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

Abstract

The present invention addresses the problem of providing a resist composition capable of forming a resist pattern with which sufficient resolution and exposure latitude can be obtained. The present invention also addresses the problem of providing: a method for producing a resist pattern using the resist composition; and a method for producing a plated molded article. The present invention relates to: a resist composition containing a resin (A1) containing a structural unit having an acid-labile group, a photosensitizer (I), and an acid generator (B), the acid generator (B) containing a compound having a maximum molar absorption coefficient of 6000 (L / (mol.cm)) or less in the wavelength range of 355-375 nm; the content of the photosensitizer (I) is 10% by mass or less in the solid content of the resist composition, and when a film is formed using the resist composition with a film thickness, the minimum transmittance of the film for radiation in the wavelength range of 355-375 nm is 23% or more.

Description

TECHNICAL FIELD

[0001] The present application relates to a resist composition, a method for producing a resist pattern, and a method for producing a plated molded article. BACKGROUND

[0002] A resist composition is described in Patent Literatures 1 and 2.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT LITERATURES

[0005] Patent Literature 1: Japanese Patent Application Publication No. 2021-135507

[0006] Patent Literature 2: Japanese Patent Application Publication No. 2023-502762 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] A resist pattern obtained using a conventional resist composition as described in Patent Literatures 1 and 2 has room for further improvement in resolution and exposure margin.

[0009] Therefore, an object of the present application is to provide a resist composition capable of forming a resist pattern that can achieve sufficient resolution and exposure margin. Another object is to provide a method for producing a resist pattern and a method for producing a plated molded article using the resist composition.

[0010] MEANS FOR SOLVING THE PROBLEMS

[0011] The present inventors have found that a resist composition containing a resin containing a structural unit having an acid-labile group, a specific amount of a photosensitizer, and an acid generator containing a compound having a specific molar absorption coefficient can solve the above problems.

[0012] The present application provides the following inventions.

[0013] [1] A resist composition containing a resin (Al) containing a structural unit having an acid-labile group, a photosensitizer (I), and an acid generator (B),

[0014] The acid generator (B) contains a compound having a maximum molar absorption coefficient of 6000 (L / (mol·cm)) or less in the range of wavelengths of 355 to 375 nm,

[0015] The content of the photosensitizer (I) is 10% by mass or less in the solid content of the resist composition,

[0016] In the case where the above-described resist composition is used to form a film with a use film thickness, the minimum transmittance of the above-described film to a ray having a wavelength in the range of 355 to 375 nm is 23% or more.

[0017] [2] The resist composition described in [1], wherein the use film thickness is 4 μm or more.

[0018] [3] The resist composition described in [1] or [2], wherein the photosensitizer (I) contains a compound having a quinonediazido sulfonyl group.

[0019] [4] The resist composition described in any one of [1] to [3], wherein the photosensitizer (I) contains a compound having a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0020]

[0021] [In formula (a) and formula (b), represents a bonding end.]

[0022]

[0023] [In formula (c), represents a bonding end.]

[0024] [5] The resist composition described in any one of [1] to [4], wherein the acid generator (B) contains a compound having an oxime skeleton or an amide skeleton.

[0025] [6] The resist composition described in any one of [1] to [5], wherein the acid generator (B) contains a compound having an oxime sulfonate group or an amide sulfonate group.

[0026] [7] The resist composition described in any one of [1] to [6], wherein the resin (Al) containing a structural unit having an acid-labile group is a resin containing a structural unit having a group represented by formula (10) or a group represented by formula (20).

[0027]

[0028] [In formula (10), R a1 , R a2 , and R a3 independently of one another 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 and, together with the carbon atom to which they are bonded, form a ring having 3 to 20 carbon atoms, and R a3represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. maand naindependently of each other represent 0 or 1, and at least one of maand narepresent 1. represents a bonding end.

[0029]

[0030] [In formula (20), R a1’ and R a2’ independently of each other represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. Alternatively, R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are mutually bonded and form, together with the carbon atom to which they are bonded and X, a heterocyclic ring having 3 to 20 carbon atoms. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms can be replaced with an oxygen atom or a sulfur atom. X represents an oxygen atom or a sulfur atom. na'represents 0 or 1. represents a bonding end.

[0031] [8] The resist composition described in any one of [1] to [7], wherein the resin (Al) containing a structural unit having an acid-labile group is a resin containing at least one selected from the group consisting of a structural unit represented by formula (al-1), a structural unit represented by formula (al-2), a structural unit represented by formula (a3A), and a structural unit represented by formula (a3B).

[0032]

[0033] [In formula (al-1), R a1 , R a2 , and R a3 independently of each other 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 mutually bonded and form, together with the carbon atom to which they are bonded, a ring having 3 to 20 carbon atoms, 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.]

[0034]

[0035] [In formula (al-2), R a1’ and R a2’ independently of each other represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R a3’represents a hydrocarbon group having 1 to 20 carbon atoms. Alternatively, R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are mutually bonded and form, together with the carbon atom and the oxygen atom to which they are bonded, a heterocyclic ring having 3 to 20 carbon atoms. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms can be replaced with 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, the plurality of R a6 may be the same or different.

[0036]

[0037] In formula (a3A), R a1 , R a2 , and R a3 independently of one another 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 mutually bonded and form, together with the carbon atom to which they are bonded, a ring having 3 to 20 carbon atoms, 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 ab represents a hydroxyl 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, the plurality of R ab may be the same or different.

[0038]

[0039] In formula (a3B), R a1’ and R a2’ independently of one another represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. Alternatively, R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are mutually bonded and form, together with the carbon atom and the oxygen atom to which they are bonded, a heterocyclic ring having 3 to 20 carbon atoms. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms can be replaced with an oxygen atom or a sulfur atom. R ab represents a hydroxyl 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, the plurality of R ab may be the same or different.

[0040] [9] The resist composition according to any one of [1] to [8] further contains a quencher (C).

[0041]

[10] A method for manufacturing a resist pattern, comprising:

[0042] (1) The process of applying the resist composition described in any one of [1] to [9] to the metal surface of a substrate having a metal surface;

[0043] (2) The process of drying the coated composition to form a composition layer;

[0044] (3) The process of exposing the composite layer; and

[0045] (4) The process of developing the exposed composite layer.

[0046]

[11] A method for manufacturing a plated model, comprising:

[0047] (1) The process of applying the resist composition described in any one of [1] to [9] to the metal surface of a substrate having a metal surface;

[0048] (2) The process of drying the coated composition to form a composition layer;

[0049] (3) The process of exposing the composite layer;

[0050] (4) The process of developing the exposed composite layer;

[0051] (5) The process of using the obtained resist pattern as a mold to form a plated object; and

[0052] (6) The process of peeling off the resist pattern.

[0053] Invention Effects

[0054] By using the resist composition of the present invention, a resist pattern can be formed with excellent precision, and the resist pattern can be formed with excellent precision into a plated shape. Detailed Implementation

[0055] In this specification, unless otherwise specified, in the description of the structural formula of a compound, "hydrocarbon group" refers to a linear or branched chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group composed of combinations of these groups. Regarding this "hydrocarbon group," when a number of carbon atoms is specified, the aforementioned groups may be used within the permissible range of that number of carbon atoms. Among these groups, all stereoisomers are included where stereoisomers are present.

[0056] In the present specification, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid", and "(meth)acrylate" means "at least one of acrylate and methacrylate".

[0057] In the groups described in the present specification, as for the groups that can adopt both linear and branched structures, the meaning including either is explained.

[0058] "Group formed by combination" means a group formed by bonding two or more of the exemplified groups, and the valence of these groups can be appropriately changed depending on the bonding mode.

[0059] "From" or "derived" means that the polymerizable C=C bond contained in the molecule becomes a -C-C- group (single bond) by polymerization.

[0060] In the case where stereoisomers exist, all stereoisomers are included.

[0061] Each group, depending on the number of substituents and the like, sometimes has a hydrogen atom at any position and in any amount contained in the group replaced with a bonding end.

[0062] The number of carbon atoms in the substituent is not included in the number of carbon atoms of the substituent.

[0063] In the present specification, "solid content of the resist composition" means the total of the components after removing the solvent (D) described later from the total amount of the resist composition.

[0064] 1. Resist composition

[0065] The resist composition of the present application contains: a resin containing a structural unit having an acid-labile group (hereinafter, sometimes referred to as "resin (Al)", a photosensitizer (hereinafter, sometimes referred to as "photosensitizer (I)", and an acid generator (hereinafter, sometimes referred to as "acid generator (B)").

[0066] The resist composition of the present application preferably contains, in addition to the resin (Al), the photosensitizer (I), and the acid generator (B), an alkali-soluble resin (hereinafter, sometimes referred to as "resin (A2)", a quencher (hereinafter, sometimes referred to as "quencher (C)", and / or a solvent (hereinafter, sometimes referred to as "solvent (D)").

[0067] <Photosensitizer (I)>

[0068] The photosensitive agent (I) is capable of inhibiting the dissolution of the resin in a developer (an aqueous alkali solution) in a light-unexposed (unexposed) portion by interacting with the hydrophilic group of the resin, and is capable of promoting the dissolution of the resin in the developer (an aqueous alkali solution) in a light-exposed (exposed) portion by producing carboxylic acid through the decomposition of the quinonediazide group to produce carboxylic acid. In addition, in the light-unexposed (unexposed) portion, the resin is crosslinked in the presence of the developer (an aqueous alkali solution), and thus has resistance to the developer (an aqueous alkali solution) and a plating solution, and thus the accuracy of a plated molded article is improved. The photosensitive agent (I) mainly acts on the alkali-soluble resin (hereinafter, sometimes referred to as "resin (A2)") described later.

[0069] The photosensitive agent (I) preferably contains a compound having a quinonediazide sulfonyl group (hereinafter, sometimes referred to as "compound (I-1)").

[0070] The compound (I-1) is not particularly limited as long as it has one or more quinonediazide sulfonyl groups in the molecule. The molecular weight of a compound obtained by replacing all of the quinonediazide sulfonyl groups present in the molecule of the compound (I-1) with hydrogen atoms is preferably 3000 or less, more preferably 2000 or less, and further preferably 1500 to 400.

[0071] As the compound having a quinonediazide sulfonyl group, there are a compound having a naphthoquinonediazide sulfonyl group, a compound having a benzoquinonediazide sulfonyl group, a compound having an anthraquinonediazide sulfonyl group, and the like, and preferably a compound having a naphthoquinonediazide sulfonyl group or a compound having a benzoquinonediazide sulfonyl group. As the compound having a naphthoquinonediazide sulfonyl group, a compound having a 1,2-naphthoquinonediazide sulfonyl group is preferable, a compound having a group represented by formula (a) or a group represented by formula (b) is more preferable, and a compound having a group represented by formula (a) is further preferable. As the compound having a benzoquinonediazide sulfonyl group, a compound having a 1,2-benzoquinonediazide sulfonyl group is preferable, and a compound having a group represented by formula (c) is more preferable.

[0072]

[0073] [In formula (a) and formula (b), represents a bonding end.]

[0074]

[0075] [In formula (c), represents a bonding end.]

[0076] The compound obtained by replacing all the quinone diazidosulfonyl groups present in the molecule of a compound having a quinone diazidosulfonyl group with hydrogen atoms is preferably an aromatic compound having a phenolic hydroxyl group. The compound having a quinone diazidosulfonyl group is preferably a compound obtained by quinone diazidosulfonation of an aromatic compound having a phenolic hydroxyl group. The compound having a quinone diazidosulfonyl group is more preferably selected from at least one of the following: compounds of formula (II) (hereinafter, sometimes referred to as "compound (II)"); compounds of formula (III) (hereinafter, sometimes referred to as "compound (III)"); compounds of formula (IV) (hereinafter, sometimes referred to as "compound (IV)"); and compounds of formula (V) (hereinafter, sometimes referred to as "compound (V)").

[0077]

[0078] In formula (II),

[0079] R 11 ~R 14 Each of these groups independently represents a hydrogen atom, a hydroxyl 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 can be an oxygen atom, a carbonyl group, or -NR. d1 -Displacement.

[0080] R d1 It represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0081] R 15 ~R 30 Each of these independently represents a hydrogen atom, a hydroxyl group, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0082] R 11 ~R 30 At least one of them is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0083]

[0084] In formula (III),

[0085] R 31 ~R 39 Each of the following independently represents a hydrogen atom, a hydroxyl 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). 31 ~R 39 At least one of them is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0086] P 1 ~P 5 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, the methylene group included in the hydrocarbon group having 1 to 18 carbon atoms can be replaced with an oxygen atom, a carbonyl group or -NR d2 - substitution, P 1 and P 2 may be bonded to each other and form a ring together with the 2 carbon atoms to which they are bonded. 4 and P 5 may be bonded to each other and form a ring together with the carbon atoms to which they are bonded.

[0087] R d2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0088]

[0089] [In formula (IV),

[0090] R 40 ~R 53 each independently represents a hydrogen atom, a hydroxyl 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 40 ~R 53 of which at least 1 is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c).

[0091] n a represents any one of integers from 1 to 5. In the case where n a is any one of integers of 2 or more, a plurality of R 49 ~R 52 may be the same as or different from each other.

[0092]

[0093] [In formula (V),

[0094] R f1 , R f2 and R g1 ~R g8 each independently represents a hydrogen atom, a hydroxyl 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 f1 , R f2 and R g1 ~R g8 of which at least 1 is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c).

[0095] P6 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 can be substituted with at least one selected from a hydroxyl group and an alkyl group having 1 to 6 carbon atoms.

[0096] P 7 represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms which can have a substituent, and a methylene group included in the hydrocarbon group having 1 to 18 carbon atoms can be replaced with an oxygen atom, a carbonyl group, or -NR d3 - is replaced with P. 6 and P 7 may be bonded to each other and form a ring together with the carbon atom to which they are bonded.

[0097] n v represents 1 or 2.

[0098] R d3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0099] As the hydrocarbon group having 1 to 18 carbon atoms, there can be mentioned a chain hydrocarbon group having 1 to 18 carbon atoms (including a straight-chain or branched-chain saturated chain hydrocarbon group (alkyl group) having 1 to 18 carbon atoms, a straight-chain or branched-chain unsaturated chain hydrocarbon group (alkenyl group, alkynyl group) having 2 to 18 carbon atoms, and the like), 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, and the like), an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the like, and a group formed by combining two or more of these groups can also be mentioned.

[0100] The alkyl group having 1 to 18 carbon atoms can be either straight-chain or branched-chain, and there can be mentioned, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group or a sec-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, and the like. Among them, a straight-chain alkyl group is preferred.

[0101] The alkenyl group having 2 to 18 carbon atoms can be either straight-chain or branched-chain, and there can be mentioned, for example, 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 iso-octenyl group, a nonenyl group, and the like.

[0102] The alkynyl group having 2 to 18 carbon atoms can be either of a linear or branched chain, and examples include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, tert-butynyl, pentynyl, hexynyl, octynyl, nonynyl, and the like. The chain hydrocarbon group having 1 to 18 carbon atoms is preferably 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 8 carbon atoms, more further preferably 1 to 6 carbon atoms, and still further preferably 1 to 4 carbon atoms.

[0103] As the monocyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms, examples include monocyclic saturated alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like, and monocyclic unsaturated alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, and the like. As the polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms, examples include polycyclic saturated alicyclic hydrocarbon groups such as decalinyl, adamantyl, norbornyl, and the like. The alicyclic hydrocarbon group having 3 to 18 carbon atoms is preferably 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms, and further preferably 3 to 10 carbon atoms.

[0104] As the aromatic hydrocarbon group having 6 to 18 carbon atoms, examples include phenyl, naphthyl, anthryl, biphenyl, phenanthryl, and the like. The aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.

[0105] As the alkyl group having 1 to 6 carbon atoms, a group corresponding to an alkyl group having 1 to 6 carbon atoms can be selected from the above-described alkyl group having 1 to 18 carbon atoms.

[0106] As the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms of P 6 , examples include phenyl, naphthyl, and the like. As the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms of P 6 , examples include phenylene, naphthylene, and the like.

[0107] As the ring formed by P 1 and P 2 bonding to each other and together with the 2 carbon atoms to which they are bonded, and the ring formed by P 4 and P 5 bonding to each other and together with the carbon atoms to which they are bonded, each independently, examples include monocyclic or polycyclic alicyclic hydrocarbon rings having 3 to 18 carbon atoms, and the like. As these rings, examples include cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, and the like, cycloalkane rings; decalin ring, adamantane ring, norbornane ring, and the like. The alicyclic hydrocarbon ring having 3 to 18 carbon atoms is preferably 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms, and further preferably 3 to 10 carbon atoms.

[0108] As the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms of P 7As the substituent of the hydrocarbon group having 1 to 18 carbon atoms in the above-mentioned groups, a halogen atom, a hydroxyl 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 can be given.

