the general formulas (a2-r-1) to (a2-r-7), Ra'21 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Of these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred. Ra' 21 The alkoxy group in the formula (1) is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably a linear or branched chain group. Specifically, the alkoxy group in the formula (1) is preferably an alkoxy group having 1 to 6 carbon atoms. 21 Examples of the alkyl group include a group in which the alkyl groups mentioned above are linked to an oxygen atom (—O—). Ra' 21 The halogen atom in is preferably a fluorine atom. Ra' 21 The halogenated alkyl group in the formula Ra' is 21 Examples of the halogenated alkyl group include groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is particularly preferred.

[0118] Ra' 21 In the -COOR" and -OC(=O)R" groups, R" is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group. The alkyl group in R'' may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms. When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is particularly preferably a methyl group or an ethyl group. When R" is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane. More specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Examples of the lactone-containing cyclic group in R″ include the same groups as those represented by the general formulae (a2-r-1) to (a2-r-7) above. Ra' 21 The hydroxyalkyl group in the formula (I) preferably has 1 to 6 carbon atoms, and specifically, the hydroxyalkyl group in the formula (I) is preferably the hydroxyalkyl group in the formula (I). 21 and a group in which at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

[0119] Ra' 21 Among the above, each of the groups is preferably independently a hydrogen atom or a cyano group.

[0120] In the general formulae (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having from 1 to 5 carbon atoms in A" is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples include groups in which -O- or -S- is present at the terminal or between carbon atoms of the alkylene group, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, and -CH2-S-CH2-. A" is preferably an alkylene group having from 1 to 5 carbon atoms or -O-, more preferably an alkylene group having from 1 to 5 carbon atoms, and most preferably a methylene group.

[0121] Specific examples of the groups represented by the general formulae (a2-r-1) to (a2-r-7) are listed below.

[0122] [ka]

[0123] [ka]

[0124] In the general formulae (b5-r-1) and (b5-r-2), B″ represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom. B" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.

[0125] In the general formulae (b5-r-1) to (b5-r-4), Rb' 51are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group, and among these, are each independently preferably a hydrogen atom or a cyano group.

[0126] Specific examples of the groups represented by general formulae (b5-r-1) to (b5-r-4) are listed below, in which "Ac" represents an acetyl group.

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] Yb 0 The cyclic group in may have a substituent, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, etc. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. As the halogen atom as a substituent, a fluorine atom, a bromine atom, or an iodine atom is preferred. Examples of halogenated alkyl groups as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl groups, ethyl groups, propyl groups, n-butyl groups, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms. The carbonyl group as a substituent is a group that substitutes a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0131] Yb 0 The cyclic hydrocarbon group in may be a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused. Examples of the fused ring include a polycycloalkane having a bridged ring polycyclic skeleton to which one or more aromatic rings are fused. Specific examples of the bridged ring polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane. The fused ring group is preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane, and more preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicyclo[2.2.2]octane. 0 Specific examples of the fused ring group in the formula (b0) include groups represented by the following formulas (r-br-1) to (r-br-2). 0 Rx represents the bond that connects to 0 represents a substituent.

[0132] [ka]

[0133] Yb 0 Examples of the substituent that the fused cyclic group in the formula (I) may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. Examples of the alkyl group, alkoxy group, halogen atom and halogenated alkyl group as the substituent of the fused cyclic group include the same as those exemplified as the substituent of the cyclic group. Examples of the aromatic hydrocarbon group as the substituent of the fused ring group include a group in which one hydrogen atom has been removed from an aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), and heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6). Examples of the alicyclic hydrocarbon group as a substituent of the fused cyclic group include groups in which one hydrogen atom has been removed from a monocycloalkane such as cyclopentane or cyclohexane; groups in which one hydrogen atom has been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane; lactone-containing cyclic groups represented by the general formulae (a2-r-1) to (a2-r-7) above; —SO2- containing cyclic groups represented by the general formulae (b5-r-1) to (b5-r-4) above; and heterocyclic groups represented by the formulae (r-hr-7) to (r-hr-16) above.

[0134] The substituent of the fused cyclic group may be an alkyl group partially substituted with a heteroatom-containing group. In the alkyl group as a substituent of the fused cyclic group, for example, some of the hydrogen atoms may be substituted with a heteroatom-containing group. Alternatively, in the alkyl group as a substituent of the fused cyclic group, some of the carbon atoms (e.g., methylene groups) constituting the hydrocarbon chain may be substituted with a heteroatom-containing group. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0135] Examples of the heteroatom-containing group that substitutes a hydrogen atom of an alkyl group include a hydroxyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a carboxy group.

