Resist composition, dry film resist, method for producing dry film resist, method for forming resist pattern, and method for manufacturing plated molded article

Abstract

To provide a method for producing a dry film resist, a pattern formation method, and a method for manufacturing a plated molded article.SOLUTION: There are provided: a resist composition which contains a resin (A1) having a group represented by formula (1), a resin (A2) containing a structural unit represented by formula (a3), and an acid generator (B1); a dry film resist; a method for producing the dry film resist; a method for forming a resist pattern; and a method for manufacturing a plated molded article.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist composition, a dry film resist, a method for producing a dry film resist, a method for forming a resist pattern, and a method for producing a plated object. [Background technology]

[0002] Patent Document 1 describes a resist composition containing a resin having a repeating unit in which a phenolic hydroxyl group is protected with a tertiary alkyl group (e.g., Polymer-1) and a resin having a repeating unit of a polyacrylic acid ester polymer (e.g., Polymer-4). TIFF2025162967000001.tif69170 Patent Document 2 describes a resist dry film that uses a resist composition containing a resin having a repeating unit of a hydroxystyrene structure. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-232607 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-57612 Summary of the Invention [Problem to be solved by the invention]

[0004] When forming a resist pattern using the resist composition described in Patent Document 1, there is a problem in that resolution will not occur unless a post-exposure bake is performed after exposure to promote diffusion of the photoacid generator. When a resist pattern obtained using the resist composition described in Patent Document 2 is used for plating, there is still room for improvement in forming a plated object. Therefore, an object of the present invention is to provide a resist composition that can form a resist pattern that can be resolved without a heat treatment after exposure and that has sufficient resistance to plating treatment. [Means for solving the problem]

[0005] The present invention provides the following inventions. [1] A resin (A1) having a group represented by formula (1), a resin (A2) containing a structural unit represented by formula (a3); an acid generator (B); A resist composition comprising: TIFF2025162967000002.tif22170[In formula (1), R a1 and R a2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R a3 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2 and R a3 are bonded to each other, and R a2 and the carbon atom to which R is bonded a3 forms a heterocyclic ring having 3 to 20 carbon atoms together with X to which it is bonded, and the methylene groups contained in the hydrocarbon group and the heterocyclic ring may be replaced with oxygen atoms or sulfur atoms. X represents an oxygen atom or a sulfur atom. na represents 0 or 1. * denotes a binding site.] TIFF2025162967000003.tif36170[In formula (a3), R a31 and R a32 each independently represents an alkyl group having 1 to 12 carbon atoms, and a methylene group contained in the alkyl group may be replaced with an oxygen atom. o, p, q, and r each independently represent 0 or a positive number less than 1, and at least one of o and p represents a positive number less than 1; when o is 0, p and q each represent a positive number less than 1; when p is 0, o and r each represent a positive number less than 1; when q is 0, o and r each represent a positive number less than 1; and when r is 0, p and q each represent a positive number less than 1, provided that o+p+q+r=1 is satisfied. [2] The resist composition according to [1], wherein the resin (A1) contains a structural unit represented by formula (a1-1) or formula (a1-2). TIFF2025162967000004.tif65170 [In formula (a1-1) and formula (a1-2), R a1 , R a2 , R a3 has the same meaning as in formula (1). R a4 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. R a5 represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a11 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkanediyl group is -O-, -CO- or -NR a6 - may be replaced with R a6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. na1A represents an integer of 1 to 5, and when na1A is 2 or more, the groups in the parentheses may be the same or different from each other. na11A represents an integer of 0 to 4, and when na11A is 2 or more, a plurality of R a5 may be the same or different, provided that 1≦na1A+na11A≦5 is satisfied. na1B represents an integer of 1 to 4, and when na1B is 2 or more, the groups in the parentheses may be the same or different from each other. na11B represents an integer of 0 to 3, and when na11B is 2 or more, a plurality of R a5 may be the same or different, provided that 1≦na1B+na11B≦4 is satisfied. [3] The resist composition according to [2], wherein the resin (A1) contains a structural unit represented by formula (a1-1): [4] The resist composition according to any one of [1] to [3], wherein the resin (A1) further contains a structural unit represented by formula (a2-1): TIFF2025162967000005.tif58170[In formula (a2-1), R a24 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. R a25 represents a halogen atom, a carboxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a21 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkanediyl group is -O-, -CO- or -NR a26 - may be replaced with R a26 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. na2 represents an integer of 1 to 5. na21 represents an integer of 0 to 4, and satisfies 1≦na2+na21≦5. When na21 is 2 or more, a plurality of R a25 may be the same or different from each other. [5] 0.05≦o+p≦0.30 is satisfied; The resist composition according to any one of [1] to [4], wherein q and r each represent a positive number less than 1. [6] The resist composition according to any one of [1] to [5], further comprising a novolak resin (A3). [7] Further, an adhesion improver (E) is contained, The resist composition according to any one of [1] to [6], wherein the adhesion improver (E) comprises at least one selected from the group consisting of sulfur-containing compounds, aromatic hydroxy compounds, benzotriazole-based compounds, triazine-based compounds, and silicon-containing compounds. [8] a support film; a resist composition layer laminated on the support film and containing the resist composition according to any one of [1] to [7]. [9] (1a) applying the resist composition according to any one of [1] to [7] to a support film to form a photoresist composition layer; (2a) a step of drying the resist composition layer.

[10] (1b) A step of applying the resist composition according to any one of [1] to [7] onto a substrate and drying the resist composition to form a resist composition layer; (2b) exposing the resist composition layer to ultraviolet light with a wavelength of 500 nm or less; (3b) A pattern forming method comprising the step of developing the exposed resist composition layer without heating it.

[11] (1c) laminating the dry film resist according to [8] on a substrate; (2c) peeling at least a portion of the support film from the resist composition layer, and exposing the resist composition layer to ultraviolet light with a wavelength of 500 nm or less; (3c) A pattern forming method comprising the step of developing the exposed resist composition layer without heating it.

[12] A step of forming a resist pattern on a substrate having a conductive layer using the resist composition according to any one of [1] to [7] so that a portion of the conductive layer is exposed; forming a plating object using the resist pattern as a template; a step of removing the resist pattern after forming the plated object. [Effects of the Invention]

[0006] By using the resist composition of the present invention, it is possible to provide a resist pattern that exhibits both excellent resolution and plating resistance. The resist composition of the present invention can form a resist pattern that has excellent resolution and plating resistance, even without a post-exposure bake (PEB) treatment after exposure. Furthermore, when a thick dry film resist (resist composition layer) is formed using the resist composition of the present invention, the thick resist pattern formed using this also exhibits excellent resolution and plating resistance. DETAILED DESCRIPTION OF THE INVENTION

[0007] In this specification, unless otherwise specified, in the description of the structural formula of a compound, the term "hydrocarbon group" means a linear or branched chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining these groups. When the number of carbon atoms in the "hydrocarbon group" is specified, the group may be any of the above groups within the range permitted by the number of carbon atoms. When stereoisomers exist, all stereoisomers are included. In this specification, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid," and "(meth)acrylate" means "at least one of acrylate and methacrylate." In the groups described herein, those that can have both a linear structure and a branched structure are interpreted as including both. A "combined group" means a group in which two or more of the exemplified groups are bonded together, and the valence of these groups may be changed appropriately depending on the bonding form. The terms "derived from" or "derived from" refer to a polymerizable C=C bond contained in the molecule that is polymerized to a -CC- group (single bond). When stereoisomers exist, all stereoisomers are included. In each group, depending on the number of substituents, any number of hydrogen atoms in the group may be replaced with bonds at any positions. The number of carbon atoms in a substituent is not included in the number of carbon atoms of the substituted group. In this specification, the term "solids content of a resist composition" refers to the sum of all components in the resist composition excluding the solvent (D), which will be described later.

[0008] <Resist composition> The resist composition of the present invention contains a resin having a group represented by formula (1) (hereinafter may be referred to as "resin (A1)"), a resin (A2) having a structural unit represented by formula (a3) ​​(hereinafter may be referred to as "resin (A2)"), and an acid generator (hereinafter may be referred to as "acid generator (B)"). Furthermore, the resist composition of the present invention may optionally contain an adhesion improver (hereinafter, may be referred to as "adhesion improver (E)"), and a resin containing a structural unit represented by formula (a4) (hereinafter, may be referred to as "resin (A3)"). Furthermore, the resist composition of the present invention may contain, as necessary, a quencher (hereinafter, sometimes referred to as "quencher (C)"), a solvent (hereinafter, sometimes referred to as "solvent (D)"), and other components (hereinafter, sometimes referred to as "other components (F)").

[0009] <Resin (A1)> Resin (A1) is a resin containing a structural unit having an acid labile group (a structural unit having an acid labile group may be referred to as "structural unit (a1)"), and contains a structural unit having a group represented by formula (1) as the acid labile group. Resin (A1) may optionally contain structural units known in the art, in addition to the structural unit having a group represented by formula (1).

[0010] <Group represented by formula (1)> The structural unit (a1) includes a structural unit having a group represented by formula (1). TIFF2025162967000006.tif25170[In formula (1), R a1 and R a2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3 represents a hydrocarbon group having 1 to 20 carbon atoms; a1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2 and R a3 are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. A methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with an oxygen atom or a sulfur atom. X represents an oxygen atom or a sulfur atom. na represents 0 or 1. * represents a bond.]

[0011] R a1 , R a2 and R a3 Examples of the hydrocarbon group having 1 to 20 carbon atoms include chain hydrocarbon groups having 1 to 20 carbon atoms (such as alkyl groups, alkenyl groups, and alkynyl groups), alicyclic hydrocarbon groups having 3 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, and groups having 4 to 20 carbon atoms that are combinations of these groups. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl group. Examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. Examples of the alkynyl group having 2 to 20 carbon atoms include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. The chain hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 18 carbon atoms, more preferably has 1 to 16 carbon atoms, even more preferably has 1 to 12 carbon atoms, still more preferably has 1 to 8 carbon atoms, and even more preferably has 1 to 6 carbon atoms. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornyl. The alicyclic hydrocarbon group having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl. The aromatic hydrocarbon group may further have a substituent, and examples of the substituent include an aryloxy group having 6 to 10 carbon atoms. The aromatic hydrocarbon group having 6 to 20 carbon atoms preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms. Among the groups having 4 to 20 carbon atoms in which the above groups are combined, examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined (groups having 4 to 20 carbon atoms) include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, an isobornyl group, a 2-alkyladamantan-2-yl group, and a 1-(adamantan-1-yl)alkane-1-yl group. Examples of the group in which an alkyl group and an aromatic hydrocarbon group are combined (groups having 7 to 20 carbon atoms) include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of groups in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined (groups having 9 to 20 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group, and specific examples include a p-cyclohexylphenyl group, a p-adamantylphenyl group, and a phenylcyclohexyl group.

[0012] R a2 and R a3 When -C(R) are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, the heterocycle may be monocyclic or polycyclic. a1 )(R a2 )-XR a3 Examples of R include the following groups: a1 has the same meaning as above, and * represents a binding site. TIFF2025162967000007.tif29170

[0013] R a1 is preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom. R a2 is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or R a3 and form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded and X, and is preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or R a3 and more preferably bonded to the carbon atom to which they are bonded and X to form a heterocyclic ring having 3 to 12 carbon atoms, even more preferably a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a methyl group or an ethyl group. R a3 is a hydrocarbon group having 1 to 18 carbon atoms, or R a2 and form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded and X, and is preferably a hydrocarbon group having 1 to 12 carbon atoms or R a2and more preferably bonded to form a heterocyclic ring having 3 to 12 carbon atoms together with the carbon atom to which they are bonded and X. R a1 , R a2 and R a3 Examples of the hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group having a combination of these and having 4 to 18 carbon atoms. These groups can be arbitrarily selected from those listed above. X is preferably an oxygen atom. na is preferably 0.

