Resist composition, method for producing resist pattern, and method for producing plated molded article

Abstract

To provide: a resist composition which is excellent in storage stability, has sufficient resistance to a plating treatment, and is capable of forming a resist pattern with high precision; a method for producing a resist pattern using the resist composition; and a method for producing a plated molded article using a resist pattern.SOLUTION: A resist composition comprises a resin (A1) including a structural unit having a group represented by formula (20), an alkali-soluble resin (A2), an acid generator (B) represented by a specific formula, and a compound (C) represented by formula (I). In formula (20), Ra1' and Ra2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and Ra3' represents a hydrocarbon group having 1 to 20 carbon atoms. In formula (I), ring W1 represents a heterocyclic ring having a nitrogen atom, or the like.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resist composition, a method for manufacturing a resist pattern, and a method for manufacturing an electroformed article.

Background Art

[0002] Patent Documents 1 to 4 describe resist compositions.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] When electroplating is performed using a resist pattern obtained by using a conventional resist composition as described in Patent Document 1, there is still room for further improvement in accurately forming an electroformed article. In addition, there is also room for further improvement in the storage stability of the resist composition. Therefore, an object of the present invention is to provide a resist composition having excellent storage stability, sufficient resistance to electroplating, and capable of accurately forming a resist pattern. Another object of the present invention is to provide a method for manufacturing a resist pattern using the resist composition, and a method for manufacturing an electroformed article.

Means for Solving the Problems

[0005] The present inventors have found that a resist composition containing a resin (A1) containing a structural unit having a predetermined acid-labile group (a group represented by formula (20)), an alkali-soluble resin (A2), an acid generator (B) containing a compound represented by formula (b0), and a compound (C) represented by formula (I) can solve the above problems. The present invention provides the following inventions. [1] A resin (A1) containing a structural unit having a group represented by formula (20), an alkali-soluble resin (A2), an acid generator (B) containing a compound represented by formula (b0), and a compound (C) represented by formula (I), a resist composition containing the same. TIFF2025110891000001.tif25170 [In formula (20), R a1’ and R a2’ each independently represent 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. The 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 by an oxygen atom or a sulfur atom. X represents an oxygen atom or a sulfur atom. na’ represents 0 or 1. * represents a bond.] TIFF2025110891000002.tif36170 [In formula (b0), R b1 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be replaced by an oxygen atom or a carbonyl group. X represents an oxygen atom or a sulfur atom. R 01 represents a hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be replaced by an oxygen atom, a sulfur atom, or a carbonyl group. x0 represents an integer from 1 to 6. When x0 is 2 or more, the groups in the plurality of parentheses may be the same or different. TIFF2025110891000003.tif17170 [In formula (I), ring W 1 represents a heterocyclic ring having a nitrogen atom as an atom constituting the ring, or a benzene ring having a substituted or unsubstituted amino group. The heterocyclic ring may have a heteroatom other than the nitrogen atom, and the heterocyclic ring and the benzene ring may have a substituent other than a substituted or unsubstituted amino group. A 1 represents a phenyl group or a naphthyl group. n represents 2 or 3, and the plurality of A 1 may be the same or different. [2] The resist composition according to [1], wherein the resin (A1) is a resin containing a structural unit represented by formula (a1-2) or a resin containing a structural unit represented by formula (a3B). TIFF2025110891000004.tif55170 [In formula (a1-2), R a1’ and R a2’ each independently represent 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The 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 by an oxygen atom or a sulfur atom. R a5 represents a hydrogen atom or a methyl group. R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer from 0 to 4. When m is 2 or more, the plurality of R a6 may be the same or different from each other. TIFF2025110891000005.tif39170 [In formula (a3B), 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced by an oxygen atom or a sulfur atom. R ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2 or 3. When p is 2 or 3, R ab may be the same or different.] [3] In the compound (C), in formula (I), ring W 1 is a heterocyclic ring having one or more nitrogen atoms and one or more oxygen atoms or sulfur atoms as ring-constituting atoms, a heterocyclic ring having two or more nitrogen atoms as ring-constituting atoms, a benzene ring having one or more substituted or unsubstituted amino groups and one or more hydroxy groups, or a benzene ring having two or more substituted or unsubstituted amino groups, and the resist composition according to [1] or [2]. [4] The resist composition according to any one of [1] to [3], further containing a compound (E) having a quinonediazide sulfonyl group. [5] A method for producing a resist pattern, comprising (1) a step of applying the resist composition according to any one of [1] to [4] onto the metal surface of a substrate having a metal surface, (2) a step of drying the applied composition to form a composition layer, (3) a step of exposing the composition layer, and (4) a step of developing the composition layer after exposure The manufacturing method including. [6] A method for manufacturing an electroformed object, comprising: (1) applying the resist composition according to any one of [1] to [4] onto the metal surface of a substrate having a metal surface; (2) drying the applied composition to form a composition layer; (3) exposing the composition layer; (4) developing the composition layer after exposure; (5) using the obtained resist pattern as a mold to form an electroformed object; and (6) peeling off the resist pattern .

Advantages of the Invention

[0006] The resist composition of the present invention has excellent storage stability. By using this resist composition, a resist pattern can be accurately formed. Furthermore, the resist pattern can accurately form an electroformed object. In addition, the resist composition of the present invention has excellent plating resistance and excellent adhesion between the substrate and the resist. Moreover, the thickness of the plating pattern obtained by using the resist composition of the present invention is uniform.

Brief Description of the Drawings

[0007]

Figure 1

Embodiments for Carrying Out the Invention

[0008] In this specification, unless otherwise specified, in the description of the structural formula of a compound, "aliphatic hydrocarbon group" means a linear or branched aliphatic hydrocarbon group, and "alicyclic hydrocarbon group" means a group obtained by removing from the ring of an alicyclic hydrocarbon the number of hydrogen atoms corresponding to the valence. "Aromatic hydrocarbon group" also includes a group in which a hydrocarbon group is bonded to an aromatic ring. When stereoisomers exist, all stereoisomers are included. In this specification, "(meth)acrylic acid" means "at least one selected from acrylic acid and methacrylic acid", and "(meth)acrylate" means "at least one selected from acrylate and methacrylate". Among the groups described in this specification, those that can take both a linear structure and a branched structure are interpreted to include both. In this specification, the "solid content of the resist composition" means the total of the components excluding the solvent (D) described later from the total amount of the resist composition.

[0009] 1. Resist composition The resist composition of the present invention contains a resin having a structural unit represented by formula (20) (hereinafter may be referred to as "resin (A1)"), an alkali-soluble resin (hereinafter may be referred to as "resin (A2)"), an acid generator containing a compound represented by formula (b0) (hereinafter may be referred to as "acid generator (B)"), and a compound represented by formula (I) (hereinafter may be referred to as "compound (C)"). Further, it may contain a compound having a quinonediazidosulfonyl group (hereinafter may be referred to as "compound (E)").

[0010] <Resin (A1)> Resin (A1) includes a structural unit having an acid-labile group (hereinafter may be referred to as "structural unit (a1)") and a structural unit having a group represented by formula (20) (hereinafter may be referred to as "structural unit (a12)"). The acid-labile group means a group containing a group that can be eliminated by contact with an acid (may be referred to as an eliminable group). When resin (A1) comes into contact with an acid, the eliminable group is eliminated from the acid-labile group, and a hydrophilic group (for example, a hydroxy group (such as a phenolic hydroxy group) or a carboxy group) is formed. Resin (A1) increases its solubility in an alkaline aqueous solution by contact with an acid. That is, resin (A1) is preferably insoluble or hardly soluble in an alkaline aqueous solution before contact with an acid and becomes soluble in an alkaline aqueous solution after contact with an acid. The resin (A1), within the range of having the above properties, as a structural unit having an acid-labile group, in addition to the structural unit (a12), further, as another structural unit having an acid-labile group, for example, a structural unit having a group represented by the formula (10) (hereinafter sometimes referred to as "structural unit (a11)"), and a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)"), etc., may contain structural units known in the art.

[0011] Examples of the acid for eliminating the leaving group contained in the acid-labile group include carboxylic acid, sulfonic acid, etc. In the composition of the present invention, in the photolithography process, examples include carboxylic acid compounds, sulfonic acid compounds, etc. generated by irradiating (exposing) the acid generator (B) described later with light.

[0012] <Group represented by formula (20)> The resin (A1) contains a structural unit having a group represented by the formula (20) as an acid-labile group. TIFF2025110891000006.tif28170 [In formula (20), R a1’ and R a2’ each independently represent 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. The 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 by an oxygen atom or a sulfur atom. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.]

[0013] R a1’ ~R a3’Examples of the hydrocarbon group having 1 to 20 carbon atoms include linear 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 formed by combining 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, a dodecyl group, and the like. Examples of the alkenyl group having 2 to 20 carbon atoms include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, a nonenyl group, and the like. 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, a nonynyl group, and the like. The linear hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 18 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and even more preferably 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 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. 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 still more preferably 3 to 12 carbon atoms. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. The aromatic hydrocarbon group may further have a substituent, and examples of the substituent include aryloxy groups 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 still more preferably 6 to 10 carbon atoms. Among the groups having 4 to 20 carbon atoms formed by combining the above groups, examples of the group formed by combining an alkyl group and an alicyclic hydrocarbon group (group having 4 to 20 carbon atoms) include methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group, isobornyl group, 2-alkyladamantan-2-yl group, 1-(adamantan-1-yl)alkane-1-yl group, etc. Examples of the group formed by combining an alkyl group and an aromatic hydrocarbon group (group having 7 to 20 carbon atoms) include aralkyl groups and aromatic hydrocarbon groups having an alkyl group. Specifically, benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc. Examples of the group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (group having 9 to 20 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group. Specifically, p-cyclohexylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. R a2’ and R a3’ When they 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, -C(R a1’ )(R a2’ )-X-R a3’Examples thereof include the following groups. The heterocyclic ring having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and still more preferably 3 to 12 carbon atoms. * represents a bond. TIFF2025110891000007.tif18170R 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 still more preferably a hydrogen atom. R a2' is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or R a3’ is preferably bonded to form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded and X, or is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or R a3’ is 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, more preferably a hydrocarbon group having 1 to 12 carbon atoms, and still more preferably a methyl group or an ethyl group. R a3’ is a hydrocarbon group having 1 to 18 carbon atoms, or R a2' is preferably bonded to form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded and X, or is a hydrocarbon group having 1 to 12 carbon atoms, or R a2’ is 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. 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 4 to 18 carbon atoms formed by combining these. 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 the formula (20) include, for example, the following groups. TIFF2025110891000008.tif100170

[0015] Examples of the group represented by formula (20) include the group represented by formula (2) and the group represented by formula (2'), etc. TIFF2025110891000009.tif55170[In formulas (2) and (2'), R a1’ and R a2’ each independently represent 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced by an oxygen atom or a sulfur atom. * represents a bond.]

[0016] <Structural unit (a12) having the group represented by formula (20)> The resin (A1) containing a structural unit having the group represented by formula (20) can be produced, for example, by polymerizing a monomer component containing an ethylenically unsaturated compound that leads to a structural unit (a12) having the group represented by formula (20). The resin (A1) may have only one type of structural unit (a12) or may have a plurality of types.

[0017] As the structural unit (a12), a structural unit represented by formula (a1-2) (hereinafter sometimes referred to as "structural unit (a1-2)") is preferable.

[0018] TIFF2025110891000010.tif55170

[0019] R a1’ and R a2’ each independently represent 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The 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 by an oxygen atom or a sulfur atom. R a5 represents a hydrogen atom or a methyl group. R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, a plurality of R a6 may be the same as or different from each other.]

[0020] In formula (a1-2), R a5 is preferably a hydrogen atom. 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 preferably forms a heterocyclic ring having 3 to 18 carbon atoms together with R a3’ and the carbon atom and oxygen atom to which they are bonded. It is more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or forms a heterocyclic ring having 3 to 12 carbon atoms together with R a3’ and the carbon atom and oxygen atom to which they are bonded. Even more preferably, it is a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a methyl group or an ethyl group.

[0021] R a3’ is a hydrocarbon group having 1 to 18 carbon atoms, or preferably forms a heterocyclic ring having 3 to 18 carbon atoms together with R a2' and the carbon atom and oxygen atom to which they are bonded. It is preferably a hydrocarbon group having 1 to 12 carbon atoms, or a2’It is more preferable that they are combined to form a heterocyclic ring having 3 to 12 carbon atoms together with the carbon atom and oxygen atom to which they are attached. 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 4 to 18 carbon atoms formed by combining these. These groups can be arbitrarily selected from those listed above. The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. When the aromatic hydrocarbon group has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms.

[0022] R a6 Examples of the alkyl group having 1 to 6 carbon atoms of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. R a6 Examples of the alkoxy group having 1 to 6 carbon atoms of R include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and the like. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. R a6 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, still 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. m is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0. In formula (a1-2), -O-C(R a1’ )(R a2’ )-O-R a3’The group represented by is preferably bonded to the 3-position or 4-position of the benzene ring (m-position or p-position with respect to the main chain bonded to the benzene ring), and more preferably bonded to the 4-position (p-position) of the benzene ring.