[0109] As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be given, and a fluorine atom is preferred.

[0110] As the alkoxy group having 1 to 12 carbon atoms, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like can be given.

[0111] As the acyl group having 2 to 4 carbon atoms, an acetyl group, a propionyl group, a butyryl group, and the like can be given.

[0112] As the acyloxy group having 2 to 4 carbon atoms, an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like can be given.

[0113] As the P 6 and P 7 The ring formed by the mutual bonding of the carbon atoms to which they are bonded can be a monocyclic or polycyclic alicyclic hydrocarbon ring having 3 to 18 carbon atoms. As such a ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a decalin ring, an adamantane ring, norbornane ring, and the like can be given. The alicyclic hydrocarbon ring having 3 to 18 carbon atoms is preferably an alicyclic hydrocarbon ring having 3 to 16 carbon atoms, more preferably an alicyclic hydrocarbon ring having 3 to 12 carbon atoms, and further preferably an alicyclic hydrocarbon ring having 3 to 10 carbon atoms.

[0114] As a specific example of the compound (II), a compound represented by formula (II-1) to (II-3) can be given.

[0115]

[0116] Here, R s2 Each independently represents the group represented by formula (a), the group represented by formula (b), the group represented by formula (c), or a hydroxyl group. R s2 At least one of the groups represented by formula (a), the group represented by formula (b), or the group represented by formula (c) in each compound.

[0117] As a specific example of the compound (III), a compound represented by formula (III-1-1) to (III-3-8) can be given.

[0118]

[0119]

[0120]

[0121] Here, R t1Each of these groups independently represents the group shown in formula (a), formula (b), formula (c), or a hydroxyl group. The R in each compound... t1 At least one of them is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0122] Specific examples of compounds (IV) include those shown in formulas (IV-1-1) to (IV-5-2).

[0123]

[0124]

[0125] Here, R t1 R t3 R t6 R t7 R t9 R t10 and R t13 Each of these groups independently represents the group shown in formula (a), formula (b), formula (c), or a hydroxyl group. The R in each compound... t1 R t3 R t6 R t7 R t9 R t10 and R t13 At least one of them is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0126] As specific examples of compound (V), compounds represented by formulas (V-1-1) to (V-3-1) can be cited.

[0127]

[0128] Here, R v Each of these groups independently represents the group shown in formula (a), formula (b), formula (c), or a hydroxyl group. The R in each compound... v At least one of them is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0129] The compound (I-1) can be produced, for example, according to the description of Japanese Patent Application Publication No. 2-84650, Japanese Patent Application Publication No. 3-185447, Japanese Patent Application Publication No. 3-191351, Japanese Patent Application Publication No. 5-323597, Japanese Patent Application Publication No. 8-245461, Japanese Patent Application Publication No. 9-110762, or the like. The compound (I-1) can be produced, for example, by reacting an aromatic compound having a phenolic hydroxyl group (for example, a compound in which all of the quinonediazide sulfonyl groups in the molecule of the above-described compound (II) to (V) are replaced with hydrogen atoms, or the like) with a quinonediazide sulfonyl halide (for example, 1,2-naphthoquinonediazide sulfonyl chloride, 1,2-benzoquinonediazide sulfonyl chloride, or the like quinonediazide sulfonyl chloride, 1,2-naphthoquinonediazide sulfonyl bromide, 1,2-benzoquinonediazide sulfonyl bromide, or the like quinonediazide sulfonyl bromide, or the like) in the presence of a weak base, and performing complete esterification or partial esterification.

[0130] The aromatic compound having a phenolic hydroxyl group can be easily obtained from the market, and can be produced using a publicly known method.

[0131] The content of the photosensitizer (I) in the resist composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, further preferably 0.05% by mass or more, more further preferably 0.1% by mass or more, and still more further preferably 0.5% by mass or more. In addition, it is 10% by mass or less, preferably 9.9% by mass or less, and more preferably 9.8% by mass or less. Specifically, it is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 10% by mass or less, further preferably 0.1% by mass or more and 10% by mass or less, more further preferably 0.5% by mass or more and 10% by mass or less, and still more further preferably 1% by mass or more and 10% by mass or less.

[0132] The content of the photosensitizer (I) in the resist composition can be determined, for example, using a publicly known analysis method such as liquid chromatography or gas chromatography.

[0133] As the photosensitizer (I), the compound (III) and the compound (IV) are preferred, and the compound (III) is more preferred.

[0134] <Resin (A1)>

[0135] The resin (A1) contains a structural unit having an acid-labile group (hereinafter, sometimes referred to as "structural unit (a1)").

[0136] The acid-labile group refers to a group including a group (sometimes referred to as a leaving group) that can be detached by contact with an acid. By contacting the resin (Al) with an acid, the leaving group is detached from the acid-labile group, and a hydrophilic group (for example, a hydroxyl group (phenolic hydroxyl group or the like) or a carboxyl group) is formed. By contact with an acid, the solubility of the resin (Al) in an aqueous alkali solution increases. That is, the resin (Al) is preferably insoluble or hardly soluble in an aqueous alkali solution before contact with an acid, and becomes soluble in an aqueous alkali solution after contact with an acid.

[0137] The resin (Al) can further include, within the range of having the above-described properties, a structural unit (hereinafter, sometimes referred to as "structural unit (a2)") not having an acid-labile group, and the like, in addition to the structural unit having an acid-labile group.

[0138] As the acid that detaches the leaving group included in the acid-labile group, for example, a carboxylic acid, a sulfonic acid, and the like can be given. In the composition of the present application, a carboxylic acid compound, a sulfonic acid compound, and the like generated by performing light irradiation (exposure) on the acid generator (B) described later in a photolithography process can be given.

[0139] As the acid-labile group, for example, a group represented by formula (10), a group represented by formula (20), and the like can be given.

[0140]

[0141] [In formula (10), R a1 , R a2 , and R a3 independently of one another 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 one another and, together with the carbon atom to which they are bonded, form a ring having 3 to 20 carbon atoms, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. maand naeach independently represent 0 or 1, and at least one of maand narepresent 1. represents a bonding end.]

[0142]

[0143] [In formula (20), R a1’ and R a2’ independently of one another represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. Alternatively, R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’The carbon atoms bonded to each other, together with X, form heterocycles with 3 to 20 carbon atoms. The hydrocarbon groups with 1 to 20 carbon atoms and the methylene groups in the heterocycles with 3 to 20 carbon atoms can be replaced by oxygen or sulfur atoms. X represents an oxygen or sulfur atom. na' represents 0 or 1. Indicates the bonding end.

[0144] The R group shown in formula (10) a1 ~R a3 The alkyl group having 1 to 8 carbon atoms can be either straight-chain or branched, and examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. R a1 ~R a3 The alkyl group having 1 to 8 carbon atoms is preferably having 1 to 6 carbon atoms, and more preferably having 1 to 4 carbon atoms.

[0145] R a1 ~R a3 The alicyclic hydrocarbon group having 3 to 20 carbon atoms can be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl cycloalkyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bond end).

[0146]

[0147] R a1 ~R a3 The alicyclic hydrocarbon group with 3 to 20 carbon atoms is preferably 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and even more preferably 3 to 12 carbon atoms.

[0148] As R a1 and R a2 -C(R) when they bond together and form a ring with 3 to 20 carbon atoms a1 (R) a2 (R) a3 Examples of such groups include those described below. The ring having 3 to 20 carbon atoms is preferably 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and even more preferably 3 to 12 carbon atoms. This indicates the bonding end with -O-.

[0149]

[0150] R a1 Preferably, it is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or with R a2bonded and forming a ring of 3 to 18 carbon atoms together with the carbon atom to which they are bonded, more preferably an alkyl group of 1 to 4 carbon atoms or an alicyclic hydrocarbon group of 3 to 12 carbon atoms, or a2 bonded and forming a ring of 3 to 12 carbon atoms together with the carbon atom to which they are bonded.

[0151] R a2 preferably an alkyl group of 1 to 6 carbon atoms or an alicyclic hydrocarbon group of 3 to 18 carbon atoms, more preferably an alkyl group of 1 to 4 carbon atoms or an alicyclic hydrocarbon group of 3 to 12 carbon atoms. a1 bonded and forming a ring of 3 to 18 carbon atoms together with the carbon atom to which they are bonded, more preferably an alkyl group of 1 to 4 carbon atoms or an alicyclic hydrocarbon group of 3 to 12 carbon atoms, or a1 bonded and forming a ring of 3 to 12 carbon atoms together with the carbon atom to which they are bonded.

[0152] R a3 preferably an alkyl group of 1 to 6 carbon atoms or an alicyclic hydrocarbon group of 3 to 18 carbon atoms, more preferably an alkyl group of 1 to 4 carbon atoms or an alicyclic hydrocarbon group of 3 to 12 carbon atoms.

[0153] ma is preferably 0. na is preferably 1.

[0154] As the group represented by formula (10), there can be mentioned, for example, a group in which R a1 , R a2 and R a3 are each independently an alkyl group of 1 to 3 carbon atoms (preferably a tert-butoxycarbonyl group); R a1 and R a2 are each independently an alkyl group of 1 to 3 carbon atoms, and R a3 is a group in which R a1 and R a2 are mutually bonded and form a cyclopentane ring or a cyclohexane ring together with the carbon atom to which they are bonded, and R a3 is an alkyl group of 1 to 3 carbon atoms, and the like.

[0155] As the group represented by formula (10), there can be mentioned, for example, a group in which R

[0156]

[0157] As the group represented by formula (20), R a1’ to R a3’ are each independently a hydrocarbon group of 1 to 20 carbon atoms, there can be mentioned a chain hydrocarbon group (alkyl group, alkenyl group, alkynyl group, etc.) of 1 to 20 carbon atoms, an alicyclic hydrocarbon group of 3 to 20 carbon atoms, an aromatic hydrocarbon group of 6 to 20 carbon atoms, etc., and a group of 4 to 20 carbon atoms formed by combining them.

[0158] As the alkyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, and the like can be given.

[0159] As the alkenyl group having 2 to 20 carbon atoms, for example, vinyl, propenyl, isopropenyl, butenyl, isobutenyl, t-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, nonenyl, and the like can be given.

[0160] As the alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, t-butynyl, pentynyl, hexynyl, octynyl, nonynyl, and the like can be given.

[0161] The chain hydrocarbon group having 1 to 20 carbon atoms is preferably a chain hydrocarbon group having 1 to 18 carbon atoms, more preferably a chain hydrocarbon group having 1 to 16 carbon atoms, further preferably a chain hydrocarbon group having 1 to 12 carbon atoms, more further preferably a chain hydrocarbon group having 1 to 8 carbon atoms, still further preferably a chain hydrocarbon group having 1 to 6 carbon atoms.

[0162] As the alicyclic hydrocarbon group having 3 to 20 carbon atoms, for example, a monocyclic alicyclic hydrocarbon group such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like; a polycyclic alicyclic hydrocarbon group such as decalinyl, adamantyl, norbornyl, and the like can be given. The alicyclic hydrocarbon group having 3 to 20 carbon atoms is preferably a group having 3 to 18 carbon atoms, more preferably a group having 3 to 16 carbon atoms, further preferably a group having 3 to 12 carbon atoms.

[0163] As the aromatic hydrocarbon group having 6 to 20 carbon atoms, for example, an aryl group such as phenyl, naphthyl, anthryl, biphenyl, phenanthryl, and the like can be given. The aromatic hydrocarbon group can further have a substituent, and as the substituent, for example, an aryloxy group having 6 to 10 carbon atoms can be given. The aromatic hydrocarbon group having 6 to 20 carbon atoms is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms, further preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0164] As the group having 4 to 20 carbon atoms which is a combination of an alkyl group and an alicyclic hydrocarbon group (a group having 4 to 20 carbon atoms), for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methyl-norbornyl group, an isobornyl group, a 2-alkyladamant-2-yl group, a 1-(adamant-1-yl)alkane-1-yl group, and the like can be given.

[0165] As the group having 7 to 20 carbon atoms which is a combination of an alkyl group and an aromatic hydrocarbon group, for example, an aralkyl group, an aromatic hydrocarbon group having an alkyl group, specifically, a benzyl group, a phenethyl group, a phenylpropyl group, a triphenylmethyl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-t-butylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, and the like can be given.

[0166] As the group (group having 9 to 20 carbon atoms) which is a combination of an alicyclic hydrocarbon group and an aromatic hydrocarbon group, for example, there are mentioned an aromatic hydrocarbon group having an alicyclic hydrocarbon group, an alicyclic hydrocarbon group having an aromatic hydrocarbon group, specifically, p-cyclohexylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, and the like.

[0167] In the case where R a2’ and R a3’ are bonded to each other and form, together with the carbon atom to which they are bonded and X, a heterocyclic ring having 3 to 20 carbon atoms, as -C(R a1’ )(R a2’ )-X-R a3’ , there are mentioned, for example, the following groups. The heterocyclic ring having 3 to 20 carbon atoms is preferably a heterocyclic ring having 3 to 18 carbon atoms, more preferably a heterocyclic ring having 3 to 16 carbon atoms, and further preferably a heterocyclic ring having 3 to 12 carbon atoms. represents a bonding site.

[0168]

[0169] 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 further preferably a hydrogen atom.

[0170] R a2’ is preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or is bonded to R a3’ and forms, together with the carbon atom to which they are bonded and X, a heterocyclic ring having 3 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or is bonded to R a3’ and forms, together with the carbon atom to which they are bonded and X, a heterocyclic ring having 3 to 12 carbon atoms, and further preferably a hydrocarbon group having 1 to 12 carbon atoms, and more further preferably a methyl group or an ethyl group.

[0171] R a3’ is preferably a hydrocarbon group having 1 to 18 carbon atoms, or is bonded to R a2’ and forms, together with the carbon atom to which they are bonded and X, a heterocyclic ring having 3 to 18 carbon atoms, more preferably a hydrocarbon group having 1 to 12 carbon atoms, or is bonded to R a2’ and forms, together with the carbon atom to which they are bonded and X, a heterocyclic ring having 3 to 12 carbon atoms.

[0172] As the hydrocarbon group mentioned above, there are mentioned 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 which is a combination thereof. These groups can be arbitrarily selected from the groups listed above.

[0173] X is preferably an oxygen atom.

[0174] n is preferably 0.

[0175] As the group represented by formula (20), specific examples include, for example, the following groups.

[0176]

[0177] As the group represented by formula (10), specific examples include the group represented by formula (1) and the group represented by formula (1'), and the like.

[0178]

[0179] [In formula (1) and formula (1'), R a1 , R a2 and R a3 independently of one another 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 and, together with the carbon atom to which they are bonded, form a ring having 3 to 20 carbon atoms, 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 bonding end.]

[0180] As the group represented by formula (20), specific examples include the group represented by formula (2) and the group represented by formula (2'), and the like.

[0181]

[0182] [In formula (2) and formula (2'), R a1’ and R a2’ independently of one another represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. 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 and, together with the carbon atom and the oxygen atom to which they are bonded, form a heterocyclic ring having 3 to 20 carbon atoms. A methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms can be replaced with an oxygen atom or a sulfur atom. represents a bonding end.]

[0183] <Structural Unit (a1) Having an Acid-labile Group>

[0184] The resin (A1) containing the structural unit (a1) having an acid-labile group can be produced, for example, by polymerizing a monomer component containing an olefinically unsaturated compound into which the structural unit (a1) is introduced. As the acid-labile group contained in the structural unit (a1), the group represented by the formula (10) and / or the group represented by the formula (20) described above are preferred.

[0185] The resin (A1) can have only one kind of the structural unit (a1) or can have a plurality of kinds thereof.

[0186] As the structural unit (a1), the structural unit represented by the formula (a1-1) (hereinafter, sometimes referred to as "structural unit (a1-1)") and the structural unit represented by the formula (a1-2) (hereinafter, sometimes referred to as "structural unit (a1-2)") are preferred.

[0187]

[0188] In the formula (a1-1) and the formula (a1-2),

[0189] R a1 , R a2 and R a3 independently of one another 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 and, together with the carbon atom to which they are bonded, form a ring having 3 to 20 carbon atoms, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

[0190] R a1’ and R a2’ independently of one another represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. 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 and, together with the carbon atom and the oxygen atom to which they are bonded, form a heterocyclic ring having 3 to 20 carbon atoms. A methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms can be replaced with an oxygen atom or a sulfur atom.

[0191] R a4 and R a5 independently of one another represent a hydrogen atom or a methyl group.

[0192] R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

[0193] m represents an integer of 0 to 4. When m is 2 or more, the plurality of R a6 may be the same as or different from each other.

[0194] In formula (a1-1), R a4 is preferably a methyl group.

[0195] R a1 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or is bonded to R a2 and forms a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and is more preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or is bonded to R a2 and forms a ring having 3 to 12 carbon atoms together with the carbon atom to which they are bonded.