[0014] Specific examples of the group represented by formula (1) include the following groups. TIFF2025162967000008.tif98170

[0015] <Structural Unit (a1-1) and Structural Unit (a1-2): Structural Unit Having a Group Represented by Formula (1)> Examples of structural units having a group represented by formula (1) include structural units represented by the following formulas (a1-1) and (a1-2) (hereinafter, sometimes referred to as "structural unit (a1-1)" and "structural unit (a1-2)", respectively). <Structural unit (a1-1): structural unit having a group represented by formula (1)> The structural unit (a1-1) is a structural unit represented by the following formula (a1-1). TIFF2025162967000009.tif67170[In formula (a1-1), R a1 , R a2 , R a3 has the same meaning as in formula (1). R a4 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. R a5represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a11 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkanediyl group is -O-, -CO- or -NR a6 - may be replaced with R a6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. na1A represents an integer of 1 to 5, and when na1A is 2 or more, the groups in the parentheses may be the same or different from each other. na11A represents a positive number between 0 and 4. When na11A is 2 or more, multiple R a5 may be the same or different, provided that 1≦na1A+na11A≦5 is satisfied.

[0016] In formula (a1-1), R a1 , R a2 and R a3 Specific and preferred examples of R a1 , R a2 and R a3 Suitable examples of the above include the same groups.

[0017] R a4 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R a4 The alkyl group having 1 to 6 carbon atoms may be a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. R a4Examples of the haloalkyl group having 1 to 6 carbon atoms include groups in which a hydrogen atom contained in the above alkyl group is replaced with the above halogen atom, such as a fluorinated alkyl group having 1 to 6 carbon atoms, a chlorinated alkyl group having 1 to 6 carbon atoms, a brominated alkyl group having 1 to 6 carbon atoms, or an iodinated alkyl group having 1 to 6 carbon atoms, and among these, a perfluoroalkyl group having 1 to 3 carbon atoms is preferred. R a4 is preferably a hydrogen atom or a methyl group.

[0018] A a11 Examples of the alkanediyl group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, and a dodecane-1,12-diyl group. and branched alkanediyl groups such as butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, heptane-1,6-diyl, octane-1,8-diyl, nonane-1,9-diyl, and decane-1,10-diyl. a11 When is an alkanediyl group, the alkanediyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. R a6 Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. A a11 The alkanediyl group contains -CH2-, -O-, -CO-, or -NR a6 When the hydrocarbon group is substituted with a carbon atom, the number of carbon atoms before the substitution is regarded as the number of carbon atoms of the hydrocarbon group. A a11Examples of the alkanediyl group having 1 to 12 carbon atoms in which -CH2- is replaced with -O- or -CO- include a hydroxy group (a group in which -CH2- in a methyl group is replaced with -O-), a carboxy group (a group in which -CH2-CH2- in an ethyl group is replaced with -O-CO-), a carbonyl group (a group in which -CH2- in a methylene group is replaced with -CO-), an oxy group (a group in which -CH2- in a methylene group is replaced with -O-), an amino group (a group in which -CH2- in an alkanediyl group is replaced with -NR a6 -), alkoxy group (a group in which -CH2- at any position in an alkyl group is replaced with -O-), alkoxycarbonyl group (a group in which -CH2-CH2- at any position in an alkyl group is replaced with -O-CO-), alkylcarbonyl group (a group in which -CH2- at any position in an alkyl group is replaced with -CO-), alkylamino group (a group in which -CH2- in an alkyl group is replaced with -NR a6 These substituted groups include the same groups as those exemplified in this specification, within the range permitted by the upper limit of the number of carbon atoms. For example, A a11 -CH2- in the alkanediyl group having 1 to 12 carbon atoms is -O-, -CO- or -NR a6 The groups substituted are *-O-, *-CO-O-, *-O-CO-, *-CO-OA a12 -CO-O-, *-O-CO-A a12 -O-, *-OA a12 -CO-O-, *-CO-OA a12 -O-CO-, *-O-CO-A a12 -O-CO-, etc. Among them, *-CO-O-, *-CO-OA a12 -CO-O- or *-OA a12 -CO-O-, *-CO-NR a6 - is preferred, where A a12 represents an alkanediyl group having 1 to 8 carbon atoms, and * represents R a4 represents the bonding site that is attached to the carbon atom to which A is attached. a12 The alkanediyl group of A is, within the limits of the upper limit of the carbon number, a11The same alkanediyl groups as those shown in the above are exemplified. A a11 is a single bond, *-CO-O- or *-CO-OA a12 -CO-O- is preferred, a single bond, *-CO-O- or *-CO-O-CH2-CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred.

[0019] R a5 Examples of the halogen atom, alkyl group having 1 to 6 carbon atoms and haloalkyl group having 1 to 6 carbon atoms include R a4 Examples of the halogen atom include the halogen atoms, alkyl groups having 1 to 6 carbon atoms, and haloalkyl groups having 1 to 6 carbon atoms. R a5 Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The number of carbon atoms in the alkoxy group is preferably 1 to 4, more preferably 1 to 3, still more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a5 Examples of the alkoxyalkyl group having 2 to 12 carbon atoms include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a5 Examples of the alkoxyalkoxy group having 2 to 12 carbon atoms include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group. R a5Examples of the alkylcarbonyl group having 2 to 4 carbon atoms include an acetyl group, a propionyl group, a butyryl group, etc. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a5 Examples of the alkylcarbonyloxy group having 2 to 4 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a5 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms; more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and still more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0020] na1A is preferably 1, 2 or 3, and more preferably 1 or 2. na11A is preferably 0, 1, 2 or 3, and more preferably 0 or 1. -O-CR a1 R a2 -OR a3 is preferably bonded to the 3- or 4-position of the benzene ring, and more preferably to the 4-position of the benzene ring.

[0021] Examples of the group represented by formula (a1-1) include structural units represented by the following formulas: In the following structural units, R a4 Specific examples of the structural unit (a1-1) include structural units in which the hydrogen atom corresponding to the following is replaced with a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. TIFF2025162967000010.tif123170

[0022] <Structural unit (a1-2): structural unit having a group represented by formula (1)> The structural unit (a1-2) is a structural unit represented by the following formula (a1-2). TIFF2025162967000011.tif44170[In formula (a1-2), R a1 , R a2 , R a3 has the same meaning as in formula (1). R a5 represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. na1B represents an integer of 1 to 4, and when na1B is 2 or more, the groups in the parentheses may be the same or different from each other. na11B represents a positive number between 0 and 3. When na11B is 2 or more, multiple R a5 may be the same or different, provided that 1≦na1B+na11B≦4 is satisfied.

[0023] In formula (a1-2), R a1 , R a2 and R a3 Suitable examples of the formula (a1-1) include the R a1 , R a2 and R a3 Suitable examples of the above include the same groups.

[0024] In formula (a1-2), R a5 Examples of the halogen atom, the alkyl group having 1 to 6 carbon atoms, the haloalkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, the alkoxyalkyl group having 2 to 12 carbon atoms, the alkoxyalkoxy group having 2 to 12 carbon atoms, the alkylcarbonyl group having 2 to 4 carbon atoms, and the alkylcarbonyloxy group having 2 to 4 carbon atoms include R a5 Specific examples are the same as those of the groups listed in 1. In formula (a1-2), R a5 is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, even more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group.

[0025] na1B is preferably 1 or 2, and more preferably 1. na11B is preferably 0, 1 or 2, and more preferably 0 or 1.

[0026] Examples of the structural unit represented by formula (a1-2) include structural units represented by the following formulas: TIFF2025162967000012.tif56170

[0027] Resin (A1) may contain one or more structural units (a1-1) or one or more structural units (a1-2). When resin (A1) contains structural units (a1-1) or (a1-2), the total content of structural units (a1-1) or (a1-2) is preferably 3 to 80 mol%, more preferably 5 to 60 mol%, even more preferably 10 to 55 mol%, still more preferably 15 to 50 mol%, and even more preferably 20 to 45 mol%, based on all structural units in resin (A1). The structural unit having a group represented by formula (1) is preferably the structural unit (a1-1).

[0028] Resin (A1) may contain a conventionally known structural unit having an acid labile group other than the group represented by formula (1). When resin (A1) contains a structural unit having an acid labile group other than the group represented by formula (1), the total content of structural units having an acid labile group other than the group represented by formula (1) is preferably 0 mol % to 10 mol %, more preferably 0 mol % to 5 mol %, and even more preferably 0 to 3 mol %, based on all structural units of resin (A1).

[0029] <Structural unit (a2)> Resin (A1) may further contain a structural unit that does not have an acid labile group (a structural unit that does not contain an acid labile group may be referred to as "structural unit (a2)"). As the structural unit (a2), structural units known in the art may be used. Examples of the structural unit (a2) include structural units represented by the following formula (a2-1), formula (a2-2), formula (a2-3), or formula (a2-4) (hereinafter, these may be referred to as "structural unit (a2-1)," "structural unit (a2-2)," "structural unit (a2-3)," or "structural unit (a2-4)," respectively). TIFF2025162967000013.tif57170 [In formula (a2-1), formula (a2-2), formula (a2-3) and formula (a2-4), R a24 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. R a25 represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. R a26 represents a hydrocarbon group having 1 to 12 carbon atoms, excluding groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. A methylene group contained in the hydrocarbon group having 1 to 12 carbon atoms may be substituted with an oxygen atom or a carbonyl group, provided that a methylene group bonded to an oxygen atom and a methylene group bonded to the methylene group are not substituted with an oxygen atom. R a27 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, excluding groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. A a21 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkanediyl group is -O-, -CO- or -NR a6 - may be replaced with L a2 represents an alkanediyl group having 2 to 6 carbon atoms, excluding groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. na2 represents an integer of 1 to 5. na21 represents an integer of 0 to 4, and satisfies 1≦na2+na21≦5. When na21 is 2 or more, a plurality of R a25 may be the same or different from each other. na22 represents an integer of 0 to 5, and satisfies 0≦na21+na22≦5, and when na22 is 2 or more, the groups in the parentheses may be the same or different. na23 represents an integer of 1 to 30, and when na22 is 2 or more, a plurality of L a2 may be the same or different from each other.

[0030] In formulas (a2-1) to (a2-4), R a24 Specific and preferred examples of R a4 Suitable examples of the above include the same groups.

[0031] In formula (a2-1) and formula (a2-2), R a25 Specific and preferred examples of R a5 Suitable examples of the above include the same groups.

[0032] In formula (a2-2), R a26 Examples of the hydrocarbon group of R include groups in which the bond to the oxygen atom is not a tertiary carbon atom, that is, groups in which one or more atoms other than carbon atoms, such as hydrogen atoms, are bonded to the bonded carbon. a26 Examples of the hydrocarbon group in formula (a1-1) include a methylene group bonded to an oxygen atom and a group in which the methylene group bonded to the methylene group is not substituted with an oxygen atom, i.e., a group that does not contain an acetal structure. Therefore, the structural unit represented by formula (a2-2) does not contain a structural unit represented by formula (a1-1). R a26is preferably a hydrocarbon group having 1 to 10 carbon atoms, or a group in which a methylene group contained in the hydrocarbon group is replaced with an oxygen atom or a carbonyl group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group formed by combining these and having 6 to 10 carbon atoms, or a group in which a methylene group contained in these groups is replaced with an oxygen atom or a carbonyl group, and even more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, a phenyl group, or a group formed by combining these and having 6 to 10 carbon atoms, or a group in which the methylene group adjacent to the oxygen atom of these groups is replaced with a carbonyl group.

[0033] In formula (a2-1), na2 is preferably 1, 2 or 3, and more preferably 1 or 2. In the formula (a2-1) and the formula (a2-2), na21 is preferably 0, 1, 2 or 3, and more preferably 0 or 1. In formula (a2-2), na22 is preferably 1, 2 or 3, and more preferably 1 or 2.