[0136] Examples of heteroatom-containing groups substituting carbon atoms constituting the hydrocarbon chain of an alkyl group include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, etc. Preferred heteroatom-containing groups are -O-, -C(=O)-O-, -OC(=O)-, and -S(=O)2-O-, with -C(=O)-O- being more preferred.

[0137] The substituent of the fused ring group is -C(=O)-O-Rx 01 Examples of such groups include groups represented by Rx 01 represents an alkyl group, which may be linear, branched, or cyclic. Examples of linear alkyl groups include those having from 1 to 5 carbon atoms, with methyl, ethyl, n-propyl, and n-butyl groups being preferred. Examples of branched alkyl groups include those having from 3 to 5 carbon atoms, with isopropyl, tert-butyl, sec-butyl, and isobutyl being preferred. Examples of cyclic alkyl groups include those in which one hydrogen atom has been removed from a cycloalkane having from 1 to 8 carbon atoms, with cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl being preferred, and cyclopentyl and cyclohexyl being more preferred.

[0138] Yb 0 Examples of the cyclic groups include an adamantyl group which may have a substituent; a cyclic group having a steroid skeleton which may have a substituent; a lactone-containing cyclic group represented by each of the formulae (a2-r-1) to (a2-r-7); and a -SO group represented by each of the formulae (b5-r-1) to (b5-r-4). 2 -containing cyclic groups; fused cyclic groups containing a fused ring formed by condensing an aliphatic hydrocarbon ring with an aromatic ring; and aromatic hydrocarbon groups which may have a substituent. As the fused cyclic groups, groups represented by the formula (r-br-1) or (r-br-2) are preferred. Examples of the substituents of the adamantyl group include a hydroxy group and a carbonyl group.

[0139] L 0 -Yb 0-OC(=O)-Yb 0 L if not 0 Examples of the divalent linking group include -C(=O)-O-; -S(=O) 2 a divalent linking group containing —O—; a group represented by the formula (L01-3) (wherein nb03 is 1 and Lb 031 and Lb 032 are all single bonds). Examples of the divalent linking group containing -C(=O)-O- include a group represented by the formula (L01-1) above, and preferably a group represented by the formula (L0-1-1), (L0-1-2) or (L0-1-5). Examples of the divalent linking group containing -S(=O)2-O- include a group represented by the formula (L01-2) above, and preferably a group represented by the formula (L0-1-4) or (L0-1-5).

[0140] L 0 -Yb 0 -OC(=O)-Yb 0 If: In this case, Yb 0 is an alicyclic group which may have a substituent, a fused ring group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent. In the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group.

[0141] Yb 0 The alicyclic group which may have a substituent in "L 0 -Yb 0 -OC(=O)-Yb 0 Examples of the alicyclic group include groups in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane; cyclic groups having a steroid skeleton; lactone-containing cyclic groups represented by the aforementioned formulae (a2-r-1) to (a2-r-7); —SO2- containing cyclic groups represented by the aforementioned formulae (b5-r-1) to (b5-r-4); and heterocyclic groups represented by the aforementioned chemical formulae (r-hr-1) to (r-hr-16). Yb 0 The substituents of the alicyclic group include "L 0 -Yb0 -OC(=O)-Yb 0 Examples of cases where the above is not the case include "if

[0142] Yb 0 The fused ring group of an aliphatic ring and an aromatic ring in 0 -Yb 0 -OC(=O)-Yb 0 Examples of the fused cyclic group include the groups represented by the formula (r-br-1) or (r-br-2) above. Yb 0 The substituents of the fused ring group include "L 0 -Yb 0 -OC(=O)-Yb 0 Examples of cases where the above is not the case include "if

[0143] Yb 0 The aromatic hydrocarbon group having a substituent in "L 0 -Yb 0 -OC(=O)-Yb 0 However, in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. The aromatic ring may have an alkyl group, an alkoxy group, or both an alkyl group and an alkoxy group. The aromatic ring preferably has an alkoxy group.

[0144] The aromatic ring may have a substituent other than an alkyl group or an alkoxy group. Examples of the substituent include a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. Among these, the aromatic ring preferably has a halogen atom as a substituent, and more preferably has an iodine atom as a substituent.

[0145] Yb 0 The aromatic ring contained in the aromatic hydrocarbon group in the formula (I) is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.

[0146] L 0-Yb 0 -OC(=O)-Yb 0 In this case, the formula (b0) can be expressed by the following formula (b02-1).

