Resist composition, method for producing resist pattern, and method for producing plated mold

Abstract

The present invention provides a resist composition having sufficient resistance to plating treatment and capable of forming a resist pattern with excellent precision. It also provides a method for manufacturing a resist pattern using the resist composition, and a method for manufacturing a plated molded article using the resist pattern. The present invention relates to a resist composition containing a compound (I) having a quinonediazide sulfonyl group, a resin (A1) containing a structural unit having an acid-labile group, an alkali-soluble resin (A2), and an acid generator (B), a method for manufacturing a resist pattern using the resist composition, and a method for manufacturing a plated molded article using the resist pattern.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a resist composition, a resist pattern, and a method for manufacturing a plated model. Background Technology

[0002] Patent document 1 describes an anti-corrosion composition containing a compound having a naphthoquinone diazidosulfonyl group.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2018-101129 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] When plating is performed using a resist pattern obtained by using a conventional resist composition as described in Patent Document 1, there is room for further improvement in forming the plating pattern with excellent precision.

[0008] Therefore, the object of the present invention is to provide a resist composition that has sufficient resistance to plating treatment and is capable of forming resist patterns with excellent precision. Furthermore, the object is to provide a method for manufacturing a resist pattern using the resist composition.

[0009] means for solving problems

[0010] The inventors have discovered that the following resist composition can solve the above-mentioned problems, the resist composition comprising: a compound having a quinone diazidosulfonyl group, a resin containing a structural unit having a group that is unstable to acid, an alkali-soluble resin, and an acid generating agent.

[0011] The present invention provides the following invention.

[0012] [1] An anti-corrosion composition comprising: a compound having a quinone diazidosulfonyl group (I), a resin (A1) containing a structural unit having a group that is unstable to acid, an alkali-soluble resin (A2), and an acid generating agent (B).

[0013] [2] According to the corrosion resist composition described in [1], wherein,

[0014] Compound (I) having a quinone diazidosulfonyl group is a compound having a group shown in formula (a), formula (b), or formula (c).

[0015]

[0016] [In equations (a) and (b), * denotes the bond end.]

[0017]

[0018] [In equation (c), * denotes the bonded end.]

[0019] [3] According to the corrosion resist composition described in [2], wherein,

[0020] The compound (I) having a quinone diazidosulfonyl group is selected from at least one of the compounds shown in formula (II), formula (III), formula (IV) and formula (V).

[0021]

[0022] In formula (II),

[0023] R 11 ~R 14 Each of the following 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 in the hydrocarbon group having 1 to 18 carbon atoms may optionally be replaced by an oxygen atom, a carbonyl group, or -NR. d1 -

[0024] R d1 It represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0025] 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).

[0026] 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).

[0027]

[0028] In formula (III),

[0029] 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).

[0030] P 1 ~P 5 Each of these groups independently represents a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms, wherein the methylene group in the hydrocarbon group having 1 to 18 carbon atoms may optionally be replaced by an oxygen atom, a carbonyl group, or -NR. d2 -, P 1 and P 2 The atoms can be arbitrarily bonded to each other and together with the two carbon atoms they are bonded to form a ring. 4 and P 5 They can be arbitrarily bonded together and form rings with the carbon atoms they are bonded to.

[0031] R d2 This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0032]

[0033] In formula (IV),

[0034] R 40 ~R 53 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). 40 ~R 53 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).

[0035] n a Represents any integer from 1 to 5. In n a In the case of any integer greater than 2, multiple R 49 ~R 52 Choose either the same as or different from each other.

[0036]

[0037] In formula (V),

[0038] R f1 R f2 and R g1 ~R g8 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). f1 R f2 and R g1 ~R g8 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).

[0039] P 6It represents an aromatic hydrocarbon group with 6 to 12 carbon atoms in a monovalent state or an aromatic hydrocarbon group with 6 to 12 carbon atoms in a divalent state. The aromatic hydrocarbon group may be optionally substituted by at least one of a hydroxyl group and an alkyl group having 1 to 6 carbon atoms.

[0040] P 7 Represents a hydrogen atom, and optionally a hydrocarbon group having 1 to 18 carbon atoms with substituents, wherein the methylene group containing 1 to 18 carbon atoms is optionally replaced by an oxygen atom, a carbonyl group, or -NR. d3 -. P 6 and P 7 They can be arbitrarily bonded together to form a ring.

[0041] n v It represents 1 or 2.

[0042] R d3 This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0043] [4] The corrosion resist composition according to any one of [1] to [3], wherein,

[0044] A resin (A1) containing structural units having groups that are unstable to acids is a resin containing structural units having groups shown in formula (10) or formula (20).

[0045]

[0046] In equation (10), R a1 R a2 and R a3 Each group independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 They bond to each other and together with the carbon atoms they are bonded to form rings with 3 to 20 carbon atoms, and R a3 This indicates an alkyl group with 1 to 8 carbon atoms or an alicyclic hydrocarbon group with 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * indicates a bond terminator.

[0047]

[0048] In equation (20), R a1’ and R a2’ R represents a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms, which can be independently represented by each other. a3’ This indicates a hydrocarbon group with 1 to 20 carbon atoms. Alternatively, R... a1’ Represents a hydrocarbon group with 1 to 20 hydrogen or carbon atoms, and R a2’ and R a3’The carbon atoms bonded to each other, along with X, form a heterocycle with 3 to 20 carbon atoms. The alkyl group with 1 to 20 carbon atoms and the methylene group in the heterocycle with 3 to 20 carbon atoms may be optionally replaced by an oxygen or sulfur atom. X represents an oxygen or sulfur atom. na' represents 0 or 1. * represents a bond terminator.

[0049] [5] The corrosion resist composition according to any one of [1] to [4], wherein,

[0050] A resin (A1) containing structural units having groups that are unstable to acids is a resin containing structural units shown in formula (a1-1) or formula (a1-2).

[0051]

[0052] In formula (a1-1),

[0053] R a1 R a2 and R a3 Each group independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 They bond to each other and together with the carbon atoms they are bonded to form rings with 3 to 20 carbon atoms, and R a3 It represents an alkyl group with 1 to 8 carbon atoms or an alicyclic hydrocarbon group with 3 to 20 carbon atoms.