[0034] In formula (a2-3) and formula (a2-4), R a27 Examples of the hydrocarbon group having 1 to 12 carbon atoms include chain hydrocarbon groups having 1 to 12 carbon atoms (such as alkyl groups, alkenyl groups, and alkynyl groups), alicyclic hydrocarbon groups having 3 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 12 carbon atoms, and groups having 4 to 12 carbon atoms formed by combining these groups. Examples of the alkyl group having 1 to 12 carbon atoms 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, 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. Examples of the alkenyl group having 2 to 12 carbon atoms include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. Examples of the alkynyl group having 2 to 12 carbon atoms include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. The chain hydrocarbon group having 1 to 12 carbon atoms preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alicyclic hydrocarbon group having 3 to 12 carbon atoms may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond): TIFF2025162967000014.tif22170 The alicyclic hydrocarbon group having 3 to 12 carbon atoms preferably has 3 to 10 carbon atoms, and more preferably has 3 to 8 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, etc. The aromatic hydrocarbon group having 6 to 12 carbon atoms preferably has 6 to 10 carbon atoms. Examples of groups having 4 to 12 carbon atoms formed by combining the above groups, such as groups formed by combining an alkyl group with an alicyclic hydrocarbon group (groups having 4 to 12 carbon atoms), include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, and a norbornylethyl group. Examples of the group (a group having 7 to 12 carbon atoms) in which an alkyl group is combined with an aromatic hydrocarbon group include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of groups combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (groups having 9 to 12 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group, and specific examples include a p-cyclohexylphenyl group and a phenylcyclohexyl group.

[0035] In formula (a2-3), R a27 is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and even more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 3 to 8 carbon atoms, provided that this excludes groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. In formula (a2-4), R a27 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms, except for groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom.

[0036] L a2 is preferably an alkanediyl group having 2 to 4 carbon atoms (for example, an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, or a butane-1,4-diyl group), more preferably an alkanediyl group having 2 to 3 carbon atoms (for example, an ethane-1,2-diyl group, a propane-1,3-diyl group, or a propane-1,2-diyl group), and even more preferably an ethane-1,2-diyl group.

[0037] na23 is preferably an integer of 1 to 20, more preferably an integer of 1 to 16, even more preferably an integer of 1 to 14, even more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6. The structural unit (a2-1) is preferably a structural unit represented by formula (a2-1-1), formula (a2-1-2), formula (a2-1-3) or formula (a2-1-4).

[0038] Furthermore, the monomer from which the structural unit (a2-1) is derived is described, for example, in JP-A-2010-204634.

[0039] Specific examples of the structural unit (a2-1) include the structural units represented by the following formulae: a24 Specific examples of the structural unit (a2-1) include structural units in which the hydrogen atom or methyl group corresponding to the following is replaced with a halogen atom, an alkyl group having 2 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. TIFF2025162967000015.tif40170

[0040] Specific examples of the structural unit (a2-2) include the structural units represented by the following formulae: a24 Specific examples of the structural unit (a2-1) include structural units in which the hydrogen atom corresponding to the following is replaced with a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. TIFF2025162967000016.tif96170

[0041] Examples of the monomer from which the structural unit (a2-3) is derived include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and hexyl (meth)acrylate; monocyclic (meth)acrylic acid esters such as (meth)acrylic acid cycloalkyl esters such as cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate; Polycyclic (meth)acrylic acid esters such as adamantyl (meth)acrylate and norbornyl (meth)acrylate; Examples thereof include aryl (meth)acrylate esters such as phenyl (meth)acrylate and benzyl (meth)acrylate.

[0042] Examples of monomers that derive the structural unit (a2-4) include (meth)acrylic acid esters such as (poly)ethylene glycol monomethyl ether (meth)acrylates ((poly)alkylene glycol monoalkyl ether (meth)acrylates), such as ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, pentaethylene glycol monomethyl ether (meth)acrylate, hexaethylene glycol monomethyl ether (meth)acrylate, heptaethylene glycol monomethyl ether (meth)acrylate, nonaethylene glycol monomethyl ether (meth)acrylate, and octaethylene glycol monomethyl ether (meth)acrylate.

[0043] Furthermore, examples of monomers that derive the structural unit (a2) include carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; and styrenes such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 4-isopropoxystyrene, and hydroxystyrene.

[0044] When the resin (A1) contains the structural unit (a2-1), the structural unit (a2-2), the structural unit (a2-3), and / or the structural unit (a2-4), the total content of these is preferably 1 to 90 mol%, more preferably 1 to 85 mol%, even more preferably 5 to 80 mol%, and particularly preferably 5 to 75 mol%, based on all structural units in the resin (A1).

[0045] When the resin (A1) contains the structural unit (a2), the content ratio of the structural unit (a1) to the structural unit (a2) (structural unit (a1):structural unit (a2)) is preferably 10:90 to 80:20, more preferably 15:85 to 60:40, and even more preferably 15:85 to 45:55, on a molar basis.

[0046] The resin (A1) is preferably a resin having the structural unit (a1-1) and the structural unit (a2-1) or the structural unit (a2-2).

[0047] Examples of the combination of structural units contained in the resin (A1) include those represented by formulae (A1-1) to (A1-22). TIFF2025162967000017.tif230170

[0048] TIFF2025162967000018.tif214170

[0049] TIFF2025162967000019.tif184170

[0050] In the above structural formula, R a4 and R a24 Specific examples of the structural units include structural units in which a hydrogen atom or methyl group corresponding to the above is replaced with a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms.

[0051] The resin (A1) can be produced by polymerizing, by a polymerization method (for example, a radical polymerization method), a monomer that derives the structural unit (a1) containing the group represented by the above-mentioned formula (1), a monomer that derives the structural unit (a2) as needed, and other monomers that derive structural units that are known in the art.

[0052] Furthermore, among the resins (A1), a resin containing the structural unit (a1-1) and formula (a2-1) can be obtained, for example, by reacting a resin containing the structural unit (a2-1) with an acetal-based protecting group under acidic conditions to protect some of the phenolic hydroxy groups contained in the structural unit (a2-1). Examples of the acetal-based protecting group include alkyl vinyl ether, 3,4-dihydro-2H-pyran, or a group represented by formula (1'). TIFF2025162967000020.tif23170 [In formula (1'), all symbols have the same meaning as in formula (1)] The content of each structural unit contained in the resin (A1) can be adjusted by the amount of monomer used in the polymerization and the amount of formula (1') used.

[0053] The weight-average molecular weight of the resin (A1) is preferably 3,000 or more, more preferably 4,000 or more, and preferably 600,000 or less, more preferably 500,000 or less. The weight-average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. Detailed analysis conditions for this analysis are described in the Examples of the present application.

[0054] <Resin (A2)> The resist composition of the present invention contains a resin (A2) that includes a structural unit represented by formula (a3) ​​as an alkali-soluble resin. An alkali-soluble resin is a resin that has an acidic group (sometimes called a hydrophilic group) and is soluble in an alkaline developer. Examples of the acidic group include a carboxy group, a sulfo group, and a hydroxy group (such as a phenolic hydroxyl group). Examples of alkali-soluble resins include resins that have a residual film ratio of 0% to 90% when developed with an alkaline developer under actual use conditions, preferably 0% to 85%, and more preferably 0% to 80%. The remaining film ratio can be measured, for example, as follows. After dissolving the resin in an organic solvent, the solution is filtered using a filter if necessary. Then, the solution is applied to a substrate using a spin coater or the like, and heated to remove the organic solvent. The resulting organic film on the substrate is measured using a film thickness meter, developed with a 2.38% by mass alkaline aqueous solution, and the film thickness after development is measured again using the film thickness meter. The remaining film ratio can be obtained by dividing the measured film thickness after development by the film thickness before development. The development conditions are those under actual use conditions. For example, the development temperature can be 5 to 60°C, and the development time can be 5 to 600 seconds. The alkaline developer can be any of various alkaline aqueous solutions used in this field, such as aqueous solutions of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline).

[0055] Resin (A2) is a resin containing a structural unit represented by formula (a3), and is at least a resin obtained by polymerizing acrylic acid and an alkyl methacrylate ester, or a resin obtained by polymerizing methacrylic acid and an alkyl acrylate ester. TIFF2025162967000021.tif37170[In formula (a3), R a31 and R a32 each independently represents an alkyl group having 1 to 12 carbon atoms, and a methylene group contained in the alkyl group may be replaced with an oxygen atom. o, p, q, and r each independently represent 0 or a positive number less than 1, and at least one of o and p represents a positive number less than 1; when o is 0, p and q each represent a positive number less than 1; when p is 0, o and r each represent a positive number less than 1; when q is 0, o and r each represent a positive number less than 1; and when r is 0, p and q each represent a positive number less than 1, provided that o+p+q+r=1 is satisfied.

[0056] R a31 and R a32Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl group. R a31 and R a32 are each preferably independently a methyl group or an ethyl group.

[0057] The total content of structural units derived from acrylic acid and methacrylic acid in resin (A2) is preferably 5 mol % or more and 30 mol % or less relative to all structural units constituting resin (A2), that is, it is preferable to satisfy 0.05≦o+p≦0.30.

[0058] The total content of structural units derived from alkyl acrylate and alkyl methacrylate in resin (A2) is preferably 70 mol % or more and 95 mol % or less based on all structural units constituting resin (A2), that is, it is preferable to satisfy 0.70≦q+r≦0.95.

[0059] Resin (A2) preferably contains both structural units derived from an alkyl acrylate ester and structural units derived from an alkyl methacrylate ester, that is, q and r each preferably represent a positive number of 1 or less.

[0060] In the resin (A2), the ratio of the total content of structural units derived from methacrylic acid and structural units derived from an alkyl methacrylate to the total content of structural units derived from an alkyl acrylate is preferably 30:70 to 70:30, that is, it is preferable that 0.4≦(p+r) / (o+q)≦2.3 is satisfied.

[0061] Resin (A2) may contain structural units other than the structural unit represented by formula (a3) ​​that are conventionally known in the art, so long as it is an alkali-soluble resin. However, the total content of structural units represented by formula (a3) ​​in resin (A2) is preferably 80 mol % or more, more preferably 90 mol % or more, of all structural units constituting resin (A2).

[0062] Resin (A2) can be produced by polymerizing a monomer that leads to a structural unit derived from acrylic acid, methacrylic acid, or an alkyl acrylate ester, and a monomer that leads to a structural unit derived from an alkyl methacrylate ester, using a polymerization method (e.g., radical polymerization). The content of each structural unit contained in resin (A2) can be adjusted by the amount of each monomer used in the polymerization.

[0063] Examples of monomers that lead to structural units derived from alkyl acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, tert-butyl acrylate, and hexyl acrylate. Examples of monomers that lead to structural units derived from alkyl methacrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate, tert-butyl methacrylate, and hexyl methacrylate.

[0064] The alkali-soluble resin (A2) may be used alone or in combination of two or more kinds.

[0065] The resist composition of the present invention may contain an alkali-soluble resin in addition to the resin (A2), if necessary.

[0066] Examples of alkali-soluble resins other than the resin (A2) include novolak resins (A3), resins containing structural units derived from hydroxystyrene, resins containing structural units derived from (meth)acrylic acid esters, and polyalkylene glycols.

[0067] <Novolac resin (A3)> The novolak resin (A3) is a resin obtained by condensing a phenol compound and an aldehyde in the presence of a catalyst, and is, for example, a resin containing a structural unit represented by the following formula (a4): The resist composition of the present invention can contain the novolak resin (A3) containing the structural unit represented by (a4) as the alkali-soluble resin. TIFF2025162967000022.tif35170[In formula (a4), R a45 represents a halogen atom, a carboxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. na4 represents an integer of 1 to 4, and when na4 is 2 or greater, the groups in the parentheses may be the same or different from each other. na41 represents a positive number between 0 and 3. When na41 is 2 or more, multiple R a45 may be the same or different, provided that 1≦na4+na41≦4 is satisfied.

[0068] In formula (a4), R a45 Examples of the halogen atom, the alkyl group having 1 to 6 carbon atoms, the haloalkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, the alkoxyalkyl group having 2 to 12 carbon atoms, the alkoxyalkoxy group having 2 to 12 carbon atoms, the alkylcarbonyl group having 2 to 4 carbon atoms, and the alkylcarbonyloxy group having 2 to 4 carbon atoms include R a5 Specific examples are the same as those of the groups listed in 1. In formula (a4), R a45is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, even more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group.