[0147] [ka] [In the formula, Ar, Rf 0 , Rb 0 , n01, and n02 are Ar, Rf in the formula (b0). 0 , Rb 0 , n01, and n02, respectively. 00 is an alicyclic group which may have a substituent, a fused ring group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent, and in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. m is an integer of 1 or more, and M m+ represents a cation with a valence of m.]

[0148] The component (B0) is preferably a compound represented by the following general formula (b0-1).

[0149] [ka] [In the formula, Rf 01 represents a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 01 represents a divalent linking group containing -C(=O)-O-, -OC(=O)- or -OS(=O)2-. 01 represents a cyclic group. 01 represents an organic group. n011 is an integer of 1 or more, n021 is an integer of 0 or more, and n011+n021≦4. However, L 01 -Yb 01 -OC(=O)-Yb 01 If Yb 01is an alicyclic group which may have a substituent, a fused cyclic group of an aliphatic ring and an aromatic ring which may have a substituent, or an aromatic hydrocarbon group which has a substituent, and in the aromatic hydrocarbon group, at least one hydrogen atom of the aromatic ring is substituted with an alkyl group or an alkoxy group. 01 may be the same or different. When n021 is 2 or more, multiple Rb 01 may be the same or different, m is an integer of 1 or more, and M m+ represents a cation with a valence of m.]

[0150] In the formula (b0-1), Rf 01 , Rb 01 , L 01 , and Yb 01 is Rf in the formula (b0). 0 , Rb 0 , L 0 , and Yb 0 are the same as those shown above. n011 is preferably an integer of 1 or more and 4 or less, more preferably an integer of 2 or more and 4 or less, even more preferably 3 or 4, and particularly preferably 4. n021 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, even more preferably 0 or 1, and particularly preferably 0.

[0151] The component (B0) is more preferably a compound represented by the following general formula (b0-1-1).

[0152] [ka] [In the formula, L 01 and Yb 01 is L in the formula (b0-1). 01 and Yb 01 m is an integer equal to or greater than 1, and M m+ represents an m-valent organic cation.

[0153] Specific examples of the component (B0) are shown below, but are not limited to these. In the following formula, m is an integer of 1 or more, and M m+ represents a cation with a valence of m.

[0154] [ka]

[0155] [ka]

[0156] [ka]

[0157] {cation part} In the above formula (b0), M m+ represents an m-valent onium cation. The onium cation is preferably a sulfonium cation or an iodonium cation. m is an integer of 1 or more.

[0158] Preferred cationic moieties ((M m+ ) 1 / m ) includes organic cations represented by the following general formulas (ca-1) to (ca-3), respectively.

[0159] [ka] [In the formula, R 201 ~R 207 R each independently represents an aryl group, an alkyl group, or an alkenyl group which may have a substituent. 201 ~R 203 , R 206 ~R 207 may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. 201represents -C(=O)- or -C(=O)-O-.]

[0160] In the above general formulas (ca-1) to (ca-3), R 201 ~R 207 The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferred. R 201 ~R 207 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 The alkenyl group in the formula (I) preferably has 2 or more and 10 or less carbon atoms. R 201 ~R 207 , and R 210 Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulae (ca-r-1) to (ca-r-7).

[0161] [ka] [In the formula, R' 201 are each independently a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0162] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0163] R' 201The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, even more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituent. R' 201 Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. R' 201 Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 or more and 4 or less, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.

[0164] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 or more and 20 or less carbon atoms, and more preferably has 3 or more and 12 or less carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkane is more preferably a polycycloalkane having a bridged ring polycyclic skeleton, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a fused ring polycyclic skeleton, such as a cyclic group having a steroid skeleton.

[0165] Among them, R' 201 The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0166] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0167] Also, R' 201 The cyclic hydrocarbon group in may contain a heteroatom, such as a heterocycle, etc. Specific examples include the lactone-containing cyclic groups represented by the general formulae (a2-r-1) to (a2-r-7) above, the —SO2-containing cyclic groups represented by the general formulae (b5-r-1) to (b5-r-4) above, and other heterocyclic groups represented by the chemical formulae (r-hr-1) to (r-hr-16) above.

[0168] R' 201 Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. As the halogen atom as a substituent, a fluorine atom is preferred. Examples of halogenated alkyl groups as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl groups, ethyl groups, propyl groups, n-butyl groups, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms. The carbonyl group as a substituent is a group that substitutes a methylene group (-CH2-) that constitutes a cyclic hydrocarbon group.