[0023] Examples of the structural unit (a1-2) include structural units represented by any of Formula (a1-2-1) to Formula (a1-2-14). TIFF2025110891000011.tif128170

[0024] In the above structural unit, the hydrogen atom corresponding to R a5 The structural unit in which the hydrogen atom is replaced by a methyl group can also be cited as a specific example of the structural unit (a1-2). As the structural unit (a1-2), the structural units represented by Formula (a1-2-2), Formula (a1-2-3), Formula (a1-2-4), Formula (a1-2-9), and Formula (a1-2-14) are preferable, and the structural units represented by Formula (a1-2-2), Formula (a1-2-3), Formula (a1-2-4), and Formula (a1-2-9) are more preferable.

[0025] The resin (A1) containing the structural unit having the group represented by Formula (20) is preferably a resin containing the structural unit (a1-2). The content ratio of the structural unit (a1-2) in the resin (A1) is preferably 3 to 80 mol%, more preferably 5 to 60 mol%, still more preferably 10 to 55 mol%, even more preferably 15 to 50 mol%, and still even more preferably 20 to 45 mol% with respect to all the structural units of the resin (A1).

[0026] <Acid labile group other than the group represented by Formula (20)> The resin (A1) contains the structural unit (a12) having the group represented by Formula (20), and may contain, if necessary, a structural unit having an acid labile group other than the group represented by Formula (20). Examples of the acid labile group other than the group represented by Formula (20) include the group represented by Formula (10). TIFF2025110891000012.tif24170[In Formula (10), R a1 、Ra2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.]

[0027] The R represented by the formula (10) a1 ~R a3 The alkyl group having 1 to 8 carbon atoms may be either linear or branched, 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, and the like. R a1 ~R a3 The alkyl group having 1 to 8 carbon atoms preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. R a1 ~R a3 The alicyclic hydrocarbon group having 3 to 20 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, the following group (* represents a bond.), and the like. TIFF2025110891000013.tif24170R a1 ~R a3 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 still more preferably 3 to 12 carbon atoms.

[0028] R a1 and R a2 When R a1 (R a2)(R a3 ) Examples thereof include the following groups. The ring having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and still more preferably 3 to 12 carbon atoms. * represents a bond to -O-. TIFF2025110891000014.tif35170

[0029] R a1 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a2 preferably combines with to form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are attached, and is an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a2 more preferably combines with to form a ring having 3 to 12 carbon atoms together with the carbon atom to which they are attached. R a2 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a1 preferably combines with to form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are attached, and is an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a1 more preferably combines with to form a ring having 3 to 12 carbon atoms together with the carbon atom to which they are attached. R a3 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms. ma is preferably 0. na is preferably 1.

[0030] Examples of the group represented by the formula (10) include, for example, R a1 、R a2 and R a3 are each independently an alkyl group having 1 to 3 carbon atoms (preferably a tert-butoxycarbonyl group); R a1 and R a2 are each independently an alkyl group having 1 to 3 carbon atoms, and R a3a group that is a cyclopentyl group or a cyclohexyl group; R a1 and R a2 are bonded to each other to form a cyclopentane ring or a cyclohexane ring together with the carbon atom to which they are bonded, and R a3 is a group such as an alkyl group having 1 to 3 carbon atoms, etc.

[0031] Specific examples of the group represented by formula (10) include, for example, the following groups. TIFF2025110891000015.tif88170

[0032] Specific examples of the group represented by formula (10) include, specifically, the group represented by formula (1) and the group represented by formula (1'), etc. TIFF2025110891000016.tif49170[In formula (1) and formula (1'), R a1 , R a2 and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. * represents a bond.]

[0033] <Structural unit having an acid-labile group other than the group represented by formula (20)> When the resin (A1) contains, as a structural unit having an acid-labile group other than the group represented by formula (20), for example, a structural unit (a11) having a group represented by formula (10), the resin (A1) containing the structural unit (a12) and the structural unit (a11) can be produced, for example, by polymerizing a monomer component containing an ethylenically unsaturated compound that leads to the structural unit (a12) and an ethylenically unsaturated compound that leads to the structural unit (a11). The resin (A1) may have only one type of the structural unit (a11) or may have a plurality of types.

[0034] As the structural unit (a11), a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as "structural unit (a1-1)") is preferable. TIFF2025110891000017.tif49170

[0035] [In the formula (a1-1), R a1 , R a2 and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R a4 represents a hydrogen atom or a methyl group.]

[0036] In the formula (a1-1), R a4 is preferably a methyl group. R a1 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a2 is preferably bonded to form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and is an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a2 is more preferably bonded to form a ring having 3 to 12 carbon atoms together with the carbon atom to which they are bonded. R a2 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a1 is preferably bonded to form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and is an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a1 is more preferably bonded to form a ring having 3 to 12 carbon atoms together with the carbon atom to which they are bonded. R a3is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms.

[0037] Examples of the structural unit (a1-1) include structural units represented by any of formula (a1-1-1) to formula (a1-1-17). TIFF2025110891000018.tif109170

[0038] When the resin (A1) contains the structural unit (a1-1), the content ratio is the same as that of the above-described structural unit (a1-2).

[0039] <Structural unit (a2) having no acid-labile group> The resin (A1) contains a structural unit (a12) having a group represented by formula (20), and may optionally contain other structural units (a2) having no acid-labile group. When containing the structural unit (a2), the resin (A1) containing the structural unit (a12) and the structural unit (a2) can be produced, for example, by polymerizing a monomer component containing an ethylenically unsaturated compound leading to the structural unit (a12) and an ethylenically unsaturated compound leading to the structural unit (a2). In the resin (A1), the structural unit (a2) having no acid-labile group may contain only one kind or may contain a plurality of kinds.

[0040] Examples of the structural unit (a2) include structural units represented by any of formula (a2-1) to formula (a2-3) (hereinafter, may be referred to as "structural unit (a2-1)" etc. according to the formula number). TIFF2025110891000019.tif57170

[0041] [In formula (a2-1), formula (a2-2) and formula (a2-3), R a7 、R a8 and R a9 each independently represent a hydrogen atom or a methyl group. R a10represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m’ represents an integer from 0 to 4. When m’ is 2 or more, a plurality of R a10 may be the same as or different from each other. R a11 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, provided that a group in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom is excluded. R a12 represents an alkyl group having 1 to 6 carbon atoms, provided that a group in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom is excluded. L a1 represents an alkanediyl group having 2 to 6 carbon atoms, provided that a group in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom is excluded. n represents an integer from 1 to 30. When n is 2 or more, a plurality of L a1 may be the same as or different from each other.]

[0042] R a10 Examples of the alkyl group having 1 to 6 carbon atoms represented by R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like. The alkyl group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. R a10 Examples of the alkoxy group having 1 to 6 carbon atoms represented by R include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and the like. The alkoxy group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. R a11 Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R include a chain hydrocarbon group having 1 to 12 carbon atoms (such as an alkyl group, an alkenyl group, and an alkynyl group), an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a group having 4 to 12 carbon atoms formed by combining these. 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, an n-decyl group, etc. Examples of the alkenyl group having 2 to 12 carbon atoms include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, a nonenyl group, etc. Examples of the alkynyl group having 2 to 12 carbon atoms include an ethynyl group, a propynyl group, an isopropyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, a nonynyl group, etc. 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 still 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, a cyclooctyl group, etc. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond). TIFF2025110891000020.tif24170 The alicyclic hydrocarbon group having 3 to 12 carbon atoms preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. Examples of the aromatic hydrocarbon group 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 the group having 4 to 12 carbon atoms formed by combining the above groups include a group formed by combining an alkyl group and an alicyclic hydrocarbon group (a group having 4 to 12 carbon atoms), such as a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, a norbornylethyl group, etc. Examples of a group combining an alkyl group and an aromatic hydrocarbon group (a group having 7 to 12 carbon atoms) include an aralkyl group and an aromatic hydrocarbon group having an alkyl group. Specifically, 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, a 2-methyl-6-ethylphenyl group, and the like. Examples of a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (a group having 9 to 12 carbon atoms) include an aromatic hydrocarbon group having an alicyclic hydrocarbon group and an alicyclic hydrocarbon group having an aromatic hydrocarbon group. Specifically, examples include a p-cyclohexylphenyl group, a phenylcyclohexyl group, and the like.

[0043] R a12 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 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, and the like. The alkyl group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0044] L a1 Examples of the alkanediyl group having 2 to 6 carbon atoms represented by L may be either linear or branched. For example, 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 ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a propane-1,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like can be mentioned. The alkanediyl group having 2 to 6 carbon atoms preferably has 2 to 4 carbon atoms, and more preferably has 2 to 3 carbon atoms.

[0045] R a7 is preferably a hydrogen atom. R a8 and Ra9 is preferably a methyl group independently of each other. R a10 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, still more preferably, for example, a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group. m’ is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0. R a11 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 still 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 a group in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom is excluded. L a1 is preferably an alkanediyl group having 2 to 4 carbon atoms (for example, ethane-1,2-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group), more preferably an alkanediyl group having 2 to 3 carbon atoms (for example, ethane-1,2-diyl group, propane-1,3-diyl group, propane-1,2-diyl group), and still more preferably an ethane-1,2-diyl group. n is preferably an integer of 1 to 20, more preferably an integer of 1 to 16, still more preferably an integer of 1 to 14, even more preferably an integer of 1 to 10, and even still more preferably an integer of 1 to 6. R a12 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, provided that a group in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom is excluded.

[0046] As the structural unit (a2-1), a structural unit represented by the formula (a2-1-1), formula (a2-1-2), formula (a2-1-3) or formula (a2-1-4) is preferable. Further, the monomer that leads to the structural unit (a2-1) is described, for example, in JP-A-2010-204634. TIFF2025110891000021.tif39170

[0047] Examples of the monomer that leads to the structural unit (a2-2) include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate; monocyclic (meth)acrylic acid esters such as cycloalkyl (meth)acrylates like cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate; polycyclic (meth)acrylic acid esters such as adamantyl (meth)acrylate, norbornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate.

[0048] Examples of the monomer that leads to the structural unit (a2-3) include (meth)acrylic acid esters such as (poly)ethylene glycol monomethyl ether (meth)acrylate ((poly)alkylene glycol monoalkyl ether (meth)acrylate) like 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, octaethylene glycol monomethyl ether (meth)acrylate, etc.

[0049] Furthermore, examples of the monomer that leads to the structural unit (a2) include carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc., hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc., and styrenes such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 4-isopropoxystyrene, etc.

[0050] The structural unit (a2) may be, for example, a structural unit represented by the formula (a2-4). TIFF2025110891000022.tif52170[In the formula (a2-4), R a13 represents a hydrogen atom or a methyl group. R a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R a15 represents a hydrocarbon group having 1 to 12 carbon atoms, provided that a group in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom is excluded. The methylene group contained in the hydrocarbon group having 1 to 12 carbon atoms may be substituted with an oxygen atom or a carbonyl group. However, the methylene group bonded to the oxygen atom and the methylene group bonded to the methylene group are not substituted with an oxygen atom. "m” represents an integer of 0 to 4. When m” is 2 or more, a plurality of R a14 may be the same as or different from each other. m''' represents an integer of 0 to 4. When m''' is 2 or more, a plurality of R a15 may be the same as or different from each other. However, the sum of m” and m''' is 5 or less.

[0051] R a15 The hydrocarbon group in R includes a group in which the bond to the oxygen atom is not a tertiary carbon atom, that is, a group in which one or more atoms other than a carbon atom such as a hydrogen atom are bonded to the bonding carbon. Further, the hydrocarbon group in R a15 includes a group in which the methylene group bonded to the oxygen atom and the methylene group bonded to the methylene group are not substituted with an oxygen atom, that is, a group that does not contain an acetal structure. Therefore, the structural unit represented by the formula (a2-4) does not include the structural unit (a1-2).

[0052] R a14 Examples of the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R a10 include the same groups as those of R R a15 Examples of the hydrocarbon group having 1 to 12 carbon atoms of R a11 include the same groups as those of R

[0053] R a13 is preferably a hydrogen atom. R a14is 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, still more preferably, for example, a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group. R a15 Among them, it is 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 by 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 having 6 to 10 carbon atoms formed by combining these, or a group in which a methylene group contained in these groups is replaced by an oxygen atom or a carbonyl group, still 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 having 6 to 10 carbon atoms formed by combining these, or a group in which a methylene group adjacent to an oxygen atom of these groups is replaced by a carbonyl group. "m” is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0. "m'''" is preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1. However, the total of m” and m''' is 5 or less.

[0054] Examples of the structural unit (a2-4) include structural units represented by formula (a2-4-1) to formula (a2-4-10). TIFF2025110891000023.tif94170

[0055] In the structural units represented by formula (a2-4-1) to formula (a2-4-10), the structural unit in which a hydrogen atom corresponding to a13 R is replaced by a methyl group can also be cited as a specific example of the structural unit (a2-4).

[0056] When the resin (A1) contains the structural unit (a2-1), the structural unit (a2-2), the structural unit (a2-3), and the structural unit (a2-4), their total content ratio is preferably 1 to 90 mol%, more preferably 1 to 85 mol%, still more preferably 5 to 80 mol%, and particularly preferably 5 to 75 mol% with respect to all the structural units of the resin (A1).

[0057] 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 on a molar basis, more preferably 15:85 to 60:40, and still more preferably 15:85 to 45:55.