[0069] na4 is preferably 1 or 2, and more preferably 1. na41 is preferably 0, 1 or 2, and more preferably 0 or 1.

[0070] The weight-average molecular weight of the novolak resin (A3) is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and even more preferably 6,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, even more preferably 9,000 or less, and even more preferably 8,000 or less. By adjusting the weight-average molecular weight within this range, thinning and residues after development can be effectively prevented. The weight-average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. Detailed analysis conditions for this analysis are described in the Examples of this application.

[0071] The novolak resin (A3) may be used alone or in combination of two or more kinds.

[0072] The mass ratio of the content of resin (A1) in the resist composition to the total content of alkali-soluble resins (resin (A1):total alkali-soluble resins) is typically 20:80 to 80:20. In particular, the alkali-soluble resin is preferably composed of resin (A2) and resin (A3), and the mass ratio of the content of resin (A1) in the resist composition to the total content of resin (A2) and resin (A3) ((A1):(A2)+(A3)) is typically 20:80 to 80:20, preferably 30:70 to 70:30, and more preferably 40:60 to 60:40. Setting the mass ratio within this range is advantageous because it can further improve the precision of plated objects.

[0073] The mass ratio of the content of resin (A2) in the resist composition to the content of alkali-soluble resins other than resin (A2) (resin (A2):total of alkali-soluble resins other than resin (A2)) is generally preferably 10:90 to 90:10, and more preferably 20:80 to 70:30.

[0074] In the resist composition of the present invention, the content of the resin components, including resin (A1), resin (A2), and resin (A3), is preferably 80% by mass or more and 99.99% by mass or less, based on the total solid content of the resist composition. The content of resin (A1) is preferably 1% by mass or more and 98% by mass or less, more preferably 5% by mass or more and 90% by mass or less, and even more preferably 30% by mass or more and 80% by mass or less, based on the total solid content of the resist composition. The content of resin (A2) is preferably 1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 30% by mass or less, based on the total solid content of the resist composition. The content of resin (A3) is preferably 1% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, based on the total solid content of the resist composition. The solid content and the content of each component contained in the resist composition of the present invention can be measured using known analytical methods, such as liquid chromatography or gas chromatography.

[0075] <Acid generator (B)> The acid generator (B) is a compound that can be decomposed by light irradiation (exposure) to generate an acid. The generated acid can eliminate a leaving group contained in the acid labile group of the resin (A1), converting the acid labile group to a hydrophilic group (e.g., a carboxy group, a hydroxy group (phenolic hydroxyl group, etc.)). In other words, by exposing a resist composition containing the resin (A1) to light, the resist can be made soluble in a developer (an alkaline aqueous solution). The acid generator (B) may be either a nonionic or ionic type. Examples of nonionic acid generators include organic halides, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), and sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane). Representative examples of ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts). Examples of anions of onium salts include sulfonate anions, sulfonylimide anions, and sulfonylmethide anions.

[0076] The acid generator (B) may be a compound that generates an acid when exposed to radiation, as described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent No. 3,914,407, or European Patent No. 126,712. Compounds produced by known methods may also be used. The acid generator (B) may be used singly or in combination of two or more.

[0077] As the nonionic acid generator, a compound having a group represented by formula (B1) (* represents a bond) is preferred. TIFF2025162967000023.tif22170[In formula (B1), R b1 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom or a carbonyl group.] The nitrogen atom may have a double bond.

[0078] R b1 Examples of the hydrocarbon group having 1 to 18 carbon atoms in the hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom include linear or branched chain hydrocarbon groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, and groups having 4 to 18 carbon atoms which are combinations of these groups. As the linear or branched chain hydrocarbon group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms is preferred, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. Among these, linear groups are preferred. Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group. The aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably an aryl group having 6 to 18 carbon atoms, and examples thereof include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Among the groups having 4 to 18 carbon atoms formed by combining the above groups, examples of the group (group having 4 to 18 carbon atoms) formed by combining a chain hydrocarbon group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, an isobornyl group, a 2-alkyladamantan-2-yl group, and a 1-(adamantan-1-yl)alkane-1-yl group. Examples of groups in which a chain hydrocarbon group and an aromatic hydrocarbon group are combined (groups having 7 to 18 carbon atoms) include aralkyl groups and aromatic hydrocarbon groups having an alkyl group, and specific examples thereof include benzyl groups, phenethyl groups, phenylpropyl groups, trityl groups, naphthylmethyl groups, naphthylethyl groups, p-methylphenyl groups, p-tert-butylphenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, 2,6-diethylphenyl groups, and 2-methyl-6-ethylphenyl groups. Examples of groups in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined (groups having 9 to 18 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group, and specific examples include a p-cyclohexylphenyl group, a p-adamantylphenyl group, and a phenylcyclohexyl group. R b1 Of the hydrocarbon groups having 1 to 18 carbon atoms represented by the formula (I), an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is even more preferred.

[0079] R b1 Examples of the group in which a methylene group contained in an alicyclic hydrocarbon group having 3 to 18 carbon atoms is substituted with an oxygen atom or a carbonyl group include groups represented by formulae (Y1) to (Y12). Preferred are groups represented by formulae (Y7) to (Y9), and more preferred is a group represented by formula (Y9). TIFF2025162967000024.tif50170

[0080] The fluorine atom-containing hydrocarbon group having 1 to 18 carbon atoms is a group in which one or more hydrogen atoms contained in the above-mentioned hydrocarbon group having 1 to 18 carbon atoms have been substituted with a fluorine atom, and specific examples include fluoroalkyl groups such as a fluoromethyl group, a fluoroethyl group, a fluoropropyl group, a fluorobutyl group, a fluoropentyl group, a fluorohexyl group, a fluoroheptyl group, a fluorooctyl group, a fluorononyl group, and a fluorodecyl group; fluorocycloalkyl groups such as a fluorocyclopropyl group, a fluorocyclobutyl group, a fluorocyclopentyl group, a fluorocyclohexyl group, a fluorocycloheptyl group, a fluorocyclooctyl group, and a fluoroadamantyl group; and fluoroaryl groups such as a fluorophenyl group, a fluoronaphthyl group, and a fluoroanthryl group.

[0081] The hydrocarbon group having 1 to 18 carbon atoms and having a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, or an aromatic hydrocarbon group having 6 to 10 carbon atoms and having a fluorine atom, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0082] Examples of compounds having a group represented by formula (B1) include compounds represented by formulas (b1) to (b4). Preferred are compounds represented by formulas (b1), (b2) and (b4), and more preferred are compounds represented by formulas (b1) and (b4). TIFF2025162967000025.tif76170[In formula (b1) to formula (b4), R b1 has the same meaning as above. R b2 are each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Ring W b1 represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms or an aromatic heterocyclic ring having 6 to 14 carbon atoms. x represents an integer of 0 to 6 (preferably 0 to 5). When x is 2 or more, multiple R b2 may be the same or different. R b5 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 6 to 14 carbon atoms, which may have a substituent. R b6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0083] Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and a methyl group is preferred. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group, and a methoxy group is preferred.

[0084] Examples of the aromatic hydrocarbon ring having 6 to 14 carbon atoms include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the aromatic heterocyclic ring having 6 to 14 carbon atoms include rings having 6 to 14 atoms constituting the ring, and preferred examples include the following rings. TIFF2025162967000026.tif25170 Ring W b1 is preferably a naphthalene ring. Examples of aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. Examples of the aromatic heterocyclic group having 6 to 14 carbon atoms include groups obtained by removing a hydrogen atom from the above aromatic heterocyclic ring having 6 to 14 carbon atoms.

[0085] The compound represented by formula (b1) is preferably a compound represented by any one of formulas (b5) to (b8), and more preferably a compound represented by formula (b5). TIFF2025162967000027.tif100170[In formula (b5) to formula (b8), R b1 and R b2 , and x have the same meanings as above. y represents an integer of 0 to 4; z represents an integer of 0 to 2; X b1 and X b2 each independently represents -O-, -S- or -CO-.

[0086] Examples of the compound represented by formula (b1) include compounds represented by formulas (b1-1) to (b1-17). Preferred are compounds represented by formulas (b1-6) to (b1-10) and formulas (b1-13) to (b1-17). TIFF2025162967000028.tif199170

[0087] Examples of the compound represented by formula (b2) include compounds represented by the following formulas: TIFF2025162967000029.tif55170

[0088] Examples of the compound represented by formula (b3) include compounds represented by the following formulas: TIFF2025162967000030.tif22170

[0089] Examples of the compound represented by formula (b4) include the compounds represented by the following formula: TIFF2025162967000031.tif130170

[0090] The ionic acid generator is preferably a compound represented by formula (b9) or formula (b10). TIFF2025162967000032.tif43170 [In formula (b9) and formula (b10), R b2 has the same meaning as above. z1 represents an integer of 0 to 5. z2 represents an integer of 0 to 4. z3 represents an integer of 0 to 3. X b3 represents an oxygen atom or a sulfur atom. X b4 and X b5each independently represents an oxygen atom, a sulfur atom, or —CO—. R b8 and R b9 are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. X1 ― represents an organic anion.

[0091] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of aromatic hydrocarbon groups having 6 to 12 carbon atoms include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl. The aromatic hydrocarbon group may further have a substituent, and examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. R b8 and R b9 are each preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a phenyl group.

[0092] X1 - Examples of the organic anion represented by formula (b11) include a sulfonate anion, a bis(alkylsulfonyl)amide anion, and a tris(alkylsulfonyl)methide anion. Of these, a sulfonate anion is preferred, and a sulfonate anion represented by formula (b11) is more preferred. TIFF2025162967000033.tif23170[In formula (b11), R b10 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and a methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.] R b10 As for R in formula (B1), b1 The same groups as those shown below can be mentioned.

[0093] Examples of the compound represented by formula (b9) include the following compounds. TIFF2025162967000034.tif103170

[0094] Examples of the compound represented by formula (b10) include the following compounds. TIFF2025162967000035.tif62170

[0095] In the resist composition of the present invention, the content of the acid generator is preferably from 0.1 to 40 parts by mass, more preferably from 0.5 to 30 parts by mass, even more preferably from 0.7 to 20 parts by mass, and even more preferably from 0.9 to 5 parts by mass, relative to 100 parts by mass of the resin (A1). The resist composition of the present invention may contain one type of acid generator (B) alone or multiple types.

[0096] <Solvent (D)> The content of the solvent (D) in the resist composition is usually 45% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass or less, more preferably 90% by mass or less. The content of the solvent (D) can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0097] Examples of the solvent (D) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; and cyclic esters such as γ-butyrolactone. One type of solvent (D) may be contained alone, or two or more types may be contained.

[0098] <Quencher (C)> The resist composition of the present invention may contain a quencher (C). The quencher (C) is a compound that has the effect of capturing the acid generated from the acid generator upon exposure to light. Examples of the quencher (C) include basic nitrogen-containing organic compounds. The basic nitrogen-containing organic compound includes amines and ammonium salts. The amines include aliphatic amines (including primary amines, secondary amines, and tertiary amines), aromatic amines, etc.

[0099] Examples of the amine include compounds represented by formula (C1) or formula (C2). TIFF2025162967000036.tif20170[In formula (C1), R c1 , R c2 and R c3 represent each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the alkyl group having 1 to 6 carbon atoms and the alicyclic hydrocarbon group having 3 to 10 carbon atoms may have at least one group selected from the group consisting of a hydroxy group, an amino group, and an alkoxy group having 1 to 6 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms may have at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alicyclic hydrocarbon group having 3 to 10 carbon atoms.

[0100] Examples of the compound represented by formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, dibutylmethylamine, ... Examples of the amine include ethyldipentylamine, dihexylmethylamine, dicyclohexylmethylamine, diheptylmethylamine, methyldioctylamine, methyldinonylamine, didecylmethylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, etc. Diisopropylaniline is preferred, and 2,6-diisopropylaniline is particularly preferred.