[0169] A chain alkyl group which may have a substituent: R' 201 The chain alkyl group may be either a straight chain or a branched chain. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0170] An optionally substituted chain alkenyl group: R' 201 The chain alkenyl group may be either linear or branched, and preferably has from 2 to 10 carbon atoms, more preferably from 2 to 5 carbon atoms, even more preferably from 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include vinyl, propenyl (allyl), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl groups. Of the chain alkenyl groups mentioned above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0171] R' 201 Examples of the substituent in the chain alkyl or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, the above-mentioned R' 201 Examples of the cyclic groups include the cyclic groups shown in the formula:

[0172] R' 201 In addition to those mentioned above, the optionally substituted cyclic group, the optionally substituted chain alkyl group, or the optionally substituted chain alkenyl group also includes the same as the acid-dissociable group represented by formula (a1-r-2) above as the optionally substituted cyclic group or the optionally substituted chain alkyl group.

[0173] Among them, R' 201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane, a lactone-containing cyclic group represented by each of the general formulae (a2-r-1) to (a2-r-7), or an —SO2- containing cyclic group represented by each of the general formulae (b5-r-1) to (b5-r-4) is preferred.

[0174] In the above general formulas (ca-1) to (ca-3), R 201 ~R 203 , R 206 ~R 207When the groups bond to each other to form a ring together with the sulfur atom in the formula, they may be bonded via a heteroatom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or a functional group such as a carbonyl group, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(RN)- (wherein RN is an alkyl group having from 1 to 5 carbon atoms). The ring formed is preferably a ring containing the sulfur atom in its ring skeleton, including the sulfur atom, that is from 3 to 10-membered, and particularly preferably from 5 to 7-membered. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0175] R 208 ~R 209 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups, they may be bonded to each other to form a ring.

[0176] R 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO2- containing cyclic group. R 210 The aryl group in the formula (I) includes an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferred. R 210 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 or more and 10 or less carbon atoms. R 210 As the -SO2- containing cyclic group which may have a substituent in the formula (b5-r-1), an "-SO2- containing polycyclic group" is preferred, and a group represented by the above general formula (b5-r-1) is more preferred.

[0177] Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following chemical formulas (ca-1-1) to (ca-1-75).

[0178] [ka]

[0179] [ka]

[0180] [ka] [In the formula, g1, g2, and g3 represent the number of repeating units, where g1 is an integer of 1 or more and 5 or less, g2 is an integer of 0 or more and 20 or less, and g3 is an integer of 0 or more and 20 or less.]

[0181] [ka]

[0182] [ka]

[0183] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent, and the substituent is the same as R 201 ~R 207 , and R 210 The substituents are the same as those exemplified as the substituents that may be possessed by the group

[0184] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0185] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0186] [ka]

[0187] Among the above, the cation part ((M m+ ) 1 / m ) is preferably a cation represented by general formula (ca-1).

[0188] Specific examples of the component (B0) are shown below, but are not limited to these.

[0189] [ka]

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] The photoacid generator (B) may be used alone or in combination of two or more. The content of the photoacid generator (B) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the acid-decomposable compound (A). When the amount of the photoacid generator (B) used is within the above range, the desired effect is easily obtained.

[0194] <Organic solvent (S)> The photosensitive composition preferably contains an organic solvent. The organic solvent may be any organic solvent that can dissolve each component used to form a homogeneous solution, and any organic solvent selected from organic solvents conventionally known as solvents for compositions containing a resin as a main component can be used.

[0195] Examples of organic solvents include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; monoacetates of polyhydric alcohols such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; and compounds of polyhydric alcohols having an ether bond such as monoalkyl ethers, monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the above polyhydric alcohols or monoacetates of the above polyhydric alcohols, or monophenyl ethers. Derivatives [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane; monoacetates of polyhydric alcohols such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; and esters other than the derivatives of the aforementioned polyhydric alcohols; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene. The organic solvent components may be used alone or in a mixture of two or more. Of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0196] The content of the organic solvent contained in the photosensitive composition is not particularly limited. The organic solvent is appropriately selected depending on the coating film thickness so that the concentration of the photosensitive composition is a coatable concentration. The organic solvent is generally used so that the solids concentration of the photosensitive composition is in the range of 0.2% by mass to 70% by mass, preferably 0.2% by mass to 50% by mass.

[0197] <Other ingredients> If desired, the photosensitive composition may further contain miscible additives, such as additional resins for improving the performance of the underlayer film, surfactants for improving coatability, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, sensitizers, base multipliers, and basic compounds.

[0198] ≪Compound≫ The compound is represented by any one of formulas (A1) to (A4). Details and preferred embodiments of formulas (A1) to (A4) are the same as those of formulas (A1) to (A4) in the above-mentioned <<Photosensitive Composition>>.