[0054] R a4 This indicates a hydrogen atom or a methyl group.

[0055]

[0056] In formula (a1-2),

[0057] R a1’ and R a2’ R represents a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms, which can be independently represented by each other. a3’ This indicates a hydrocarbon group with 1 to 20 carbon atoms. Alternatively, R... a1’ Represents a hydrocarbon group with 1 to 20 hydrogen or carbon atoms, and R a2’ and R a3’ They bond to each other and together with the carbon and oxygen atoms they are bonded to form a heterocycle with 3 to 20 carbon atoms. The hydrocarbon group with 1 to 20 carbon atoms and the methylene group contained in the heterocycle with 3 to 20 carbon atoms may be optionally replaced by an oxygen atom or a sulfur atom.

[0058] R a5 It represents a hydrogen atom or a methyl group.

[0059] R a6It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0060] m represents an integer from 0 to 4. When m is greater than 2, multiple R... a6 Choose either the same as or different from each other.

[0061] [6] The corrosion resist composition according to any one of [1] to [4], wherein,

[0062] A resin (A1) containing structural units having groups that are unstable to acids is a resin containing structural units represented by formula (a3A) or formula (a3B).

[0063]

[0064] In formula (a3A), R a1 R a2 and R a3 Each group independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 They bond to each other and together with the carbon atoms they are bonded to form rings with 3 to 20 carbon atoms, and R a3 R represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ab This indicates a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R... ab Choose either the same or different.

[0065]

[0066] In formula (a3B), R a1’ and R a2’ R represents a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms, which can be independently represented by each other. a3’ This indicates a hydrocarbon group with 1 to 20 carbon atoms. Alternatively, R... a1’ Represents a hydrocarbon group with 1 to 20 hydrogen or carbon atoms, and R a2’ and R a3’ They bond to each other and together with the carbon and oxygen atoms they are bonded to form a heterocycle with 3 to 20 carbon atoms. The hydrocarbon group with 1 to 20 carbon atoms and the methylene group in the heterocycle with 3 to 20 carbon atoms may be optionally replaced by an oxygen or sulfur atom. R ab This indicates a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R... ab Choose either the same or different.

[0067] [7] The corrosion resist composition according to any one of [1] to [6], wherein,

[0068] Alkali-soluble resin (A2) is a resin containing structural units having carboxyl or hydroxyl groups and not containing structural units having groups that are unstable to acids.

[0069] [8] The corrosion resist composition described in any one of [1] to [7] further contains a quencher (C).

[0070] [9] A method for manufacturing a resist pattern, the method comprising:

[0071] (1) A process of applying the resist composition described in any one of [1] to [8] to the metal surface of a substrate having a metal surface.

[0072] (2) The process of drying the coated composition to form a composition layer.

[0073] (3) The process of exposing the composite layer, and

[0074] (4) The process of developing the exposed composite layer.

[0075]

[10] A method for manufacturing a plated molded object, the method comprising:

[0076] (1) A process of applying the resist composition described in any one of [1] to [8] to the metal surface of a substrate having a metal surface.

[0077] (2) The process of drying the coated composition to form a composition layer.

[0078] (3) The process of exposing the composite layer;

[0079] (4) The process of developing the exposed composite layer,

[0080] (5) The process of forming a plated object using the obtained resist pattern as a mold, and

[0081] (6) The process of peeling off the resist pattern.

[0082] Invention Effects

[0083] 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. Attached Figure Description

[0084] Figure 1 It is a diagram that schematically represents the maximum and minimum line widths a and b of the resist pattern lines and the spacing pattern lines. Detailed Implementation

[0085] In this specification, unless otherwise specified, in the description of the structural formula of a compound, "aliphatic hydrocarbon group" refers to a straight-chain or branched aliphatic hydrocarbon group, and "alicyclic hydrocarbon group" refers to a group obtained by removing a number of hydrogen atoms equivalent to the valence from the ring of an alicyclic hydrocarbon. "Aromatic hydrocarbon group" also includes groups with hydrocarbon groups bonded to an aromatic ring. In the presence of stereoisomers, all stereoisomers are included.

[0086] In this specification, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid", and "(meth)acrylate" means "at least one of acrylate and methacrylate".

[0087] In this specification, groups that can achieve both linear and branched structures are defined as including both.

[0088] In this specification, the term "solid component of the resist composition" refers to the total amount of components after removing the solvent (E) described later from the total amount of the resist composition.

[0089] 1. Corrosion resist composition

[0090] The resist composition of the present invention contains a compound having a quinone diazidosulfonyl group (hereinafter sometimes referred to as "compound (I)"), a resin containing a structural unit having a group unstable to acid (hereinafter sometimes referred to as "resin (A1)"), an alkali-soluble resin (hereinafter sometimes referred to as "resin (A2)"), and an acid generating agent (hereinafter sometimes referred to as "acid generating agent (B)").

[0091] The resist composition of the present invention preferably contains, in addition to compound (I), resin (A1), resin (A2) and acid generating agent (B), a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)").

[0092] <Compound (I)>

[0093] The compound (I) of the present invention is a compound having a quinone diazidosulfonyl group.

[0094] In the unexposed (unilluminated) area, compound (I) interacts with the hydrophilic groups of resin (A2), thereby inhibiting the dissolution of resin (A2) in the developer (alkaline aqueous solution). In the exposed (illuminated) area, the quinone diazide group decomposes to produce a carboxyl group, which in turn produces a carboxylic acid, promoting the dissolution of resin (A2) in the developer (alkaline aqueous solution). Furthermore, in the unexposed (unilluminated) area, resin (A2) is cross-linked in the presence of the developer (alkaline aqueous solution), thus becoming a material resistant to the developer (alkaline aqueous solution) and plating solution, thereby improving the precision of the plated model.

[0095] Compound (I) is not particularly limited as long as it is a compound having one or more quinone diazidosulfonyl groups in its molecule. The molecular weight of the compound obtained by replacing all the quinone diazidosulfonyl groups present in the molecule of compound (I) with hydrogen atoms is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 to 400.