[0101] TIFF2025162967000037.tif18170[In formula (C2), Ring W 1 represents a heterocycle containing a nitrogen atom as a ring-constituting atom, or a benzene ring having a substituted or unsubstituted amino group, and the heterocycle and the benzene ring may have at least one group selected from the group consisting of a hydroxy group and an alkyl group having 1 to 4 carbon atoms. A 1 represents a phenyl group or a naphthyl group. nc represents 2 or 3, and a plurality of A1 may be the same or different.]

[0102] The substituted or unsubstituted amino group is —N(R 4 )(R 5 ) and R 4 and R 5 are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group. Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may further have a substituent, and examples of the substituent include an aryloxy group having 6 to 10 carbon atoms.

[0103] A heterocycle containing a nitrogen atom as one of the atoms constituting the ring may be an aromatic ring or a non-aromatic ring, and may contain other heteroatoms (e.g., oxygen atoms, sulfur atoms) in addition to the nitrogen atom. The number of nitrogen atoms contained in the heterocycle is, for example, 1 to 3. Examples of the heterocycle include rings represented by any of formulas (Y13) to (Y28). When one of the hydrogen atoms contained in the ring is removed, A 1 It becomes a combination with. TIFF2025162967000038.tif61170

[0104] Ring W 1is preferably a heterocyclic ring containing a nitrogen atom as an atom constituting the ring, more preferably a 5- or 6-membered aromatic heterocyclic ring containing a nitrogen atom as an atom constituting the ring, and even more preferably a ring represented by any one of formulae (Y20) to (Y25).

[0105] Examples of the compound represented by formula (C2) include compounds represented by any of formulas (C2-1) to (C2-11). Preferred are compounds represented by any of formulas (C2-2) to (C2-8). TIFF2025162967000039.tif91170

[0106] The content of the quencher (C) in the solid content of the resist composition is preferably from 0.0001 to 5 mass%, more preferably from 0.0001 to 4 mass%, even more preferably from 0.001 to 3 mass%, even more preferably from 0.01 to 1.0 mass%, and even more preferably from 0.05 to 0.7 mass%.

[0107] <Adhesion improver (E)> The adhesion improver (E) is not particularly limited as long as it can prevent corrosion and / or improve adhesion to metals, etc. used in substrates or wiring, etc. By preventing metal corrosion, it exhibits a rust-preventing effect. In addition to these effects, it can also improve adhesion between the substrate or metal, etc. and the resist composition. Examples of the adhesion improver (E) include sulfur-containing compounds, aromatic hydroxy compounds, benzotriazole-based compounds, triazine-based compounds, and silicon-containing compounds, which can be used alone or in combination of two or more.

[0108] The sulfur-containing compound may be, for example, a compound having a sulfide bond and / or a mercapto group. The sulfur-containing compound may be a chain compound or a compound having a cyclic structure. Examples of chain compounds include dithiodiglycerol [S(CH2CH(OH)CH2(OH))2], bis(2,3-dihydroxypropylthio)ethylene [CH2CH2(SCH2CH(OH)CH2(OH))2], sodium 3-(2,3-dihydroxypropylthio)-2-methyl-propylsulfonate [CH2(OH)CH(OH)CH2SCH2CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)CH2(OH)], sodium 3-mercapto-1-propanesulfonate [HSCH2CH2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], thioglycolic acid [HSCH2CO2H], and 3-mercapto-1-propanol [HSCH2CH2CH2].

[0109] The sulfur-containing compound is preferably a compound having a sulfide bond and a mercapto group, and more preferably a heterocyclic compound having a sulfide bond and a mercapto group. The heterocyclic compound is more preferably a heterocyclic compound having a sulfide bond in the ring structure. In the sulfur-containing compound, the number of sulfide bonds and mercapto groups is not particularly limited, and each may be 1 or more. The heterocyclic ring in the heterocyclic compound may be either a monocyclic ring or a polycyclic ring, and may be either a saturated or unsaturated ring. The heterocyclic ring preferably further contains a heteroatom other than a sulfur atom. Examples of the heteroatom include an oxygen atom and a nitrogen atom, and preferably a nitrogen atom. The heterocycle is preferably a heterocycle having 2 to 12 carbon atoms, more preferably a heterocycle having 2 to 6 carbon atoms. The heterocycle is preferably a monocycle. The heterocycle is preferably an unsaturated ring. The heterocycle is preferably an unsaturated monocycle.

[0110] Examples of the heterocycle include the following heterocycles: TIFF2025162967000040.tif35170

[0111] The sulfur-containing compound may be a polymer. This polymer preferably contains a structure having a sulfide bond and a mercapto group in a side chain. The structure having a sulfide bond and a mercapto group (hereinafter sometimes referred to as unit (1)) is preferably bonded to the main chain via a linking group such as an amide bond, an ether bond, a thioether bond, or an ester bond.

[0112] The polymer may be a homopolymer or a copolymer. When the polymer is a copolymer, it may contain the above-mentioned structural unit (a1) having an acid labile group, structural unit (a2) not having an acid labile group, and the like. The weight average molecular weight of the homopolymer and copolymer is usually 3000 or more, preferably 5000 or more, and usually 100,000 or less, preferably 50,000 or less. The weight average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. When the sulfur-containing compound is a polymer, the content of the structural unit having a sulfide bond and a mercapto group is usually 0.1 to 50 mol %, preferably 0.5 to 30 mol %, and more preferably 1 to 20 mol %, based on the total structural units of the polymer of the sulfur-containing compound.

[0113] The sulfur-containing compound is preferably, for example, a compound represented by formula (IA) or a polymer having a structural unit represented by formula (IB). TIFF2025162967000041.tif25170[In formula (IA), R i11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, -SR 11 or a group represented by -NR 12 R 13 represents a group represented by the formula: R 11 , R 12 and R 13are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an acyl group having 2 to 12 carbon atoms, and these chain hydrocarbon groups, aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and acyl groups may have a hydroxy group. R i12 and R i13 are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. A and B each independently represent a nitrogen atom or a carbon atom. n1 and m1 each independently represent 0 or 1, provided that when A is a nitrogen atom, n1 represents 0, when A is a carbon atom, n1 represents 1, when B is a nitrogen atom, m1 represents 0, and when B is a carbon atom, m1 represents 1.

[0114] Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms include aryl groups having 6 to 14 carbon atoms, such as a phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. The aromatic hydrocarbon group may further have a substituent, and examples of aromatic hydrocarbon groups having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group.

[0115] R 11 is preferably a chain hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 2 to 12 carbon atoms, and R 12 and R 13 are preferably each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an acyl group having 2 to 12 carbon atoms. Examples of the acyl group having 2 to 12 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, a hexylcarbonyl group, a heptylcarbonyl group, an octylcarbonyl group, a decylcarbonyl group, a dodecylcarbonyl group, and a benzoyl group.

[0116] R i11 is more preferably a hydrogen atom or a mercapto group. R i12 and R i13 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom. At least one of A and B is preferably a nitrogen atom, and more preferably both are nitrogen atoms.

[0117] TIFF2025162967000042.tif49170[In formula (IB), R i21 and R i31 are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. A 1 and B 1 represent, independently of each other, a nitrogen atom or a carbon atom. n2 and m2 each independently represent 0 or 1. 1 When is a nitrogen atom, n2 represents 0, and A 1 is a carbon atom, n2 represents 1, and B 1 is a nitrogen atom, m2 represents 0, and B 1 is a carbon atom, m2 represents 1. Ri4 represents a hydrogen atom or a methyl group. X i1 represents a sulfur atom and an NH group. L i1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. A methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.

[0118] R i21 and R i31 Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and preferably alkyl groups having 1 to 4 carbon atoms. R i21 and R i31 Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include aryl groups having 6 to 14 carbon atoms such as a phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group, and preferably an aryl group having 6 to 10 carbon atoms. The aromatic hydrocarbon group may further have a substituent, and examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. R i21 and R i31 Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups having 3 to 18 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group, and preferably an alicyclic hydrocarbon group having 5 to 10 carbon atoms. R i21 and R i31are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0119] L i1 Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1, alkanediyl groups such as a 1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group; Phenylene group, tolylene group, naphthylene Examples of suitable arylene groups include arylene groups such as aryl groups. L i1 is preferably an alkanediyl group having 2 to 14 carbon atoms containing an ester bond or a group formed by combining an arylene group having 6 to 10 carbon atoms with an alkanediyl group having 1 to 11 carbon atoms.

[0120] The structural unit represented by formula (IB) is preferably a structural unit represented by formula (IB-1) or a structural unit represented by formula (IB-2). TIFF2025162967000043.tif79170[In formula (IB-1), R i22 and R i32 are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. A 2 and B 3 represent each independently a nitrogen atom or a carbon atom. n3 and m3 each independently represent 0 or 1. 2 is a nitrogen atom, n3 represents 0, and A 2 is a carbon atom, n3 represents 1, and B 2 is a nitrogen atom, m3 represents 0, and B 2 is a carbon atom, m3 represents 1. X i11 represents a sulfur atom and an NH group. L i2 represents a divalent hydrocarbon group having 1 to 18 carbon atoms. A methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. R i5 represents a hydrogen atom or a methyl group. In formula (IB-2), R i23 and R i33 are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. A 3 and B 3 represent, independently of each other, a nitrogen atom or a carbon atom. n4 and m4 each independently represent 0 or 1. 3 is a nitrogen atom, n4 represents 0, and A 3 is a carbon atom, n4 represents 1, and B 3 is a nitrogen atom, m4 represents 0, and B 3 is a carbon atom, m4 represents 1. X i12 represents a sulfur atom and an NH group. L i3represents a divalent hydrocarbon group having 1 to 14 carbon atoms. A methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. R i7 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R i6 represents a hydrogen atom or a methyl group. mx represents an integer from 0 to 4.

[0121] R i22 , R i32 , R i23 and R i33 As the chain hydrocarbon group having 1 to 10 carbon atoms represented by R i21 and R i31 Examples thereof include the same chain hydrocarbon groups having 1 to 10 carbon atoms as those represented by the following formula: R i22 , R i32 , R i23 and R i33 As the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R i21 and R i31 Examples of the aromatic hydrocarbon group include the same aromatic hydrocarbon groups having 6 to 14 carbon atoms as those represented by the following formula: R i22 , R i32 , R i23 and R i33 As the alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by R i21 and R i31 Examples thereof include the same alicyclic hydrocarbon groups having 3 to 18 carbon atoms as those represented by the following formula:

[0122] L i2Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1, alkanediyl groups such as a 1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group; Examples of the arylene group include a phenylene group, a tolylene group, and a naphthylene group. L i2 is preferably an alkanediyl group having 1 to 14 carbon atoms, and more preferably an alkanediyl group having 1 to 11 carbon atoms.

[0123] L i3Examples of the divalent hydrocarbon group having 1 to 14 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, and an undecane-1,11-diyl group. alkanediyl groups such as a dodecane-1,12-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. L i3 is preferably an alkanediyl group having 1 to 14 carbon atoms, and more preferably an alkanediyl group having 1 to 11 carbon atoms. Based on the position of the phenyl group that is bonded to the main chain, L i3 is preferably bonded at the p-position.

[0124] R i7 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R i7 Examples of the alkoxy group having 1 to 6 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0125] Examples of sulfur-containing compounds include compounds represented by any of formulas (I-1) to (I-26). Of these, preferred are compounds represented by formulas (I-1) to (I-13), and more preferred are compounds represented by formulas (I-1), (I-4), and (I-11). TIFF2025162967000044.tif68170

[0126] TIFF2025162967000045.tif88170

[0127] Examples of the sulfur-containing compound include a homopolymer consisting of any one of the structural units represented by formulae (I-27) to (I-38) and a copolymer containing one or more of these structural units. Copolymers containing one or more of the structural units represented by formulae (I-27) to (I-36) are preferred, and copolymers containing a structural unit represented by formula (I-33) are more preferred. TIFF2025162967000046.tif146170

[0128] Examples of such copolymers include copolymers comprising structural units represented by formulas (I-39) to (I-48). Among these, polymers having structural units represented by formulas (I-39) to (I-44) are preferred.