[0196] R a2 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or is bonded to R a1 and forms a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and is more preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or is bonded to R a1 and forms a ring having 3 to 12 carbon atoms together with the carbon atom to which they are bonded.

[0197] 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 is more preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms.

[0198] In formula (a1-2), R a5 is preferably a hydrogen atom.

[0199] R a1’ is preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and is more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and is further preferably a hydrogen atom.

[0200] R a2’ is preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or is bonded to R a3’ and forms a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom and the oxygen atom to which they are bonded, and is more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or is bonded to R a3’ and forms a heterocyclic ring having 3 to 12 carbon atoms together with the carbon atom and the oxygen atom to which they are bonded, and is further preferably a hydrocarbon group having 1 to 12 carbon atoms, and is more further preferably a methyl group or an ethyl group.

[0201] R a3’ is preferably a hydrocarbon group having 1 to 18 carbon atoms, or is bonded to Ra2’ bonded and together with the carbon atom and the oxygen atom to which they are bonded form a heterocyclic ring having 3 to 18 carbon atoms, more preferably a hydrocarbon group having 1 to 12 carbon atoms, or R a2’ bonded and together with the carbon atom and the oxygen atom to which they are bonded form a heterocyclic ring having 3 to 12 carbon atoms.

[0202] As the hydrocarbon group, there can be mentioned 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 which is a combination of these groups. These groups can be arbitrarily selected from the groups 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. In the case where the aromatic hydrocarbon group has a substituent, as the substituent, there is preferably an aryloxy group having 6 to 10 carbon atoms.

[0203] As the hydrocarbon group, there can be mentioned 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 which is a combination of these groups. These groups can be arbitrarily selected from the groups 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. In the case where the aromatic hydrocarbon group has a substituent, as the substituent, there is preferably an aryloxy group having 6 to 10 carbon atoms. a6 As the alkyl group having 1 to 6 carbon atoms of R a6 As the alkoxy group having 1 to 6 carbon atoms of R

[0204] 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, further preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and still further preferably a methyl group or a methoxy group.

[0205] m is preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0206] In formula (a1-2), the group represented by -O-C(R a1’ )(R a2’ )-O-R a3’ is preferably bonded to the 3-position or the 4-position (meta- or para-position with respect to the main chain bonded to the benzene ring) of the benzene ring, and more preferably to the 4-position (para-position) of the benzene ring.

[0207] As the structural unit (a1-1), there can be mentioned, for example, any one of the structural units represented by formulae (a1-1-1) to (a1-1-17).

[0208]

[0209]

[0210] As the structural unit (a1-2), for example, a structural unit represented by any one of Formulae (a1-2-1) to (a1-2-14) can be given.

[0211]

[0212] Among the above structural units, a structural unit in which the hydrogen atom equivalent to R a5 A structural unit in which the hydrogen atom equivalent to R

[0213] The structural unit (a1-2) is preferably a structural unit represented by Formula (a1-2-2), Formula (a1-2-3), Formula (a1-2-4), Formula (a1-2-9), or Formula (a1-2-14), more preferably a structural unit represented by Formula (a1-2-2), Formula (a1-2-3), Formula (a1-2-4), or Formula (a1-2-9).

[0214] The resin (A1) containing a structural unit having an acid-labile group is preferably a resin containing the structural unit (a1-2).

[0215] In the case where the resin (A1) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content ratio of these structural units is preferably 3 to 80 mol%, more preferably 5 to 60 mol%, further preferably 10 to 55 mol%, still further preferably 15 to 50 mol%, and yet further preferably 20 to 45 mol% with respect to the total structural units of the resin (A1).

[0216] <Structural unit (a2) not having an acid-labile group>

[0217] The resin (A1) can contain a structural unit (a1) having an acid-labile group and, as needed, a structural unit (a2) not having an acid-labile group. The resin (A1) containing the structural unit (a1) and the structural unit (a2) can be, for example, produced by polymerizing monomer components containing an olefinically unsaturated compound into which the structural unit (a1) is introduced and an olefinically unsaturated compound into which the structural unit (a2) is introduced. As the acid-labile group contained in the structural unit (a1), the group represented by Formula (10) and / or the group represented by Formula (20) described above is preferred.

[0218] In the resin (A1), one kind of structural unit (a2) not having an acid-labile group can be contained alone, or a plurality of kinds thereof can be contained.

[0219] As the structural unit (a2), for example, a structural unit represented by any one of Formulae (a2-1) to (a2-3) (hereinafter, sometimes referred to as "structural unit (a2-1)" and the like according to the formula number) can be given.

[0220]

[0221] In Formulae (a2-1), (a2-2), and (a2-3),

[0222] R a7 , R a8 , and R a9 independently of one another represent a hydrogen atom or a methyl group.

[0223] R a10 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

[0224] m' represents an integer of 0 to 4. When m' is 2 or more, a plurality of R a10 may be the same as or different from one another.

[0225] R a11 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Among them, a group in which a carbon atom bonded to an oxygen atom is a tertiary carbon atom is excluded.

[0226] R a12 represents an alkyl group having 1 to 6 carbon atoms. Among them, a group in which a carbon atom bonded to an oxygen atom is a tertiary carbon atom is excluded.

[0227] L a1 represents an alkanediyl group having 2 to 6 carbon atoms. Among them, a group in which a carbon atom bonded to an oxygen atom is a tertiary carbon atom is excluded.

[0228] n represents an integer of 1 to 30. When n is 2 or more, a plurality of L a1 may be the same as or different from one another.

[0229] As the alkyl group having 1 to 6 carbon atoms represented by R a10 , for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like can be given. 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.

[0230] As the alkoxy group having 1 to 6 carbon atoms represented by R a10 , for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, and the like can be given. 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.

[0231] As the alkyl group having 1 to 6 carbon atoms represented by R a11Examples of the hydrocarbon group having 1 to 12 carbon atoms include chain hydrocarbon groups having 1 to 12 carbon atoms (alkyl groups, alkenyl groups, alkynyl groups, and the like), alicyclic hydrocarbon groups having 3 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 12 carbon atoms, and groups having 4 to 12 carbon atoms formed by combining these groups.

[0232] Examples of the alkyl group having 1 to 12 carbon atoms include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the like.

[0233] Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, t-butenyl, pentenyl, hexenyl, heptenyl, octenyl, iso-octenyl, nonenyl, and the like.

[0234] Examples of the alkynyl group having 2 to 12 carbon atoms include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, t-butynyl, pentynyl, hexynyl, octynyl, nonynyl, and the like.

[0235] The chain hydrocarbon group having 1 to 12 carbon atoms is preferably a chain hydrocarbon group having 1 to 10 carbon atoms, more preferably a chain hydrocarbon group having 1 to 8 carbon atoms, and further preferably a chain hydrocarbon group having 1 to 6 carbon atoms.

[0236] The alicyclic hydrocarbon group having 3 to 12 carbon atoms can be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Examples of the polycyclic alicyclic hydrocarbon group include, for example, decalinyl, adamantyl, norbornyl, and the following groups (the asterisk indicates the bonding end).

[0237]

[0238] The alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and more preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms.

[0239] Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include phenyl, naphthyl, and the like. The aromatic hydrocarbon group having 6 to 12 carbon atoms is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0240] Examples of the group having 4 to 12 carbon atoms formed by combining the above groups include, as groups (groups having 4 to 12 carbon atoms) formed by combining an alkyl group and an alicyclic hydrocarbon group, for example, methylcyclohexyl, dimethylcyclohexyl, methyl-norbornyl, cyclohexylmethyl, adamantylmethyl, norbornylethyl, and the like.

[0241] As a group (a group having 7 to 12 carbon atoms) in which an alkyl group and an aromatic hydrocarbon group are combined, for example, an aralkyl group, an aromatic hydrocarbon group having an alkyl group, specifically, a benzyl group, a phenethyl group, a phenylpropyl group, a triphenylmethyl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-t-butylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, and the like can be given.

[0242] As a group (a group having 9 to 12 carbon atoms) in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined, for example, an aromatic hydrocarbon group having an alicyclic hydrocarbon group, an alicyclic hydrocarbon group having an aromatic hydrocarbon group, specifically, a p-cyclohexylphenyl group, a phenylcyclohexyl group, and the like can be given.

[0243] As R a12 having 1 to 6 carbon atoms, for example, 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 can be given. 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.

[0244] As L a1 having 2 to 6 carbon atoms, either of a straight chain or a branched chain, 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 given. The alkanediyl group having 2 to 6 carbon atoms is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an alkanediyl group having 2 to 3 carbon atoms.

[0245] R a7 is preferably a hydrogen atom.

[0246] R a8 and R a9 are each independently preferably a methyl group.

[0247] R a10 is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, for example, further preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more further preferably a methyl group or a methoxy group.

[0248] m' is preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0249] R a11Preferably, it is 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, further preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 3 to 8 carbon atoms. Among them, a group in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom is excluded.

[0250] L a1 Preferably, it is an alkanediyl group having 2 to 4 carbon atoms (e.g., ethane-1, 2-diyl, propane-1, 3-diyl, propane-1, 2-diyl, butane-1, 4-diyl), more preferably an alkanediyl group having 2 to 3 carbon atoms (e.g., ethane-1, 2-diyl, propane-1, 3-diyl, propane-1, 2-diyl), further preferably ethane-1, 2-diyl.

[0251] n is preferably an integer of 1 to 20, more preferably an integer of 1 to 16, further preferably an integer of 1 to 14, more further preferably an integer of 1 to 10, still further preferably an integer of 1 to 6.

[0252] R a12 Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Among them, a group in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom is excluded.

[0253] As the structural unit (a2-1), a structural unit represented by formula (a2-1-1), formula (a2-1-2), formula (a2-1-3), or formula (a2-1-4) is preferable. In addition, a monomer into which the structural unit (a2-1) is introduced is described, for example, in Japanese Patent Application Publication No. 2010-204634.

[0254]

[0255] As the monomer into which the structural unit (a2-2) is introduced, for example, an alkyl (meth)acrylate such as (meth)acrylate methyl ester, (meth)acrylate ethyl ester, (meth)acrylate propyl ester, (meth)acrylate butyl ester, (meth)acrylate hexyl ester;

[0256] a cycloalkyl (meth)acrylate such as (meth)acrylate cyclopentyl ester, (meth)acrylate cyclohexyl ester, and the like, a monocyclic (meth)acrylate;

[0257] a polycyclic (meth)acrylate such as (meth)acrylate adamantyl ester, (meth)acrylate norbornyl ester, and the like;

[0258] an aryl (meth)acrylate such as (meth)acrylate phenyl ester, (meth)acrylate benzyl ester, and the like.

[0259] As the monomer to introduce the structural unit (a2-3), for example, 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, and the like (poly)ethylene glycol monomethyl ether (meth)acrylate ((poly)alkylene glycol monoalkyl ether (meth)acrylate) can be given.

[0260] Further, as the monomer to introduce the structural unit (a2), for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like carboxylic acids, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and the like (meth)acrylic acid hydroxyalkyl esters, styrene, a-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 4-isopropoxystyrene, and the like styrenes can be given.

[0261] The structural unit (a2) may, for example, also be a structural unit represented by formula (a2-4).

[0262]

[0263] [In formula (a2-4),

[0264] R a13 represents a hydrogen atom or a methyl group.

[0265] R a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

[0266] R a15 represents a hydrocarbon group having 1 to 12 carbon atoms. Among them, 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 can be replaced with an oxygen atom or a carbonyl group. Among them, the methylene group bonded to the oxygen atom and the methylene group bonded to the methylene group are not replaced with an oxygen atom.

[0267] 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.

[0268] 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.

[0269] wherein the total of m" and m'" is 5 or less.

[0270] R a15 The hydrocarbon group in R a15 The hydrocarbon group in R

[0271] Therefore, the structural unit represented by formula (a2-4) does not include the structural unit (al-2).

[0272] The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms as R a14 are the same groups as R a10 .

[0273] The hydrocarbon group having 1 to 12 carbon atoms as R a15 are the same groups as R a11 .

[0274] R a13 is preferably a hydrogen atom.

[0275] R a14 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, for example, further preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more further preferably a methyl group or a methoxy group.

[0276] wherein R a15 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 with an oxygen atom or a carbonyl group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group having 6 to 10 carbon atoms formed by combining these groups, or a group in which a methylene group contained in these groups is replaced with an oxygen atom or a carbonyl group, and further 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 groups, or a group in which a methylene group adjacent to an oxygen atom in these groups is replaced with a carbonyl group.

[0277] m" is preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0278] m'" is preferably 0 to 3, more preferably 0 to 2, and further preferably 0 or 1.

[0279] wherein the total of m" and m'" is 5 or less.

[0280] As the structural unit (a2-4), for example, a structural unit represented by formula (a2-4-1) to formula (a2-4-10) can be given.

[0281]

[0282] In the structural units represented by formula (a2-4-1) to formula (a2-4-10), the hydrogen atom equivalent to R a13 A structural unit in which the hydrogen atom equivalent to R

[0283] In the case where the resin (Al) contains the structural unit (a2-1), the structural unit (a2-2), the structural unit (a2-3), and the structural unit (a2-4), it is preferred that the total content ratio thereof with respect to the total structural units of the resin (Al) is 1 to 90 mol%, more preferably 1 to 85 mol%, further preferably 5 to 80 mol%, particularly preferably 5 to 75 mol%.

[0284] In the case where the resin (Al) contains the structural unit (a2), the content ratio of the structural unit (al) to the structural unit (a2) [structural unit (al) : structural unit (a2)] is preferably 10 : 90 to 80 : 20, more preferably 15 : 85 to 60 : 40, further preferably 15 : 85 to 45 : 55, on a molar basis.

[0285] As the combination of the structural units contained in the resin (Al), a combination represented by formula (Al-1) to formula (Al-46) can be given.

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294] In the above structural formulae, the hydrogen atom equivalent to R a5As the structural unit, a structural unit in which an equivalent hydrogen atom is substituted with a methyl group or a methyl group is substituted with a hydrogen atom can also be exemplified. In addition, in one resin, a structural unit having a hydrogen atom and a methyl group can be mixed.

[0295] The resin (Al) is preferably a resin containing the structural unit (al) and the structural unit (a2), and more preferably a resin containing the structural unit (al-1) and / or the structural unit (al-2) and the structural unit (a2).

[0296] The resin (Al) can also be a resin obtained by reacting a resin containing at least one selected from a carboxyl group and a phenolic hydroxyl group in a side chain with a compound containing at least two or more vinyloxy groups in one molecule (hereinafter, sometimes referred to as "resin (Alb)").

[0297] The resin (Alb) 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. As such a resin, for example, a resin containing the structural unit (a2-1) can be reacted with a compound containing two or more vinyloxy groups in one molecule. In addition, it can also be a resin obtained by using a linear phenol formaldehyde resin described later as the resin containing a phenolic hydroxyl group, and reacting the linear phenol formaldehyde resin with the above-mentioned compound containing a vinyloxy group. Furthermore, it can also be a resin obtained by mixing a resin containing the structural unit (a2-1) with a linear phenol formaldehyde resin, and reacting the above-mentioned compound containing a vinyloxy group with the obtained resin mixture. In addition, it can also be used in combination with a resin obtained by reacting a resin containing the structural unit (a2-1) with the above-mentioned compound containing a vinyloxy group, and a resin obtained by reacting a linear phenol formaldehyde resin with the above-mentioned compound containing a vinyloxy group.

[0298] In the synthesis of the resin (Alb), the amount of use of the compound containing at least two or more vinyloxy groups in one molecule with respect to the carboxyl group and the phenolic hydroxyl group is preferably 60:40 to 99:1, and more preferably 70:30 to 95:5, on a molar basis.

[0299] As the resin (Alb), for example, the resins described in Japanese Patent Application Laid-Open (JP-A) No. 2008-134515 and Japanese Patent Application Laid-Open (JP-A) No. 2008-46594 can be exemplified.

[0300] As the compound containing at least two or more vinyloxy groups in one molecule, for example, 1,4-cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, and the like can be exemplified.

[0301] In the case where the resin (Alb) is a resin obtained by mixing a resin containing the structural unit (a2-1) with a novolak resin and reacting a compound containing a vinyloxy group with the resulting resin mixture, the content ratio of the novolak resin with respect to the total amount of the resin (Alb) is 30 to 70 mass%.

[0302] The resin (Al) can be produced by polymerizing monomer components including an ethylenically unsaturated compound corresponding to the above structural unit (al) and, as necessary, an ethylenically unsaturated compound corresponding to the structural unit (a2) by using a publicly known polymerization method such as a radical polymerization method.

[0303] The weight average molecular weight of the resin (Al) is preferably 3,000 or more, more preferably 4,000 or more, and preferably 600,000 or less, more preferably 500,000 or less. Note that the weight average molecular weight is obtained as a conversion value based on a standard polystyrene by gel permeation chromatography analysis. The detailed analysis conditions of this analysis are described in the Examples of the present application.