[0096] Examples of compounds having a quinone diazidosulfonyl group include compounds having a naphthoquinone diazidosulfonyl group, compounds having a benzoquinone diazidosulfonyl group, and compounds having anthraquinone diazidosulfonyl group. Compounds having a naphthoquinone diazidosulfonyl group and compounds having a benzoquinone diazidosulfonyl group are preferred. Among compounds having a naphthoquinone diazidosulfonyl group, compounds having a 1,2-naphthoquinone diazidosulfonyl group are preferred, more preferably compounds having a group shown in formula (a) or formula (b), and even more preferably compounds having a group shown in formula (a). Among compounds having a benzoquinone diazidosulfonyl group, compounds having a 1,2-benzoquinone diazidosulfonyl group are preferred, more preferably compounds having a group shown in formula (c).

[0097]

[0098] [In equations (a) and (b), * denotes the bond end.]

[0099]

[0100] [In equation (c), * denotes the bonded end.]

[0101] The compound obtained by replacing all intramolecular quinone diazidosulfonyl groups with hydrogen atoms in a compound having a quinone diazidosulfonyl group 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)").

[0102]

[0103] In formula (II),

[0104] R 11 ~R 14 Each of the following 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 in the hydrocarbon group having 1 to 18 carbon atoms may optionally be replaced by an oxygen atom, a carbonyl group, or -NR. d1 -

[0105] R d1 It represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0106] 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).

[0107] 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).

[0108]

[0109] In formula (III),

[0110] 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).

[0111] P 1 ~P 5 Each of these groups independently represents a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms, wherein the methylene group in the hydrocarbon group having 1 to 18 carbon atoms may optionally be replaced by an oxygen atom, a carbonyl group, or -NR. d2 -, P 1 and P 2 The atoms can be arbitrarily bonded to each other and together with the two carbon atoms they are bonded to form a ring. 4 and P 5 They can be arbitrarily bonded together and form rings with the carbon atoms they are bonded to.

[0112] R d2 This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0113]

[0114] In formula (IV),

[0115] R 40 ~R 53 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). 40 ~R 53 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).

[0116] n a Represents any integer from 1 to 5. In n a In the case of any integer greater than 2, multiple R 49 ~R 52 Choose either the same as or different from each other.

[0117]

[0118] In formula (V),

[0119] R f1 R f2 and R g1 ~R g8 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). f1 R f2 and R g1 ~R g8 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).

[0120] P6 It represents an aromatic hydrocarbon group with 6 to 12 carbon atoms in a monovalent state or an aromatic hydrocarbon group with 6 to 12 carbon atoms in a divalent state. The aromatic hydrocarbon group may be optionally substituted by at least one of a hydroxyl group and an alkyl group having 1 to 6 carbon atoms.

[0121] P 7 Represents a hydrogen atom, and optionally a hydrocarbon group having 1 to 18 carbon atoms with substituents, wherein the methylene group containing 1 to 18 carbon atoms is optionally replaced by an oxygen atom, a carbonyl group, or -NR. d3 -. P 6 and P 7 They can be arbitrarily bonded together to form a ring.

[0122] n v It represents 1 or 2.

[0123] R d3 This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0124] Examples of hydrocarbon groups with 1 to 18 carbon atoms include chain hydrocarbon groups with 1 to 18 carbon atoms (including straight-chain or branched saturated chain hydrocarbon groups (alkyl) with 1 to 18 carbon atoms, and straight-chain or branched unsaturated chain hydrocarbon groups (alkenyl, ynyl) with 2 to 18 carbon atoms), monocyclic or polycyclic alicyclic hydrocarbon groups with 3 to 18 carbon atoms (including saturated alicyclic hydrocarbon groups with 3 to 18 carbon atoms, and unsaturated alicyclic hydrocarbon groups with 3 to 18 carbon atoms), and aromatic hydrocarbon groups with 6 to 18 carbon atoms. It can also be a group obtained by combining two or more of these groups.

[0125] The alkyl group having 1 to 18 carbon atoms can be either straight-chain or branched, and examples include methyl, ethyl, propyl, isopropyl, tert- or sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. Among them, straight-chain alkyl groups are preferred.

[0126] Alkenes with 2 to 18 carbon atoms can be either straight-chain or branched, and examples include vinyl, propenyl, isopropenyl, methacryl, methylbutenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, nonenyl, etc.

[0127] The alkynyl group with 2 to 18 carbon atoms can be either straight-chain or branched, for example, ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, tert-butynyl, pentyynyl, hexynyl, octyynyl, nonynyl, etc.

[0128] The chain hydrocarbon group having 1 to 18 carbon atoms is preferably having 1 to 16 carbon atoms, more preferably having 1 to 12 carbon atoms, even more preferably having 1 to 8 carbon atoms, even more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 4 carbon atoms.

[0129] Examples of monocyclic alicyclic hydrocarbon groups with 3 to 18 carbon atoms include monocyclic saturated alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, as well as monocyclic unsaturated alicyclic hydrocarbon groups such as cyclopropenyl and cyclobutenyl. Examples of polycyclic alicyclic hydrocarbon groups with 3 to 18 carbon atoms include polycyclic saturated alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornyl. The alicyclic hydrocarbon group with 3 to 18 carbon atoms is preferably 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms.

[0130] Examples of aromatic hydrocarbon groups with 6 to 18 carbon atoms include phenyl, naphthyl, anthraceneyl, biphenyl, and phenanthrene. Preferably, the aromatic hydrocarbon group with 6 to 18 carbon atoms has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.

[0131] As an alkyl group having 1 to 6 carbon atoms, a group equivalent to an alkyl group having 1 to 6 carbon atoms can be selected from the aforementioned alkyl groups having 1 to 18 carbon atoms.