[0129] TIFF2025162967000047.tif228170

[0130] TIFF2025162967000048.tif152170

[0131] The sulfur-containing compound may be synthesized by a known method (for example, JP 2010-79081 A) or may be a commercially available product. The polymer containing a sulfur-containing compound may be a commercially available product (for example, bismuthiol (manufactured by Tokyo Chemical Industry Co., Ltd.) or may be synthesized by a known method (for example, JP 2001-75277 A).

[0132] Examples of aromatic hydroxy compounds include phenol, cresol, xylenol, pyrocatechol (=1,2-dihydroxybenzene), tert-butylcatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and gallic acid.

[0133] An example of the benzotriazole compound is a compound represented by formula (IX). TIFF2025162967000049.tif27170[In formula (IX), R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a carboxy group, an amino group, a hydroxy group, a cyano group, a formyl group, a sulfonylalkyl group or a sulfo group. Q is a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aryl group, or **-R 3X -N(R 4X )(R 5X ) and the hydrocarbon group may have an amide bond or an ester bond in the structure. R 3X represents an alkanediyl group having 1 to 6 carbon atoms. ** represents a bond to a nitrogen atom contained in the ring. R 4X and R 5X each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms.]

[0134] R 1 , R 2 The hydrocarbon group having 1 to 10 carbon atoms for Q may be either a chain hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and may have saturated and / or unsaturated bonds. The chain hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group, and 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, a tert-butyl group, an n-pentyl group, a methylpentyl group, an n-hexyl group, and an n-heptyl group. The aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably an aryl group, and examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may further have a substituent, and examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the substituent that the hydrocarbon group having 1 to 10 carbon atoms may have include a hydroxyalkyl group and an alkoxyalkyl group. R 3X The alkanediyl group having 1 to 6 carbon atoms may be either linear or branched, and examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, and a propane-1,2-diyl group. R 4X and R 5XExamples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R 4X and R 5X Examples of the hydroxyalkyl group having 1 to 6 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a dihydroxyethyl group. R 4X and R 5X Examples of the alkoxyalkyl group having 2 to 6 carbon atoms include a methoxymethyl group, a methoxyethyl group, and a dimethoxyethyl group.

[0135] When the resist composition of the present invention is applied to a substrate on which Cu is formed, Q in formula (IX) is **-R 3X -N(R 4X )(R 5X ) is preferred. 4X and R 5X When at least one of the groups is an alkyl group having 1 to 6 carbon atoms, the benzotriazole compound has poor water solubility, but is preferably used when there is another component that can dissolve this compound.

[0136] Furthermore, when the resist composition of the present invention is applied to a substrate having an inorganic material layer (e.g., a polysilicon film, an amorphous silicon film, etc.), Q in formula (IX) preferably represents a water-soluble group. Specifically, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a hydroxy group, etc. are preferred. This allows the substrate to exhibit corrosion resistance more effectively.

[0137] Examples of benzotriazole compounds include benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethylbenzotriazole, 1-methylbenzotriazole, 5-benzotriazolecarboxylic acid, 1-methoxybenzotriazole, 1-(2,2-dihydroxyethyl)benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethane, and 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bispropane.

[0138] The triazine-based compound includes a compound represented by formula (II). TIFF2025162967000050.tif24170[In formula (II), R 6 , R 7 and R 8 represent each independently a halogen atom, a hydrogen atom, a hydroxy group, an amino group, a mercapto group, an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, or an amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include the same as those mentioned above. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

[0139] An example of the triazine compound is 1,3,5-triazine-2,4,6-trithiol.

[0140] An example of the silicon-containing compound is a compound represented by formula (IIA). TIFF2025162967000051.tif28170[In formula (IIA), R j1 represents a chain hydrocarbon group having 1 to 5 carbon atoms or a mercaptoalkyl group having 1 to 5 carbon atoms. R j2 ~R j4 each independently represents a chain hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a mercapto group, or a mercaptoalkyl group having 1 to 5 carbon atoms; R j2 ~R j4 At least one of them is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms. t i represents an integer from 1 to 10.

[0141] Examples of the chain hydrocarbon group having 1 to 5 carbon atoms include alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group and an ethoxy group. Examples of the mercaptoalkyl group having 1 to 5 carbon atoms include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group.

[0142] R j1 is preferably a methyl group, an ethyl group, or a mercaptoalkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or a mercaptopropyl group (particularly, a 3-mercaptopropyl group). R j2 ~R j4 are preferably each independently a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more preferably a methyl group or a methoxy group, provided that at least one of these is preferably a mercapto group or a mercaptoalkyl group having 1 to 3 carbon atoms, and more preferably a mercapto group or a mercaptopropyl group. R j2 and Rj3 may be the same or different from each other, but are preferably the same from the viewpoint of productivity.

[0143] Examples of the compound of formula (IIA) include compounds represented by the following formulae (II-1) to (II-7). TIFF2025162967000052.tif174170Of these, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like are preferred.

[0144] The content of the adhesion improver (E) relative to the total amount of solids in the resist composition is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, even more preferably 0.005% by mass or more, and particularly preferably 0.008% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 4% by mass or less, still more preferably 3% by mass or less, especially preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. By setting the content within this range, a resist composition that can form a high-precision resist pattern can be obtained, and adhesion between the resist pattern and the substrate can be ensured.

[0145] <Other ingredients> The resist composition of the present invention may optionally contain components other than those described above (hereinafter, these may be referred to as "other components (F)"). There are no particular limitations on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes, can be used. When other component (F) is used, the content thereof is appropriately selected depending on the type of other component (F).

[0146] <Preparation of Resist Composition> The resist composition of the present invention can be prepared by mixing resin (A1), resin (A2), acid generator (B), and, if necessary, resin (A3), resins other than resins (A1) to (A3), quencher (C), solvent (D), adhesion improver (E), and other components (F). The order of mixing is arbitrary and is not particularly limited. The temperature during mixing can be selected from 10 to 40°C depending on the type of resin, the solubility of the resin in solvent (D), and other factors. The mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing method is also not particularly limited, and stirring and mixing can be used. After mixing the components, it is preferable to filter the mixture using a filter with a pore size of about 0.003 to 50 μm.

[0147] <Dry film resist> One embodiment of the dry film resist of the present invention is a resist dry film including a support film and a resist composition layer laminated on the support and containing the resist composition of the present invention. One embodiment of the dry film of the present invention may optionally include a protective film laminated on the resist composition layer laminated on the support.

[0148] The support film and the protective film are not particularly limited as long as they can be peeled from the composition layer without damaging the morphology of the resist composition layer, and a single film or a multilayer film formed by laminating films made of multiple polymers can be used. For example, plastic films such as nylon film, polyethylene (PE) film, polyethylene terephthalate (PET) film, polyethylene naphthalate film, polyphenylene sulfide (PPS) film, polypropylene (PP) film, polystyrene film, polymethylpentene (TPX) film, polycarbonate, fluorine-containing film, special polyvinyl alcohol (PVA) film, and polyester film subjected to a release treatment can be used. The thickness of each of the support film and the protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoints of production stability and preventing the film from becoming wound around the core.

[0149] The thickness of the resist composition layer is preferably from 1 μm to 500 μm, and more preferably from 5 μm to 450 μm.

[0150] The method for producing a dry film resist of the present invention will be described. The method for producing a dry film of the present invention includes the steps of (1a) applying the resist composition of the present invention to a support film to form a photoresist composition layer, and (2a) drying the resist composition layer. If necessary, the method may include the step of laminating a protective film on the resist composition layer after drying the resist composition layer.

[0151] The resist composition layer of the present invention can be laminated on a support film by any method known in the art. For example, the resist composition layer can be uniformly coated using a commonly used device such as a forward roll coater, a reverse roll coater, a comma coater, a die coater, a lip coater, a gravure coater, a dip coater, an air knife coater, a capillary coater, a raising and rising (R&R) coater, a blade coater, a bar coater, an applicator, or an extrusion molding machine.

[0152] The resist composition layer on the support film can be dried by, for example, air drying, heat drying using an oven or a hot plate, or vacuum drying. The heating temperature is preferably 40°C to 150°C, more preferably 50°C to 130°C, and the heating time is preferably 1 to 40 minutes, more preferably 2 to 30 minutes. The pressure during vacuum drying is preferably 1 to 1.0 × 10 5 It is preferable that the pressure is about Pa.

[0153] After drying, a protective film can be laminated on the resist composition layer by any method known in the art, for example, by pressing and laminating using a roll laminator.

[0154] In the present invention, by forming a resist material solution on a support film under specific forming conditions and using a forming machine on a production line, it is possible to continuously form a roll film and produce a roll film that can be handled in a desired shape, and the same is true when a protective film is formed on a resist dry film layer.

[0155] <Method of manufacturing a resist pattern> One aspect of the method for producing (forming) a resist pattern of the present invention is a method for producing a resist pattern using a resist composition of the present invention, and another aspect of the method for producing a resist pattern of the present invention is a method for producing a resist pattern using a dry film resist of the present invention.

[0156] <Method of manufacturing a resist pattern using a resist composition> A method for producing a resist pattern using the resist composition of the present invention will now be described. A method for producing a resist pattern using the resist composition of the present invention includes the steps of: (1b) applying the resist composition of the present invention onto a substrate and drying the resist composition to form a resist composition layer; (2b) exposing the resist composition layer to ultraviolet light having a wavelength of 500 nm or less; and (3b) developing the exposed resist composition without heating.

[0157] The resist composition can be applied to the substrate by any method known in the art, and can be applied using a commonly used device such as a spin coater. The substrate onto which the resist composition is applied may be an inorganic substrate such as a silicon wafer, on which a semiconductor element (e.g., a transistor, a diode, etc.) may be formed in advance. When the resist composition of the present invention is used for bump formation, the substrate is preferably one on which a conductive material is further laminated. The conductive material may be at least one metal selected from the group consisting of gold, copper, nickel, tin, palladium, and silver, or an alloy containing at least one metal selected from the group, and preferably copper or an alloy containing copper. Before applying the resist composition, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate. The applied resist composition is dried to remove the solvent and form a composition layer. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a vacuum device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 30 to 600 seconds. The pressure during vacuum drying is preferably 1 to 1.0 × 10 5 It is preferable that the pressure is about Pa. After drying the resist composition, the film thickness of the resulting composition is preferably 1 to 500 μm, more preferably 1 to 300 μm, and even more preferably 1.5 μm to 130 μm. After drying the resist composition, in order to achieve a desired resist composition layer thickness, a process of applying the resist composition of the present invention to the dried resist composition layer or laminating a resist composition layer of the dry film resist of the present invention on the dried resist composition layer before exposure, followed by drying may be repeated. If necessary, a composition other than the resist composition of the present invention or a resist composition layer other than the dry film resist of the present invention may also be laminated.

[0158] As the exposure light source, various types can be used, including light sources that emit light with a wavelength of 345 to 436 nm (g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), i-line (wavelength: 365 nm)), those that emit ultraviolet laser light such as KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), and F2 excimer laser (wavelength: 157 nm), those that emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range by wavelength conversion of laser light from a solid-state laser light source (YAG or semiconductor laser, etc.), and those that irradiate electron beams or extreme ultraviolet light (EUV). In this specification, irradiation with these types of radiation may be collectively referred to as "exposure." During exposure, exposure is usually performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure may be performed by direct writing without using a mask.

[0159] The exposed resist composition layer is developed without being subjected to a heat treatment. Specifically, the exposed resist composition layer is not maintained at a temperature of 30° C. or higher, and is preferably maintained at an ambient temperature typically used in resist pattern production (e.g., the ambient temperature in a clean room, specifically 23±5° C.).

[0160] Development is usually carried out using a developing device and a developer. Examples of development methods include a dipping method, a puddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably, for example, 5 to 60°C, and the development time is preferably, for example, 5 to 600 seconds. By selecting the type of developer as follows, a positive resist pattern or a negative resist pattern can be produced.