[0058] Examples of the combination of the structural units contained in the resin (A1) include those represented by the formula (A1-1) to the formula (A1-34). TIFF2025110891000024.tif253170TIFF2025110891000025.tif236170TIFF2025110891000026.tif211170TIFF2025110891000027.tif244170TIFF2025110891000028.tif229170In the above structural formula, the hydrogen atom corresponding to R in the formula (a1-2) a5 Structural units in which the hydrogen atom corresponding to etc. is replaced by a methyl group, or structural units in which the methyl group is replaced by a hydrogen atom can also be cited as specific examples of the above structural units. Also, in one resin, structural units having a hydrogen atom and a methyl group may be mixed.

[0059] The resin (A1) is preferably a resin containing the structural unit (a12) and the structural unit (a2), and more preferably a resin containing the structural unit (a1-2) and the structural unit (a2).

[0060] The resist composition of the present invention may contain, as a resin having an acid-labile group, a resin other than resin (A1), for example, a resin containing at least one selected from a carboxy group and a phenolic hydroxyl group in a side chain, and a resin (hereinafter sometimes referred to as "resin (A1b)") obtained by reacting a compound containing at least two or more vinyloxy groups in one molecule. Resin (A1b) is preferably a resin obtained by reacting a resin containing a phenolic hydroxyl group with a compound containing two or more vinyloxy groups in one molecule. Such a resin can be obtained, for example, by reacting a resin containing structural unit (a2-1) with a compound containing two or more vinyloxy groups in one molecule. Further, as the resin containing a phenolic hydroxyl group, a novolak resin described later may be used, and a resin obtained by reacting this novolak resin with the aforementioned vinyloxy group-containing compound may also be used. Furthermore, a resin obtained by mixing a resin containing structural unit (a2-1) and a novolak resin and reacting the resulting resin mixture with the aforementioned vinyloxy group-containing compound may also be used. Also, a resin obtained by reacting a resin containing structural unit (a2-1) and the aforementioned vinyloxy group-containing compound and a resin obtained by reacting a novolak resin and the aforementioned vinyloxy group-containing compound may be used in combination.

[0061] In the synthesis of resin (A1b), the usage ratio [carboxy group and phenolic hydroxyl group: vinyloxy group] of the compound containing at least two or more vinyloxy groups in one molecule with respect to the carboxy group and the phenolic hydroxyl group is preferably 60:40 to 99:1, more preferably 70:30 to 95:5 on a molar basis.

[0062] Examples of resin (A1b) include resins described in JP-A-2008-134515 and JP-A-2008-46594.

[0063] Examples of the compound having at least two or more vinyloxy groups in one molecule include 1,4-cyclohexanedimethanol divinyl ether and ethylene glycol divinyl ether.

[0064] When the resin (A1b) is a resin obtained by mixing a resin containing a structural unit (a2-1) and a novolak resin and reacting the resulting resin mixture with a vinyl oxy group-containing compound, the content of the novolak resin is 30 to 70% by mass based on the total amount of the resin (A1b).

[0065] The resin (A1) can be produced by polymerizing a monomer component containing an ethylenically unsaturated compound corresponding to the above-described structural unit (a12) and, if necessary, an ethylenically unsaturated compound corresponding to the structural unit (a11) and / or an ethylenically unsaturated compound corresponding to the structural unit (a2) by a known polymerization method (for example, a radical polymerization method). 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 as a conversion value based on standard polystyrene by gel permeation chromatography analysis. The detailed analysis conditions for this analysis are described in the examples of the present application.

[0066] The content of the resin (A1) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 30% by mass or more, preferably 95% by mass or less, more preferably 85% by mass or less, and still more preferably 70% by mass or less based on the total amount of the resins contained in the resist composition.

[0067] The resin (A1) may be a novolak resin (hereinafter sometimes referred to as "resin (A1c)") in which a group represented by the formula (20) is introduced as an acid-labile group containing a group cleavable by the action of an acid. This resin is one in which some or all of the phenolic hydroxyl groups of the novolak resin described later are protected with a group represented by the formula (20), which is an acid-labile group containing a group cleavable by the action of an acid, or one in which some or all of the phenolic hydroxyl groups of the novolak resin described later are substituted with a group represented by the formula (20), which is an acid-labile group containing a group cleavable by the action of an acid. This resin is also referred to as a novolak resin having a group represented by the formula (20) as an acid-labile group (a group containing a group detachable by contact with an acid).

[0068] The novolak resin is a resin obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenol compound") and an aldehyde under an acid catalyst. Examples of the phenolic compound include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,5-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxyphenol, 2-methoxyresorcinol, hydroquinone, 4-tert-butylcatechol, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and polyhydroxytriphenylmethane compounds obtained by condensation of xylenol and hydroxybenzaldehyde. These may be used alone or in combination of two or more. Among them, as the phenolic compound, for example, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol are preferable.

[0069] Examples of aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyl aldehyde, isobutyl aldehyde, acrolein, and crotonaldehyde; alicyclic aldehydes such as cyclohexane aldehyde, cyclopentane aldehyde, or furyl acrolein; aromatic aldehydes such as furfural, benzaldehyde, o-, m-, or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4-, or 3,5-dimethylbenzaldehyde, o-, m-, or p-hydroxybenzaldehyde, o-, m-, or p-nitrobenzaldehyde; araliphatic aldehydes such as phenylacetaldehyde or cinnamaldehyde, etc. These may be used alone or in combination of two or more. Among them, formaldehyde is preferred because it is easily available industrially.

[0070] Examples of the catalyst during addition condensation include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid, and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid, and p-toluenesulfonic acid; divalent metal salts such as zinc acetate, zinc chloride, and magnesium acetate, etc. These may be used alone or in combination of two or more. The amount of the catalyst used is usually 0.01 to 1 mol per 1 mol of aldehyde.

[0071] The condensation reaction can be carried out according to a conventional method. For example, it is carried out at a temperature in the range of 60 to 150 °C for about 2 to 30 hours. The condensation reaction may be carried out in the presence of a solvent. Examples of the solvent include ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, acetone, etc. After the reaction is completed, for example, if necessary, an organic solvent insoluble in water is added to the reaction mixture, the reaction mixture is washed with water, and then concentrated to obtain a novolak resin. Also, after the reaction is completed, a basic compound may be added to remove the acid catalyst and neutralize it, and the neutralization salt may be removed by washing with water.

[0072] In the above novolak resin, its weight average molecular weight is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, still more preferably 10,000 or less, even more preferably 9,000 or less, and even more preferably 8,000 or less. In the present specification, the weight average molecular weight is determined as a conversion value based on standard polystyrene by gel permeation chromatography analysis. The detailed analysis conditions for this analysis are described in the examples of the present application. The group represented by formula (20) is introduced into a part or all of the phenolic hydroxyl groups in the novolak resin obtained by condensation as described above.

[0073] As the acid labile group introduced into the phenolic hydroxyl group of the novolak resin, the group represented by formula (20) is preferably the group represented by formula (2). Specifically, for example, butyloxyethoxy group, ethoxypropyloxy group, ethoxybutyloxy group, tetrahydro-2-pyranyloxy group, tetrahydro-2-furyloxy group, methoxyethoxy group, 1-ethoxyethoxy group, propyloxyethoxy group, cyclohexyloxyethoxy group, 1-(2-methylpropoxy)ethoxy group, 1-(2-methoxyethoxy)ethoxy group, 1-(2-acetoxyethoxy)ethoxy group, 1-[2-(1-adamantyloxy)ethoxy]ethoxy group, 1-[2-(1-adamantanecarbonyloxy)ethoxy]ethoxy group, 3-oxocyclohexyloxy group, 4-methyltetrahydro-2-pyrone-4-yloxy group, etc. can be mentioned. Among them, at least one selected from the group consisting of ethoxyethoxy group, ethoxypropyloxy group, ethoxybutyloxy group, isopropyloxyethoxy group, cyclohexyloxyethoxy group, 1-(2-methylpropoxy)ethoxy group is preferable, at least one selected from the group consisting of ethoxyethoxy group, isopropyloxyethoxy group and cyclohexyloxyethoxy group is more preferable, and 1-ethoxyethoxy group is still more preferable.

[0074] As one embodiment of the novolak resin (A1c) having the group represented by the formula (20), for example, a resin containing a structural unit represented by the formula (a3B) (hereinafter sometimes referred to as "structural unit (a3B)") can be mentioned. TIFF2025110891000029.tif37170[In the formula (a3B), R a1’ and R a2’ each independently represent 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The 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 by an oxygen atom or a sulfur atom. R ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.]

[0075] R ab Examples of the alkyl group having 1 to 6 carbon atoms represented by include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group. R ab Examples of the alkoxy group having 1 to 6 carbon atoms represented by include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and the like. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, and still more preferably a methoxy group. R abis 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, still 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. p is preferably 0 to 2, more preferably 0 or 1.

[0076] The resin (A1c) has a group represented by the formula (20), and may be a novolak resin having, if necessary, an acid-labile group other than the group represented by the formula (20), for example, a group represented by the formula (10). When having a group represented by the formula (10) as an acid-labile group, the group represented by the formula (10) is introduced into a part or all of the phenolic hydroxyl groups in the novolak resin obtained by condensation as described above.

[0077] As the acid-labile group introduced into the phenolic hydroxyl group of the novolak resin, the group represented by the formula (10) is preferably a group represented by the formula (1'). Specifically, for example, a tert-butoxycarbonyloxy group, a 1-methylcyclopentan-1-yloxycarbonyloxy group, a 1-(cyclopentan-1-yl)-1-methylalkoxycarbonyloxy group, etc. can be mentioned.

[0078] As one embodiment of the novolak resin (A1c) having a group represented by the formula (10), for example, a resin containing a structural unit represented by the formula (a3A) (hereinafter sometimes referred to as "structural unit (a3A)") can be mentioned. TIFF2025110891000030.tif40170[In the formula (a3A), R a1 , R a2 and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R a3represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different. ]

[0079] Examples of the combination of structural units contained in the novolak resin (A1c) having the group represented by formula (20) include those represented by formula (A1c-1) to formula (A1c-12). TIFF2025110891000031.tif96170TIFF2025110891000032.tif193170

[0080] The introduction ratio (introduction rate) of the group represented by formula (20) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more with respect to the phenolic hydroxyl group of the novolak resin of the resin (A1c). Also, it is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. Furthermore, there is an optimal introduction rate depending on the acid-labile group. When the resin (A1c) has a group represented by formula (10), the introduction ratio (introduction rate) is the same as the introduction ratio (introduction rate) of the group represented by formula (20) described above. When the resin (A1) has an acid-labile group (2), the introduction ratio of the acid-labile group (2) is preferably 20 mol% or more, more preferably 30 mol% or more with respect to the phenolic hydroxyl group described above. When the resin (A1) has an ethoxyethoxy group as an acid-labile group, 30 to 60 mol% is even more preferable. When it has a propyloxyethoxy group, 20 to 60 mol% is even more preferable. When it has a cyclohexyloxyethoxy group, 20 to 60 mol% is even more preferable. By setting it within this range, the resolution, residual film rate, and heat resistance after pattern formation in a resist composition using this resin can be effectively ensured. The introduction ratio of the acid-labile group is, for example, 1It can be measured by 1H-NMR.

[0081] Examples of the method for introducing an acid-labile group into the phenolic hydroxyl group of a novolak resin include methods known in the art. For example, when introducing an ethoxyethoxy group as the acid-labile group, a predetermined amount of ethyl vinyl ether is added to the novolak resin at room temperature under an acid catalyst, and the reaction is carried out for a predetermined time under the acid catalyst. Then, diethyl ether is added and washed with water.

[0082] The weight average molecular weight of the resin (A1c) is preferably 3,000 or more, more preferably 4,000 or more, preferably 200,000 or less, and more preferably 100,000 or less. The weight average molecular weight is determined as a conversion value based on standard polystyrene by gel permeation chromatography analysis. The detailed analysis conditions for this analysis are described in the examples of the present application.

[0083] The content of the resin (A1c) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 30% by mass or more, preferably 95% by mass or less, more preferably 85% by mass or less, and still more preferably 70% by mass or less based on the total amount of the resins contained in the resist composition.

[0084] <Resin (A2)> The resin (A2) is an alkali-soluble resin. An alkali-soluble resin is a resin having an acidic group (sometimes referred to as a hydrophilic group) and soluble in an alkali developer. Examples of the acidic group include a carboxy group, a sulfo group, a hydroxy group (such as a phenolic hydroxyl group), and the like. Examples of the alkali-soluble resin include alkali-soluble resins known in the resist field, such as novolak resins, resins containing structural unit (a2-1) and not containing structural unit (a1), such as resins containing structural units derived from hydroxystyrene, resins containing structural units derived from (meth)acrylic acid esters, and polyalkylene glycols. Preferably, it is a novolak resin. The alkali-soluble resin preferably does not have an acid-labile group. That is, the alkali-soluble resin preferably contains a structural unit having an acidic group and does not contain a structural unit having an acid-labile group. The alkali-soluble resin preferably does not change its solubility in an alkaline aqueous solution upon contact with an acid. The alkali-soluble resin may be used alone or in combination of two or more. In resin (A2), the total content ratio of the structural units having an acidic group is preferably 3 to 100 mol%, more preferably 5 to 100 mol%, still more preferably 10 to 100 mol%, even more preferably 30 to 100 mol%, still even more preferably 50 to 100 mol%, even still more preferably 60 to 100 mol%, particularly preferably 70 to 100 mol%, and especially preferably 80 to 100 mol% with respect to all the structural units of resin (A2). Resin (A2) may contain only one type of structural unit having an acidic group or may contain a plurality of types.