[0304] The content ratio of the resin (Al) with respect to the total amount of the resin contained in the resist composition is preferably 10 mass% or more, more preferably 15 mass% or more, and further preferably 30 mass% or more, and is preferably 95 mass% or less, more preferably 85 mass% or less, and further preferably 70 mass% or less.

[0305] The resin (Al) can also be a novolak resin into which an acid-labile group including a group capable of being cleaved by the action of an acid is introduced (hereinafter, sometimes referred to as "resin (Alc)"). This resin refers to a resin in which part or all of the phenolic hydroxyl groups of the novolak resin described later are protected with an acid-labile group including a group capable of being cleaved by the action of an acid, or a resin in which part or all of the phenolic hydroxyl groups of the novolak resin described later are replaced with an acid-labile group including a group capable of being cleaved by the action of an acid. This resin is also referred to as a novolak resin having an acid-labile group (a group including a group capable of being detached by contact with an acid).

[0306] The novolak resin is, for example, a resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol compound") with an aldehyde in the presence of an acid catalyst.

[0307] As the phenolic compound, for example, 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-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 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, p-benzoquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, gallate, a-naphthol, β-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, polyhydroxytriphenylmethane compounds obtained by condensation of xylenol with hydroxybenzaldehyde, and the like can be mentioned. They can be used alone or in combination of two or more.

[0308] Among them, as the phenolic compound, for example, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 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.

[0309] As the aldehyde, for example, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, propylene aldehyde and crotonaldehyde; alicyclic aldehydes such as cyclohexylmethanal, cyclopentylmethanal or furanpropionaldehyde; 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; aromatic aliphatic aldehydes such as phenylacetaldehyde or cinnamaldehyde; and the like can be mentioned. They can be used alone or in combination of two or more. Among them, from the aspect of industrial availability, formaldehyde is preferable.

[0310] As the catalyst in the addition condensation, for example, 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; and the like can be mentioned. They can be used alone or in combination of two or more. The amount of the catalyst used is usually 0.01 to 1 mole per 1 mole of the aldehyde.

[0311] 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 can be carried out in the presence of a solvent. As the solvent, for example, ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, acetone, and the like can be mentioned. After the completion of the reaction, for example, a water-insoluble solvent is added to the reaction mixture as necessary, and the reaction mixture is washed with water and then concentrated, whereby a novolak resin can be obtained. Alternatively, after the completion of the reaction, in order to remove the acid catalyst, a basic compound can be added to neutralize it, and the neutralization salt can be removed by water washing.

[0312] In the above novolak resin, the weight average molecular weight is preferably 3,000 or more, more preferably 4,000 or more, further preferably 5,000 or more, preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, more further preferably 9,000 or less, still further preferably 8,000 or less.

[0313] In the present specification, the weight average molecular weight is obtained by gel permeation chromatography analysis in the form of a conversion value based on a polystyrene standard. The detailed analysis conditions of the analysis are described in the examples of the present application.

[0314] The acid-labile group introduced into the novolak resin is not particularly limited as long as it contains a group that can be cleaved by the action of an acid, and groups known as acid-labile groups can be mentioned. The acid-labile group is introduced into some or all of the phenolic hydroxyl groups in the novolak resin obtained by condensation as described above.

[0315] As the acid-labile group introduced into the phenolic hydroxyl group in the novolak resin, for example, the group represented by formula (10) or the group represented by formula (20) described above, and the like can be mentioned. The group represented by formula (1') or the group represented by formula (2) is preferred.

[0316] As the acid-labile group, specifically, there can be mentioned, for example, t-butyloxycarbonyloxy group, 1-methylcyclopentane-1- yloxy carbonyloxy group, 1-(cyclopentane-1-yl)-1-methyloxycarbonyloxy group, butoxyethyloxy group, ethoxypropyloxy group, ethoxybutyloxy group, tetrahydro-2-pyranyloxy group, tetrahydro-2-furanyloxy group, methoxyethyloxy group, 1-ethoxyethyloxy group, propyloxyethyloxy group, cyclohexyloxyethyloxy group, 1-(2-methylpropyloxy)ethyloxy group, 1-(2-methoxyethyloxy)ethyloxy group, 1-(2-acetyloxyethyloxy)ethyloxy group, 1- [2-(1-adamantyloxy)ethyloxy]ethyloxy group, 1-[2-(1-adamantyloxycarbonyl)ethyloxy]ethyloxy group, 3-oxocyclohexyloxy group, 4-methyltetrahydro-2-pyranylen-4-yloxy group, and the like. Among them, at least one kind selected from the group consisting of ethoxyethyloxy group, ethoxypropyloxy group, ethoxybutyloxy group, isopropoxyethyloxy group, cyclohexyloxyethyloxy group, and 1-(2-methylpropyloxy)ethyloxy group is preferred, at least one kind selected from the group consisting of ethoxyethyloxy group, isopropoxyethyloxy group, and cyclohexyloxyethyloxy group is more preferred, and 1-ethoxyethyloxy group is further preferred.

[0317] As one mode of the linear phenol novolac resin (A1c) having an acid-labile group, there can be mentioned, for example, a resin containing a structural unit represented by formula (a3A) (hereinafter, sometimes referred to as "structural unit (a3A)") or a structural unit represented by formula (a3B) (hereinafter, sometimes referred to as "structural unit (a3B)").

[0318]

[0319] [In formula (a3A), R a1 , R a2 , and R a3 independently of one another 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 and, together with the carbon atom to which they are bonded, form a ring having 3 to 20 carbon atoms, 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 ab represents a hydroxyl 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.]

[0320]

[0321] [In formula (a3B), R a1’ and R a2’ independently of one another represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R a3’represents a hydrocarbon group having 1 to 20 carbon atoms. 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 and, together with the carbon atom and the oxygen atom to which they are bonded, form a heterocyclic ring having 3 to 20 carbon atoms. The methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms can be replaced with an oxygen atom or a sulfur atom. R ab represents a hydroxyl 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. In the case where p is 2 or 3, R ab may be the same or different.

[0322] As the alkyl group having 1 to 6 carbon atoms represented by R ab , for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like can be given. 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 further preferably a methyl group.

[0323] As the alkoxy group having 1 to 6 carbon atoms represented by R ab , for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, and the like can be given. 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 further preferably a methoxy group. R ab 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, and further preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and still further preferably a methyl group or a methoxy group.

[0324] p is preferably 0 to 2, and more preferably 0 or 1.

[0325] As the combination of the structural units contained in the linear phenol novolac resin (A1c) having an acid-labile group, for example, the combinations represented by formula (A1c-1) to formula (A1c-12) can be given.

[0326]

[0327] The introduction ratio of the acid-labile group with respect to the phenolic hydroxyl group possessed by the linear phenol novolac resin of the resin (A1c) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. In addition, it is preferably 80 mol% or less, more preferably 70 mol% or less, and further preferably 60 mol% or less. Furthermore, depending on the acid-labile group, there is an optimum introduction ratio.

[0328] In the case where the resin (Al) has the acid-labile group (2), the introduction ratio of the acid-labile group (2) with respect to the phenolic hydroxyl group is preferably 20 mol% or more, more preferably 30 mol% or more. In the case where the resin (Al) has ethoxyethoxy as the acid-labile group, it is further preferably 30 to 60 mol%, in the case where it has propoxyethoxy, it is further preferably 20 to 60 mol%, and in the case where it has cyclohexyloxyethoxy, it is further preferably 20 to 60 mol%. By setting to this range, resolution after pattern formation, residual film rate, and heat resistance of a resist composition using the resin can be effectively ensured.

[0329] The introduction ratio of the acid-labile group can be measured, for example, by 1 H-NMR.

[0330] Methods of introducing the acid-labile group into the phenolic hydroxyl group of the linear phenol formaldehyde resin include publicly known methods in the field. For example, in the case where ethoxyethoxy is introduced as the acid-labile group, methods such as the following can be mentioned: a prescribed amount of ethyl vinyl ether is added to the linear phenol formaldehyde resin at room temperature under an acid catalyst, and allowed to react for a prescribed time under the acid catalyst, then diethyl ether is added, and washed with water.

[0331] The weight average molecular weight of the resin (Alc) is preferably 3,000 or more, more preferably 4,000 or more, and preferably 200,000 or less, more preferably 100,000 or less. Note that the weight average molecular weight is measured by gel permeation chromatography analysis, as a conversion value based on a standard polystyrene. Detailed analysis conditions of the analysis are described in the examples of the present application.

[0332] The content ratio of the resin (Alc) with respect to the total amount of the resin contained in the resist composition is preferably 10 mass% or more, more preferably 15 mass% or more, and further preferably 30 mass% or more, and is preferably 95 mass% or less, more preferably 85 mass% or less, and further preferably 70 mass% or less.

[0333] <Resin (A2)>

[0334] The resin (A2) is preferably an alkali-soluble resin. The alkali-soluble resin is a resin having an acid group (sometimes referred to as a hydrophilic group) and being soluble in an alkali developer. The acid group is, for example, a carboxyl group, a sulfo group, a hydroxyl group (phenolic hydroxyl group, etc.).

[0335] As the alkali-soluble resin, an alkali-soluble resin known in the field of resists can be mentioned, and for example, a linear phenol resin, a resin containing a structural unit (a2-1) and not containing a structural unit (a1), for example, a resin containing a structural unit derived from a hydroxystyrene, a resin containing a structural unit derived from a (meth)acrylate, and a polyalkylene glycol, and the like can be mentioned. A linear phenol resin is preferred. The alkali-soluble resin preferably does not have an acid-labile group. That is, the alkali-soluble resin is preferably a resin containing a structural unit having an acid group and not containing a structural unit having an acid-labile group. The alkali-soluble resin preferably does not change in solubility in an aqueous alkali solution due to contact with an acid. The alkali-soluble resin can be used alone or in combination of two or more.

[0336] In the resin (A2), the total content ratio of the structural units having an acid group is preferably 3 to 100 mol%, more preferably 5 to 100 mol%, further preferably 10 to 100 mol%, more further preferably 30 to 100 mol%, still further preferably 50 to 100 mol%, yet further preferably 60 to 100 mol%, particularly preferably 70 to 100 mol%, and especially preferably 80 to 100 mol%, with respect to the total structural units of the resin (A2).

[0337] The resin (A2) can contain only one kind of structural unit having an acid group or can contain a plurality of kinds.

[0338] As the alkali-soluble resin, for example, a resin having a residual film ratio of 0% or more and 90% or less when developed with an alkali developer under actual use conditions can be mentioned. The residual film ratio is preferably 0% or more and 85% or less, and more preferably 0% or more and 80% or less.

[0339] The residual film ratio can be measured, for example, as follows. After dissolving the resin in an organic solvent, if necessary, filtering using a filter, next, coating on a substrate using a spin coater or the like, followed by heating, and removing the organic solvent. The organic film obtained on the substrate is measured using a film thickness meter, developed with an aqueous alkali solution having a concentration of 2.38 mass%, and the film thickness after development is measured again using a film thickness meter. The residual film ratio can be obtained by dividing the film thickness after development by the film thickness before development. The development conditions are actual use conditions. For example, the development temperature can be mentioned as 5 to 60°C, and the development time can be mentioned as 5 to 600 seconds. The alkali developer can be mentioned as various aqueous alkali solutions used in the field, and for example, an aqueous solution of tetramethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline), and the like can be mentioned.

[0340] The linear phenol resin refers to a resin obtained by condensing a phenol compound with an aldehyde in the presence of a catalyst, and for example, can be selected from the resins described in the resin (A1c) mentioned above.

[0341] As one mode of the linear phenol formaldehyde resin, for example, a resin containing a structural unit represented by formula (a4) (hereinafter, sometimes referred to as "structural unit (a4)") can be given.

[0342]

[0343] In formula (a4), R ac represents a hydroxyl 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. In the case where p1 is 2 or 3, R ac may be the same or different. q1 represents 1, 2, or 3. Among them, the total of p1 and q1 is 4 or less.

[0344] As the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R ac , the same groups as R ab can be given.

[0345] R ac 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, further preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more further preferably a methyl group or a methoxy group.

[0346] p1 is preferably 0 to 2, and more preferably 1 or 2.

[0347] q1 is preferably 1 or 2, and more preferably 1.

[0348] The weight average molecular weight of the linear phenol formaldehyde resin is preferably 3,000 or more, more preferably 4,000 or more, further preferably 5,000 or more, more further preferably 6,000 or more, preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, more further preferably 9,000 or less, and still further preferably 8,000 or less. By being in this range, development after thinning and the remaining of residues can be effectively prevented. The weight average molecular weight is obtained by gel permeation chromatography analysis in the form of a conversion value based on a standard polystyrene. The detailed analysis conditions of this analysis are described in the examples of the present application.

[0349] As the resin containing a structural unit derived from a hydroxystyrene, for example, a resin containing a structural unit derived from a hydroxystyrene (p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene), an isopropenylphenol (p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol) and the like, which is a monomer having a phenolic hydroxyl group, can be given, and specifically, a resin containing a structural unit represented by formula (a2-1) can be given. The resin containing a structural unit derived from a hydroxystyrene can contain a structural unit derived from a monomer other than the structural unit derived from the above-mentioned monomer, and the monomer exemplified in the resin containing a structural unit derived from a (meth)acrylate to be described later.

[0350] The resin containing a structural unit derived from a hydroxystyrene is typically a poly(vinylphenol) (poly(hydroxystyrene)), and preferably a poly(p-vinylphenol) (poly(p-hydroxystyrene)). Specifically, a resin containing a structural unit represented by formula (a2-1) can be given. Such a poly(vinylphenol) can be obtained, for example, by polymerizing a monomer described in Japanese Patent Application Publication No. 2010-204634.

[0351] As the resin containing a structural unit derived from a (meth)acrylate, for example, a resin obtained by using a compound described below as a monomer, polymerizing one kind or a combination of two or more kinds of the monomer by a conventional method can be given. That is, the resin containing a structural unit derived from a (meth)acrylate can be given as a resin containing a structural unit derived from a monomer described below. A monomer having a carboxyl group such as a (meth)acrylic acid;

[0352] A monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and the like;

[0353] A monomer 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 and the like.

[0354] The above monomers can also be used in combination with methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, and the like (alkyl (meth)acrylates); cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like (cycloalkyl (meth)acrylates); adamantyl (meth)acrylate, norbornyl (meth)acrylate, and the like (polycyclic (meth)acrylates); phenyl (meth)acrylate, benzyl (meth)acrylate, and the like (aryl (meth)acrylates); ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, and the like (ethylene glycol monoalkyl ether (meth)acrylates (alkylene glycol monoalkyl ether (meth)acrylates)); and the like. In addition to the above monomers, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 4-isopropoxystyrene, and the like (styrenes); crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like (carboxylic acids); and the like (hydroxystyrenes exemplified in the above resin containing a structural unit derived from a hydroxystyrene) can also be used in combination. As the structural unit derived from the above monomers, the structural units represented by formula (a2-1) to formula (a2-4) can also be mentioned.

[0355] The polyalkylene glycol refers to a high molecule obtained by addition polymerization of an alkylene oxide and an alcohol. As the alcohol, for example, butanol, ethylene glycol, propylene glycol, glycerol, pentaerythritol, and the like can be mentioned. As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, and the like can be mentioned. As the polyalkylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like can be mentioned.

[0356] The content of the resin (A2) is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less, and more further preferably 65% by mass or less, relative to the total amount of the resin contained in the resist composition.

[0357] The resin (A2) is capable of adjusting the solubility of the resist in a developer (an aqueous alkali solution) by interaction with the photosensitizer (I), and is further capable of improving the precision of the plated molded article by having resistance to the developer (aqueous alkali solution) and the plating solution by crosslinking with the photosensitizer (I).

[0358] The mass ratio of the content of the resin (A1) and the resin (A2) contained in the resist composition ((A1) : (A2)) is usually 20:80 to 80:20, and preferably 30:70 to 70:30. If it is set to this range, the precision of the plated molded article can be further improved, and thus it is suitable.

[0359] The content of the resin (A1) and the resin (A2) in the resist composition of the present application is preferably 80 mass% or more and 99 mass% or less, relative to the total amount of the solid components of the resist composition. The content of the resin (A1) is preferably 1 mass% or more and 98 mass% or less, and more preferably 5 mass% or more and 90 mass% or less, relative to the total amount of the solid components of the resist composition. The content of the resin (A2) is preferably 1 mass% or more and 98 mass% or less, and more preferably 5 mass% or more and 90 mass% or less, relative to the total amount of the solid components of the resist composition. The content of each component contained in the resist composition of the present application and the solid components can be measured, for example, using a known analysis method such as liquid chromatography or gas chromatography.