[0161] When a positive resist pattern is produced from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may also contain a surfactant. After development, the resist pattern is preferably washed with ultrapure water, and then water remaining on the substrate and pattern is removed. When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used as the developer. Examples of organic solvents contained in organic developers include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole. The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. Among these, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant and a small amount of water. During development, development may be stopped by replacing the organic developer with a different type of solvent. The developed resist pattern is preferably washed with a rinse solution. There are no particular limitations on the rinse solution as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

[0162] By exposing a resist obtained using the resist composition of the present invention, a resist pattern with a highly accurate shape can be formed.

[0163] <Method of manufacturing a resist pattern using a dry film resist> A method for producing a resist pattern using the dry film resist of the present invention will now be described. A method for producing a resist pattern using the resist composition of the present invention includes: (1c) a step of laminating the dry film resist of the present invention onto a substrate; (2c) an exposure step of peeling at least a portion of the support film from the resist composition layer and exposing the resist composition layer to ultraviolet light having a wavelength of 500 nm or less; and (3c) a step of developing the exposed resist composition layer without heating.

[0164] The method for laminating the dry film on the substrate can be a conventionally known method, for example, a vacuum laminator or a roll coater can be used. Specifically, when using a vacuum laminator, after peeling off the protective film of the dry film resist of the present invention, the vacuum chamber of the vacuum laminator is set to a desired vacuum level, and the resist composition layer on the support film can be adhered to the substrate. When using a roll coater, the protective film can be peeled off from the dry film resist of the present invention in a winding manner while being laminated on the substrate. The substrate onto which the dry film resist is laminated can be the same as the substrate onto which the resist composition is applied as described above.

[0165] After laminating the dry film resist on the substrate, the protective film can be peeled off from the resist composition layer by a method known in the art. Only the necessary portions of the support film may be peeled off, or the entire support film may be peeled off. After peeling off the support film, in order to obtain a resist composition layer with the desired thickness, the step of applying the resist composition of the present invention or laminating an additional resist composition layer of the dry film resist of the present invention on top of the resist composition layer before exposure may be repeated.

[0166] After peeling off the support film, the step of exposing the resist composition layer to ultraviolet light with a wavelength of 500 nm or less and the step of developing the exposed resist composition without heating can be performed in the same manner as in the method for producing a resist pattern using the resist composition of the present invention.

[0167] <Method of manufacturing plated objects> By using the resist composition of the present invention or the dry film resist of the present invention to form a resist pattern, the formed resist pattern is used as a mold to deposit an electrode material by plating, and after deposition, the resist pattern is peeled off, thereby producing plated objects such as bumps, metal pillars, and other connection terminals, or rewiring. In particular, resist patterns obtained using the resist composition of the present invention or the dry film resist of the present invention have excellent resolution and plating resistance, even when they are thick films (e.g., 100 μm or more). Therefore, plated objects such as bumps, metal pillars, and other connection terminals or rewiring with precise height can be produced.

[0168] The method for producing a plated object of the present invention is described below. The method of the present invention is a method for forming a resist pattern using the resist composition of the present invention or the dry film resist of the present invention, and includes the steps of (1d) applying a resist composition or laminating a resist composition layer so that the resist composition layer contacts a conductive layer of a substrate, (2d) exposing and developing the resist composition layer as described above to form a resist pattern on a substrate so that the conductive layer on the substrate is exposed, (3d) forming a plated object using the resist pattern as a mold, and (4d) peeling off the resist pattern after forming the plated object. A resist pattern formed on a substrate having a conductive layer or the like is used as a template to deposit a conductive material using a plating solution by a known method, thereby forming a plated object. Examples of the plating solution include a copper plating solution, a gold plating solution, a nickel plating solution, a solder plating solution, and a silver-tin plating solution. After the plating object is formed, the resist pattern is removed using a stripping solution by a known method. Examples of the stripping solution include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Examples of suitable esters include propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These may be used alone or in combination of two or more. By the above method, plated objects such as bumps and rewirings can be formed. When forming a plated object, the surface of the conductive layer may be subjected to an ashing process or the like to improve adhesion between the conductive layer and the plated object. Examples of ashing methods include a method using oxygen plasma.

[0169] A plated product obtained using the resist pattern of the present invention swells little in a plating bath, and therefore can be formed with high precision. [Example]

[0170] The present invention will be explained in more detail with reference to examples. In the examples, "%" and "parts" representing the content or amount used are by mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions. Device: HLC-8320GPC model (Tosoh Corporation) Column: TSKgel Multipore HXL-M x 3 + guard column (Tosoh Corporation) Eluent: tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation)

[0171] Synthesis Example 1 [Synthesis of Resin A1-1] 20 parts of poly-p-hydroxystyrene (S-4P; Maruzen Petrochemical Co., Ltd.) was dissolved in 240 parts of methyl isobutyl ketone at room temperature and concentrated using an evaporator. The concentrated resin solution and 0.003 parts of p-toluenesulfonic acid dihydrate were added to a four-neck flask equipped with a reflux condenser, a stirrer, and a thermometer. While maintaining the resulting mixture at 20-25°C, 5.05 parts of ethyl vinyl ether was added dropwise to the resulting mixture over 10 minutes. The mixture was stirred at 20-25°C for 2 hours. The resulting reaction mixture was diluted with 200 parts of methyl isobutyl ketone, washed with ion-exchanged water, and separated five times. The resulting organic layer was concentrated to 45 parts using an evaporator, and then 150 parts of propylene glycol monomethyl ether acetate was added and concentrated again to obtain 78 parts of a propylene glycol monomethyl ether acetate solution of Resin A1-1 (solids content: 29%). Resin A1-1 is a resin having the following structural unit: Resin A1-1 has a weight average molecular weight of 1.16×10 4 The ratio of hydroxy groups in poly-p-hydroxystyrene that were substituted with ethoxyethoxy groups was 40.9%. TIFF2025162967000053.tif50170

[0172] Synthesis Example 2 [Synthesis of Resin AX1-1] A four-neck flask equipped with a stirrer, reflux condenser, and thermometer was charged with 30 parts of methyl isobutyl ketone. After purging with nitrogen, the mixture was heated to 82°C. A solution of 6 parts of t-butoxystyrene, 12.9 parts of 4-acetoxystyrene (molar ratio of t-butoxystyrene:4-acetoxystyrene=30:70), and 0.75 parts of azobisisobutyronitrile dissolved in methyl isobutyl ketone was added dropwise over 1 hour. Stirring was then continued for 6 hours while maintaining the temperature at 82°C. The reaction solution was cooled, and the resulting reaction solution was poured into a mixed solution of 184 parts of methanol and 61 parts of ion-exchanged water to reprecipitate the resin. After filtration, the resulting resin was dissolved in 40 parts of methyl isobutyl ketone, and 9.7 parts of ethanolamine, 1.94 parts of 4-dimethylaminopyridine, and 20 parts of methanol were added. The mixture was heated to reflux at 60°C for 15 hours. After cooling, the mixture was concentrated, and 40 parts of methyl isobutyl ketone was added to dissolve the resin. 10 parts of acetic acid and 30 parts of ion-exchanged water were added, and the mixture was stirred and then filtered. The resulting solution was poured into a large amount of a mixed solution of ion-exchanged water and methanol to precipitate a resin, which was then filtered and recovered. 140 parts of propylene glycol monomethyl ether acetate was added to the resulting resin, and the resin was dissolved and concentrated. 70 parts of propylene glycol monomethyl ether acetate was added, and the mixture was concentrated again to obtain 45 parts of a propylene glycol monomethyl ether acetate solution of Resin AX1-1 (solid content 30%, yield 85%). The weight-average molecular weight of Resin AX1-1 was 1.33 x 10 4 It was. TIFF2025162967000054.tif49170

[0173] Synthesis Example 3 [Synthesis of Resin A2-1] A four-neck flask equipped with a reflux condenser, a stirrer, and a thermometer was charged with 70 parts of ethyl acetate and heated to 55°C. To this was added dropwise a mixture of 15 parts of methacrylic acid, 58 parts of ethyl acrylate, 41 parts of methyl methacrylate (molar ratio of methacrylic acid:ethyl acrylate:methyl methacrylate=15:50:35), 3.46 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 100 parts of ethyl acetate over 2 hours. The mixture was stirred for 3 hours while maintaining the temperature at 50-55°C. The resulting reaction mixture was cooled to below 40°C, diluted with 125 parts of ethyl acetate, and poured into a large amount of a mixture of ion-exchanged water and methanol to precipitate a resin, which was then filtered and recovered. To the resulting resin, 650 parts of propylene glycol monomethyl ether acetate was added, dissolved, and concentrated. Then, 650 parts of propylene glycol monomethyl ether acetate was added, and the mixture was concentrated again to obtain 190 parts of a propylene glycol monomethyl ether acetate solution of Resin A2-1 (solid content 45%, yield 75%). The weight-average molecular weight of Resin A2-1 was 3.79 × 10 4 It was. TIFF2025162967000055.tif33170

[0174] Synthesis Example 4 [Synthesis of Resin A2-2] A four-neck flask equipped with a reflux condenser, a stirrer, and a thermometer was charged with 70 parts of ethyl acetate and heated to 55°C. To this was added dropwise a mixture of 10 parts of methacrylic acid, 58 parts of ethyl acrylate, 47 parts of methyl methacrylate (molar ratio of methacrylic acid:ethyl acrylate:methyl methacrylate=10:50:40), 3.46 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 100 parts of ethyl acetate over 2 hours. The mixture was stirred for 3 hours while maintaining the temperature at 50-55°C. The resulting reaction mixture was cooled to below 40°C, diluted with 125 parts of ethyl acetate, and poured into a large amount of a mixture of ion-exchanged water and methanol to precipitate a resin, which was then filtered and recovered. To the resulting resin, 650 parts of propylene glycol monomethyl ether acetate was added, dissolved, and concentrated. Then, 650 parts of propylene glycol monomethyl ether acetate was added, and the mixture was concentrated again to obtain 186 parts of a propylene glycol monomethyl ether acetate solution of Resin A2-2 (solid content 45%, yield 73%). The weight-average molecular weight of Resin A2-2 was 3.85 × 10 4 It was. TIFF2025162967000056.tif32170

[0175] Synthesis Example 5 [Synthesis of Resin A2-3] A four-neck flask equipped with a reflux condenser, a stirrer, and a thermometer was charged with 70 parts of ethyl acetate and heated to 55°C. To this was added dropwise a mixture of 8 parts of methacrylic acid, 58 parts of ethyl acrylate, 49 parts of methyl methacrylate (molar ratio of methacrylic acid:ethyl acrylate:methyl methacrylate=8:50:42), 3.46 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 100 parts of ethyl acetate over 2 hours. The mixture was stirred for 3 hours while maintaining the temperature at 50-55°C. The resulting reaction mixture was cooled to below 40°C, diluted with 125 parts of ethyl acetate, and poured into a large amount of a mixture of ion-exchanged water and methanol to precipitate a resin, which was then filtered and recovered. To the resulting resin, 650 parts of propylene glycol monomethyl ether acetate was added, dissolved, and concentrated. Then, 650 parts of propylene glycol monomethyl ether acetate was added, and the mixture was concentrated again to obtain 184 parts of a propylene glycol monomethyl ether acetate solution of Resin A2-3 (solid content 45%, yield 72%). The weight-average molecular weight of Resin A2-3 was 3.64 × 10 4 It was. TIFF2025162967000057.tif32170