[0199] <Method for producing structure having phase-separated structure> The method for producing a structure having a phase-separated structure includes forming an underlayer film on a substrate (hereinafter also referred to as "step (i)"), forming an upper layer film containing a block copolymer on the underlayer film (hereinafter also referred to as "step (ii)"), and phase-separating the block copolymer in the upper layer film (hereinafter also referred to as "step (iii)").

[0200] <Process (i)> In step (i), an underlayer film 3 is formed on a substrate 1. Step (i) will be specifically described below with reference to FIG.

[0201] In the embodiment shown in FIG. 1, first, a photosensitive composition is applied onto a substrate 1 to form a photosensitive film 2 (FIG. 1(I)). Next, the photosensitive film 2 is exposed to light selectively at certain positions to form an underlayer film 3 (FIG. 1(II)).

[0202] The type of substrate 1 is not particularly limited as long as it can be coated with a photosensitive composition on its surface. Examples include substrates made of inorganic materials such as silicon, metals (copper, chromium, iron, aluminum, etc.), glass, titanium oxide, silica, and mica; substrates made of oxides such as SiO2; substrates made of nitrides such as SiN; substrates made of oxynitrides such as SiON; and substrates made of organic materials such as acrylic resin, polystyrene, cellulose, cellulose acetate, and phenolic resin. Among these, silicon substrates (Si substrates) or metal substrates are preferred, Si substrates or copper substrates (Cu substrates) are more preferred, and Si substrates are particularly preferred. There are no particular limitations on the size or shape of the substrate 1. The substrate 1 does not necessarily have to have a smooth surface, and substrates of various shapes can be appropriately selected. Examples include substrates with a curved surface, flat plates with an uneven surface, and substrates in the shape of flakes.

[0203] The surface of the substrate 1 may be provided with an inorganic and / or organic film. Examples of inorganic films include inorganic anti-reflective coatings (inorganic BARCs), and examples of organic films include organic anti-reflective coatings (organic BARCs). The inorganic film can be formed, for example, by applying an inorganic anti-reflective coating composition made of a silicon-based material or the like onto a substrate and baking it. The organic film can be formed, for example, by applying an organic film-forming material, in which the resin components constituting the film are dissolved in an organic solvent, onto a substrate using a spinner or the like, and baking the material under heating conditions of preferably 200°C to 300°C, preferably 30 to 300 seconds, more preferably 60 to 180 seconds. This organic film-forming material does not necessarily need to be sensitive to light or electron beams, as is the case with resist films, and may or may not be sensitive. Specifically, resists and resins commonly used in the manufacture of semiconductor devices and liquid crystal display devices can be used. In addition, the organic film-forming material is preferably a material capable of forming an organic film that can be etched, particularly dry-etched, so that an organic film pattern can be formed by etching an organic film using a block copolymer pattern formed by processing the upper layer film. Among these, a material capable of forming an organic film that can be etched by oxygen plasma etching or the like is preferred. Such an organic film-forming material may be a material that has been conventionally used to form organic films such as organic BARC. Examples include the ARC series manufactured by Nissan Chemical Industries, Ltd., the AR series manufactured by Rohm and Haas, and the SWK series manufactured by Tokyo Ohka Kogyo Co., Ltd.

[0204] The method for applying the photosensitive composition onto the substrate 1 to form the photosensitive film 2 is not particularly limited, and the photosensitive film 2 can be formed by a conventionally known method. For example, the photosensitive film 2 can be formed by applying the photosensitive composition onto the substrate 1 by a conventionally known method such as spin coating or using a spinner to form a coating film, and then drying the coating film. The coating film can be dried by any method that volatilizes the solvent contained in the photosensitive composition and fixes the acid-decomposable compound (A) to the substrate 1, and examples of such methods include baking. In this case, the baking temperature is preferably 80° C. or higher and 300° C. or lower, and more preferably 180° C. or higher and 270° C. or lower. The baking time is preferably 30 seconds or higher and 600 seconds or lower, and more preferably 60 seconds or higher and 600 seconds or lower. The thickness of the photosensitive film 2 after drying of the coating is preferably about 1 nm or more and 150 nm or less, and more preferably about 1 nm or more and 100 nm or less.

[0205] The substrate 1 may be surface-treated in advance. By treating the surface of the substrate 1, the coating properties of the photosensitive composition are improved and the acid-decomposable compound (A) is more easily fixed to the substrate 1. As the surface treatment method, a conventionally known method can be used, for example, oxygen plasma treatment, ozone oxidation treatment, acid-alkali treatment, chemical modification treatment, and the like.