[0360] <Acid generator (B)>

[0361] The acid generator (B) is a compound that can generate an acid by decomposition through light irradiation (exposure). The generated acid can cause the leaving group contained in the acid-labile group of the resin (A1) to be detached, and convert the acid-labile group to a hydrophilic group (for example, a carboxyl group, a hydroxyl group (phenolic hydroxyl group, etc.)). That is, by exposing the resist composition containing the resin (A1) to light, the resist can be made soluble with respect to a developer (an aqueous alkali solution).

[0362] The acid generator (B) must contain a compound having a maximum molar absorption coefficient of 6000 (L / (mol·cm)) or less in the range of wavelengths of 355 nm to 375 nm (hereinafter, sometimes referred to as "compound (B-1)").

[0363] The molar absorption coefficient is preferably 5800 (L / (mol cm)) or less, more preferably 5500 (L / (mol cm)) or less, and further preferably 5200 (L / (mol cm)) or less. In addition, it is preferably 100 (L / (mol cm)) or more, more preferably 200 (L / (mol cm)) or more, further preferably 300 (L / (mol cm)) or more, and more further preferably 500 (L / (mol cm)) or more. The molar absorption coefficient is calculated by the method described in the Examples. With respect to the molar absorption coefficient of the acid generator, under actual use conditions, specifically, in the resist composition, the wave form of the absorbance sometimes slightly shifts to the short wavelength side or the long wavelength side due to the interaction with other components or the like, and therefore, in the present application, the molar absorption coefficient in the range of wavelengths from 355 nm to 375 nm, which includes several wavelengths on the short wavelength side and the long wavelength side in addition to the center wavelength of 365 nm (i-line), is evaluated.

[0364] The acid generator (B) preferably contains a compound having an oxime skeleton or an amide skeleton. In particular, the compound (B-1) is preferably a compound having an oxime skeleton or an amide skeleton. Note that, in the present specification, an amide skeleton is a skeleton in which one carbonyl group (-CO-) is bonded to a nitrogen atom, and an imide skeleton is a skeleton in which two carbonyl groups (-CO-) are bonded to a nitrogen atom, and the two are different.

[0365] As the compound (B-1), a compound having a group represented by the following formula (p0) or a group represented by formula (q0) can be given.

[0366]

[0367] [In formula (p0) and formula (q0), * indicates a bonding end.]

[0368] As the compound (B-1), further preferably a compound having an oxime sulfonate group or an amide sulfonate group. Note that, in the present specification, an amide sulfonate group is a group in which one carbonyl group (-CO-) and one sulfonyloxy group (-O-SO2-) are bonded to a nitrogen atom, and an imide sulfonate group is a group in which two carbonyl groups (-CO-) and one sulfonyloxy group (-O-SO2-) are bonded to a nitrogen atom, and the two are different.

[0369] As the compound (B-1), a compound having a group represented by the following formula (p1) or a group represented by formula (q1) can be given.

[0370]

[0371] [In formula (p1) and formula (q1), * indicates a bonding end.]

[0372] As the compound (B-1), compounds represented by formula (b2) to formula (b4) can be given. Compounds represented by formula (b2) or formula (b4) are preferred, and compounds represented by formula (b4) are more preferred.

[0373]

[0374] [In formula (b2) to formula (b4),

[0375] R b1 represents a hydrocarbon group having 1 to 18 carbon atoms which can have a fluorine atom, and the methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms can be replaced with an oxygen atom or a carbonyl group.

[0376] R b3 , R b4 , and R b5 independently of one another represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

[0377] Ring W b2 represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms, or an aromatic heterocyclic ring having 6 to 14 carbon atoms.

[0378] R b6 represents a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms.

[0379] x2and x3independently of one another represent any one integer of 0 to 5. In the case where x2or x3is 2 or more, a plurality of R b3 or R b4 may be the same or different.

[0380] x4represents any one integer of 0 to 6. In the case where x4is 2 or more, a plurality of R b5 may be the same or different.

[0381] As the hydrocarbon group having 1 to 18 carbon atoms which can have a fluorine atom, of the R b1 , 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 obtained by combining these groups can be given.

[0382] As the linear or branched chain hydrocarbon group having 1 to 18 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms is preferred, and for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and the like can be given. Among them, a linear group is preferred.

[0383] Examples of alicyclic hydrocarbon groups with 3 to 18 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl.

[0384] As an aromatic hydrocarbon group with 6 to 18 carbon atoms, aryl groups with 6 to 18 carbon atoms are preferred, and examples include phenyl, naphthyl, anthracene, biphenyl, phenanthrene and other aryl groups.

[0385] Examples of groups with 4 to 18 carbon atoms that are formed by combining the above-mentioned groups include methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, isobornyl, 2-alkyladamantane-2-yl, 1-(adamantane-1-yl)alkane-1-yl, etc.

[0386] As a group (a group with 7 to 18 carbon atoms) formed by combining a chain hydrocarbon group and an aromatic hydrocarbon group, examples include aralkyl groups and aromatic hydrocarbon groups having alkyl groups. Specifically, examples include benzyl, phenethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, isopropylphenyl, mesitylene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.

[0387] As a group (a group with 9 to 18 carbon atoms) formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, examples include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group. Specifically, examples include p-cyclohexylphenyl, p-adamantylphenyl, phenylcyclohexyl, etc.

[0388] R b1 Among the hydrocarbon groups with 1 to 18 carbon atoms shown, alkyl groups with 1 to 10 carbon atoms or aromatic hydrocarbon groups with 6 to 10 carbon atoms are preferred, alkyl groups with 1 to 8 carbon atoms are more preferred, and alkyl groups with 1 to 4 carbon atoms are even more preferred.

[0389] As R b1 The group in which the methylene group of the alicyclic hydrocarbon group with 3 to 18 carbon atoms is replaced by an oxygen atom or a carbonyl group can be exemplified by groups shown in formulas (Y1) to (Y12). Groups shown in formulas (Y7) to (Y9) are preferred, and groups shown in formula (Y9) are more preferred.

[0390]

[0391] As the carbon number 1 to 18 hydrocarbon group having a fluorine atom, a carbon number 1 to 18 hydrocarbon group mentioned above in which one or more hydrogen atoms contained in the carbon number 1 to 18 hydrocarbon group are replaced with a fluorine atom is exemplified, and specifically, a fluorine alkyl group such as fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl, fluorohexyl, fluorine heptyl, fluorooctyl, fluorononyl, fluorodecyl, a fluorine cycloalkyl group such as fluorocyclopropyl, fluorocyclobutyl, fluorocyclopentyl, fluorocyclohexyl, fluorocycloheptyl, fluorocyclooctyl, fluorodiadamantyl, a fluorine aromatic group such as fluorophenyl, fluoronaphthyl, fluoranthryl, and the like are exemplified.

[0392] As the carbon number 1 to 18 hydrocarbon group having a fluorine atom, a carbon number 1 to 10 alkyl group having a fluorine atom, or a carbon number 6 to 10 aromatic hydrocarbon group having a fluorine atom is preferred, and a carbon number 1 to 8 perfluoroalkyl group is more preferred, and a carbon number 1 to 4 perfluoroalkyl group is further preferred.

[0393] As the carbon number 1 to 8 alkyl group of R b3 , R b4 , R b5 , and R b6 , methyl, ethyl, propyl, butyl, pentyl, and the like are exemplified, and methyl is preferred.

[0394] As the carbon number 1 to 8 alkoxy group of R b3 , R b4 , and R b5 , methoxy, ethoxy, propoxy, butoxy, pentoxy, and the like are exemplified, and methoxy is preferred.

[0395] As the carbon number 6 to 14 aromatic hydrocarbon ring of ring W b2 , a benzene ring, a naphthalene ring, an anthracene ring, and the like are exemplified.

[0396] As the carbon number 6 to 14 aromatic heterocyclic ring of ring W b2 , a ring having a ring-forming atom number of 6 to 14 is exemplified, and preferably, the following rings are exemplified.

[0397]

[0398] Ring W b2 is preferably a naphthalene ring.

[0399] x2, x3, and x4 are preferably independently any one of an integer of 0 to 4, and more preferably any one of an integer of 0 to 2.

[0400] As the compound represented by formula (b2), a compound represented by the following formula, and the like are exemplified.

[0401]

[0402] As the compound represented by formula (b3), for example, a compound represented by the following formula can be given.

[0403]

[0404] As the compound represented by formula (b4), for example, a compound represented by the following formula can be given.

[0405]

[0406] The acid generator (B) can further include other acid generators, within a range not adversely affecting the effects of the present application.

[0407] The other acid generators can use either of nonionic and ionic systems.

[0408] As the nonionic acid generator, for example, an organic halide, a sulfonic acid ester (for example, 2-nitrobenzyl ester, an aromatic sulfonic acid ester, an oxime sulfonic acid ester, an N-sulfonyloxy imide, a sulfonyloxy ketone, diazonium naphthoquinone 4-sulfonic acid ester), a sulfone (for example, disulfone, ketone sulfone, sulfonyl diazomethane), and the like can be given.

[0409] As the ionic acid generator, for example, an onium salt (for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt) including an onium cation is representative. As the anion of the onium salt, a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion, and the like can be given.

[0410] As the other acid generator, a compound generating an acid by irradiation of a ray described in Japanese Patent Application Laid-Open No. 63-26653, Japanese Patent Application Laid-Open No. 55-164824, Japanese Patent Application Laid-Open No. 62-69263, Japanese Patent Application Laid-Open No. 63-146038, Japanese Patent Application Laid-Open No. 63-163452, Japanese Patent Application Laid-Open No. 62-153853, Japanese Patent Application Laid-Open No. 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, and the like can be used. In addition, a compound manufactured by a publicly known method can also be used. The other acid generator can be used alone as one kind, or two or more kinds in combination.

[0411] As the nonionic acid generator in the other acid generator, for example, a compound represented by formula (b1) can be given.

[0412]

[0413] [In formula (b1),

[0414] R b1 denotes the same meaning as described above.

[0415] R b2 represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

[0416] Ring W b1 represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms or an aromatic heterocyclic ring having 6 to 14 carbon atoms.

[0417] x represents any one of integers from 0 to 6. In the case where x is 2 or more, a plurality of R b2 may be the same or different.

[0418] As the compound represented by formula (bl), a compound represented by any one of formula (b5) to formula (b8) is preferable, and a compound represented by formula (b5) is more preferable.

[0419]

[0420] [In formula (b5) to formula (b8),

[0421] R b1 , R b2 and x represent the same meanings as described above.

[0422] y represents any one of integers from 0 to 4, and z represents any one of integers from 0 to 2. In the case where y is 2 or more, a plurality of R b2 may be the same or different. In the case where z is 2, 2 R b2 may be the same or different.

[0423] X b1 and X b2 each independently represents -0-, -S- or -CO.

[0424] As the alkyl group having 1 to 8 carbon atoms of R b2 , for example, methyl group, ethyl group, propyl group, butyl group, pentyl group and the like can be mentioned, and methyl group is preferable.

[0425] As the alkoxy group having 1 to 8 carbon atoms of R b2 , for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group and the like can be mentioned, and methoxy group is preferable.

[0426] As the aromatic hydrocarbon ring having 6 to 14 carbon atoms of ring W b1 , for example, benzene ring, naphthalene ring, anthracene ring and the like can be mentioned.

[0427] As the aromatic heterocyclic ring having 6 to 14 carbon atoms of ring W b1 , a ring having 6 to 14 atoms constituting the ring can be mentioned, and preferably the following rings can be mentioned.

[0428]

[0429] Ring W b1 is preferably a naphthalene ring.

[0430] As the compound represented by formula (b1), for example, a compound represented by formula (b1-1) to formula (b1-17) and the like can be given. Preferred are a compound represented by formula (b1-6), formula (b1-7), formula (b1-10), formula (b1-13), and formula (b1-15).

[0431]

[0432] Among other acid generators, as the ion-based acid generator, a compound represented by formula (b9) or formula (b10) is preferred.

[0433]

[0434] [In formula (b9) and formula (b10),

[0435] A b1 and A b2 independently of one another represent an oxygen atom or a sulfur atom.

[0436] R b8 , R b9 , R b10 , and R b11 independently of one another represent an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

[0437] X1 - and X2 - represent an organic anion.

[0438] As the alkyl group having 1 to 10 carbon atoms, for example, 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 can be given.

[0439] As the aromatic hydrocarbon group having 6 to 12 carbon atoms, for example, an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, and the like can be given. The aromatic hydrocarbon group can further have a substituent, and as the aromatic hydrocarbon group having a substituent, for example, an aralkyl group, 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 cumyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, and the like can be given.

[0440] R b8 , R b9 , R b10 , and R b11 are each preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a phenyl group.

[0441] as X1 - and X2 - As the organic anion represented by X1

[0442]

[0443] In formula (b11), as the organic anion represented by X1

[0444] R b12 represents a hydrocarbon group having 1 to 18 carbon atoms which can have a fluorine atom, and the methylene group contained in the hydrocarbon group can be replaced with an oxygen atom or a carbonyl group.

[0445] As R b12 , the same groups as R b1 in formula (B1) can be given.

[0446] As the compound represented by formula (b9), the following compounds, etc. can be given.

[0447]

[0448] As the compound represented by formula (b10), the following compounds, etc. can be given.

[0449]

[0450] In the resist composition of the present application, the content of the acid generator (B) is preferably 0.1 parts by mass or more and 40 parts by mass or less, more preferably 0.3 parts by mass or more and 30 parts by mass or less, further preferably 0.5 parts by mass or more and 20 parts by mass or less, still further preferably 0.7 parts by mass or more and 10 parts by mass or less, and yet further 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 application can contain one kind of acid generator (B) alone, or can contain a plurality of kinds.

[0451] In addition, in the acid generator (B), the content of the compound (B-1) is 10 to 100% by mass, preferably 30 to 100% by mass, and more preferably 40 to 100% by mass, with respect to the total mass of the acid generator (B).

[0452] <Solvent (D)>

[0453] The content of the solvent (D) in the resist composition is usually 35% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass or less, more preferably 90% by mass or less. The content of the solvent (D) can be measured, for example, by a known analysis method such as liquid chromatography or gas chromatography.

[0454] As the solvent (D), 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; cyclic esters such as γ-butyrolactone; and the like can be given. One kind of the solvent (D) can be contained alone, or two or more kinds can be contained.

[0455] <Quenching agent (C)>

[0456] The resist composition of the present application can contain a quenching agent (hereinafter, sometimes referred to as "quenching agent (C)").

[0457] The quenching agent (C) is a compound having an action of capturing an acid generated from an acid generator by exposure. As the quenching agent (C), a basic nitrogen-containing organic compound can be given. As the basic nitrogen-containing organic compound, an amine and an ammonium salt can be given. As the amine, an aliphatic amine (including a primary amine, a secondary amine, and a tertiary amine), an aromatic amine, and the like can be given.

[0458] As the amine, a compound represented by Formula (C1) or Formula (C2), for example, can be given.

[0459]

[0460] [In Formula (C1), R c1 , R c2 , and R c3 independently of one another represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, the alkyl group having 1 to 6 carbon atoms and the alicyclic hydrocarbon group having 3 to 10 carbon atoms can have at least one selected from a hydroxyl group, an amino group, and an alkoxy group having 1 to 6 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms can have at least one selected from an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alicyclic hydrocarbon group having 3 to 10 carbon atoms.]

[0461] As the alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like can be given.

[0462] As the alicyclic hydrocarbon group having 3 to 10 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, and the like can be given.

[0463] As the aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms, for example, phenyl, naphthyl, and the like can be given.

[0464] As the alkoxy group having 1 to 6 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, and the like can be given, and methoxy is preferable.

[0465] As the compound represented by formula (Cl), for example, 1-naphthylamine, 2-naphthylamine, aniline, diisopropyl aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, dibutylmethylamine, methyldipentylamine, dihexylmethylamine, dicyclohexylmethylamine, diheptylmethylamine, methyldioctylamine, methyldinonylamine, didecylmethylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, tri[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, and the like can be given. Diisopropyl aniline is preferable, and 2,6-diisopropyl aniline is particularly preferable.

[0466]

[0467] In formula (C2),

[0468] Ring W 1 represents a heterocycle including a nitrogen atom among atoms constituting the ring, or a benzene ring having a substituted or unsubstituted amino group, and the heterocycle and the benzene ring can have at least one selected from a hydroxyl group and an alkyl group having 1 to 4 carbon atoms.

[0469] A 1 represents a phenyl group or a naphthyl group.

[0470] nc represents 2 or 3, and a plurality of A 1 may be the same or different.

[0471] The above-mentioned substituted or unsubstituted amino group is represented by -N(R 4 ) (R 5 ) represents R4 and R 5 They can be used to represent hydrogen atoms, chain hydrocarbon groups with 1 to 10 carbon atoms, alicyclic hydrocarbon groups with 3 to 10 carbon atoms, or aromatic hydrocarbon groups with 6 to 14 carbon atoms, independently of each other.