[0132] As P 1 and P 2 The mutual bonding and the ring formed by the two carbon atoms they are bonded to, and P 4 and P 5 The rings formed by mutual bonding and the carbon atoms bonded to them can be exemplified independently as monocyclic or polycyclic alicyclic hydrocarbon rings with 3 to 18 carbon atoms. Examples of such rings include cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, and other cycloalkanes; as well as decahydronaphthalene rings, adamantane rings, and norbornene rings. The alicyclic hydrocarbon ring with 3 to 18 carbon atoms is preferably 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms.

[0133] As P 7 Substituents for hydrocarbon groups with 1 to 18 carbon atoms can include halogen atoms, hydroxyl groups, alkoxy groups with 1 to 12 carbon atoms, acyl groups with 2 to 4 carbon atoms, and acyloxy groups with 2 to 4 carbon atoms.

[0134] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with fluorine being the preferred option.

[0135] Examples of alkoxy groups with 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, and butoxy.

[0136] Examples of acyl groups with 2 to 4 carbon atoms include acetyl, propionyl, and butyryl.

[0137] Examples of acyloxy groups with 2 to 4 carbon atoms include acetoxy, propionyloxy, and butyryloxy.

[0138] As specific examples of compound (II), compounds represented by formulas (II-1) to (II-3) can be cited.

[0139]

[0140] Here, R s2 Each of these groups independently represents the group shown in formula (a), formula (b), formula (c), or a hydroxyl group. The R of each compound... s2 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).

[0141] As specific examples of compound (III), compounds represented by formulas (III-1-1) to (III-3-8) can be cited.

[0142]

[0143]

[0144] Here, R t1 Each of these groups independently represents the group shown in formula (a), formula (b), formula (c), or a hydroxyl group. The R of 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).

[0145] As specific examples of compounds (IV), compounds represented by formulas (IV-1-1) to (IV-5-2) can be cited.

[0146]

[0147] 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 of each compound... t1 R t3 R t6 Rt7 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).

[0148] As specific examples of compound (V), compounds represented by formulas (V-1-1) to (V-3-1) can be cited.

[0149]

[0150] 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 of 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).

[0151] Compound (I) can be manufactured, for example, according to the records in Japanese Patent Application Publication Nos. 2-84650, 3-185447, 3-191351, 5-323597, 8-245461, and 9-110762. Compound (I) can be manufactured, for example, by reacting an aromatic compound having a phenolic hydroxyl group (e.g., a compound in which all the quinone diazidosulfonyl groups in the molecules of compounds (II) to (V) above are replaced with hydrogen atoms) and a quinone diazidosulfonyl halide (e.g., quinone diazidosulfonyl chlorides such as 1,2-naphthoquinone diazidosulfonyl chloride and 1,2-benzoquinone diazidosulfonyl chloride, and quinone diazidosulfonyl bromide such as 1,2-naphthoquinone diazidosulfonyl bromide) in the presence of a weak base, by complete or partial esterification.

[0152] Aromatic compounds with phenolic hydroxyl groups are readily available from the market and can also be manufactured using known methods.

[0153] Regarding the content of compound (I), in the solid component of the resist composition, it is preferably 0.05% by mass or more and 25% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, further preferably 0.5% by mass or more and 15% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less.

[0154] The content of compound (I) in the resist composition can be determined, for example, using known analytical tools such as liquid chromatography or gas chromatography.

[0155] As compound (I), compounds (III) and (IV) are preferred, and compound (III) is more preferred.

[0156] <Resin (A1)>

[0157] The resin (A1) contains structural units (hereinafter sometimes referred to as "structural units (a1)") with groups that are unstable to acids.

[0158] Acid-insensitive groups refer to groups containing groups that can detach upon contact with an acid (sometimes called leaving groups). By contacting the resin (A1) with an acid, the leaving group detaches from the acid-insensitive group, forming a hydrophilic group (e.g., hydroxyl (phenolic hydroxyl, etc.) or carboxyl group). The resin (A1) increases its solubility in alkaline aqueous solutions due to contact with the acid. That is, the resin (A1) is preferably insoluble or sparingly soluble in alkaline aqueous solutions before contact with the acid, but becomes soluble in alkaline aqueous solutions after contact with the acid.

[0159] The resin (A1) may contain structural units known in the art, in addition to structural units containing groups that are unstable to acid (hereinafter sometimes referred to as "structural units (a2)"), in addition to structural units containing groups that are unstable to acid.

[0160] Examples of acids that remove leaving groups from groups that are unstable to acids include carboxylic acids and sulfonic acids. Examples of compositions of the present invention include carboxylic acid compounds and sulfonic acid compounds generated by irradiating (exposing) the acid generator (B) described later during a photolithography process.

[0161] Examples of groups that are unstable to acids include those shown in formula (10) and those shown in formula (20).

[0162]

[0163] In equation (10), R a1 R a2 and R a3 Each group independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 They bond to each other and together with the carbon atoms they are bonded to form rings with 3 to 20 carbon atoms, and R a3 This indicates an alkyl group with 1 to 8 carbon atoms or an alicyclic hydrocarbon group with 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * indicates a bond terminator.

[0164]

[0165] In equation (20), R a1’ and R a2’ R represents a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms, which can be independently represented by each other. a3’ This indicates a hydrocarbon group with 1 to 20 carbon atoms. Alternatively, R... a1’ Represents a hydrocarbon group with 1 to 20 hydrogen or carbon atoms, and R a2’ and R a3’ The carbon atoms bonded to each other, along with X, form a heterocycle with 3 to 20 carbon atoms. The alkyl group with 1 to 20 carbon atoms and the methylene group in the heterocycle with 3 to 20 carbon atoms may be optionally replaced by an oxygen or sulfur atom. X represents an oxygen or sulfur atom. na' represents 0 or 1. * represents a bond terminator.

[0166] R shown in equation (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.

[0167] 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).

[0168]

[0169] 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.

[0170] 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 the following. 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. * indicates a bonding end with -O-.

[0171]

[0172] 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 a2 The bonds together with the carbon atoms they are bonded to form a ring with 3 to 18 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms or an alicyclic hydrocarbon group with 3 to 12 carbon atoms, or with R a2 The bonds combine with the carbon atoms they are bonded to to form rings with 3 to 12 carbon atoms.