[0206] As a method for position-selectively exposing the photosensitive film 2, for example, exposure through a mask may be used. Exposure is performed by irradiating radiation such as ultraviolet light, ArF excimer laser, KrF excimer laser, F2 excimer laser, extreme ultraviolet light (EUV), vacuum ultraviolet light (VUV), electron beam, X-ray, soft X-ray, etc. Even under low exposure conditions, the polarity of the film surface can be changed by exposure, so the exposure dose is set to 10 mJ / cm. 2 More than 300mJ / cm 2 Preferably, it is 20 mJ / cm or less. 2 More than 200mJ / cm 2 More preferably, it is 30 mJ / cm or less. 2 More than 150mJ / cm 2 It is even more preferable that:

[0207] The exposed photosensitive film 2 is rinsed with a rinse liquid such as a solvent, and the acid-decomposable portion of the acid-decomposable compound (A) is removed by rinsing. The rinse liquid may be any liquid capable of dissolving the acid-decomposed portion, and may be a solvent such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), or ethyl lactate (EL), or a commercially available thinner solution. After rinsing, post-baking is performed. The temperature conditions for post-baking are preferably 40° C. or higher and 200° C. or lower, and more preferably 50° C. or higher and 150° C. or lower. The baking time is preferably 30 seconds or higher and 300 seconds or lower, more preferably 40 seconds or higher and 200 seconds or lower, and even more preferably 50 seconds or higher and 100 seconds or lower.

[0208] These procedures result in an underlayer film having exposed and unexposed regions with different polarities (hydrophilicity), which is used as a template for phase separation of the block copolymer in the following step.

[0209] <Process (ii)> In step (ii), an upper layer film containing a block copolymer is formed on the lower layer film 3 . The block copolymer is not particularly limited, and any conventionally known block copolymer can be used, such as a block copolymer in which a block having a structural unit containing an aromatic group is bonded to a block having a structural unit derived from an (α-substituted) acrylic acid ester (e.g., a polystyrene-polymethyl methacrylate (PS-PMMA) block copolymer). The method for forming the upper layer film on the lower layer film 3 is not particularly limited, and examples thereof include a method in which a resin composition for forming a phase-separated structure containing a block copolymer and an organic solvent is applied to the lower layer film 3 by a conventionally known method such as using spin coating or a spinner to form a coating film, and then drying.

[0210] <Step (iii)> In step (iii), the block copolymer is phase-separated in the upper layer film. By heating and annealing the substrate 1 after step (ii), the block copolymer is selectively removed to form a phase-separated structure that exposes at least a portion of the surface of the substrate 1. In other words, a structure containing a phase-separated structure is produced on the substrate 1.

[0211] <Optional process> The method for producing a structure having a phase-separated structure may include steps (optional steps) other than steps (i) to (iii). Such an optional step includes a step of selectively removing a phase of at least one type of block from among the blocks constituting the block copolymer in the upper layer film (hereinafter referred to as "step (iv)").

[0212] Regarding step (iv) In step (iv), a phase consisting of at least one type of block constituting the block copolymer is selectively removed from the upper layer film formed on the lower layer film 3. This results in the formation of a fine pattern (polymer nanostructure).

[0213] As a method for selectively removing the phase consisting of blocks, there are methods such as a method of subjecting the upper layer film to oxygen plasma treatment and a method of subjecting the upper layer film to hydrogen plasma treatment. [Example]

[0214] The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[0215] The materials used in the examples and comparative examples will be described below. <Acid decomposable compounds> UL-1: A random copolymer (number average molecular weight: 15,200, dispersity: 1.29) having structural units represented by the following formula: In the following formula, the number in the parentheses to the right of each structural unit represents the content (mol %) of the structural unit in the copolymer. [ka]

[0216] [Synthesis of UL-2 precursor and UL-2] [ka] (In the above reaction formula, n is the repeating number of styrene units, and m is the repeating number of lactic acid units.)