[0472] Examples of chain hydrocarbon groups with 1 to 10 carbon atoms include alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0473] Examples of alicyclic hydrocarbon groups with 3 to 10 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornyl.

[0474] Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms include aryl groups such as phenyl, naphthyl, anthracene, biphenyl, and phenanthrene. Aromatic hydrocarbon groups may further have substituents, such as aryloxy groups having 6 to 10 carbon atoms.

[0475] A heterocycle containing nitrogen atoms in its ring can be an aromatic ring or a non-aromatic ring, and may also contain other heteroatoms (e.g., oxygen or sulfur atoms) along with the nitrogen atom. The number of nitrogen atoms in this heterocycle is, for example, 1 to 3. Examples of such heterocycles include those shown in formulas (Y13) to (Y28). Removing one of the hydrogen atoms from the ring results in a ring with nitrogen atoms... 1 The bonding ends.

[0476]

[0477] Ring W 1 Preferably, it is a heterocycle containing nitrogen atoms in the atoms constituting the ring; more preferably, it is an aromatic heterocycle of a 5-membered ring or a 6-membered ring containing nitrogen atoms in the atoms constituting the ring; and even more preferably, it is a ring represented by any one of formulas (Y20) to (Y25).

[0478] Examples of compounds represented by formula (C2) include compounds represented by any of formulas (C2-1) to (C2-11). Preferably, compounds represented by any of formulas (C2-2) to (C2-8) are preferred.

[0479]

[0480] The content of the quencher (C) is preferably 0.0001 to 5% by mass, more preferably 0.0001 to 4% by mass, further preferably 0.001 to 3% by mass, more further preferably 0.01 to 1.0% by mass, still further preferably 0.05 to 0.8% by mass, and more further preferably 0.1 to 0.7% by mass, in the solid content of the resist composition.

[0481] <Adhesion Improver (E)>

[0482] The adhesion improver (E) is not particularly limited as long as it can prevent corrosion and / or improve adhesion to metals and the like used in substrates or wiring and the like. It functions to prevent rust by preventing corrosion of the metal. In addition, it can improve the adhesion of the substrate or metal and the like to the resist composition while these effects are exerted.

[0483] As the adhesion improver (E), for example, sulfur-containing compounds, aromatic hydroxyl compounds, benzotriazole-based compounds, triazine-based compounds, and silicon-containing compounds can be given. They can be used alone or in combination with two or more.

[0484] As the sulfur-containing compound, for example, a compound having a sulfide bond and / or a mercapto group is sufficient. The sulfur-containing compound can be a chain compound or a compound having a cyclic structure.

[0485] As the chain compound, for example, dithiodiglycerol [S(CH2CH(OH)CH2(OH))2], bis(2,3-dihydroxypropylthio)ethylene [CH2CH2(SCH2CH(OH)CH2(OH))2], 3-(2,3-dihydroxypropylthio)-2-methyl-propane sulfonic acid sodium [CH2(OH)CH(OH)CH2SCH2CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)CH2(OH)], 3-mercapto-1-propane sulfonic acid sodium [HSCH2CH2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], mercaptoacetic acid [HSCH2CO2H], 3-mercapto-1-propanol [HSCH2CH2CH2], and the like can be given.

[0486] The sulfur-containing compound is preferably a compound having a sulfide bond and a mercapto group, and more preferably a heterocyclic compound having a sulfide bond and a mercapto group. The heterocyclic compound is more preferably a heterocyclic compound having a sulfide bond in the ring structure. In the sulfur-containing compound, the number of sulfide bonds and mercapto groups is not particularly limited, and each is one or more.

[0487] The heterocycle of the heterocyclic compound can be either of a monocyclic and a polycyclic ring, and either of a saturated and an unsaturated ring. The heterocycle preferably further contains a heteroatom other than a sulfur atom. As the heteroatom, an oxygen atom, a nitrogen atom, and preferably a nitrogen atom can be given.

[0488] As the heterocycle, a heterocycle having 2 to 12 carbon atoms is preferred, and a heterocycle having 2 to 6 carbon atoms is more preferred. The heterocycle is preferably a monocyclic ring. The heterocycle is preferably unsaturated. The heterocycle is preferably unsaturated and a monocyclic ring.

[0489] As the heterocycle, a heterocycle such as the following can be given.

[0490]

[0491] The sulfur-containing compound can be a polymer. The polymer preferably contains a structure having a thioether bond and a mercapto group in a side chain. A structure having a thioether bond and a mercapto group (hereinafter, sometimes referred to as unit (1)) is preferably bonded to a main chain with an amide bond, an ether bond, a thioether bond, an ester bond, or the like.

[0492] The polymer can be either of a homopolymer and a copolymer.

[0493] In the case where the polymer is a copolymer, the above-described structural unit (al) having an acid-labile group, a structural unit (a2) not having an acid-labile group, or the like can be contained.

[0494] The weight average molecular weight of the above-described homopolymer and copolymer is usually 3,000 or more, preferably 5,000 or more, and usually 100,000 or less, preferably 50,000 or less. The weight average molecular weight is obtained as a converted value based on a standard polystyrene by gel permeation chromatography analysis.

[0495] In the case where the sulfur-containing compound is a polymer, the content of the structural unit having a thioether bond and a mercapto group is usually 0.1 to 50 mol%, preferably 0.5 to 30 mol%, and more preferably 1 to 20 mol% relative to the total structural units of the polymer of the sulfur-containing compound.

[0496] 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).

[0497]

[0498] [In formula (IA),

[0499] 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, a group represented by -SR 11 or a group represented by -NR 12R 13 the group shown.

[0500] R 11 , R 12 , and R 13 independently of one another 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 group, aromatic hydrocarbon group, alicyclic hydrocarbon group, and acyl group can have a hydroxyl group.

[0501] R i12 , and R i13 independently of one another 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 independently of one another represent a nitrogen atom or a carbon atom.

[0502] n1and m1independently of one another represent 0 or 1. Among them, in the case where A is a nitrogen atom, n1represents 0, in the case where A is a carbon atom, n1represents 1, in the case where B is a nitrogen atom, m1represents 0, and in the case where B is a carbon atom, m1represents 1.

[0503] As the chain hydrocarbon group having 1 to 10 carbon atoms, there can be mentioned, for example, 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, and the like.

[0504] As the aromatic hydrocarbon group having 6 to 14 carbon atoms, there can be mentioned, for example, aryl groups having 6 to 14 carbon atoms such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, and the like. The aromatic hydrocarbon group can further have a substituent, and as the aromatic hydrocarbon group having a substituent, there can be mentioned, for example, aralkyl group, aromatic hydrocarbon group having an alkyl group, specifically, benzyl group, phenethyl group, phenylpropyl group, triphenylmethyl group, naphthylmethyl group, naphthylethyl group, p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, and the like.

[0505] As the alicyclic hydrocarbon group having 3 to 18 carbon atoms, there can be mentioned, for example, monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, and polycyclic alicyclic hydrocarbon groups such as decalinyl group, adamantyl group, norbornyl group, and the like.

[0506] R 11 is preferably a chain hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 2 to 12 carbon atoms, R 12 , and R 13 independently of one another are preferably 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.

[0507] As the acyl group having 2 to 12 carbon atoms, there are mentioned, for example, acetyl, propionyl, butyryl, valeryl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, decylcarbonyl, dodecylcarbonyl, benzoyl and the like.

[0508] R i11 More preferably, it is a hydrogen atom or a mercapto group.

[0509] R i12 and R i13 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom.

[0510] Preferably, at least one of A and B is a nitrogen atom, more preferably both are nitrogen atoms.

[0511]

[0512] In formula (IB), R

[0513] R i21 and R i31 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. 1 and B 1 independently represent a nitrogen atom or a carbon atom.

[0514] n2and m2independently represent 0 or 1. Among them, in the case where A 1 is a nitrogen atom, n2represents 0, in the case where A 1 is a carbon atom, n2represents 1, in the case where B 1 is a nitrogen atom, m2represents 0, and in the case where B 1 is a carbon atom, m2represents 1.

[0515] R i4 represents a hydrogen atom or a methyl group.

[0516] X i1 represents a sulfur atom and an NH group.

[0517] L i1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. The methylene group contained in the hydrocarbon group can be replaced with an oxygen atom or a carbonyl group.

[0518] As the chain hydrocarbon group having 1 to 10 carbon atoms of R i21 and R i31 , there are mentioned, for example, alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like, preferably alkyl groups having 1 to 4 carbon atoms.

[0519] As the chain hydrocarbon group having 1 to 10 carbon atoms of Ri21 and R i31 of 6 to 14 carbons, for example, aryl groups of 6 to 14 carbons such as phenyl, naphthyl, anthryl, biphenyl, phenanthryl, and the like, are preferable. The aromatic hydrocarbon group can further have a substituent, and as the aromatic hydrocarbon group having a substituent, for example, aralkyl groups, aromatic hydrocarbon groups having an alkyl group, specifically, benzyl, phenethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, cumyl, mesityl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, and the like are preferable.

[0520] R i21 and R i31 of 3 to 18 carbons, for example, monocyclic alicyclic hydrocarbon groups of 3 to 18 carbons such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the like are preferable. The alicyclic hydrocarbon group of 5 to 10 carbons is preferable.

[0521] R i21 and R i31 are each independently preferably a hydrogen atom or an alkyl group of 1 to 4 carbons.

[0522] R i1 of 1 to 20 carbons, for example, methylene, ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, undecane-1, 11-diyl, dodecane-1, 12-diyl, tridecane-1, 13-diyl, tetradecane-1, 14-diyl, pentadecane-1, 15-diyl, hexadecane-1, 16-diyl, and heptadecane-1, 17-diyl, ethane-1, 1-diyl, propane-1, 1-diyl, propane-1, 2-diyl, propane-2, 2-diyl, pentane-2, 4-diyl, 2-methylpropane-1, 3-diyl, 2-methylpropane-1, 2-diyl, pentane-1, 4-diyl, 2-methylbutane-1, 4-diyl, and the like are preferable.

[0523] cyclobutane-1, 3-diyl, cyclopentane-1, 3-diyl, cyclohexane-1, 4-diyl, cyclooctane-1, 5-diyl, and the like as monocyclic alicyclic saturated hydrocarbon groups of 2 valences;

[0524] norbornane-1, 4-diyl, norbornane-2, 5-diyl, adamantane-1, 5-diyl, adamantane-2, 6-diyl, and the like as polycyclic alicyclic saturated hydrocarbon groups of 2 valences, and the like are preferable.

[0525] Phenylene, tolylene, naphthylene and the like arylene groups.

[0526] L i1 A group formed by combining an alkanediyl group having 2 to 14 carbon atoms or an arylene group having 6 to 10 carbon atoms with an alkanediyl group having 1 to 11 carbon atoms, preferably containing an ester bond.

[0527] The structural unit represented by formula (IB) is preferably a structural unit represented by formula (IB-1) or a structural unit represented by formula (IB-2).

[0528]

[0529] In formula (IB-1),

[0530] R i22 and R i32 independently of one another 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 2 and B 3 independently of one another represent a nitrogen atom or a carbon atom.

[0531] n3and m3independently of one another represent 0 or 1. Where A 2 is a nitrogen atom, n3represents 0, and where A 2 is a carbon atom, n3represents 1, and where B 2 is a nitrogen atom, m3represents 0, and where B 2 is a carbon atom, m3represents 1.

[0532] X i11 represents a sulfur atom and an NH group.

[0533] L i2 represents a divalent hydrocarbon group having 1 to 18 carbon atoms. The methylene group contained in the hydrocarbon group can be replaced with an oxygen atom or a carbonyl group.

[0534] R i5 represents a hydrogen atom or a methyl group.

[0535] In formula (IB-2),

[0536] R i23 and R i33 independently of one another 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 3 and B 3 independently of one another represent a nitrogen atom or a carbon atom.

[0537] n4and m4independently of one another represent 0 or 1. Where A 3 is a nitrogen atom, n4represents 0, and where A 3 is a carbon atom, n4represents 1, and where B 3 is a nitrogen atom, m4represents 0, and where B 3 is a carbon atom, m4represents 1.

[0538] X i12 represents a sulfur atom and an NH group.

[0539] L i3 represents a divalent hydrocarbon group having 1 to 14 carbon atoms. The methylene group contained in the hydrocarbon group can be replaced with an oxygen atom or a carbonyl group.

[0540] R i7 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

[0541] R i6 represents a hydrogen atom or a methyl group.

[0542] mxrepresents an integer of 0 to 4.

[0543] As the chain hydrocarbon group having 1 to 10 carbon atoms represented by R i22 , R i32 , R i23 and R i33 , the same groups as the chain hydrocarbon group having 1 to 10 carbon atoms represented by R i21 and R i31 can be mentioned.

[0544] As the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R i22 , R i32 , R i23 and R i33 , the same groups as the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R i21 and R i31 can be mentioned.

[0545] As the alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by R i22 , R i32 , R i23 and R i33 , the same groups as the alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by R i21 and R i31 can be mentioned.

[0546] As L i2Examples of divalent hydrocarbon groups with 1 to 18 carbon atoms shown include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, and tetradecane. -1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, and other alkyldiyl groups;

[0547] Cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl, etc. are monocyclic divalent alicyclic saturated hydrocarbon groups of cycloalkyldiyl groups;

[0548] Norbornene-1,4-diyl, norbornene-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, and other polycyclic divalent alicyclic saturated hydrocarbon groups;

[0549] Aryl groups such as phenylene, tolyl, and naphthylene.

[0550] L i2 Preferably, it is an alkyldiyl group with 1 to 14 carbon atoms, and more preferably an alkyldiyl group with 1 to 11 carbon atoms.

[0551] As L i3 Examples of divalent hydrocarbon groups with 1 to 14 carbon atoms shown include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl alkyldiyl groups.

[0552] Cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl, etc. are monocyclic divalent alicyclic saturated hydrocarbon groups of cycloalkyldiyl groups;

[0553] A bicyclic 2-valent alicyclic saturated hydrocarbon group such as naphthene-1,4-diyl, naphthene-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, and the like.

[0554] L i3 An alkanediyl group having preferably 1 to 14 carbon atoms, and more preferably 1 to 11 carbon atoms is preferred.

[0555] L i3 Bonding to the para position is preferred.

[0556] As the alkyl group having 1 to 6 carbon atoms represented by R i7 Mentioned as the alkyl group having 1 to 6 carbon atoms represented by R

[0557] As the alkoxy group having 1 to 6 carbon atoms represented by R i7 Mentioned as the alkoxy group having 1 to 6 carbon atoms represented by R

[0558] As the sulfur-containing compound, mention can be made of, for example, a compound represented by any one of the compounds represented by formula (I-1) to formula (I-26). Among these, compounds represented by formula (I-1) to formula (I-13) are preferred, and compounds represented by formula (I-1), formula (I-4), and formula (I-11) are more preferred.

[0559]

[0560]

[0561] As the sulfur-containing compound, mention can be made of, for example, a homopolymer containing 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.

[0562] A copolymer containing one or more of the structural units represented by formula (I-27) to formula (I-36) is preferred, and a copolymer containing the structural unit represented by formula (I-33) is more preferred.

[0563]

[0564] As such a copolymer, mention can be made of, for example, a copolymer containing the structural units represented by formula (I-39) to formula (I-48). Among these, a polymer having the structural units represented by formula (I-39) to formula (I-44) is preferred.

[0565]

[0566]

[0567] The sulfur-containing compound can be a compound synthesized by a publicly known method (for example, Japanese Patent Application Laid-Open No. 2010-79081) or a commercially available product. The polymer containing the sulfur-containing compound can be a commercially available product (for example, thio-bismuthine (manufactured by Tokyo Chemical Industry Co., Ltd., etc.) or a polymer synthesized by a publicly known method (for example, Japanese Patent Application Laid-Open No. 2001-75277).

[0568] As the aromatic hydroxy compound, for example, phenol, cresol, xylenol, catechol (= 1,2-dihydroxybenzene), tert-butylcatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzene triol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, amino-resorcinol, 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 can be given.

[0569] As the benzotriazole-based compound, for example, a compound represented by Formula (IX) can be given.

[0570]

[0571] [In Formula (IX),

[0572] R 1 and R 2 independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which can have a substituent, a carboxyl group, an amino group, a hydroxyl group, a cyano group, a formyl group, a sulfonylalkyl group, or a sulfo group.

[0573] Q represents a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms which can have a substituent, an aryl group, or -R 3X -N(R 4X )(R 5X , the above hydrocarbon group can have an amide bond, an ester bond in the structure.

[0574] R 3X represents an alkanediyl group having 1 to 6 carbon atoms. represents a bonding end to a nitrogen atom contained in the ring.

[0575] R 4X and R 5X independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms.