[0085] Examples of the alkali-soluble resin include resins having a remaining film ratio of 0% or more and 90% or less when developed with an alkaline developer under actual use conditions. The remaining film ratio is preferably 0% or more and 85% or less, and more preferably 0% or more and 80% or less.

[0086] The residual film rate can be measured, for example, as follows. After dissolving the resin in an organic solvent, filtration is performed using a filter if necessary, and then it is applied onto a substrate using a spin coater or the like, followed by heating to remove the organic solvent. The organic film on the obtained substrate is measured with a film thickness meter, developed with a 2.38 mass% aqueous alkali solution, and again, the film thickness after development is measured with a film thickness meter. The residual film rate can be obtained by dividing the film thickness after development by the film thickness before development with respect to the measured value thus obtained. The development conditions are the actual use conditions. For example, the development temperature may be 5 to 60°C, and the development time may be 5 to 600 seconds. Examples of the alkali developer include various alkaline aqueous solutions used in this field, such as aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline).

[0087] A novolak resin is a resin obtained by condensing a phenol compound and an aldehyde in the presence of a catalyst, and can be selected, for example, from those described in the resin (A1c) above. As one aspect of the novolak resin, for example, a resin containing a structural unit represented by the formula (a4) (hereinafter sometimes referred to as "structural unit (a4)") can be mentioned. TIFF2025110891000033.tif27170[In the formula (a4), R ac represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p1 represents 0, 1, 2, or 3. When p1 is 2 or 3, R ac may be the same or different. q1 represents 1, 2, or 3. However, the sum of p1 and q1 is 4 or less.] R ac Examples of the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R ab include the same groups as those of R R acis 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, still 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. p1 is preferably from 0 to 2, more preferably 1 or 2. q1 is preferably 1 or 2, more preferably 1. The novolak resin preferably has a weight average molecular weight of 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, even more preferably 6,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, still more preferably 10,000 or less, even more preferably 9,000 or less, and even more preferably 8,000 or less. By setting the range within this value, it is possible to effectively prevent thinning of the film and remaining of residues after development. The weight average molecular weight is determined as a conversion value based on standard polystyrene by gel permeation chromatography analysis. The detailed analysis conditions for this analysis are described in the examples of the present application.

[0088] Examples of the resin containing a structural unit derived from hydroxystyrene include resins containing a structural unit derived from a monomer having a phenolic hydroxyl group such as hydroxystyrenes (p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene), isopropenylphenols (p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol), etc. Specifically, resins containing a structural unit represented by formula (a2-1) can be mentioned. The resin containing a structural unit derived from hydroxystyrene may contain, in addition to the structural unit derived from the above monomers, a structural unit derived from a monomer exemplified in the resin containing a structural unit derived from (meth)acrylate described below. The resin containing a structural unit derived from hydroxystyrene is typically poly(vinylphenol) (poly(hydroxystyrene)), preferably poly(p-vinylphenol) (poly(p-hydroxystyrene)). Specifically, resins composed of structural units represented by formula (a2-1) can be mentioned. Such poly(vinylphenol) can be obtained, for example, by polymerizing the monomers described in JP-A-2010-204634.

[0089] Examples of the resin containing a structural unit derived from a (meth)acrylate ester include those obtained by using the following compounds as monomers, combining one or more of these monomers, and polymerizing them by a conventional method. That is, the resin containing a structural unit derived from a (meth)acrylate ester includes resins containing structural units derived from the following monomers. Monomers having a carboxy group such as (meth)acrylic acid; Monomers having a hydroxy group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Monomers having a plurality of ether bonds such as polyethylene glycol monomethyl ether (meth)acrylate (polyalkylene glycol monoalkyl ether (meth)acrylate) such as 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, octaethylene glycol monomethyl ether (meth)acrylate, nonaethylene glycol monomethyl ether (meth)acrylate.

[0090] The above monomer and alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate; monocyclic (meth)acrylic acid esters such as cycloalkyl (meth)acrylates like cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate; polycyclic (meth)acrylic acid esters such as adamantyl (meth)acrylate, norbornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate; ethylene 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 (alkylene glycol monoalkyl ether (meth)acrylates) etc. may be used in combination. Further, in addition to the above monomers, styrenes such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 4-isopropoxystyrene; carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; hydroxystyrenes etc. exemplified in the resin containing the structural unit derived from the above hydroxystyrene may be used in combination. As the structural units derived from the monomers as described above, the structural units represented by formula (a2-1) to formula (a2-4) are also included. A polyalkylene glycol is a polymer obtained by addition polymerization of an alkylene oxide to alcohols. Examples of the alcohols include butanol, ethylene glycol, propylene glycol, glycerin, pentaerythritol etc. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide etc. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polybutylene glycol etc.

[0091] The content of the resin (A2) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and even more preferably 65% by mass or less, based on the total amount of the resins contained in the resist composition.

[0092] The resist composition of the present invention contains a resin (A1) containing a structural unit having a group represented by the formula (20), an alkali-soluble resin (A2), an acid generator (B) containing a compound represented by the formula (b0), and a compound (C) represented by the formula (I). The resin (A2) can adjust the solubility of the resist in a developer (alkali aqueous solution), for example, by interaction with a compound (E) or the like, and can have resistance to a developer (alkali aqueous solution) and a plating solution by crosslinking with a compound (E) or the like, so that the accuracy of the plated molded article can be improved.

[0093] The mass ratio ((A1):(A2)) of the contents of the resin (A1) and the resin (A2) contained in the resist composition is usually 20:80 to 80:20, preferably 30:70 to 70:30. Setting within this range is suitable because the accuracy of the plated molded article can be further improved.

[0094] In the resist composition of the present invention, the contents of the resin (A1) and the resin (A2) are preferably 80% by mass or more and 99% by mass or less based on the total amount of the solid content of the resist composition. The content of the 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, based on the total amount of the solid content of the resist composition. The content of the resin (A2) 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, based on the total amount of the solid content of the resist composition. The solid content and the contents of the respective components contained in the resist composition of the present invention can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0095] <Acid generator (B)> The acid generator (B) is a compound that can decompose upon light irradiation (exposure) to generate an acid. The generated acid can cause the leaving group contained in the acid-labile group (such as the group represented by formula (20)) of the resin (A1) to leave, and convert the acid-labile group into a hydrophilic group (for example, a carboxy group, a hydroxy group (such as a phenolic hydroxy group)). That is, by exposing the resist composition containing the resin (A1), the resist can be made soluble in a developer (an alkaline aqueous solution).

[0096] The acid generator (B) is characterized by containing a compound (B0) represented by formula (b0) (hereinafter sometimes referred to as "compound (B0)"), and may contain other acid generators as necessary. The compound (B0) is a sulfonate compound represented by formula (b0). TIFF2025110891000034.tif34170[In formula (b0), R b1 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom or a carbonyl group. X represents an oxygen atom or a sulfur atom. R 01 represents a hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom, a sulfur atom, or a carbonyl group. x0 represents an integer of 1 to 6. When x0 is 2 or more, the groups in the plurality of parentheses may be the same or different.]

[0097] 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 for R include a linear or branched chain hydrocarbon 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, and a group having 4 to 18 carbon atoms formed by combining 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 preferable, 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 and the like. Among these, linear ones are preferable. As the alicyclic hydrocarbon group having 3 to 18 carbon atoms, examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group and the like. As the aromatic hydrocarbon group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms is preferable, and examples thereof include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group and the like. Among the groups having 4 to 18 carbon atoms formed by combining the above groups, examples of the group formed by combining a chain hydrocarbon group and an alicyclic hydrocarbon group (group having 4 to 18 carbon atoms) include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornil group, an isobornyl group, a 2-alkyladamantan-2-yl group, a 1-(adamantan-1-yl)alkane-1-yl group and the like. Examples of the group formed by combining a chain hydrocarbon group and an aromatic hydrocarbon group (group having 7 to 18 carbon atoms) include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specifically, 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, a 2-methyl-6-ethylphenyl group and the like. Examples of the group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (group having 9 to 18 carbon atoms) include an aromatic hydrocarbon group having an alicyclic hydrocarbon group and an alicyclic hydrocarbon group having an aromatic hydrocarbon group, and specifically, a p-cyclohexylphenyl group, a p-adamantylphenyl group, a phenylcyclohexyl group and the like. R b1Of the hydrocarbon groups having 1 to 18 carbon atoms represented by, preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

[0098] R b1 Examples of the group in which the methylene group contained in the alicyclic hydrocarbon group having 3 to 18 carbon atoms in is substituted with an oxygen atom or a carbonyl group include groups represented by formula (Y1) to formula (Y12). Preferably, it is a group represented by formula (Y7) to formula (Y9), and more preferably, it is a group represented by formula (Y9). TIFF2025110891000035.tif57170

[0099] Examples of the hydrocarbon group having 1 to 18 carbon atoms having a fluorine atom include groups in which one or more hydrogen atoms contained in the above hydrocarbon group having 1 to 18 carbon atoms are substituted with fluorine atoms. Specifically, for example, fluoromethyl group, fluoroethyl group, fluoropropyl group, fluorobutyl group, fluoropentyl group, fluorohexyl group, fluoroheptyl group, fluorooctyl group, fluorononyl group, fluorodecyl group and other fluoroalkyl groups; fluorocyclopropyl group, fluorocyclobutyl group, fluorocyclopentyl group, fluorocyclohexyl group, fluorocycloheptyl, fluorocyclooctyl group, fluoroadamantyl group and other fluorocycloalkyl groups; fluorophenyl group, fluoronaphthyl group, fluoroanthryl group and other fluoroaryl groups.

[0100] Examples of the hydrocarbon group having 1 to 18 carbon atoms having a fluorine atom include preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an aromatic hydrocarbon group having 6 to 10 carbon atoms having a fluorine atom, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0101] R 01 Examples of the hydrocarbon group having 1 to 18 carbon atoms of include the above R b1Examples of the hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom include those exemplified as the hydrocarbon group having 1 to 18 carbon atoms. Further, the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom, a sulfur atom, or a carbonyl group. R 01 Among the hydrocarbon groups having 1 to 18 carbon atoms represented by 01 , preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these groups, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. x0 is preferably any integer from 1 to 5, more preferably any integer from 1 to 4, still more preferably any integer from 1 to 3, even more preferably 1 or 2, and still even more preferably 1.

[0102] Examples of the compound represented by formula (b0) include compounds represented by any of formula (b0-1) to formula (b0-21). Preferably, it is a compound represented by any of formula (b0-1) to formula (b0-13), and more preferably a compound represented by formula (b0-1), formula (b0-3), or formula (b0-5) to formula (b0-7). TIFF2025110891000036.tif115170TIFF2025110891000037.tif114170

[0103] The acid generator (B) may further contain other acid generators as long as it does not adversely affect the effects of the present invention. As the other acid generator, either a nonionic type or an ionic type may be used. Examples of nonionic acid generators include organic halides, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Examples of ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of anions of onium salts include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, etc.

[0104] As other acid generators, compounds that generate acid by radiation 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. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. can be used. Further, compounds produced by known methods may also be used. Other acid generators may be used singly or in combination of two or more.

[0105] Among other acid generators, examples of nonionic acid generators include compounds represented by formula (b1) to formula (b3). Compounds represented by formula (b1) and formula (b2) are preferred, and compounds represented by formula (b2) are more preferred. TIFF2025110891000038.tif92170[In formula (b1) to formula (b3), R b1 represents the same meaning as described above. R b2 、R b3 and R b4 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Ring W b1represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms or an aromatic heterocyclic ring having 6 to 14 carbon atoms. x1 represents any integer from 0 to 6. When x1 is 2 or more, a plurality of Rs b2 may be the same or different. x2 represents any integer from 0 to 5. When x2 is 2 or more, a plurality of Rs b3 may be the same or different. x3 represents any integer from 0 to 5. When x3 is 2 or more, a plurality of Rs b4 may be the same or different.]

[0106] Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc., preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc., preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group.

[0107] Examples of the aromatic hydrocarbon ring having 6 to 14 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, etc. Examples of the aromatic heterocyclic ring having 6 to 14 carbon atoms include rings having 6 to 14 atoms constituting the ring, and preferably the following rings are included. TIFF2025110891000039.tif22170 Ring W b1 is preferably a naphthalene ring.

[0108] As the compound represented by the formula (b1), a compound represented by any of the formulas (b4) to (b7) is preferable, and a compound represented by the formula (b4) is more preferable. TIFF2025110891000040.tif103170 [In the formulas (b4) to (b7), R b1 、R b2 and x1 represent the same meaning as described above. y represents an integer of any one of 0 to 4. When y is 2 or more, a plurality of Rs b2 may be the same or different. z represents an integer of any one of 0 to 2. When z is 2, two Rs b2 may be the same or different. X b1 and X b2 each independently represents -O-, -S- or -CO-.