[0176] Synthesis Example 6 [Synthesis of Resin AX2-1] A four-neck flask equipped with a reflux condenser, a stirrer, and a thermometer was charged with 70 parts of ethyl acetate and heated to 55°C. To this was added dropwise a mixture of 8 parts of acrylic acid, 100 parts of ethyl acrylate (molar ratio of acrylic acid:ethyl acrylate=10:90), 3.31 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 100 parts of ethyl acetate over 2 hours. The mixture was stirred for 3 hours while maintaining the temperature at 50-55°C. The resulting reaction mixture was cooled to below 40°C, diluted with 110 parts of ethyl acetate, and poured into a large amount of a mixed solution of ion-exchanged water and methanol to precipitate a resin, which was then filtered and recovered. To the resulting resin, 600 parts of propylene glycol monomethyl ether acetate was added, dissolved, and concentrated. Then, 600 parts of propylene glycol monomethyl ether acetate was added, and the mixture was concentrated again to obtain 173 parts of a propylene glycol monomethyl ether acetate solution of Resin AX2-1 (solid content 45%, yield 72%). The weight-average molecular weight of Resin AX2-1 was 6.67 × 104 It was. TIFF2025162967000058.tif33170

[0177] Synthesis Example 7 [Synthesis of Resin A3-1] A four-neck flask equipped with a stirrer, reflux condenser, and thermometer was charged with 413.5 parts of 2,5-xylenol, 103.4 parts of salicylaldehyde, 20.1 parts of p-toluenesulfonic acid, and 826.9 parts of methanol. The mixture was heated to reflux and maintained at this temperature for 4 hours. After cooling, 1320 parts of methyl isobutyl ketone was added, and 1075 parts of the solvent was distilled off at normal pressure. 762.7 parts of m-cresol and 29.0 parts of 2-tert-butyl-5-methylphenol were added, and the mixture was heated to 65°C. 678 parts of 37% aqueous formalin solution was added dropwise over 1.5 hours, adjusting the temperature to 87°C at the end of the addition. The resulting mixture was maintained at 87°C for 10 hours, after which 1115 parts of methyl isobutyl ketone was added. The mixture was washed three times with deionized water. 500 parts of methyl isobutyl ketone was added to the resulting mixture, and the mixture was concentrated under reduced pressure until the total volume reached 3435 parts. To the resulting mixture, 3796 parts of methyl isobutyl ketone and 4990 parts of n-heptane were added, and the mixture was heated to 60°C and stirred for 1 hour. The mixture was then separated, and the lower layer containing the resin was removed, diluted with 3500 parts of propylene glycol monomethyl ether acetate, and concentrated to obtain 1690 parts of a propylene glycol monomethyl ether acetate solution of Resin A3-1 (solid content 43%). The weight average molecular weight of Novolac Resin A3-1 was 7 x 10 3 Furthermore, the residual film ratio after development with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was 74%. The residual film ratio was measured by the method described in the section <Resin (A2)> of the Detailed Description of the Invention.

[0178] <Preparation of Resist Composition> The components shown in Table 1 were mixed and dissolved to obtain a mixture, which was then filtered through a fluororesin filter with a pore size of 15 μm to prepare a resist composition.

[0179] [Table 1]

[0180] <Resin> A1-1: Resin A1-1 AX1-1: Resin AX1-1 A2-1: Resin A2-1 A2-2: Resin A2-2 A2-3: Resin A2-3 AX2-1: Resin AX2-1 A3-1: Resin A3-1

[0181] <Acid generator (B)> B-1: N-hydroxynaphthalimide triflate (Heraeus) TIFF2025162967000060.tif23170B-2: Compound represented by the following formula (synthesized by the method described in WO2016 / 072049) TIFF2025162967000061.tif37170B-3: Compound represented by the following formula (synthesized in the same manner as described in WO2016 / 072049, except that (+)-10-camphorsulfonyl chloride was replaced with 1-octanesulfonyl chloride) TIFF2025162967000062.tif29170

[0182] <Quencher (C)> C-1: 2,4,5-triphenylimidazole (Tokyo Chemical Industry Co., Ltd.) C-2: N,N-dicyclohexylmethylamine (Aldrich) <Solvent (D)> D-1: Propylene glycol monomethyl ether acetate

[0183] <Creating dry film resist> The resist compositions (compositions 1 to 5, comparative compositions 1 and 2) listed in Table 1 were coated using a die coater as the film coater and a polyethylene terephthalate (PET) film (thickness 38 μm) as the support film so that the film thickness after drying would be as listed in Table 2, and then dried in a temperature-rising oven at 70°C for 5 minutes and then at 130°C for 5 minutes. A polyethylene (PE) film was laminated as a protective film on the surface of the prepared dry film to obtain the dry film resists listed in Table 2.

[0184] [Table 2]

[0185] (evaluation of i-line exposure of dry film resist) Examples 1 to 5, Comparative Examples 1 to 2 Using a vacuum laminator PVL0202S (Nisshinbo Mechatronics Inc.), the vacuum chamber was set to a vacuum of 50 Pa, and the resist composition layers on the support films of the dry film resists of Films 1 to 5 and Comparative Films 1 and 2 were adhered to a 4-inch silicon wafer substrate with copper vapor-deposited on it. The resist composition layers were then pre-baked on a direct hot plate at 120°C for 300 seconds to form resist composition layers. Next, the composition layer formed on the wafer was exposed to light through a mask to form a 1:1 contact hole pattern (hole diameter: 30, 40, 50 μm, pitch: 60, 80, 100 μm) using an i-line stepper (NSR-2005i9C; manufactured by Nikon Corporation, NA=0.5) while gradually changing the exposure dose. After exposure, the resist was left standing in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 100 seconds (puddle development) without post-exposure baking, and this process was repeated five times to obtain a resist pattern. The resist pattern obtained after development was observed with a scanning electron microscope, and the exposure dose required to obtain a 50 μm hole pattern was defined as the effective sensitivity.

[0186] Reference examples 1 and 2 In the i-line exposure evaluation of the above dry film resist, comparative films 2 and 3 were used instead of film 1, and after exposure, the dry film resist was subjected to post-exposure baking on a hot plate at 90°C for 90 seconds, in the same manner as in Example 1, except that the comparative films 2 and 3 were used instead of film 1, and after exposure, the dry film resist was subjected to post-exposure baking on a hot plate at 90°C for 90 seconds.

[0187] <Resolution evaluation> The resist pattern obtained at the effective sensitivity was observed under a scanning electron microscope, and the minimum hole diameter of the mask of the contact hole pattern that could be resolved was measured. The hole diameter of one arbitrarily selected hole from the resolved contact hole pattern was marked as "◎" if it was 100-80% of the hole diameter of the mask, "〇" if it was 80-50%, and "△" if it was 50-10%.

[0188] <Plating resistance evaluation> A patterned wafer was prepared using the effective sensitivity obtained in the i-line exposure evaluation, and then immersed in a Cu plating solution for 15 minutes. After immersion, the patterned wafer was observed under an optical microscope to observe the contact hole pattern with a line width of 50 μm. If the resist pattern dissolved in the plating solution after 10 minutes of immersion and a change was observed in the resist pattern, it was marked with an "X", if there was no change in the resist pattern after 15 minutes of immersion, it was marked with a "△", and if there was no change in the resist pattern after 20 minutes of immersion, it was marked with an "O".

[0189] Table 3 shows the evaluation of resolution and plating resistance for each of Examples 1 to 5, Comparative Examples 1 and 2, and Reference Examples 1 and 2. [Table 3]

[0190] From Table 1, it was confirmed that the resist patterns of Examples 1 to 5 had good resolution and plating resistance even without post-exposure baking (PEB) despite having a film thickness as large as 130 μm. On the other hand, it was confirmed that the resist pattern of Comparative Example 1 did not resolve and had poor plating resistance without PEB. It was confirmed that the resist pattern of Comparative Example 2 achieved resolution by PEB, but residues were generated. [Industrial Applicability]

[0191] The resist composition of the present invention is capable of forming a resist pattern that exhibits both excellent resolution and plating resistance, and is suitable for semiconductor microfabrication, making it extremely useful industrially.

Claims

1. a resin (A1) having a group represented by formula (1); a resin (A2) containing a structural unit represented by formula (a3); an acid generator (B); A resist composition comprising: [In formula (1), R ａ１ and R ａ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ａ３ represents a hydrocarbon group having 1 to 20 carbon atoms, or R ａ１ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ａ２ and R ａ３ are bonded to each other, and R ａ２ and the carbon atom to which R ａ３ forms a heterocyclic ring having 3 to 20 carbon atoms together with X to which it is bonded, and the methylene groups contained in the hydrocarbon group and the heterocyclic ring may be replaced by oxygen atoms or sulfur atoms. X represents an oxygen atom or a sulfur atom. na represents 0 or 1. * indicates a binding site.] [In formula (a3), R ａ３１ and R ａ３２ each independently represents an alkyl group having 1 to 12 carbon atoms, and a methylene group contained in the alkyl group may be replaced with an oxygen atom. o, p, q, and r each independently represent 0 or a positive number less than 1, and at least one of o and p represents a positive number less than 1. When o is 0, p and q each represent a positive number less than 1. When p is 0, o and r each represent a positive number less than 1. When q is 0, o and r each represent a positive number less than 1. When r is 0, p and q each represent a positive number less than 1. However, the relationship o + p + q + r = 1 is satisfied.

2. 2. The resist composition according to claim 1, wherein the resin (A1) contains a structural unit represented by formula (a1-1) or formula (a1-2). [In formula (a1-1) and formula (a1-2), R ａ１ , R ａ２ , R ａ３ represents the same meaning as in formula (1). R ａ４ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. R ａ５ represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A ａ１１ represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and —CH ２ - represents -O-, -CO- or -NR ａ６ May be replaced with -. R ａ６ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. na1A represents an integer of 1 to 5, and when na1A is 2 or more, the groups in the parentheses may be the same or different from each other. na11A represents an integer of 0 to 4, and when na11A is 2 or more, a plurality of R ａ５ may be the same or different, provided that 1≦na1A+na11A≦5 is satisfied. na1B represents an integer of 1 to 4, and when na1B is 2 or more, the groups in the parentheses may be the same or different from each other. na11B represents an integer of 0 to 3, and when na11B is 2 or more, a plurality of R ａ５ may be the same or different, provided that 1≦na1B+na11B≦4 is satisfied.

3. 3. The resist composition according to claim 2, wherein the resin (A1) contains a structural unit represented by formula (a1-1).

4. 2. The resist composition according to claim 1, wherein the resin (A1) further contains a structural unit represented by formula (a2-1). [In formula (a2-1), R ａ２４ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms. R ａ２５ represents a halogen atom, a carboxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A ａ２１ represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and —CH ２ - represents -O-, -CO- or -NR ａ２６ May be replaced with -. R ａ２６ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. na2 represents an integer of 1 to 5. na21 represents an integer of 0 to 4, and satisfies 1≦na2+na21≦5. When na21 is 2 or more, a plurality of R ａ２５ may be the same or different from each other.

5. 0.05≦o+p≦0.30 is satisfied, 2. The resist composition according to claim 1, wherein q and r each represent a positive number less than 1.

6. 2. The resist composition according to claim 1, further comprising a novolak resin (A3).

7. further comprising an adhesion improver (E), 2. The resist composition according to claim 1, wherein the adhesion improver (E) comprises at least one selected from the group consisting of sulfur-containing compounds, aromatic hydroxy compounds, benzotriazole-based compounds, triazine-based compounds, and silicon-containing compounds.

8. A support film; A dry film resist comprising: a resist composition layer laminated on the support film, the resist composition layer comprising the resist composition according to claim 1.

9. (1a) applying the resist composition according to claim 1 to a support film to form a photoresist composition layer; (2a) a step of drying the resist composition layer.

10. (1b) applying the resist composition according to claim 1 onto a substrate and drying the resist composition to form a resist composition layer; (2b) exposing the resist composition layer to ultraviolet light with a wavelength of 500 nm or less; (3b) A pattern forming method, comprising the step of developing the exposed resist composition layer without heating it.

11. (1c) laminating the dry film resist according to claim 8 on a substrate; (2c) peeling at least a portion of the support film from the resist composition layer, and exposing the resist composition layer to ultraviolet light having a wavelength of 500 nm or less; (3c) A pattern forming method, comprising the step of developing the exposed resist composition layer without heating it.

12. forming a resist pattern on a substrate having a conductive layer using the resist composition according to claim 1 so that a portion of the conductive layer is exposed; forming a plating object using the resist pattern as a template; a step of removing the resist pattern after forming the plated object.

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