[0576] R 1 , R 2The hydrocarbon group having 1 to 10 carbon atoms of Q can be any one of an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and can have a saturated and / or unsaturated bond.

[0577] As the aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkyl group is preferable, and as the alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a methylpentyl group, an n-hexyl group, an n-heptyl group, and the like can be given.

[0578] As the aromatic hydrocarbon group having 6 to 10 carbon atoms, an aryl group is preferable, and as the aryl group, for example, a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, and the like can be given. The aromatic hydrocarbon group can further have a substituent, and as the aromatic hydrocarbon group having a substituent, for example, an aralkyl group, 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-t-butylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, and the like can be given.

[0579] As the substituent which the hydrocarbon group having 1 to 10 carbon atoms can have, for example, a hydroxyalkyl group, an alkoxyalkyl group, and the like can be given.

[0580] As the alkandiyl group having 1 to 6 carbon atoms of R 3X , either of a straight chain or a branched chain can be given, and for example, a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, and the like can be given.

[0581] As the alkyl group having 1 to 6 carbon atoms of R 4X and R 5X , for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like can be given.

[0582] As the hydroxyalkyl group having 1 to 6 carbon atoms of R 4X and R 5X , for example, a hydroxymethyl group, a hydroxyethyl group, a dihydroxyethyl group, and the like can be given.

[0583] As the alkoxyalkyl group having 2 to 6 carbon atoms of R 4X and R 5X , for example, a methoxymethyl group, a methoxyethyl group, a dimethoxyethyl group, and the like can be given.

[0584] In the case where the resist composition of the present application is applied to a substrate on which Cu is formed, in formula (IX), Q is preferably a compound represented by -R 3X 4X 5X , and R 4X and R 5X ​​​In the case where at least one of R1to R4in the formula (I) is an alkyl group having 1 to 6 carbon atoms, the benzotriazole-based compound lacks water solubility, however, in the presence of another component capable of dissolving the compound, it is preferable to use.

[0585] Further, in the case where the resist composition of the present application is applied to a substrate having an inorganic material layer (for example, a polysilicon film, an amorphous silicon film, or the like), in the formula (IX), a group showing water solubility is preferable as Q. 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, or the like is preferable. Thereby, the corrosion resistance of the substrate can be more effectively exerted.

[0586] As the benzotriazole-based compound, for example, benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethylbenzotriazole, 1-benzotriazole methyl formate, 5-benzotriazole formic 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 can be mentioned.

[0587] As the triazine-based compound, a compound represented by the formula (II) can be mentioned.

[0588]

[0589] [In the formula (II), R1to R4independently represent a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a mercapto group, a hydrocarbon group having 1 to 10 carbon atoms which can be substituted, an alkoxy group having 1 to 10 carbon atoms which can be substituted, or a hydrocarbon group having 1 to 10 carbon atoms which substitutes an amino group.]

[0590] R 6 , R 7 , and R 8 independently represent a halogen atom, a hydrogen atom, a hydroxy group, an amino group, a mercapto group, a hydrocarbon group having 1 to 10 carbon atoms which can be substituted, an alkoxy group having 1 to 10 carbon atoms which can be substituted, or a hydrocarbon group having 1 to 10 carbon atoms which substitutes an amino group.]

[0591] As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned.

[0592] The hydrocarbon group having 1 to 10 carbon atoms can be the same hydrocarbon group as mentioned above.

[0593] As the alkoxy group having 1 to 10 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, and the like can be mentioned.

[0594] As the triazine-based compound, for example, 1,3,5-triazine-2,4,6-trithiol and the like can be given.

[0595] As the silicon-containing compound, for example, a compound represented by formula (IIA) can be given.

[0596]

[0597] [In formula (IIA), R1to R4independently of one another represent a carbon number 1 to 5 aliphatic hydrocarbon group or a carbon number 1 to 5 mercaptoalkyl group.

[0598] R j1 represents a carbon number 1 to 5 aliphatic hydrocarbon group or a carbon number 1 to 5 mercaptoalkyl group.

[0599] R j2 to R4independently of one another represent a carbon number 1 to 5 aliphatic hydrocarbon group, a carbon number 1 to 5 alkoxy group, a mercapto group or a carbon number 1 to 5 mercaptoalkyl group, R j4 to R4independently of one another represent a carbon number 1 to 5 aliphatic hydrocarbon group, a carbon number 1 to 5 alkoxy group, a mercapto group or a carbon number 1 to 5 mercaptoalkyl group, R j2 to R4independently of one another represent a carbon number 1 to 5 aliphatic hydrocarbon group, a carbon number 1 to 5 alkoxy group, a mercapto group or a carbon number 1 to 5 mercaptoalkyl group, R j4 to R4independently of one another represent a carbon number 1 to 5 aliphatic hydrocarbon group, a carbon number 1 to 5 alkoxy group, a mercapto group or a carbon number 1 to 5 mercaptoalkyl group, R

[0600] t i represents an integer of 1 to 10.

[0601] As the carbon number 1 to 5 aliphatic hydrocarbon group, for example, a carbon number 1 to 5 alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like can be given.

[0602] As the carbon number 1 to 5 alkoxy group, a methoxy group, an ethoxy group and the like can be given.

[0603] As the carbon number 1 to 5 mercaptoalkyl group, for example, a methylmercapto group, an ethylmercapto group, a propylmercapto group and the like can be given.

[0604] R j1 is preferably a methyl group, an ethyl group, a carbon number 1 to 3 mercaptoalkyl group, more preferably a methyl group, a mercaptopropyl group (particularly a 3-mercapto propyl group).

[0605] R j2 to R4independently of one another represent a carbon number 1 to 5 aliphatic hydrocarbon group, a carbon number 1 to 5 alkoxy group, a mercapto group or a carbon number 1 to 5 mercaptoalkyl group, R j4 independently of one another are preferably a methyl group, an ethyl group, a methoxy group, an ethoxy group, more preferably a methyl group, a methoxy group. Of these, at least one of them is preferably a mercapto group or a carbon number 1 to 3 mercaptoalkyl group, more preferably a mercapto group or a mercaptopropyl group. j2 and R j3 may be the same as or different from each other, and from the viewpoint of productivity, it is preferable that they are the same.

[0606] As the compound of formula (IIA), for example, a compound represented by formula (II-1) to formula (II-7) shown below can be given.

[0607]

[0608] Among them, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like are preferred.

[0609] The content of the adhesion improver (E) is preferably 0.001 mass% or more, more preferably 0.002 mass% or more, further preferably 0.005 mass% or more, particularly preferably 0.008 mass% or more, and in addition, is preferably 20 mass% or less, more preferably 10 mass% or less, further preferably 4 mass% or less, more further preferably 3 mass% or less, particularly preferably 1 mass% or less, and especially preferably 0.1 mass% or less, with respect to the total amount of the solid components of the resist composition. By setting to this range, a resist composition capable of forming a high-precision resist pattern can be produced, and the adhesion of the resist pattern to the substrate can be ensured.

[0610] <Other Components>

[0611] The resist composition of the present application can contain components other than the above components (hereinafter, sometimes referred to as "other components (F)") as necessary. The other components (F) are not particularly limited, and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, and the like can be used.

[0612] In the case where the other components (F) are used, the content thereof is appropriately selected depending on the kind of the other components (F).

[0613] 2. Preparation of resist composition

[0614] The resist composition of the present application can be produced by mixing the resin (Al), the photosensitizer (I), and the acid generator (B), and the resin (A2), the resin other than the resin (Al) and the resin (A2), the quenching agent (C), the solvent (D), the adhesion improver (E), and the other components (F) as necessary. The order of mixing is arbitrary and is not particularly limited. The temperature at the time of mixing can be appropriately selected from 10 to 40°C depending on the kind of the resin and the like, the solubility of the resin and the like in the solvent (D), and the like. The mixing time can be appropriately selected from 0.5 to 24 hours depending on the mixing temperature. Note that the mixing method is not particularly limited, and stirring and the like can be used.

[0615] After mixing the components, filtration is preferably performed using a filter having a pore size of about 0.003 to 50 μm.

[0616] The minimum transmittance of the rays in the range of wavelengths of 355 to 375 nm is preferably 25% or more, more preferably 27% or more, further preferably 29% or more, and still further preferably 30% or more. In addition, it is preferably 99% or less, and more preferably 98% or less. The transmittance is calculated by the method described in the Examples.

[0617] Here, the use film thickness of the resist composition of the present application refers to the film thickness of the composition layer formed from the resist composition, and refers to the film thickness of the resist film or resist pattern produced from the resist composition. As described later, it can be set to the film thickness of the composition layer formed by applying the resist composition onto a substrate and performing drying and heating (pre-baking).

[0618] The use film thickness is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and further preferably 4 μm or more. In addition, it is usually 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less, and further preferably 100 μm or less. In addition, it is usually in the range of 1 to 300 μm, preferably in the range of 1 to 200 μm, more preferably in the range of 2 to 200 μm, further preferably in the range of 3 to 150 μm, and still further preferably in the range of 4 to 150 μm.

[0619] The resist composition of the present application contains the photosensitizer (I) and the acid generator (B). The photosensitizer (I) and the acid generator (B) sometimes have an influence on the light transmittance, and therefore, in the resist pattern formed using the resist composition containing these components, sometimes insufficient resolution and exposure latitude cannot be obtained. In particular, if the content of the above components is increased or the use film thickness is thickened, the above tendency sometimes becomes remarkable.

[0620] In the present application, the resist composition contains the photosensitizer (I) in a specific content and the acid generator (B) having a specific molar absorption coefficient, and when a film is formed using the resist composition in a use film thickness, by making the minimum transmittance of the rays in the range of wavelengths of 355 to 375 nm 23% or more, a resist pattern having good resolution and exposure latitude can be formed. The reason why this effect is exerted is not necessarily clear, but it is considered that, in the resist composition, by adjusting the content of the photosensitizer (I) to a specific range, selecting the acid generator (B) having a molar absorption coefficient in a specific range, and adjusting the transmittance of the rays in the resist film to a specific range, sufficient resolution and exposure latitude can be ensured in the resist pattern.

[0621] 3. Method for producing resist pattern

[0622] The production method of a resist pattern of the present application includes:

[0623] (1) a step of applying the resist composition of the present application on a metal surface of a substrate having a metal surface;

[0624] (2) a step of drying the applied resist composition to form a composition layer;

[0625] (3) a step of exposing the composition layer; and

[0626] (4) a step of developing the exposed composition layer.

[0627] The application of the resist composition on the substrate can be performed using a commonly used device such as a spin coater. Alternatively, a photosensitive dry film obtained by applying the resist composition on a base film can be laminated on the substrate.

[0628] As the substrate, an inorganic substrate such as a silicon wafer can be mentioned, and a semiconductor element (e.g., a transistor, a diode, etc.) or the like can be formed on the substrate in advance. In the case where the resist composition of the present application is used for bump formation, a substrate further laminated with a conductive material is preferred as the substrate. As the conductive material, 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 is mentioned, and copper or an alloy containing copper is preferred.

[0629] The substrate can be subjected to cleaning before the application of the resist composition, and an antireflection film or the like can be formed on the substrate.

[0630] By drying the applied composition, the solvent is removed, and a composition layer is formed. The drying is performed, for example, by using a heating device such as a hot plate to evaporate the solvent (so-called pre-baking), or by using a pressure reducing device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 30 to 600 seconds. In addition, the pressure at the time of pressure reduction drying is preferably 1 to 1.0 x 10 5 Pa or less.

[0631] After drying, the film thickness of the obtained composition is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and further preferably 4 μm or more. In addition, it is usually 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less, and further preferably 100 μm or less. In addition, it is usually in the range of 1 to 300 μm, preferably in the range of 1 to 200 μm, more preferably in the range of 2 to 200 μm, further preferably in the range of 3 to 150 μm, and more further preferably in the range of 4 to 150 μm.

[0632] The resulting composition layer is generally exposed using an exposure machine. As the exposure light source, various devices such as a device that emits laser light in the ultraviolet region (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), a device that emits high-frequency laser light in the far ultraviolet region or vacuum ultraviolet region by wavelength conversion of laser light from a solid laser source (YAG or semiconductor laser, etc.), a device that irradiates an electron beam, extreme ultraviolet light (EUV), and the like can be used. Among these, the i line is preferred. Note that in the present specification, the operation of irradiating these rays is sometimes collectively referred to as "exposure". At the time of exposure, exposure is generally performed through a mask corresponding to the desired pattern. In the case where the exposure light source is an electron beam, exposure can be performed by direct drawing without using a mask.

[0633] In order to promote the elimination reaction of the acid-labile group of the resin (Al), a heating treatment (so-called post-exposure bake) can also be applied to the composition layer after exposure. The heating temperature is generally about 50 to 200°C, and is preferably about 70 to 150°C. As the heating time, 40 to 400 seconds are generally used, and 50 to 350 seconds are preferred.

[0634] A developing device is generally used, and the composition layer after heating is developed using a developing solution. As the developing method, the dipping method, paddle method, spray method, dynamic coating method, and the like can be given. 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 developing solution as shown below, either a positive resist pattern or a negative resist pattern can be produced.

[0635] In the case of producing a positive resist pattern from the resist composition of the present application, an alkali developing solution is used as the developing solution. The alkali developing solution is any of various aqueous alkali solutions used in the field. Examples include aqueous solutions of tetramethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline), and the like. A surfactant can also be contained in the alkali developing solution.

[0636] The resist pattern after development is preferably washed with ultrapure water, and then the water remaining on the substrate and the pattern is removed.

[0637] In the case of producing a negative resist pattern from the resist composition of the present application, an organic solvent-containing developing solution (hereinafter sometimes referred to as "organic developing solution") is used as the developing solution.

[0638] As the organic solvent contained in the organic developer, there are, for example, 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; and the like.

[0639] In the organic developer, the content ratio 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 further preferably substantially only the organic solvent.

[0640] Among them, as the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. In the organic developer, the total content ratio 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 further preferably substantially only butyl acetate and / or 2-heptanone.

[0641] A surfactant can be contained in the organic developer. In addition, a trace amount of water can also be contained in the organic developer.

[0642] At the time of development, the development can be stopped by replacing with a solvent of a different kind from the organic developer.

[0643] The resist pattern after development is preferably cleaned with a rinsing solution. As the rinsing solution, there is no particular limitation as long as it is a rinsing solution that does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.

[0644] The rinsing solution remaining on the substrate and the pattern is preferably removed after cleaning.

[0645] By exposing the resist obtained by using the resist composition of the present application, a resist pattern of a high-precision shape can be formed.

[0646] 4. Method for producing plated molded article

[0647] By using the resist pattern formed by the above method as a mold, plating is performed to build up an electrode material, and the resist pattern is peeled off, whereby a plating molded object such as a bump and a rewiring can be formed.

[0648] The method for manufacturing a plating molded object of the present application includes:

[0649] (5) a step of forming a plating molded object using the resist pattern as a mold; and

[0650] (6) a step of peeling off the resist pattern.

[0651] A plating material is deposited using a plating solution by a known method using the resist pattern formed on the substrate having the conductive layer as a mold.

[0652] As the plating solution, a copper plating solution, a gold plating solution, a nickel plating solution, a solder plating solution, a silver-tin plating solution, and the like can be given.

[0653] After the plating pattern is formed, the resist pattern is removed using a stripping solution by a known method.

[0654] As the stripping solution, 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 2-hydroxypropionic acid methyl ester, 2-hydroxypropionic acid ethyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester, 3-ethoxypropionic acid ethyl ester, ethoxyacetic acid ethyl ester, oxyacetic acid ethyl ester, 2-hydroxy-3-methylbutyric acid methyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate can be given. One of them can be used alone, or two or more of them can be used in combination.

[0655] By the above method, a plating pattern such as a bump and a redistribution layer can be formed.

[0656] Note that, in forming the plating pattern, in order to improve the adhesion of the conductive layer to the plating pattern, the surface of the conductive layer can be subjected to ashing treatment or the like. As the ashing treatment method, a method using oxygen plasma or the like can be given.

[0657] The plating pattern obtained using the resist pattern of the present application has less swelling in the plating bath, and thus the plating pattern can be formed with high precision.

[0658] 5. Use

[0659] The resist composition of the present application is useful for producing a thick resist film. For example, it is useful for producing a resist film having a film thickness of 1 μm or more. In this case, the film thickness of the resist film is preferably 2 μm or more, more preferably 3 μm or more, and further preferably 4 μm or more. In addition, it is preferably 200 μm or less, more preferably 150 μm or less, and further preferably 100 μm or less.

[0660] In addition, the resist composition of the present application is useful for manufacturing bumps, re-wiring by a plating process. In the case of manufacturing bumps and re-wiring using the resist composition, it is generally possible to form by the following steps. Thereby, it is possible to manufacture a resist pattern of which pattern shape is particularly excellent.