[0109] x1 is preferably an integer of any one of 0 to 5, more preferably an integer of any one of 0 to 4, still more preferably an integer of any one of 0 to 3, even more preferably an integer of any one of 0 to 2, and even more preferably 0 or 1. x2 is preferably an integer of any one of 0 to 4, more preferably an integer of any one of 0 to 3, still more preferably an integer of any one of 0 to 2, and even more preferably 0 or 1. x3 is preferably an integer of any one of 0 to 4, more preferably an integer of any one of 0 to 3, still more preferably an integer of any one of 0 to 2, and even more preferably 0 or 1. y is preferably an integer of any one of 0 to 3, more preferably an integer of any one of 0 to 2, and even more preferably 0 or 1. z is preferably 0 or 1.

[0110] Examples of the compound represented by the formula (b1) include compounds represented by the formulas (b1-1) to (b1-17). Preferably, they are compounds represented by the formula (b1-6), the formula (b1-7), the formula (b1-10), the formula (b1-13) and the formula (b1-15). TIFF2025110891000041.tif198170

[0111] Examples of the compound represented by the formula (b2) include compounds represented by the following formula. TIFF2025110891000042.tif57170

[0112] Examples of the compound represented by the formula (b3) include compounds represented by the following formulas. TIFF2025110891000043.tif18170

[0113] Among other acid generators, as the ionic acid generator, a compound represented by the formula (b8) or the formula (b9) is preferable. TIFF2025110891000044.tif37170[In the formulas (b8) and (b9), A b1 and A b2 each independently represents an oxygen atom or a sulfur atom. R b8 、R b9 、R b10 and R b11 each independently represents an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. X1 - and X2 - represent an organic anion.]

[0114] 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, an octyl group and the like. Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group and the like. 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 specifically, 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, a 2-methyl-6-ethylphenyl group and the like. R b8 、R b9 、R b10 and R b11is each preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a phenyl group.

[0115] X1 - and X2 - Examples of the organic anion represented by include sulfonate anions, bis(alkylsulfonyl)amide anions, tris(alkylsulfonyl)methide anions, etc. Preferably, it is a sulfonate anion, and more preferably a sulfonate anion represented by the formula (b10). TIFF2025110891000045.tif22170[In the formula (b10), R b12 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.] R b12 Examples of are the same groups as R b1 in the formula (B1).

[0116] Examples of the compound represented by the formula (b8) include the following compounds. TIFF2025110891000046.tif103170

[0117] Examples of the compound represented by the formula (b9) include the following compounds. TIFF2025110891000047.tif62170

[0118] In the resist composition of the present invention, the content of the acid generator (B) is preferably 0.1 part by mass or more and 40 parts by mass or less, more preferably 0.5 part by mass or more and 30 parts by mass or less, still more preferably 1 part by mass or more and 20 parts by mass or less, and even more preferably 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin (A). The resist composition of the present invention may contain one kind of the acid generator (B) alone or a plurality of kinds. In addition, among the acid generators (B), the content of the compound (B0) is 10 to 100% by mass, preferably 30 to 100% by mass, more preferably 40 to 100% by mass, still more preferably 50 to 100% by mass, and even more preferably 55 to 100% by mass with respect to the total mass of the acid generator (B).

[0119] <Compound (C)> The resist composition of the present invention contains a compound (C) represented by the formula (I) (hereinafter sometimes referred to as "compound (C)"). Compound (C) is a compound having an action of capturing an acid generated from an acid generator upon exposure, and may also be referred to as quencher (C). TIFF2025110891000048.tif19170

[0120] [In formula (I), ring W 1 represents a heterocyclic ring having a nitrogen atom as an atom constituting the ring, or a benzene ring having a substituted or unsubstituted amino group. The heterocyclic ring may have a heteroatom other than the nitrogen atom, and the heterocyclic ring and the benzene ring may have a substituent other than the substituted or unsubstituted amino group. A 1 represents a phenyl group or a naphthyl group. n represents 2 or 3, and a plurality of A 1 may be the same or different.] The heterocyclic ring may be an aromatic ring or a non-aromatic ring. The number of nitrogen atoms in the heterocyclic ring is, for example, 1 to 3. The heterocyclic ring may have another heteroatom together with the nitrogen atom. Examples of the heteroatom include an oxygen atom, a sulfur atom, and the like. The substituted or unsubstituted amino group of the benzene ring is, for example, -NR 1 R 2 (R 1 and R 2Each independently represents a hydrogen atom, a linear 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. It is represented by.). The heterocyclic ring and the benzene ring may have substituents other than a substituted or unsubstituted amino group. Examples of the substituent include a hydroxy group, an alkyl group having 1 to 4 carbon atoms, and the like. Examples of the heterocyclic ring and the benzene ring include a ring represented by any of Formula (Y13) to Formula (Y34). TIFF2025110891000049.tif109170

[0121] [In the formula, R 1 and R 2 Each independently represents a hydrogen atom, a linear 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. o represents any integer from 1 to 4. The heterocyclic ring and the benzene ring may have a hydroxy group or an alkyl group having 1 to 4 carbon atoms. The bond is at an arbitrary position.]

[0122] Ring W 1 Preferably, it is a heterocyclic ring having at least one nitrogen atom and at least one oxygen atom or sulfur atom as atoms constituting the ring, a heterocyclic ring having at least two nitrogen atoms as atoms constituting the ring, a benzene ring having at least one substituted or unsubstituted amino group and at least one hydroxy group, or a benzene ring having at least two substituted or unsubstituted amino groups. Further, the heterocyclic ring is preferably a 5-membered or 6-membered aromatic heterocyclic ring.

[0123] Examples of the heterocyclic ring having at least one nitrogen atom and at least one oxygen atom or sulfur atom as atoms constituting the ring include the following. TIFF2025110891000050.tif32170

[0124] Examples of the heterocyclic ring having at least two nitrogen atoms as atoms constituting the ring include the following. TIFF2025110891000051.tif64170

[0125] Examples of the benzene ring having one or more substituted or unsubstituted amino groups and one or more hydroxy groups include the following. TIFF2025110891000052.tif39170[Wherein, R 1 and R 2 each independently represent 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. p represents 1, 2 or 3. q represents 1, 2 or 3.]

[0126] Examples of the benzene ring having two or more substituted or unsubstituted amino groups include the following. TIFF2025110891000053.tif34170[Wherein, R 1’ and R 2’ each independently represent 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. r represents 2, 3 or 4.]

[0127] Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include monocyclic alicyclic hydrocarbon groups such as monocyclic cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like; and polycyclic alicyclic hydrocarbon groups such as polycyclic cycloalkyl groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the like. Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. The aromatic hydrocarbon group may further have a substituent. Examples of the aromatic hydrocarbon group having a substituent include p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, and the like. Among them, ring W 1 is preferably a heterocyclic ring having two or more nitrogen atoms as atoms constituting the ring, more preferably a 5-membered or 6-membered aromatic heterocyclic ring having two or three nitrogen atoms as atoms constituting the ring, and still more preferably a ring represented by formula (C2-2) to formula (C2-11).

[0128] Examples of the compound (C) include compounds represented by any of formula (C0-1) to formula (C0-11). Preferably, it is a compound represented by any of formula (C0-2) to formula (C0-8). TIFF2025110891000054.tif105170

[0129] The compound (C) can be synthesized by a known method and is also commercially available. The content of the compound (C) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.05% by mass or more, preferably 4% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less based on the total amount of the solid content of the resist composition.

[0130] <Solvent (D)> The content of the solvent (D) is usually 45% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more in the resist composition, and usually 99.9% by mass or less, preferably 99% by mass or less, and 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.

[0131] 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. The resist composition may contain one kind of the solvent (D) alone or two or more kinds thereof.

[0132] <Compound (E)> The resist composition of the present invention may further contain a compound (E) having a quinonediazide sulfonyl group. In the unexposed portion, the compound (E) can suppress the dissolution of the resin (A2) in a developer (alkaline aqueous solution) by interacting with the hydrophilic group of the resin (A2). In the exposed portion, the quinonediazide group decomposes to generate a carboxy group, thereby generating a carboxylic acid and promoting the dissolution of the resin (A2) in a developer (alkaline aqueous solution). Further, in the unexposed portion, by crosslinking the resin (A2) in the presence of a developer (alkaline aqueous solution), the resist composition becomes resistant to the developer (alkaline aqueous solution) and a plating solution, thereby improving the accuracy of the plated product.

[0133] The compound (E) is not particularly limited as long as it has one or more quinonediazide sulfonyl groups in the molecule. It is preferable that the molecular weight of the compound obtained by replacing all the quinonediazide sulfonyl groups present in the molecule of the compound (E) with hydrogen atoms is 3000 or less, more preferably 2000 or less, and even more preferably 1500 to 400.

[0134] Examples of the compound having a quinonediazidosulfonyl group include compounds having a naphthoquinonediazidosulfonyl group, compounds having a benzoquinonediazidosulfonyl group, compounds having an anthraquinonediazidosulfonyl group, etc. Compounds having a naphthoquinonediazidosulfonyl group and compounds having a benzoquinonediazidosulfonyl group are preferred. As the compound having a naphthoquinonediazidosulfonyl group, it is preferably a compound having a 1,2-naphthoquinonediazidosulfonyl group, more preferably a compound having a group represented by formula (a) or a group represented by formula (b), and even more preferably a compound having a group represented by formula (a). As the compound having a benzoquinonediazidosulfonyl group, it is preferably a compound having a 1,2-benzoquinonediazidosulfonyl group, and more preferably a compound having a group represented by formula (c). TIFF2025110891000055.tif49170[In formula (a) and formula (b), * represents a bond.] TIFF2025110891000056.tif45170[In formula (c), * represents a bond.]

[0135] As the compound obtained by replacing all quinonediazidosulfonyl groups present in the molecule of the compound having a quinonediazidosulfonyl group with hydrogen atoms, it is preferably an aromatic compound having a phenolic hydroxyl group. As the compound having a quinonediazidosulfonyl group, it is preferably a compound obtained by quinonediazidosulfonic acid esterifying an aromatic compound having a phenolic hydroxyl group. As the compound having a quinonediazidosulfonyl group, it is more preferably at least one selected from the group consisting of the compound represented by formula (II) (hereinafter sometimes referred to as "compound (II)"), the compound represented by formula (III) (hereinafter sometimes referred to as "compound (III)"), the compound represented by formula (IV) (hereinafter sometimes referred to as "compound (IV)"), and the compound represented by formula (V) (hereinafter sometimes referred to as "compound (V)"). TIFF2025110891000057.tif57170[In formula (II), R11 ~R 14 each independently represents a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 18 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). The methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be replaced by an oxygen atom, a carbonyl group or -NR d1 -. R d1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 15 ~R 30 each independently represents a hydrogen atom, a hydroxy group, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). R 11 ~R 30 At least one of ~R is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).] TIFF2025110891000058.tif55170[In formula (III), R 31 ~R 39 each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). R 31 ~R 39 At least one of is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). P 1 ~P 5 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be replaced by an oxygen atom, a carbonyl group or -NR d2 -, and P 1 and P 2 may be bonded to each other to form a ring together with the two carbon atoms to which they are bonded. P 4 and P 5 may be bonded to each other to form a ring together with the carbon atom to which they are bonded. R d2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.] TIFF2025110891000059.tif29170[In formula (IV), R 40 ~R 53 each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). At least one of R 40 ~R 53 is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). n a represents any integer from 1 to 5. When n a is an integer of 2 or more, the plurality of R 49 ~R 52 may be the same as or different from each other.] TIFF2025110891000060.tif52170[In formula (V), R f1 R f2 and R g1 ~R g8 each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). At least one of R f1 R f2 and R g1 ~R g8 is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). P 6 represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The aromatic hydrocarbon group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms. P 7 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be replaced by an oxygen atom, a carbonyl group, or -NR d3 -. P 6 and P 7 may be bonded to each other to form a ring. n vrepresents 1 or 2. R d3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0136] Examples of the hydrocarbon group having 1 to 18 carbon atoms include a chain hydrocarbon group having 1 to 18 carbon atoms (including a linear or branched saturated chain hydrocarbon group having 1 to 18 carbon atoms (alkyl group), a linear or branched unsaturated chain hydrocarbon group having 2 to 18 carbon atoms (alkenyl group, alkynyl group), etc.), a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms (including a saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms, an unsaturated alicyclic hydrocarbon group having 3 to 18 carbon atoms, etc.), an aromatic hydrocarbon group having 6 to 18 carbon atoms, etc., and a combination of two or more of these groups may also be used. The alkyl group having 1 to 18 carbon atoms may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t- or sec-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, etc. Among them, a linear alkyl group is preferable. The alkenyl group having 2 to 18 carbon atoms may be either linear or branched, and examples thereof include an ethenyl group, a propenyl group, an isopropenyl group, a methylpropenyl group, a methylbutenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, a nonenyl group, etc. The alkynyl group having 2 to 18 carbon atoms may be either linear or branched, and examples thereof 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, a nonynyl group, etc. The chain hydrocarbon group having 1 to 18 carbon atoms preferably has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. Examples of the monocyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic saturated alicyclic hydrocarbon groups such as cycloalkyl groups like cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., and monocyclic unsaturated alicyclic hydrocarbon groups such as cyclopropenyl group, cyclobutenyl group, etc. Examples of the polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms include polycyclic saturated alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group, etc. The alicyclic hydrocarbon group having 3 to 18 carbon atoms preferably has 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 10 carbon atoms. Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. The aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.

[0137] As the alkyl group having 1 to 6 carbon atoms, a group corresponding to the alkyl group having 1 to 6 carbon atoms can be selected from the alkyl groups having 1 to 18 carbon atoms described above.