[0173] R a2 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 a1 The bonds together with the carbon atoms they are bonded to form a ring with 3 to 18 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms or an alicyclic hydrocarbon group with 3 to 12 carbon atoms, or with R a1 The bonds combine with the carbon atoms they are bonded to to form rings with 3 to 12 carbon atoms.

[0174] R a3 Preferably, it is an alkyl group with 1 to 6 carbon atoms or an alicyclic hydrocarbon group with 3 to 18 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms or an alicyclic hydrocarbon group with 3 to 12 carbon atoms.

[0175] ma is preferably 0. na is preferably 1.

[0176] As a group represented by formula (10), R can be cited as an example. a1 R a2 and R a3 Each group is an alkyl group having 1 to 3 carbon atoms (preferably a tert-butoxycarbonyl group); R a1 and R a2 Each is independently an alkyl group having 1 to 3 carbon atoms, and R a3 A group that is cyclopentyl or cyclohexyl; R a1 and R a2 They bond to each other and together with the carbon atoms they are bonded to form a cyclopentane ring or a cyclohexane ring, and R a3 Groups consisting of alkyl groups having 1 to 3 carbon atoms, etc.

[0177] As specific examples of the groups represented by formula (10), the following groups can be cited.

[0178]

[0179] R, as the group shown in formula (20) a1’ ~R a3’Examples of hydrocarbon groups with 1 to 20 carbon atoms include chain hydrocarbon groups (alkyl, alkenyl, and alkynyl groups, etc.) with 1 to 20 carbon atoms, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 20 carbon atoms, and groups with 4 to 20 carbon atoms obtained by combining them.

[0180] Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and dodecyl.

[0181] Examples of alkenyl groups with 2 to 20 carbon atoms include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl.

[0182] Examples of alkynyl groups with 2 to 20 carbon atoms include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, tert-butynyl, pentyynyl, hexynyl, octyynyl, and nonynyl.

[0183] The chain hydrocarbon group with 1 to 20 carbon atoms is preferably 1 to 18 carbon atoms, more preferably 1 to 16 carbon atoms, even more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0184] Examples of alicyclic hydrocarbon groups with 3 to 20 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. 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.

[0185] Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, naphthyl, anthracene, biphenyl, and phenanthrene. The aromatic hydrocarbon group may optionally have substituents, such as aryloxy groups having 6 to 10 carbon atoms. The aromatic hydrocarbon group having 6 to 20 carbon atoms is preferably having 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0186] Among the groups with 4 to 20 carbon atoms obtained by combining the above-mentioned groups, groups obtained by combining alkyl groups and alicyclic hydrocarbon groups (groups with 4 to 20 carbon atoms) include, for example, methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, isobornyl, 2-alkyladamantane-2-yl, 1-(adamantane-1-yl)alkane-1-yl, etc.

[0187] As a group obtained by combining alkyl and aromatic hydrocarbon groups (a group with 7 to 20 carbon atoms), for example, aralkyl or 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.

[0188] As a group obtained by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (a group with 9 to 20 carbon atoms), for example, an aromatic hydrocarbon group having an alicyclic hydrocarbon group or an alicyclic hydrocarbon group having an aromatic hydrocarbon group, specifically, p-cyclohexylphenyl, p-adamantylphenyl, phenylcyclohexyl, etc.

[0189] In R a2’ and R a3’ When they bond together and form heterocycles with 3 to 20 carbon atoms along with the carbon atoms they bond to and X, they act as -C(R a1’ (R) a2’ )-XR a3’ Examples of such groups include the following. The heterocycle 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. * indicates a bonding end.

[0190]

[0191] R a1’ Preferably, it is a hydrocarbon group with 1 to 18 carbon atoms, more preferably a hydrocarbon group with 1 to 12 carbon atoms, and even more preferably a hydrogen atom.

[0192] R a2 'Preferably, it has hydrogen atoms or a hydrocarbon group having 1 to 18 carbon atoms, or is related to R a3’ The bonds together with the carbon atoms they are bonded to and X form a heterocycle with 3 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms, or a ring with R. a3’ The bonds together with the carbon atoms they are bonded to and X form a heterocycle with 3 to 12 carbon atoms, more preferably a hydrocarbon group with 1 to 12 carbon atoms, and even more preferably methyl or ethyl.

[0193] R a3’ Preferably, it is a hydrocarbon group with 1 to 18 carbon atoms, or a group with R. a2 The bonds together with the carbon atoms they are bonded to and X form a heterocycle with 3 to 18 carbon atoms, more preferably a hydrocarbon group with 1 to 12 carbon atoms, or with R a2’ The bonds together with the carbon atoms they are bonded to and X form heterocycles with 3 to 12 carbon atoms.

[0194] Examples of the aforementioned hydrocarbon groups include alkyl groups with 1 to 18 carbon atoms, alicyclic hydrocarbon groups with 3 to 18 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or groups with 4 to 18 carbon atoms obtained by combining them. These groups can be arbitrarily selected from the groups listed above.

[0195] X is preferably an oxygen atom.

[0196] na' is preferably 0.

[0197] As specific examples of the groups shown in formula (20), the following groups can be cited.

[0198]

[0199] Specifically, as the group represented by formula (10), the group represented by formula (1) and the group represented by formula (1') can be cited.

[0200]

[0201] In equations (1) and (1'), R a1 R a2 and R a3 Each group independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 They bond to each other and together with the carbon atoms they are bonded to form rings with 3 to 20 carbon atoms, and R a3 This indicates an alkyl group with 1 to 8 carbon atoms or an alicyclic hydrocarbon group with 3 to 20 carbon atoms. * indicates a bond end.

[0202] Specifically, as the group represented by formula (20), the group represented by formula (2) and the group represented by formula (2') can be cited.