[0661] First, a conductive layer is formed by laminating a conductive material (seed metal) on a wafer on which a semiconductor element or the like is formed. Then, a resist pattern is formed on the conductive layer using the resist composition of the present application. Next, using the resist pattern as a mold, an electrode material (for example, Cu, Ni, solder or the like) is accumulated by plating, and the resist pattern and the conductive layer remaining under the resist pattern are removed by etching or the like, whereby it is possible to form bumps and re-wiring. After the conductive layer is removed, as necessary, the electrode material can be melted by heat treatment, and the obtained material is made into a bump.

[0662] EXAMPLES

[0663] The present application is further concretely explained by citing examples. In the examples, "%" and "parts" indicating content or use amount are mass-based unless otherwise specified.

[0664] The weight average molecular weight is a value obtained by gel permeation chromatography under the following conditions.

[0665] Apparatus: HLC-8320 GPC type (manufactured by Tosoh Corporation)

[0666] Column: TSKgel Multipore H XL - M x 3 + guard column (manufactured by Tosoh Corporation)

[0667] Eluent: Tetrahydrofuran

[0668] Flow rate: 1.0 mL / min

[0669] Detector: RI detector

[0670] Column temperature: 40°C

[0671] Injection amount: 100 μl

[0672] Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

[0673] Synthesis Example 1 [Synthesis of Resin (Al)-l]

[0674] Poly-p-hydroxystyrene (S-4P; manufactured by Maruzen Petrochemical Co., Ltd.) 20 parts was dissolved in methyl isobutyl ketone 240 parts 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 p-toluenesulfonic acid dihydrate 0.003 parts were added. To the resulting mixture, ethyl vinyl ether 5.05 parts was added dropwise over 10 minutes while the resulting mixture was maintained at 20 to 25°C. The mixture was stirred at 20 to 25°C for 2 hours. The resulting reaction mixture was diluted with methyl isobutyl ketone 200 parts, washed with ion exchange water, and subjected to liquid-liquid separation 5 times. After the resulting organic layer was concentrated to 45 parts using an evaporator, propylene glycol monomethyl ether acetate 150 parts was added, and concentrated again to obtain a propylene glycol monomethyl ether acetate solution of the resin (Al)-l 78 parts (solid content 29%). The resin (Al)-l is a resin having the following structural unit.

[0675] The weight average molecular weight of the resin (Al)-l was 1.16 x 10 4 The proportion of the hydroxyl group in the poly-p-hydroxystyrene which was replaced by ethoxyethoxy was 40.9%.

[0676]

[0677] Synthesis Example 2 [Synthesis of Resin (A2)-l]

[0678] To a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 2,5-dimethylphenol 413.5 parts, salicylaldehyde 103.4 parts, p-toluenesulfonic acid 20.1 parts, and methanol 826.9 parts were added, and warmed to the reflux temperature, and maintained for 4 hours. After cooling, methyl isobutyl ketone 1320 parts was added, and 1075 parts of the solvent was distilled off under normal pressure. To this, m-cresol 762.7 parts and 2-tert-butyl-5-methylphenol 29.0 parts were added, and warmed to 65°C, and while adjusting the temperature so that the temperature at the end of the dropwise addition of 37% formalin aqueous solution 678 parts would be 87°C, the formalin was added dropwise over 1.5 hours. The resulting mixture was maintained at 87°C for 10 hours, and methyl isobutyl ketone 1115 parts was added, and washed with ion exchange water 3 times. To the resulting mixture, methyl isobutyl ketone 500 parts was added, and concentrated under reduced pressure until the total amount became 3435 parts. To the resulting mixture, methyl isobutyl ketone 3796 parts and n-heptane 4990 parts were added, and warmed to 60°C and stirred for 1 hour. Then, the layers were separated, and the lower layer containing the resin was taken out, diluted with propylene glycol monomethyl ether acetate 3500 parts, and concentrated to obtain a propylene glycol monomethyl ether acetate solution of the resin (A2)-l 1690 parts (solid content 43%).

[0679] The weight average molecular weight of the linear phenol-formaldehyde resin (A2)-l was 7 x 10 3In addition, the residual film rate when developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was 74%. This residual film rate was measured using the method described in item <Resin (A2)> of the detailed description of the invention.

[0680] <Preparation of resist composition>

[0681] A mixture obtained by dissolving each component shown in Table 1 was filtered with a fluorine resin filter having a pore size of 0.5 μm to prepare a resist composition.

[0682] [Table 1]

[0683]

[0684] <Resin>

[0685] (A1)-1: Resin (A1)-1

[0686] (A2)-1: Resin (A2)-1

[0687] <Acid generator (B)>

[0688] (B)-1: N-hydroxynaphthalimide triflate (NAI-105; manufactured by Midori Chemical Co., Ltd.)

[0689]

[0690] (B)-2: Compound represented by the following formula (PAG-121; manufactured by BASF)

[0691]

[0692] (B)-3: Compound represented by the following formula (synthesized by the method described in WO2016 / 072049)

[0693]

[0694] (B)-4: Compound represented by the following formula (synthesized by the same method as described in WO2016 / 072049, by changing (+)-10-camphorsulfonyl chloride to 1-octanesulfonyl chloride)

[0695]

[0696] <Photosensitive agent (I)>

[0697] (I)-1: Synthesized by the method described in Japanese Patent Application Laid-Open No. 9-110762

[0698] Note that, with respect to R t1 , R t6, R t7 , R t9 , R t10 The reaction was almost 100% complete. Thus, it was confirmed that the hydrogen atom in 2 of the 2 hydroxyl groups in Compound 1 was replaced with a 1,2-naphthoquinonediazide sulfonyl group. The reaction was almost 100% complete. Thus, it was confirmed that the hydrogen atom in 2 of the 2 hydroxyl groups in Compound 1 was replaced with a 1,2-naphthoquinonediazide sulfonyl group. t1 , R t6 , R t7 , R t9 , R t10 The 2-substituted compound in which the hydrogen atom in 2 of the 2 hydroxyl groups in Compound 1 was replaced with a 1,2-naphthoquinonediazide sulfonyl group (MS: M+: 1080) was obtained.

[0699]

[0700] <Quenching agent (C)>

[0701] (C)-1: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0702] (C)-2: N,N-dicyclohexylmethylamine (manufactured by Aldrich Corporation)

[0703] <Solvent (D)>

[0704] (D)-1: propylene glycol monomethyl ether acetate

[0705] Examples 1 to 6, Comparative Examples 1 to 3

[0706] (Measurement of molar absorption coefficient)

[0707] Each of the acid generators (B)-1, (B)-2, (B)-3, and (B)-4 was diluted with propylene glycol monomethyl ether acetate to 0.25 mmol / L, and the absorbance at a cell length of 1 cm was measured using a UV-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-3600i Plus). The molar absorption coefficient ε n in the range of wavelengths from 355 to 375 nm was calculated by the following equation. The maximum molar absorption coefficient in the range of wavelengths from 355 to 375 nm is shown in Table 2.

[0708] ε n (L / (mol·cm)) = A n / (0.00025 mol / L x 1 cm)

[0709] ε n : Molar absorption coefficient at each wavelength

[0710] A n : Absorbance at each wavelength

[0711] [Table 2]

[0712]

[0713] (Measurement of transmittance)

[0714] The resist composition described above was spin-coated on a quartz glass substrate so that the film thickness after baking became 4 μm.

[0715] Then, a composition layer was formed by pre-baking at 100°C for 180 seconds on a hot plate.

[0716] Next, the transmittance of the composition layer formed on the quartz glass substrate was measured for rays in the range of wavelengths from 355 to 375 nm using a spectrophotometer (V-670: manufactured by Shimadzu Corporation). The minimum transmittance in the range of wavelengths from 355 to 375 nm is shown in Table 3.

[0717] (Evaluation of i-line exposure of resist composition)

[0718] The resist composition described above was spin-coated on a substrate on which copper was vapor-deposited on a 4-inch silicon wafer so that the film thickness after pre-baking became 4.0 μm.

[0719] Then, a composition layer was formed by pre-baking at 100°C for 180 seconds on a hot plate.

[0720] Next, the composition layer formed on the wafer was exposed using an i-line stepper (NSR-2005i9C; manufactured by Nikon Corporation, NA = 0.5) with the exposure dose changed in stages, through a mask for forming a 1 : 1 line-and-space pattern (line width 0.2 to 1 μm).

[0721] After exposure, post-exposure baking was performed at 70°C for 60 seconds on a hot plate, and further paddle development was performed using a 2.38 mass% aqueous tetramethylammonium hydroxide solution for 180 seconds, whereby a resist pattern was obtained.

[0722] The resist pattern obtained after development was observed using a scanning electron microscope, and the exposure dose at which a line-and-space pattern with a line width of 1 μm was obtained was taken as the effective sensitivity.

[0723] <Resolution Evaluation>

[0724] In the effective sensitivity, the minimum value of the line width of the line-and-space pattern that could be resolved was measured by observing the obtained resist pattern using a scanning electron microscope.

[0725] <Exposure Latitude (EL)>

[0726] The line-and-space pattern with a line width of 1 μm was observed using a scanning electron microscope, and the exposure dose at which the pattern began to appear was taken as the minimum exposure dose, and the underexposure latitude (EL) was calculated according to the following equation.u (Japanese: under exposure margin), less than 35% is "X", 35% or more and less than 40% is "Δ", and 40% or more is "O", and EL is evaluated.

[0727] EL u = (E op - E un ) / E op 100

[0728] E un : minimum exposure amount for developing a pattern

[0729] E op : effective sensitivity

[0730] <Plating Resistance Evaluation>

[0731] After a wafer with a pattern was produced using the effective 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 15 minutes.

[0732] The wafer with a pattern after immersion was observed with an optical microscope, and a line-and-space pattern with a line width of 1 μm was observed.

[0733] A case where the pattern was deformed within 15 minutes of immersion was recorded as "X", and a case where the pattern was not deformed within 15 minutes of immersion was recorded as "O".

[0734] [Table 3]

[0735]

[0736] Examples 7, 8, Comparative Example 4

[0737] (Measurement of transmittance)

[0738] The above resist composition was spin-coated on a quartz glass substrate so that the film thickness after baking became 18 μm.

[0739] Then, the composition layer was formed by pre-baking at 120°C for 120 seconds on a direct heating plate.

[0740] Next, the transmittance of rays in the wavelength range of 355 to 375 nm was measured for the composition layer formed on the quartz glass substrate using a spectrophotometer (V-670: manufactured by Shimadzu Corporation). The minimum transmittance in the wavelength range of 355 to 375 nm is shown in Table 4.

[0741] (i-line exposure evaluation of resist composition)

[0742] On a substrate of a 4-inch silicon wafer on which copper was vapor-deposited, the above-mentioned resist composition was spin-coated so that the film thickness after prebaking became 18.0 μm.

[0743] Then, the composition layer was formed by prebaking at 120°C for 120 seconds on a hot plate.

[0744] Next, using an i-line stepper (NSR-2005i9C; manufactured by Nikon Corp., NA = 0.5), the exposure amount was changed stepwise, and the composition layer formed on the wafer was exposed through a mask for forming a 1 : 1 contact hole pattern (aperture: 5, 3, 2, 1 μm, pitch: 10, 6, 4, 2 μm).

[0745] After the exposure, post-exposure baking was performed at 80°C for 30 seconds on a hot plate, and further paddle development was performed with a 2.38 mass% aqueous tetramethylammonium hydroxide solution for 180 seconds, whereby a resist pattern was obtained.

[0746] The resist pattern obtained after the development was observed with a scanning electron microscope, and the exposure amount at which a contact hole pattern with an aperture of 3 μm was obtained was taken as the effective sensitivity.

[0747] <Resolution Evaluation>

[0748] In the effective sensitivity, the resist pattern obtained was observed with a scanning electron microscope, and the minimum value of the aperture of the contact hole pattern that could be resolved was measured.

[0749] <Plating Resistance Evaluation>

[0750] A wafer with a pattern was produced using the effective sensitivity obtained in the above i-line exposure evaluation, and was immersed in a Cu plating bath at a bath temperature of 27°C for 10 minutes.

[0751] The wafer with a pattern after the immersion was observed with an optical microscope, and a contact hole pattern with an aperture of 3 μm was observed.

[0752] The case where the resist pattern swelled and the shape of the resist pattern was observed to change when the immersion time was 10 minutes was recorded as "X", and the case where the shape of the resist pattern did not change when the immersion time was 10 minutes was recorded as "O".

[0753] [Table 4]

[0754]

[0755] From the results of Tables 3 and 4, it is known that the minimum transmittance of the composition layer formed using the resist composition of the present application with respect to the rays in the range of wavelengths of 355 to 375 nm is each above the prescribed value. It is known that the resolution and the exposure latitude (EL) of the resist pattern obtained by performing exposure and development on the composition layer are each excellent, and further, the plating resistance is also excellent.

[0756] Industrial applicability

[0757] The resist composition of the present application is capable of producing a resist pattern having good resolution and exposure latitude, is suitable for fine processing of a semiconductor, and is extremely useful in industry.

Claims

1. A resist composition comprising a resin (Al) containing a structural unit having an acid-labile group, a photosensitizer (I), and an acid generator (B), the acid generator (B) contains a compound having a maximum molar absorption coefficient of 6000 L / (mol-cm) or less in a range of wavelengths of 355 nm to 375 nm, the content of the photosensitizer (I) is 10 mass% or less in the solid content of the resist composition, when a film is formed using the resist composition at a use film thickness, the film has a minimum transmittance of 23% or more to a ray in a range of wavelengths of 355 nm to 375 nm.

2. The resist composition according to claim 1, wherein, the use film thickness is 4 μm or more.

3. The resist composition according to claim 1 or 2, wherein, the photosensitizer (I) contains a compound having a quinonediazide sulfonyl group.

4. The resist composition according to claim 1 or 2, wherein, the photosensitizer (I) contains a compound having a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c), in formula (a) and formula (b), represents a bonding end; In formula (c), represents a bonding end.

5. The resist composition according to claim 1 or 2, wherein, the acid generator (B) contains a compound having an oxime skeleton or an amide skeleton.

6. The resist composition according to claim 1 or 2, wherein, the acid generator (B) contains a compound having an oxime sulfonate group or an amide sulfonate group.

7. The resist composition according to claim 1 or 2, wherein, the resin (Al) containing a structural unit having an acid-labile group is a resin containing a structural unit having a group represented by formula (10) or a group represented by formula (20); In formula (10), R a1 , R a2 , and R a3 independently of one another represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; or, R a1 and R a2 are bonded to each other and, together with the carbon atom to which they are bonded, form a ring having 3 to 20 carbon atoms, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; maand naeach independently represent 0 or 1, at least one of maand narepresenting 1; represents a bonding end; In formula (20), R a1’ and R a2’ independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; or, R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are mutually bonded and, together with the carbon atom and X to which they are bonded, form a heterocyclic ring having 3 to 20 carbon atoms; a methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms is optionally replaced with an oxygen atom or a sulfur atom; X represents an oxygen atom or a sulfur atom; na' represents 0 or 1; represents a bonding end.

8. The resist composition according to claim 1 or 2, wherein, the resin (Al) containing a structural unit having an acid-labile group is a resin containing at least one selected from the group consisting of a structural unit represented by formula (al-1), a structural unit represented by formula (al-2), a structural unit represented by formula (a3A), and a structural unit represented by formula (a3B); In formula (a1-1), R a1 , R a2 , and R a3 independently of one another represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; or, R a1 and R a2 are bonded to each other and, together with the carbon atom to which they are bonded, form a ring having 3 to 20 carbon atoms, 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; In formula (a1-2), R a1’ and R a2’ independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; or, R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are mutually bonded and, together with the carbon atom and the oxygen atom to which they are bonded, form a heterocyclic ring having 3 to 20 carbon atoms; a methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms is optionally replaced with 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 are optionally the same or different from each other; In formula (a3A), R a1 , R a2 , and R a3 independently of one another represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; or R a1 and R a2 are bonded to one another and, together with the carbon atom to which they are bonded, form a ring having 3 to 20 carbon atoms, 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 ab represents a hydroxyl 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 are optionally the same or different; In formula (a3B), R a1’ and R a2’ independently of one another represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; or, R a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are mutually bonded and, together with the carbon and oxygen atoms to which they are bonded, form a heterocyclic ring having 3 to 20 carbon atoms; the methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms are optionally replaced with an oxygen atom or a sulfur atom; R ab represents a hydroxyl 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 are optionally the same or different.

9. The resist composition according to claim 1 or 2, further comprising a quencher (C).

10. A method for producing a resist pattern, comprising: (1) a step of applying the resist composition according to claim 1 or 2 to a 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 exposed composition layer.

11. A method for producing a plated molded article, comprising: (1) a step of applying the resist composition according to claim 1 or 2 to a 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 exposed composition layer; (5) a step of forming a plated molded article using the obtained resist pattern as a mold; and (6) a step of peeling the resist pattern.

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