[0138] P 1 and P 2 rings formed by bonding to each other together with the two carbon atoms to which they are bonded, and P 4 and P 5 rings formed by bonding to each other together with the carbon atom to which they are bonded include, independently of each other, monocyclic or polycyclic alicyclic hydrocarbon rings having 3 to 18 carbon atoms, etc. Examples of these rings include cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, etc.; decahydronaphthalene ring, adamantane ring, norbornane ring, etc. The alicyclic hydrocarbon ring having 3 to 18 carbon atoms preferably has 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 10 carbon atoms.

[0139] P 7Examples of the substituent of the hydrocarbon group having 1 to 18 carbon atoms include a halogen atom, a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like. Examples of the acyl group having 2 to 4 carbon atoms include an acetyl group, a propionyl group, a butyryl group, and the like. Examples of the acyloxy group having 2 to 4 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like.

[0140] Specific examples of the compound (II) include, for example, compounds represented by the formulas (II-1) to (II-3). TIFF2025110891000061.tif57170 Here, R s2 each independently represents a group represented by the above formula (a), a group represented by the formula (b), a group represented by the formula (c), or a hydroxy group. At least one of R s2 in each compound is a group represented by the formula (a), a group represented by the formula (b), or a group represented by the formula (c).

[0141] Specific examples of the compound (III) include, for example, compounds represented by the formulas (III-1-1) to (III-3-8). TIFF2025110891000062.tif46170TIFF2025110891000063.tif206170 Here, R t1 each independently represents a group represented by the above formula (a), a group represented by the formula (b), a group represented by the formula (c), or a hydroxy group. At least one of R t1 in each compound is a group represented by the formula (a), a group represented by the formula (b), or a group represented by the formula (c).

[0142] Specific examples of the compound (IV) include, for example, the compounds represented by the formulas (IV-1-1) to (IV-5-2). TIFF2025110891000064.tif189170Here, R t1 、R t3 、R t6 、R t7 、R t9 、R t10 and R t13 each independently represents a group represented by the above formula (a), a group represented by the formula (b), a group represented by the formula (c), or a hydroxy group. At least one of R t1 、R t3 、R t6 、R t7 、R t9 、R t10 and R t13 in each compound is a group represented by the formula (a), a group represented by the formula (b), or a group represented by the formula (c).

[0143] Specific examples of the compound (V) include, for example, the compounds represented by the formulas (V-1-1) to (V-3-1). TIFF2025110891000065.tif119170Here, R v each independently represents a group represented by the above formula (a), a group represented by the formula (b), a group represented by the formula (c), or a hydroxy group. At least one of R v in each compound is a group represented by the formula (a), a group represented by the formula (b), or a group represented by the formula (c).

[0144] Compound (E) can be produced, for example, in accordance with the descriptions in JP-A-2-84650, JP-A-3-185447, JP-A-3-191351, JP-A-5-323597, JP-A-8-245461, JP-A-9-110762, etc. Compound (I) can be produced, for example, by reacting an aromatic compound having a phenolic hydroxyl group (for example, a compound in which all the quinonediazidosulfonyl groups in the molecules of the above-described compounds (II) to (V) are replaced with hydrogen atoms, etc.) with a quinonediazidosulfonyl halide (for example, quinonediazidosulfonyl chlorides such as 1,2-naphthoquinonediazidosulfonyl chloride, 1,2-benzoquinonediazidosulfonyl chloride, etc., quinonediazidosulfonyl bromides such as 1,2-naphthoquinonediazidosulfonyl bromide, 1,2-benzoquinonediazidosulfonyl bromide, etc.) in the presence of a weak alkali to effect complete esterification or partial esterification. The aromatic compound having a phenolic hydroxyl group can be easily obtained from the market and can also be produced by known methods.

[0145] The content of compound (E) is preferably 0.05% by mass or more and 25% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, still more preferably 0.5% by mass or more and 15% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less in the solid content of the resist composition. The content of compound (E) in the resist composition can be measured by known analytical means such as liquid chromatography or gas chromatography. As compound (E), compound (III) and compound (IV) are preferable, and compound (III) is more preferable.

[0146] <Adhesion improver (F)> The resist composition of the present invention may contain an adhesion improver (F) in order to prevent corrosion and / or improve adhesion to metals or the like used for substrates or wirings. The adhesion improver (F) exerts an anti-rust effect by preventing corrosion of metals. Also, together with these effects, it can improve the adhesion between the substrate or metal or the like and the resist composition. Examples of the adhesion improver (F) include sulfur-containing compounds, aromatic hydroxy compounds, benzotriazole-based compounds, triazine-based compounds, and silicon-containing compounds. These can be used alone or in combination of two or more.

[0147] 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 the chain compound 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], 3-mercapto-1-propanol [HSCH2CH2CH2], etc.

[0148] The sulfur-containing compound preferably has a sulfide bond and a mercapto group, and more preferably is 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 any of them may be 1 or more. The heterocyclic ring in the heterocyclic ring 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 heterocyclic ring is preferably a heterocyclic ring having 2 to 12 carbon atoms, more preferably a heterocyclic ring having 2 to 6 carbon atoms. The heterocyclic ring is preferably a monocyclic ring. The heterocyclic ring is preferably unsaturated. The heterocyclic ring is preferably unsaturated and monocyclic.

[0149] Examples of the heterocyclic ring include the following heterocyclic rings. TIFF2025110891000066.tif37170

[0150] The sulfur-containing compound may be a polymer. This polymer preferably contains a structure having a sulfide bond and a mercapto group in the side chain. The structure having a sulfide bond and a mercapto group (hereinafter sometimes referred to as unit (1)) and the main chain are preferably bonded by a linking group such as an amide bond, an ether bond, a thioether bond, or an ester bond.

[0151] The polymer may be a homopolymer or a copolymer. When the polymer is a copolymer, it may contain a structural unit (a1) having an acid-labile group, a structural unit (a2) not having an acid-labile group, and the like described above. The weight average molecular weight of the above-mentioned 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 as a conversion value based on standard polystyrene by gel permeation chromatography analysis. 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%, more preferably 1 to 20 mol% with respect to all the structural units of the polymer of the sulfur-containing compound.

[0152] 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). TIFF2025110891000067.tif26170[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 a group represented by, or -NR 12 R 13 a group represented by. R 11 R 12 and R 13 each independently represent 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 each independently represent 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. However, 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.]

[0153] Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include aryl groups having 6 to 14 carbon atoms, such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. The aromatic hydrocarbon group may further have a substituent. Examples of the aromatic hydrocarbon group having a substituent include aralkyl group and aromatic hydrocarbon group having an alkyl group. Specifically, benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc. are included. Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups, such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group, etc.

[0154] 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, independently of each other, 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 acetyl group, propionyl group, butyryl group, valeryl group, hexylcarbonyl group, heptylcarbonyl group, octylcarbonyl group, decylcarbonyl group, dodecylcarbonyl group, benzoyl group, etc.

[0155] R i11 is more preferably a hydrogen atom or a mercapto group. R i12 and R i13 are preferably, independently of each other, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom. A and B are preferably such that at least one of them is a nitrogen atom, more preferably both of them are nitrogen atoms. TIFF2025110891000068.tif50170[In formula (IB), R i21 and R i31 each independently represent a hydrogen atom, a linear 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 each independently represent a nitrogen atom or a carbon atom. n2 and m2 each independently represent 0 or 1. However, when A 1 is a nitrogen atom, n2 represents 0, and when A 1 is a carbon atom, n2 represents 1. When B 1 is a nitrogen atom, m2 represents 0, and when B 1 is a carbon atom, m2 represents 1. R i4 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. The methylene group contained in the hydrocarbon group may be replaced by an oxygen atom or a carbonyl group.]

[0156] R i21 and R i31 Examples of the linear hydrocarbon group having 1 to 10 carbon atoms for R R i21 and R i31Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include aryl groups having 6 to 14 carbon atoms such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc., and preferably aryl groups having 6 to 10 carbon atoms. The aromatic hydrocarbon group may further have a substituent. Examples of the aromatic hydrocarbon group having a substituent include aralkyl groups and aromatic hydrocarbon groups having an alkyl group. Specifically, benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc. may be mentioned. R i21 and R i31 Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups of cycloalkyl groups having 3 to 18 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc.; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group, etc. Preferably, alicyclic hydrocarbon groups having 5 to 10 carbon atoms may be mentioned. R i21 and R i31 are preferably, independently of each other, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0157] L i1Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by 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-1,14-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, a 2-methylbutane-1,4-diyl group, and the like; a monocyclic divalent alicyclic saturated hydrocarbon group such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclooctane-1,5-diyl group; a polycyclic divalent alicyclic saturated hydrocarbon group such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane-1,5-diyl group, an adamantane-2,6-diyl group; Examples thereof include arylene groups such as a phenylene group, a tolylene group, and a naphthylene group. L i1 is preferably a group formed by combining an alkanediyl group having 2 to 14 carbon atoms or an arylene group having 6 to 10 carbon atoms containing an ester bond and an alkanediyl group having 1 to 11 carbon atoms.

[0158] The structural unit represented by formula (IB) is preferably the structural unit represented by formula (IB-1) or the structural unit represented by formula (IB-2). TIFF2025110891000069.tif81170[In formula (IB-1), R i22 and R i32Each independently represents a hydrogen atom, a linear 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 Each independently represents a nitrogen atom or a carbon atom. n3 and m3 each independently represent 0 or 1. However, when A 2 is a nitrogen atom, n3 represents 0, and when A 2 is a carbon atom, n3 represents 1. When B 2 is a nitrogen atom, m3 represents 0, and when 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. The 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 Each independently represents a hydrogen atom, a linear 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 Each independently represents a nitrogen atom or a carbon atom. n4 and m4 each independently represent 0 or 1. However, when A 3 is a nitrogen atom, n4 represents 0, and when A 3 is a carbon atom, n4 represents 1. When B 3 is a nitrogen atom, m4 represents 0, and when B 3 is a carbon atom, m4 represents 1. X i12 represents a sulfur atom and an NH group. L i3 represents a divalent hydrocarbon group having 1 to 14 carbon atoms. The methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. R i7represents 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.

[0159] R i22 R i32 R i23 and R i33 Examples of the linear hydrocarbon group having 1 to 10 carbon atoms represented by R i21 and R i31 are the same as those of the linear hydrocarbon group having 1 to 10 carbon atoms represented by R R i22 R i32 R i23 and R i33 Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R i21 and R i31 are the same as those of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R R i22 R i32 R i23 and R i33 Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by R i21 and R i31 are the same as those of the alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by R

[0160] L i2Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms represented by include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and other alkanediyl groups; monocyclic divalent alicyclic saturated hydrocarbon groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group and other cycloalkanediyl groups; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group and the like; arylene groups such as phenylene group, tolylene group, naphthylene group and the like can be mentioned. L i2 is preferably an alkanediyl group having 1 to 14 carbon atoms, more preferably an alkanediyl group having 1 to 11 carbon atoms.

[0161] L i3Examples of the divalent hydrocarbon group having 1 to 14 carbon atoms represented by 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, 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, a 2-methylbutane-1,4-diyl group, and other alkanediyl groups; a monocyclic divalent alicyclic saturated hydrocarbon group such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclooctane-1,5-diyl group, and other cycloalkanediyl groups; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane-1,5-diyl group, an adamantane-2,6-diyl group, and the like. L i3 is preferably an alkanediyl group having 1 to 14 carbon atoms, more preferably an alkanediyl group having 1 to 11 carbon atoms. Based on the position where it is bonded to the main chain in the phenyl group, L i3 is preferably bonded to the p-position.

[0162] R i7 Examples of the alkyl group having 1 to 6 carbon atoms represented by include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. R i7 Examples of the alkoxy group having 1 to 6 carbon atoms represented by include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like.

[0163] Examples of the sulfur-containing compound include any compound represented by a compound represented by formula (I-1) to a compound represented by formula (I-26). Among them, compounds represented by formula (I-1) to compounds represented by formula (I-13) are preferable, and compounds represented by formula (I-1), compounds represented by formula (I-4), and compounds represented by formula (I-11) are more preferable. TIFF2025110891000070.tif81170TIFF2025110891000071.tif101170

[0164] Examples of the sulfur-containing compound include a homopolymer composed of any one of the structural units represented by formula (I-27) to formula (I-38) or a copolymer containing one or more of these structural units. Preferably, it is a copolymer containing one or more of the structural units represented by formula (I-27) to formula (I-36), and more preferably a copolymer containing the structural unit represented by formula (I-33). TIFF2025110891000072.tif145170

[0165] Examples of such a copolymer include a copolymer composed of the structural units represented by formula (I-39) to formula (I-48). Among them, polymers having the structural units represented by formula (I-39) to formula (I-44) are preferable. TIFF2025110891000073.tif246170TIFF2025110891000074.tif161170

[0166] The sulfur-containing compound may be synthesized by a known method (for example, JP-A-2010-79081) or may be a commercially available product. The polymer containing the sulfur-containing compound may be a commercially available product (for example, bismuthiol (manufactured by Tokyo Chemical Industry Co., Ltd., etc.)) or may be synthesized by a known method (for example, JP-A-2001-75277).

[0167] Examples of the aromatic hydroxy compound 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, gallic acid, and the like.