[0203]

[0204]

[0205] In equations (2) and (2'), R a1’ and R a2’ R represents a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms, which can be independently represented by each other. a3’ This indicates a hydrocarbon group with 1 to 20 carbon atoms. Alternatively, R... a1’ Represents a hydrocarbon group with 1 to 20 hydrogen or carbon atoms, and R a2’ and R a3’They bond to each other and together with the carbon and oxygen atoms they are bonded to form a heterocycle with 3 to 20 carbon atoms. The hydrocarbon group with 1 to 20 carbon atoms and the methylene group in the heterocycle with 3 to 20 carbon atoms may optionally be replaced by an oxygen or sulfur atom. * indicates a bond end.

[0206] <Structural unit (a1) containing a group unstable to acid>

[0207] A resin (A1) containing a structural unit (a1) having a group that is unstable to acid can be manufactured, for example, by polymerizing a monomer component containing an olefinic unsaturated compound that incorporates the structural unit (a1). Preferably, the group shown in formula (10) and / or the group shown in formula (20) described above are the acid-stable groups contained in the structural unit (a1).

[0208] The resin (A1) may have only one structural unit (a1) or it may have multiple structural units.

[0209] As structural unit (a1), the preferred structural unit is the structural unit shown in formula (a1-1) (hereinafter sometimes referred to as "structural unit (a1-1)") and the structural unit shown in formula (a1-2) (hereinafter sometimes referred to as "structural unit (a1-2)").

[0210]

[0211] In equations (a1-1) and (a1-2),

[0212] R a1 R a2 and R a3 Each group independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 They bond to each other and together with the carbon atoms they are bonded to form rings with 3 to 20 carbon atoms, and R a3 It represents an alkyl group with 1 to 8 carbon atoms or an alicyclic hydrocarbon group with 3 to 20 carbon atoms.

[0213] R a1’ and R a2’ R represents a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms, which can be independently represented by each other. a3’ This indicates a hydrocarbon group with 1 to 20 carbon atoms. Alternatively, R... a1’ Represents a hydrocarbon group with 1 to 20 hydrogen or carbon atoms, and R a2’ and R a3’ They bond to each other and together with the carbon and oxygen atoms they are bonded to form a heterocycle with 3 to 20 carbon atoms. The hydrocarbon group with 1 to 20 carbon atoms and the methylene group contained in the heterocycle with 3 to 20 carbon atoms may be optionally replaced by an oxygen atom or a sulfur atom.

[0214] R a4 and R a5 They can be used to represent hydrogen atoms or methyl groups independently.

[0215] R a6 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0216] m represents an integer from 0 to 4. When m is greater than 2, multiple R... a6 Choose either the same as or different from each other.

[0217] In equation (a1-1), R a4 Methyl is preferred.

[0218] 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 a2 The bonds together with the carbon atoms they are bonded to form a ring with 3 to 18 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms or an alicyclic hydrocarbon group with 3 to 12 carbon atoms, or with R a2 The bonds combine with the carbon atoms they are bonded to to form rings with 3 to 12 carbon atoms.

[0219] R a2 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 a1 The bonds together with the carbon atoms they are bonded to form a ring with 3 to 18 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms or an alicyclic hydrocarbon group with 3 to 12 carbon atoms, or with R a1 The bonds combine with the carbon atoms they are bonded to to form rings with 3 to 12 carbon atoms.

[0220] R a3 Preferably, it is an alkyl group with 1 to 6 carbon atoms or an alicyclic hydrocarbon group with 3 to 18 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms or an alicyclic hydrocarbon group with 3 to 12 carbon atoms.

[0221] In equation (a1-2), R a5 Hydrogen atoms are preferred.

[0222] R a1’ Preferably, it is a hydrocarbon group with 1 to 18 carbon atoms, more preferably a hydrocarbon group with 1 to 12 carbon atoms, and even more preferably a hydrogen atom.

[0223] R a2 'Preferably, it has hydrogen atoms or a hydrocarbon group having 1 to 18 carbon atoms, or is related to R a3’ The bonds, together with the carbon and oxygen atoms they are bonded to, form a heterocycle with 3 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms, or a group with R.a3’ The bonds together with the carbon and oxygen atoms bonded to them form a heterocycle with 3 to 12 carbon atoms, more preferably a hydrocarbon group with 1 to 12 carbon atoms, and even more preferably methyl or ethyl.

[0224] R a3’ Preferably, it is a hydrocarbon group with 1 to 18 carbon atoms, or a group with R. a2 'The bonds together with the carbon and oxygen atoms they are bonded to form a heterocycle with 3 to 18 carbon atoms, more preferably a hydrocarbon group with 1 to 12 carbon atoms, or with R a2’ The bonds combine with the carbon and oxygen atoms they are bonded to to form heterocycles with 3 to 12 carbon atoms.

[0225] Examples of the aforementioned hydrocarbon groups include alkyl groups with 1 to 18 carbon atoms, alicyclic hydrocarbon groups with 3 to 18 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or groups with 4 to 18 carbon atoms obtained by combining these. These groups can be arbitrarily selected from the groups listed above. The hydrocarbon group is preferably an alkyl group with 1 to 18 carbon atoms, an alicyclic hydrocarbon group with 3 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. When the aromatic hydrocarbon group has a substituent, the substituent is preferably an aryloxy group with 6 to 10 carbon atoms.

[0226] As R a6 The alkyl group having 1 to 6 carbon atoms includes, for example, methyl, ethyl, propyl, butyl, pentyl, and hexyl. Preferably, the alkyl group having 1 to 6 carbon atoms is an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0227] As R a6 The alkoxy group having 1 to 6 carbon atoms includes, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy. Preferably, the alkoxy group having 1 to 6 carbon atoms has 1 to 4 carbon atoms, and more preferably, it has 1 to 3 carbon atoms.

[0228] R a6 Preferably, it is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms, further preferably methyl, ethyl, methoxy or ethoxy, and even more preferably methyl or methoxy.

[0229] m is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0230] In equation (a1-2), -OC(R) a1’ (R) a2’ )-OR a3’The indicated group is preferably bonded to the 3- or 4-position of the benzene ring (meta- or para-position relative to the main chain bonded to the benzene ring), and more preferably to the 4-position (para-position) of the benzene ring.

[0231] As a structural unit (a1-1), for example, any of the structural units shown in equations (a1-1-1) to (a1-1-17) can be cited.