[0217] All reactions were carried out under an argon atmosphere. 5.0 g of hydroxy-terminated polystyrene (PS-OH) (weight average molecular weight: 4,700) and 2.1 g of DL-lactide were added to a 300 mL Schlenk flask, followed by azeotropic dehydration with the addition of 5 mL of toluene. 20 g of dichloromethane was added to the Schlenk flask to dissolve the solids, and then 20 mg of diazabicycloundecene (DBU®) was added and the reaction was carried out at 25°C. 20 mg of benzoic acid was added as a terminator to terminate the polymerization reaction. The resulting reaction solution was poured into methanol and reprecipitated. The resulting mixture was dried under reduced pressure at 40°C to obtain a white powder (5.80 g, yield: 82%) as the UL-2 precursor. A 300 mL Schlenk tube was charged with 5.50 g of UL-2 precursor (weight average molecular weight: 7,000), 367 mg of succinic anhydride, and 150 mg of 4-dimethylaminopyridine (DMAP), and 55 g of toluene was added to dissolve the solids. The solution in the Schlenk tube was heated and stirred in an oil bath at 120°C for 13 hours. The resulting reaction solution was poured into a mixed solution of isopropanol and heptane (8:2 (mass ratio)) for reprecipitation. The precipitate was dried under reduced pressure at 40°C to obtain a white powder (5.31 g, yield: 97%) of UL-2. The number average molecular weight (Mn) and polydispersity index (PDI=Mw / Mn) of UL-2 measured by size exclusion chromatography (SEC) were 8,000 and 1.06, respectively.

[0218] [Synthesis of UL-3 precursor and UL-3] [ka] (In the above reaction formula, n is the repeating number of styrene units, and m is the repeating number of ε-caprolactone units.)

[0219] A UL-3 precursor (weight-average molecular weight: 9,000) was obtained in the same manner as in the synthesis of the UL-2 precursor, except that ε-caprolactone was used instead of DL-lactide and the reaction temperature was changed from 25°C to 40°C. UL-3 was obtained in the same manner as in the synthesis of UL-2, except that the UL-3 precursor was used instead of the UL-2 precursor. The number average molecular weight (Mn) and polydispersity index (PDI=Mw / Mn) of UL-3 measured by size exclusion chromatography (SEC) were 10,000 and 1.06, respectively.

[0220] <Photoacid generator> PAG-1: A compound represented by the following formula: [ka]

[0221] <Preparation of Photosensitive Composition and Formation of Underlayer Film> Photosensitive compositions (solid content concentration: 1.4% by mass) of each example were prepared by mixing the types of acid-decomposable compounds shown in Table 1, the photoacid generator (PAG-1), propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether in the amounts shown in Table 1. The content of the photoacid generator is shown in parts by mass relative to 100 parts by mass of the acid-decomposable compound.

[0222] The photosensitive composition of each example was applied onto a silicon wafer using a spinner, the coating was baked at 200°C for 300 seconds in an air atmosphere, and then rinsed with a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (8:2 (mass ratio)), thereby forming a photosensitive film with a thickness of 2 nm. Using a KrF exposure device, the photosensitive film was irradiated with a KrF excimer laser (wavelength 248 nm) at the exposure dose shown in Table 1. The surface of the photosensitive film was rinsed with a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (8:2 (mass ratio)), and then post-baked at the temperature shown in Table 1 for 60 seconds to form an underlayer film.

[0223] <Water contact angle> For each of the photosensitive film and underlayer film formed using the photosensitive composition of each example, 2 μL of water was dropped onto the surface, and the contact angle (static contact angle) was measured (ellipse fitting method) using a DROP MASTER-700 (product name, manufactured by Kyowa Interface Science Co., Ltd.). The measured values ​​are shown in Table 1 as "Water contact angle (photosensitive film) (°)" and "Water contact angle (underlayer film) (°)," respectively.

[0224] [Table 1]

[0225] As shown in Table 1, in Examples 1 to 10, which used photosensitive compositions containing a predetermined acid-decomposable compound (A) and a photoacid generator (B), the water contact angle of the underlayer film decreased from the water contact angle of the photosensitive film, and the polarity changed, even under conditions of low exposure dose and low post-bake temperature. On the other hand, in Comparative Examples 1 to 4, which used photosensitive compositions containing a compound other than the predetermined acid-decomposable compound (A), the water contact angle of the underlayer film remained the same as the water contact angle of the photosensitive film, and the polarity did not change, even under conditions of low exposure dose and low post-bake temperature. Therefore, it can be seen that by using a photosensitive composition containing a specific acid-decomposable compound (A) and performing site-selective exposure, guide patterns with different polarities can be formed even under conditions of low exposure dose and low post-bake temperature.