[0168] Examples of the benzotriazole compound include a compound represented by the formula (IX). TIFF2025110891000075.tif30170[In the formula (IX), R 1 and R 2 each independently represent 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 represents 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 the nitrogen atom contained in the ring. R 4X and R 5X each independently represent 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.]

[0169] R 1 、R 2The hydrocarbon group having 1 to 10 carbon atoms for Q may be either an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and may have a saturated and / or unsaturated bond. As the aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkyl group is preferable. 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, an n-heptyl group, and the like. As the aromatic hydrocarbon group having 6 to 10 carbon atoms, an aryl group is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, and the like. The aromatic hydrocarbon group may further have a substituent. Examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group. Specifically, 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, a 2-methyl-6-ethylphenyl group, and the like can be mentioned. Examples of the substituent that the hydrocarbon group having 1 to 10 carbon atoms may have include a hydroxyalkyl group, an alkoxyalkyl group, and the like. R 3X The alkanediyl group having 1 to 6 carbon atoms for R may be either linear or branched. Examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, and the like. R 4X and R 5X Examples of the alkyl group having 1 to 6 carbon atoms for R and R include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. R 4X and R 5X Examples of the hydroxyalkyl group having 1 to 6 carbon atoms for R and R include a hydroxymethyl group, a hydroxyethyl group, a dihydroxyethyl group, and the like. R 4X and R 5XExamples of the alkoxyalkyl group having 2 to 6 carbon atoms include a methoxymethyl group, a methoxyethyl group, a dimethoxyethyl group and the like.

[0170] When the resist composition of the present invention is applied to a substrate on which Cu is formed, in formula (IX), Q is **-R 3X -N(R 4X )(R 5X )-represented compounds are preferred. Among them, when at least one of R 4X and R 5X is an alkyl group having 1 to 6 carbon atoms, the benzotriazole-based compound becomes less water-soluble, but is preferably used when there are other components capable of dissolving this compound.

[0171] Further, when the resist composition of the present invention is applied to a substrate having an inorganic material layer (for example, a polysilicon film, an amorphous silicon film, etc.), in formula (IX), Q 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 and the like are preferred. Thereby, the anticorrosion property of the substrate can be more effectively exhibited.

[0172] Examples of the benzotriazole-based compound include benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethylbenzotriazole, methyl 1-benzotriazolecarboxylate, 5-benzotriazolecarboxylic acid, 1-methoxy-benzotriazole, 1-(2,2-dihydroxyethyl)-benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, or 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, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bispropane, and the like.

[0173] Examples of the triazine-based compound include the compound represented by formula (II). TIFF2025110891000076.tif26170[In formula (II), R 6 、R 7 and R 8 each independently represent a halogen, 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.] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 10 carbon atoms are the same as those described above. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and the like.

[0174] Examples of the triazine-based compound include 1,3,5-triazine-2,4,6-trithiol, and the like.

[0175] Examples of the silicon-containing compound include a compound represented by formula (IIA). TIFF2025110891000077.tif31170[In formula (IIA), R j1 represents an aliphatic 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 an aliphatic 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, and at least one of R j2 ~R j4 is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms. t i represents an integer of 1 to 10.]

[0176] Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, and pentyl group. Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group and ethoxy group. Examples of the mercaptoalkyl group having 1 to 5 carbon atoms include methyl mercapto group, ethyl mercapto group, and propyl mercapto group.

[0177] 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, 3-mercaptopropyl group). R j2 ~R j4 each independently is preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more preferably a methyl group or a methoxy group. However, 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 R j3They may be the same as or different from each other, but are preferably the same from the viewpoint of productivity.

[0178] Examples of the compound of formula (IIA) include compounds represented by the following formula (II-1) to formula (II-7). TIFF2025110891000078.tif193170Among them, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and the like are preferable.

[0179] The content of the adhesion improver (F) is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, still more preferably 0.005% by mass or more, particularly preferably 0.008% by mass or more, based on the total amount of the solid content of the resist composition, and is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 4% by mass or less, even more preferably 3% by mass or less, most preferably 1% by mass or less, particularly preferably 0.1% by mass or less. By setting it within this range, a resist composition capable of forming a high-precision resist pattern can be obtained, and the adhesion between the resist pattern and the substrate can be ensured.

[0180] <Other components> The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter sometimes referred to as "other components"). There is no particular limitation on the other components, and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used. When using other components, the content thereof is appropriately selected according to the type of the other components.

[0181] 2. Preparation of resist composition The resist composition of the present invention can be prepared by mixing a resin (A1) containing a structural unit having a group represented by formula (20), an alkali-soluble resin (A2), an acid generator (B) containing a compound represented by formula (b0), a compound (C) represented by formula (I), a solvent (D) as required, a compound (E) having a quinonediazide sulfonyl group, an adhesion improver (F) and other components. The mixing order is arbitrary and not particularly limited. The temperature for mixing can be appropriately selected from 10 to 40 °C according to the type of resin and the solubility of the resin in the solvent (D). The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used. After mixing the components, it is preferable to filter using a filter with a pore size of about 0.003 to 50 μm.

[0182] 3. Method for manufacturing resist pattern The method for producing a resist pattern of the present invention comprises (1) a step of applying the resist composition of the present invention onto the metal surface of a substrate having a metal surface, (2) a step of drying the applied resist composition to form a composition layer, (3) a step of exposing the composition layer and (4) a step of developing the exposed composition layer.

[0183] To apply the resist composition onto the substrate, it can be performed by a commonly used apparatus such as a spin coater. Alternatively, a photosensitive dry film formed by applying the resist composition onto a base film may be laminated onto the substrate. Examples of the substrate include inorganic substrates such as silicon wafers, and semiconductor elements (e.g., transistors, diodes, etc.) may be formed in advance on the substrate. 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. Examples of the conductive material include 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 antireflection film or the like may be formed on the substrate. By drying the applied composition, the solvent is removed to 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 using a decompression device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 30 to 600 seconds. Also, the pressure during vacuum drying is preferably about 1 to 1.0×10 5 Pa. After drying, the film thickness of the obtained composition is preferably 1 to 150 μm, more preferably 1.5 to 100 μm. The obtained composition layer is usually exposed using an exposure machine. As the exposure light source, a light source that emits light with a wavelength of 345 to 436 nm (g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), i-line (wavelength: 365 nm)), a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm) that emits laser light in the ultraviolet region, a solid laser light source (YAG or semiconductor laser, etc.) that converts the laser light into harmonic laser light in the far ultraviolet region or vacuum ultraviolet region and emits it, an electron beam, an extreme ultraviolet light (EUV) irradiating device, etc., various ones can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure" in some cases. During exposure, usually, exposure is performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. The composition layer after exposure may be subjected to heat treatment (so-called post-exposure bake) to promote the elimination reaction in the acid-labile group of the resin (A1). The heating temperature is usually about 50 to 200 °C, preferably about 70 to 150 °C. The heating time is usually 40 to 400 seconds, preferably 50 to 350 seconds.

[0184] The heated composition layer is usually developed using a developer with a developing apparatus. Examples of the developing method include dip method, paddle method, spray method, dynamic dispense method, etc. The developing temperature is preferably, for example, 5 to 60 °C, and the developing 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 manufactured.

[0185] When manufacturing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be various alkaline aqueous solutions used in this field. For example, aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline) etc. may be mentioned. The alkaline developer may contain a surfactant. It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern. When manufacturing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic-based developer") is used as the developer. Examples of the organic solvent contained in the organic-based developer 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; aromatic hydrocarbon solvents such as anisole, etc. In the organic developing solution, the content of the organic solvent 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 still more preferably substantially only the organic solvent. Among them, as the organic developing solution, a developing solution containing butyl acetate and / or 2-heptanone is preferable. In the organic developing solution, the total content of butyl acetate and 2-heptanone 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 still more preferably substantially only butyl acetate and / or 2-heptanone. The organic developing solution may contain a surfactant. Further, the organic developing solution may contain a trace amount of water. During development, development may be stopped by replacing with a solvent of a type different from the organic developing solution. It is preferable to wash the resist pattern after development with a rinse solution. The rinse solution is not particularly limited 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 washing, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

[0186] By exposing the resist obtained using the resist composition of the present invention, a resist pattern with a highly accurate shape can be formed.

[0187] 4. Method for manufacturing electroformed article Using the resist pattern formed by the above method as a mold, an electrode material is deposited by plating, and the resist pattern is peeled off, whereby plating-shaped objects such as bumps and rewiring can be formed. The method for manufacturing a plating-shaped object of the present invention (5) a step of forming a plating-shaped object using the resist pattern as a mold, and (6) a step of peeling off the resist pattern. Using a resist pattern formed on a substrate having a conductive layer or the like as a mold, a conductive material is deposited using an electroplating solution by a known method to form an electroformed article. Examples of the electroplating solution include a copper electroplating solution, a gold electroplating solution, a nickel electroplating solution, a solder electroplating solution, a silver tin electroplating solution, and the like. After forming the electroformed article, 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; 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-methylbutyrate, 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, electroformed articles such as bumps and rewiring can be formed. In addition, when forming the plated shaped article, in order to improve the adhesion between the conductive layer and the plated shaped article, ashing treatment or the like may be performed on the surface of the conductive layer. Examples of the ashing treatment method include a method using oxygen plasma.

[0188] The plated shaped article obtained by using the resist pattern of the present invention has little swelling in the plating bath, so that the plated shaped article can be formed with high accuracy.

[0189] 5. Use The resist composition of the present invention is useful for the production of thick film resist films. For example, it is useful for producing a resist film having a film thickness of 1 to 150 μm. In addition, the resist composition of the present invention is useful for the production of bumps and rewiring by a plating process. When bumps and rewiring are produced using the resist composition, they can usually be formed by the following procedure. Thereby, a resist pattern having a particularly excellent pattern shape can be produced. First, a conductive material (seed metal) is laminated on a wafer on which a semiconductor element or the like is formed to form a conductive layer. Then, a resist pattern is formed on the conductive layer using the resist composition of the present invention. Next, using the resist pattern as a mold, an electrode material (for example, Cu, Ni, solder, etc.) is deposited by plating, and the resist pattern and the conductive layer remaining under the resist pattern are removed by etching or the like, whereby bumps and rewiring can be formed. After removing the conductive layer, if necessary, a material obtained by melting the electrode material by heat treatment may be used as a bump.

Examples

[0190] The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or the amount used are based on mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions. Apparatus: HLC-8320GPC type (manufactured by Tosoh Corporation) Column: TSKgel Multipore HXL -M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI detector Column temperature: 40 °C Injection volume: 100 μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

[0191] Synthesis Example 1 [Synthesis of Resin (A1)-1] 20 parts of poly-p-hydroxystyrene (S-4P; manufactured by Maruzen Petrochemical Co., Ltd.) was dissolved in 240 parts of methyl isobutyl ketone at room temperature and concentrated using an evaporator. To a four-necked flask equipped with a reflux condenser, a stirrer, and a thermometer, the concentrated resin solution and 0.003 parts of p-toluenesulfonic acid dihydrate were added. 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 and washed with ion-exchanged water and separated 5 times. The resulting organic layer was concentrated to 45 parts using an evaporator, 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 (solid content 29%). Resin (A1)-1 is a resin having the following structural units. The weight average molecular weight of resin (A1)-1 was 1.16×10 4 It was. The ratio of the hydroxy group in poly-p-hydroxystyrene substituted with an ethoxyethoxy group was 40.9%. TIFF2025110891000079.tif37170

[0192] Synthesis Example 2 [Synthesis of Resin (A1)-2] 120 parts of phenol novolak resin (PSM-4326 manufactured by Gunei Chemical Industry Co., Ltd.) and 960 parts of methyl isobutyl ketone were added to a flask and dissolved. The obtained phenol novolak resin solution was washed 5 times with ion-exchanged water and separated by liquid separation. The obtained organic layer was concentrated until it reached 327.3 parts. The resin content concentration in the obtained resin solution was 35.2%. 56.8 parts of the obtained resin solution, 76.52 parts of methyl isobutyl ketone, and 0.0036 part of p-toluenesulfonic acid monohydrate were added to a flask. 8.81 parts of ethyl vinyl ether was added dropwise to this mixture, and the mixture was reacted at room temperature for 3 hours. Ion-exchanged water was added to this reaction solution, stirred, allowed to stand, and the organic layer was taken out by liquid separation. This washing with ion-exchanged water was repeated 4 more times for a total of 5 washings. Then, the organic layer was taken out and concentrated. Then, in order to remove water and methyl isobutyl ketone by azeotropic distillation, propylene glycol monomethyl ether acetate was added and further concentrated to obtain 57.44 parts of a resin solution. The obtained resin solution is a solution of a resin in which the hydroxy groups of the phenol novolak resin are partially 1-ethoxyethylated. This resin 1 When analyzed by 1H-NMR, 53.0% of the hydroxy groups of the phenol novolak resin were substituted with 1-ethoxyethyl ether. Also, when the concentration of the resin solution was measured using the dry weight loss method, it was 45.0%. This resin is designated as resin (A1)-2. Resin (A1)-2 is a resin having the following structural unit. The weight average molecular weight of resin (A1)-2 was 7.2×10 3 as follows. TIFF2025110891000080.tif31170