[0232]

[0233]

[0234] As a structural unit (a1-2), for example, any of the structural units shown in equations (a1-2-1) to (a1-2-14) can be cited.

[0235]

[0236] In the above structural unit, with R a5 Structural units in which a significant number of hydrogen atoms are replaced by methyl groups can also be cited as specific examples of structural units (a1-2).

[0237] The structural unit (a1-2) is preferably the structural unit shown in formula (a1-2-2), formula (a1-2-3), formula (a1-2-4), formula (a1-2-9), and formula (a1-2-14), and more preferably the structural unit shown in formula (a1-2-2), formula (a1-2-3), formula (a1-2-4), and formula (a1-2-9).

[0238] The resin (A1) containing structural units having groups that are unstable to acid is preferably a resin containing structural units (a1-2).

[0239] When the resin (A1) contains structural units (a1-1) and / or structural units (a1-2), the total content of these structural units is preferably 3 to 80 mol% relative to all structural units of the resin (A1), more preferably 5 to 60 mol%, even more preferably 10 to 55 mol%, even more preferably 15 to 50 mol%, and even more preferably 20 to 45 mol%.

[0240] <Structural units that do not have groups unstable to acids (a2)>

[0241] The resin (A1) may comprise a structural unit (a1) having a group unstable to acid and a structural unit (a2) not having a group unstable to acid, used as needed. The resin (A1) comprising the structural unit (a1) and the structural unit (a2) can be manufactured, for example, by polymerizing a monomeric component comprising an olefinic unsaturated compound incorporating the structural unit (a1) and an olefinic unsaturated compound incorporating the structural unit (a2). As the group unstable to acid contained in the structural unit (a1), the group shown in formula (10) and / or the group shown in formula (20) described above are preferred.

[0242] The resin (A1) may contain only one type of structural unit (a2) that does not have a group that is unstable to acid, or it may contain multiple types.

[0243] As a structural unit (a2), for example, any of the structural units shown in equations (a2-1) to (a2-3) can be cited (hereinafter sometimes referred to as "structural unit (a2-1)" according to the equation number, etc.).

[0244]

[0245] In equations (a2-1), (a2-2), and (a2-3),

[0246] R a7 R a8 and R a9 They can be used to represent hydrogen atoms or methyl groups independently.

[0247] R a10 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0248] m' represents an integer from 0 to 4. When m' is greater than 2, multiple R... a10 Choose whether they are the same or different from each other.

[0249] R a11 A hydrocarbon group representing 1 to 12 hydrogen atoms or carbon atoms. This excludes groups where the carbon atom bonded to the oxygen atom is a tertiary carbon atom.

[0250] R a12 Alkyl groups having 1 to 6 carbon atoms, excluding groups where the carbon atom bonded to the oxygen atom is a tertiary carbon atom.

[0251] L a1 This refers to alkyldiyl groups with 2 to 6 carbon atoms, excluding groups where the carbon atom bonded to the oxygen atom is a tertiary carbon atom.

[0252] n represents an integer from 1 to 30. When n is 2 or higher, multiple L... a1 Choose either the same as or different from each other.

[0253] As R a10 The alkyl group having 1 to 6 carbon atoms shown can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. Preferably, the alkyl group having 1 to 6 carbon atoms has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0254] As R a10 Examples of alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy. Preferably, the alkoxy group with 1 to 6 carbon atoms has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0255] As R a11 Examples of hydrocarbon groups with 1 to 12 carbon atoms include chain hydrocarbon groups (alkyl, alkenyl, and alkynyl groups, etc.) with 1 to 12 carbon atoms, alicyclic hydrocarbon groups with 3 to 12 carbon atoms, aromatic hydrocarbon groups with 6 to 12 carbon atoms, and groups with 4 to 12 carbon atoms formed by combining them.

[0256] Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0257] Examples of alkenyl groups with 2 to 12 carbon atoms include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl.

[0258] Examples of alkynyl groups with 2 to 12 carbon atoms include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, tert-butynyl, pentyynyl, hexynyl, octyynyl, and nonynyl.

[0259] The chain hydrocarbon group having 1 to 12 carbon atoms is preferably having 1 to 10 carbon atoms, more preferably having 1 to 8 carbon atoms, and even more preferably having 1 to 6 carbon atoms.

[0260] The alicyclic hydrocarbon group having 3 to 12 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).

[0261]

[0262] The alicyclic hydrocarbon group with 3 to 12 carbon atoms is preferably 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms.

[0263] Examples of aromatic hydrocarbon groups with 6 to 12 carbon atoms include phenyl and naphthyl groups. Preferably, these aromatic hydrocarbon groups have 6 to 10 carbon atoms.

[0264] Examples of groups with 4 to 12 carbon atoms formed by combining the above-mentioned groups, and groups (with 4 to 12 carbon atoms) obtained by combining alkyl and alicyclic hydrocarbon groups, include methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, cyclohexylmethyl, adamantylmethyl, norbornylethyl, etc.

[0265] As a group obtained by combining alkyl and aromatic hydrocarbon groups (a group with 7 to 12 carbon atoms), for example, aralkyl or 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.

[0266] As a group obtained by combining alicyclic hydrocarbon groups and aromatic hydrocarbon groups (a group with 9 to 12 carbon atoms), for example, an aromatic hydrocarbon group having an alicyclic hydrocarbon group or an alicyclic hydrocarbon group having an aromatic hydrocarbon group, specifically, p-cyclohexylphenyl, phenylcyclohexyl, etc.

[0267] As R a12 Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, and n-hexyl. Preferably, the alkyl group having 1 to 6 carbon atoms has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0268] As L a1 The alkyldiyl group having 2 to 6 carbon atoms can be either straight-chain or branched, and examples include ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-2,2-diyl, propane-1,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl. This alkyldiyl group having 2 to 6 carbon atoms is preferably having 2 to 4 carbon atoms, and more preferably 2 to 3 carbon atoms.

[0269] R a7 Hydrogen atoms are preferred.

[0270] R a8 and R a9 Methyl groups are preferred independently of each other.