Claims

1. Contains an acid-decomposable compound (A) and a photoacid generator (B), The photosensitive composition, wherein the acid-decomposable compound (A) is one or more compounds represented by any one of the following formulas (A1) to (A4): R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ -O-(-C-R) ａ５ -C--)-O-R ａ６ -R ａ７ ・・・(A1) R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ -O-(----R ａ５ -O-)----R ａ６ -R ａ７ ・・・(A2) R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ ----(-O-R ａ５ ----)-O-R ａ６ -R ａ７ ・・・(A3) R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ -C--(-O-R ａ５ -O-)-C-R ａ６ -R ａ７ ・・・(A4) (In formulas (A1) to (A4), R ａ１ is an alkyl group, and R ａ２ is a hydrogen atom or an alkyl group, and R ａ３ is an aromatic group which may have a substituent, and R ａ４ is an alkylene group, and R ａ５ is a residue obtained by removing a terminal carboxy group or a terminal hydroxy group from a linear aliphatic polyester, and R ａ６ is an alkylene group, and R ａ７ is a hydroxy group, a carboxy group, a phosphate group, a mercapto group, or an amino group, and n is —CH ２ -CR ａ２ R ａ３ - is the number of repeating structural units represented by the formula (I) and is an integer of 2 or more.

2. The R ａ３ 2. The photosensitive composition according to claim 1, wherein the aromatic group which may have a substituent as represented by the formula (I) is an aromatic hydrocarbon group which may have a substituent.

3. The R ａ５ 2. The photosensitive composition according to claim 1, wherein the linear aliphatic polyester is a polycondensate of an aliphatic hydroxycarboxylic acid or a ring-opening polymer of a lactone.

4. 4. The photosensitive composition according to claim 3, wherein the polycondensate of an aliphatic hydroxycarboxylic acid or the ring-opening polymer of a lactone is at least one selected from the group consisting of polylactic acid, polyglycolic acid, polyhydroxybutyric acid, polycaprolactone, polybutyrolactone, and polyvalerolactone.

5. Contains an acid-decomposable compound (A) and a photoacid generator (B), The photosensitive film, wherein the acid-decomposable compound (A) is one or more compounds represented by any one of the following formulas (A1) to (A4): R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ -O-(-C-R) ａ５ -C--)-O-R ａ６ -R ａ７ ・・・(A1) R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ -O-(----R ａ５ -O-)----R ａ６ -R ａ７ ・・・(A2) R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ ----(-O-R ａ５ ----)-O-R ａ６ -R ａ７ ・・・(A3) R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ -C--(-O-R ａ５ -O-)-C-R ａ６ -R ａ７ ・・・(A4) (In formulas (A1) to (A4), R ａ１ is an alkyl group, and R ａ２ is a hydrogen atom or an alkyl group, and R ａ３ is an aromatic group which may have a substituent, and R ａ４ is an alkylene group, and R ａ５ is a residue obtained by removing a terminal carboxy group or a terminal hydroxy group from a linear aliphatic polyester, and R ａ６ is an alkylene group, and R ａ７ is a hydroxy group, a carboxy group, a phosphate group, a mercapto group, or an amino group, and n is —CH ２ -CR ａ２ R ａ３ - is the number of repeating structural units represented by the formula (I) and is an integer of 2 or more.

6. An underlayer membrane used as a template for phase separation of a block copolymer, comprising: The underlayer film is formed by position-selectively exposing the photosensitive film according to claim 5 , An underlayer film having exposed and unexposed regions that differ in hydrophilicity.

7. forming the underlayer film according to claim 6 on a substrate; forming an upper layer film containing the block copolymer on the underlayer film; and causing phase separation of the block copolymer in the upper layer film.

8. A compound represented by any one of the following formulas (A1) to (A4): R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ -O-(-C-R) ａ５ -C--)-O-R ａ６ -R ａ７ ・・・(A1) R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ -O-(----R ａ５ -O-)----R ａ６ -R ａ７ ・・・(A2) R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ ----(-O-R ａ５ ----)-O-R ａ６ -R ａ７ ・・・(A3) R ａ１ -(-CH ２ -CR ａ２ R ａ３ -) ｎ -R ａ４ -C--(-O-R ａ５ -O-)-C-R ａ６ -R ａ７ ・・・(A4) (In formulas (A1) to (A4), R ａ１ is an alkyl group, and R ａ２ is a hydrogen atom or an alkyl group, and R ａ３ is an aromatic group which may have a substituent, and R ａ４ is an alkylene group, and R ａ５ is a residue obtained by removing a terminal carboxy group or a terminal hydroxy group from a linear aliphatic polyester, and R ａ６ is an alkylene group, and R ａ７ is a hydroxy group, a carboxy group, a phosphate group, a mercapto group, or an amino group, and n is —CH ２ -CR ａ２ R ａ３ - is the number of repeating structural units represented by the formula (I) and is an integer of 2 or more.

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