[0193] Synthesis Example 3 [Synthesis of Resin (A1)-3] 118 g of dioxane was charged into a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, and the temperature was raised to 77°C. To the obtained mixture, 54.7 g of 1-ethylcyclopentyl methacrylate and polyethylene glycol monomethyl ether methacrylate ("Light Ester 130MA" manufactured by Kyoeisha Chemical Co., Ltd.). TIFF2025110891000081.tif is represented by 25170, and is a compound where n is approximately 9.) 29.8 g, 45.2 g of methoxydiethylene glycol methacrylate, and 0.4 g of azobisisobutyronitrile were dissolved in 59 g of dioxane, and the solution was added dropwise over 1 hour, and stirring was continued at the same temperature for 10 hours. After cooling, the resulting reaction mixture was diluted with 130 g of methanol and 92 g of propylene glycol methyl ether acetate. The diluted reaction mixture was poured into 1440 g of water to precipitate the resin. The filtered precipitate was dissolved in 184 g of propylene glycol methyl ether acetate. The resulting solution was poured into a mixed solvent of 423 g of methanol and 918 g of water to precipitate the resin again. The resulting precipitate was dissolved in propylene glycol methyl ether acetate and then concentrated to obtain a 40% concentration solution of resin (A1)-3. The weight average molecular weight of the obtained resin (A1)-3 was 1.60×10 5 It was. Resin (A1)-3 has the following structural units. TIFF2025110891000082.tif36170

[0194] Synthesis Example 4 [Synthesis of Resin (A2)-1] Into a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 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 were added. The temperature was raised until reflux, and the mixture was kept at that temperature for 4 hours. After cooling, 1320 parts of methyl isobutyl ketone was added, and 1075 parts of the solvent was distilled off at atmospheric pressure. 762.7 parts of m-cresol and 29.0 parts of 2-tert-butyl-5-methylphenol were added thereto, and the temperature was raised to 65°C. 678 parts of a 37% aqueous formalin solution was added dropwise over 1.5 hours while adjusting the temperature so that it reached 87°C at the end of the dropping. The resulting mixture was kept at 87°C for 10 hours, 1115 parts of methyl isobutyl ketone was added, and the mixture was washed by liquid separation three times with ion-exchanged water. 500 parts of methyl isobutyl ketone was added to the resulting mixture, and the mixture was concentrated under reduced pressure until the total amount reached 3435 parts. 3796 parts of methyl isobutyl ketone and 4990 parts of n-heptane were added to the resulting mixture, and the temperature was raised to 60°C and stirred for 1 hour. Then, liquid separation was carried out, and the lower layer containing the resin was taken out, 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 (A2)-1 (solid content 43%). The weight average molecular weight of novolak resin (A2)-1 was 7×10 3 It was. Further, the residual film ratio when developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was 74%. The residual film ratio was measured by the method described in the section of <resin (A2)> in the detailed description of the invention.

[0195] <Preparation of resist composition> A resist composition was prepared by filtering a mixture obtained by mixing and dissolving each component shown in Table 1 through a fluororesin filter having a pore size of 0.5 μm.

[0196]

Table 1

[0197] <Resin> (A1)-1: Resin (A1)-1 (A1)-2: Resin (A1)-2 (A1)-3: Resin (A1)-3 (A2)-1: Resin (A2)-1

[0198] <Acid generator (B)> (B0)-1: Compound represented by the following formula (ILP-113; manufactured by Helius) TIFF2025110891000084.tif32170(B1)-1: N-Hydroxynaphthalimide triflate (NIT; manufactured by Helius) TIFF2025110891000085.tif26170(B2)-1: Compound represented by the following formula (PAG-103; manufactured by BASF) TIFF2025110891000086.tif32170

[0199] <Compound (E)> (E)-1: Synthesized by the method described in JP-A-9-110762 Note that, for 1 mol of the following compound in which R t1 , R t6 , R t7 , R t9 , R t10 is a hydroxy group, 2 mol of sulfonyl chloride has reacted, and the reaction has proceeded almost 100%. Therefore, it was confirmed that it is mainly a disubstituted product in which the hydrogen atoms at two of the hydroxy groups among R t1 , R t6 , R t7 , R t9 , R t10 are substituted with 1,2-naphthoquinonediazidosulfonyl groups (MS: M+: 1080). TIFF2025110891000087.tif35170

[0200] <Quencher (C)> (C)-1: 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (C)-2: N,N-Dicyclohexylmethylamine (manufactured by Sigma-Aldrich) (C)-3: 2-Phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) <Solvent (D)> (D)-1: Propylene glycol monomethyl ether acetate <Surfactant> Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.005 parts

[0201] Examples 1 to 6, Comparative Examples 1 to 6 (i-line exposure evaluation of resist composition) The above resist composition was spin-coated on a substrate with copper vapor-deposited on a 4-inch silicon wafer so that the film thickness after pre-baking was 4.0 μm. Thereafter, it was pre-baked at 100 °C for 180 seconds on a direct hot plate to form a composition layer. Next, an i-line stepper (NSR-2005i9C; manufactured by Nikon Corporation, NA = 0.5) was used to expose the composition layer formed on the wafer through a mask for forming a 1:1 line and space pattern (line width 1 μm) while changing the exposure dose stepwise. After exposure, post-exposure baking was performed at 70 °C for 60 seconds (except for Comparative Example 4) or 90 °C for 60 seconds (Comparative Example 4) on a hot plate, and then paddle development was carried out with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 180 seconds to obtain a resist pattern. The resist pattern obtained after development was observed with a scanning electron microscope, and the exposure dose at which a 1:1 line and space pattern with a line width of 1 μm was obtained was defined as the effective sensitivity.

[0202] <Pattern shape evaluation> At the effective sensitivity, the obtained 1-μm-wide line pattern was observed with a scanning electron microscope at a magnification of 10,000 times. Those with a top shape and a bottom shape close to rectangular and good [Fig. 1(a)] were judged as "〇", those with a round top shape [Fig. 1(b)], a T-top shape [Fig. 1(c)], and a round bottom shape [Fig. 1(d)] were judged as "×".

[0203] <Resolution evaluation> The resist pattern obtained in terms of the effective sensitivity was observed with a scanning electron microscope, and the minimum value of the line width of the resolved line-and-space pattern was measured.

[0204] <Storage stability evaluation> The adjusted resist composition was stored at -5°C and 40°C for 2 weeks, and the resist composition after storage was subjected to the above i-line exposure evaluation. Those with an execution sensitivity of 40°C storage being 90 - 110% of that of -5°C storage were judged as "〇", and those less than 90% or exceeding 110% were judged as "×".

[0205] <Plating resistance evaluation> After producing a patterned wafer with the execution sensitivity obtained in the above i-line exposure evaluation, it was immersed in a Cu plating solution at a bath temperature of 27°C for 30 minutes. The patterned wafer after immersion was observed with an optical microscope, and a line-and-space pattern with a line width of 1 μm was observed. Those with pattern collapse at an immersion time of 15 minutes were designated as "×", those without pattern collapse at an immersion time of 15 minutes were designated as "〇", and those without pattern collapse at an immersion time of 30 minutes were designated as "◎".

[0206]

Table 2

[0207] <Preparation of resist composition> A mixture obtained by mixing and dissolving each component shown in Table 3 was filtered through a fluororesin filter with a pore size of 1.0 μm to prepare a resist composition.

[0208]

Table 3

[0209] Examples 7, 8, Comparative Examples 7 to 9 (i-line exposure evaluation of resist composition) The above resist composition was spin-coated on a substrate with copper vapor-deposited on a 4-inch silicon wafer so that the film thickness after pre-baking was 15.0 μm. Thereafter, a pre-bake was carried out at 110 °C for 180 seconds on a direct hot plate to form a composition layer. Next, an i-line stepper (NSR-2005i9C; manufactured by Nikon Corporation, NA = 0.5) was used to expose the composition layer formed on the wafer through a mask for forming a 1:1 contact hole pattern (hole diameter: 5, 10, 25, 50 μm, pitch: 10, 20, 50, 100 μm) while changing the exposure dose stepwise. After exposure, a post-exposure bake was carried out at 50 °C for 60 seconds on a hot plate, and then paddle development was performed for 180 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern. The resist pattern obtained after development was observed with a scanning electron microscope, and the exposure dose at which a 5-μm hole pattern was obtained was defined as the effective sensitivity.

[0210] <Pattern shape evaluation> At the effective sensitivity, the obtained 5-μm contact hole pattern was observed with a scanning electron microscope at a magnification of 10,000 times. Those with a top shape and a skirt shape close to rectangular and good [Fig. 1(a)] were judged as "〇", those with a round top shape [Fig. 1(b)], a T-top shape [Fig. 1(c)], and a round skirt shape [Fig. 1(d)] were judged as "×".

[0211] <Storage stability evaluation> The adjusted resist composition was stored at -5 °C and 40 °C for 2 weeks, and the stored resist composition was subjected to the above i-line exposure evaluation. Those in which the effective sensitivity of the composition stored at 40 °C was 90 - 110% of that of the composition stored at -5 °C were judged as "〇", and those less than 90% or exceeding 110% were judged as "×".

[0212] <Electroplating pattern formation> The substrate after the above resist pattern formation was subjected to electrolytic plating with a Sn-Ag plating solution at a bath temperature of 25 °C.

[0213] <Adhesion evaluation> The substrate after plating was observed with an optical microscope. Those in which the plating solution eroded the bottom of the resist and discoloration of the resist was observed were marked as "×", and those without discoloration were marked as "〇".

[0214] <Evaluation of plating thickness uniformity> The substrate after plating was immersed in N-methyl-2-pyrrolidone to peel off the resist, and then magnified 1500 times with a scanning electron microscope. The thicknesses of the plating patterns with hole diameters of 5, 10, 25, and 50 μm were measured at three locations for each hole diameter (a total of 12 points). The uniformity of the plating thickness was determined from the following formula. (Uniformity (%)) = {(Umax - Umin) / 2 * Uav} * 100 Umax: The maximum value of 12 points Umin: The minimum value of 12 points Uav: The average value of 12 points Those with a uniformity of 5% or more were marked as "×", those with a uniformity of 3% or more and less than 5% were marked as "○", and those with a uniformity of less than 3% were marked as "◎".

[0215]

Table 4

Industrial applicability

[0216] The resist composition of the present invention can produce a resist pattern having a good shape and plating resistance, is suitable for semiconductor microfabrication, and is extremely useful industrially.

Claims

1. A resin (A1) containing a structural unit having a group represented by formula (20), an alkali-soluble resin (A2), an acid generator (B) containing a compound represented by formula (b0), and a compound (C) represented by formula (I), A resist composition containing the above. In formula (20), 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced by an oxygen atom or a sulfur atom. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond. ] [In formula (b0), R ｂ１ represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom or a carbonyl group. X represents an oxygen atom or a sulfur atom. R ０１ represents a hydrocarbon group having 1 to 18 carbon atoms, and the methylene groups contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom, a sulfur atom, or a carbonyl group. x0 represents an integer from 1 to 6. When x0 is 2 or more, the groups within multiple parentheses may be the same or different. ] [In formula (I), ring W 1 represents a heterocyclic ring having a nitrogen atom as an atom constituting the ring, or a benzene ring having a substituted or unsubstituted amino group. The heterocyclic ring may have a hetero atom other than the nitrogen atom, and the heterocyclic ring and the benzene ring may have a substituent other than a substituted or unsubstituted amino group. A 1 represents a phenyl group or a naphthyl group. n represents 2 or 3, and a plurality of A 1 may be the same or different.]

2. The resist composition according to claim 1, wherein the resin (A1) is a resin containing a structural unit represented by formula (a1 - 2) or a resin containing a structural unit represented by formula (a3B). [In formula (a1 - 2), 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced by an oxygen atom or a sulfur atom. R a5 represents a hydrogen atom or a methyl group. R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer from 0 to 4. When m is 2 or more, the plurality of Rs a６ may be the same as or different from each other.] [In formula (a3B), R ａ１’ and R ａ２’ each independently represent 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. Alternatively, 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 to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced by an oxygen atom or a sulfur atom. R ａｂ represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ａｂ may be the same or different.]

3. In formula (I), the compound (C) is ring W 1 is a resist composition according to claim 1, which is a heterocyclic ring having one or more nitrogen atoms and one or more oxygen atoms or sulfur atoms as ring-constituting atoms, a heterocyclic ring having two or more nitrogen atoms as ring-constituting atoms, a benzene ring having one or more substituted or unsubstituted amino groups and one or more hydroxy groups, or a benzene ring having two or more substituted or unsubstituted amino groups

4. The resist composition according to claim 1, further containing a compound (E) having a quinonediazidosulfonyl group.

5. A method for manufacturing a resist pattern, comprising: (1) A step of applying the resist composition according to any one of claims 1 to 4 onto the metal surface of a substrate having a metal surface; (2) A step of drying the applied composition to form a composition layer; (3) A step of exposing the composition layer; and (4) A step of developing the composition layer after exposure A manufacturing method including the above steps.

6. A method for manufacturing an electroformed article, comprising: (1) A step of applying the resist composition according to any one of claims 1 to 4 onto the metal surface of a substrate having a metal surface; (2) A step of drying the applied composition to form a composition layer; (3) A step of exposing the composition layer; (4) A step of developing the composition layer after exposure; (5) A step of forming an electroformed article using the obtained resist pattern as a mold; and (6) A step of peeling off the resist pattern A manufacturing method including the above steps.

Images