[0271] R a10Preferably, it is an alkyl group or an alkoxy group with 1 to 4 carbon atoms, more preferably an alkyl group or an alkoxy group with 1 to 3 carbon atoms, for example, methyl, ethyl, methoxy or ethoxy, and even more preferably methyl or methoxy.

[0272] m' is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0273] R a11 Preferably, it is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; more preferably, it is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms; even more preferably, it is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 3 to 8 carbon atoms. Except for groups where the carbon atom bonded to the oxygen atom is a tertiary carbon atom.

[0274] L a1 Preferably, it is an alkyldiyl group with 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 alkyldiyl group with 2 to 3 carbon atoms (e.g., ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl), and even more preferably ethane-1,2-diyl.

[0275] n is preferably an integer from 1 to 20, more preferably an integer from 1 to 16, even more preferably an integer from 1 to 14, even more preferably an integer from 1 to 10, and even more preferably an integer from 1 to 6.

[0276] 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. Except for groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom.

[0277] As structural unit (a2-1), the structural units shown in formulas (a2-1-1), (a2-1-2), (a2-1-3), or (a2-1-4) are preferred. Furthermore, a single unit incorporating structural unit (a2-1) is described, for example, in Japanese Patent Application Publication No. 2010-204634.

[0278]

[0279] Examples of monomers that can be introduced into structural unit (a2-2) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, and other alkyl methacrylates.

[0280] Monocyclic (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and cycloalkyl (meth)acrylate;

[0281] Polycyclic (meth)acrylates such as adamantyl methacrylate and norbornyl methacrylate;

[0282] (Meth)phenyl acrylate, (meth)benzoyl acrylate and other (meth)acrylate aryl esters.

[0283] As monomers for introducing structural units (a2-3), examples include ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, pentaethylene glycol monomethyl ether (meth)acrylate, hexaethylene glycol monomethyl ether (meth)acrylate, heptaethylene glycol monomethyl ether (meth)acrylate, nonaethylene glycol monomethyl ether (meth)acrylate, octaethylene glycol monomethyl ether (meth)acrylate, etc. (poly)ethylene glycol monomethyl ether (meth)acrylate ((poly)alkylene glycol monoalkyl ether (meth)acrylate) and other (meth)acrylates.

[0284] In addition, examples of monomers that can be introduced into structural unit (a2) include carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citracic acid, medaconic acid, and itaconic acid; hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 4-isopropoxystyrene.

[0285] The structural unit (a2) can also be, for example, the structural unit shown in equation (a2-4).

[0286]

[0287] In formula (a2-4),

[0288] R a13 It represents a hydrogen atom or a methyl group.

[0289] R a14 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0290] R a15 This refers to a hydrocarbon group having 1 to 12 carbon atoms, excluding groups where the carbon atom bonded to the oxygen atom is a tertiary carbon atom. The methylene group contained in this hydrocarbon group having 1 to 12 carbon atoms may optionally be replaced by an oxygen atom or a carbonyl group. However, the methylene group bonded to the oxygen atom and the methylene group bonded to it are not replaced by an oxygen atom.

[0291] "m" represents an integer from 0 to 4. When "m" is 2 or higher, multiple R... a14 Choose whether they are the same or different from each other.

[0292] m”' represents an integer from 0 to 4. When m”' is 2 or higher, multiple R a15 Choose whether they are the same or different from each other.

[0293] The sum of m” and m”' is less than 5.

[0294] For R a15 The hydrocarbon group in the text can be exemplified by groups whose bonding terminal to the oxygen atom is not a tertiary carbon atom, i.e., groups with one or more hydrogen atoms or other atoms other than carbon atoms bonded to that bonding carbon atom. Additionally, for R... a15 The hydrocarbon group in the text can be exemplified by a methylene group bonded to an oxygen atom and a group to which the methylene group is bonded is not replaced by an oxygen atom, i.e., a group that does not contain an acetal structure.

[0295] Therefore, the structural unit shown in equation (a2-4) does not include structural unit (a1-2).

[0296] As R a14 Alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms can be exemplified by those related to R. a10 Same group.

[0297] As R a15 Hydrocarbon groups with 1 to 12 carbon atoms can be listed as examples related to R. a11 Same group.

[0298] R a13 Hydrogen atoms are preferred.

[0299] R a14 Preferably, it is an alkyl group or an alkoxy group with 1 to 4 carbon atoms, more preferably an alkyl group or an alkoxy group with 1 to 3 carbon atoms, for example, methyl, ethyl, methoxy or ethoxy, and even more preferably methyl or methoxy.

[0300] For R a15Preferably, the hydrocarbon group has 1 to 10 carbon atoms, or the group in which the methylene group is replaced by an oxygen atom or a carbonyl group. More preferably, the hydrocarbon group has 1 to 8 carbon atoms, a straight-chain or branched alkyl group, 3 to 10 carbon atoms, an aromatic hydrocarbon group has 6 to 10 carbon atoms, or a group with 6 to 10 carbon atoms formed by combining the like, or a group in which the methylene group is replaced by an oxygen atom or a carbonyl group. More preferably, the hydrocarbon group has 1 to 5 carbon atoms, a straight-chain or branched alkyl group, 5 to 10 carbon atoms, an alicyclic hydrocarbon group, a phenyl group, or a group with 6 to 10 carbon atoms formed by combining the like, or a group in which the methylene group adjacent to the oxygen atom is replaced by a carbonyl group.

[0301] m” is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0302] m”' is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0303] The sum of m” and m”' is less than 5.

[0304] As structural units (a2-4), examples of structural units shown in equations (a2-4-1) to (a2-4-10) can be cited.

[0305]

[0306] In the structural units shown by equations (a2-4-1) to (a2-4-10), respectively, R a13 Structural units in which hydrogen atoms are replaced by methyl groups can also be cited as specific examples of structural units (a2-4).

[0307] When the resin (A1) comprises structural units (a2-1), (a2-2), (a2-3), and (a2-4), the total content of these units is preferably 1 to 90 mol% relative to all structural units of the resin (A1), more preferably 1 to 85 mol%, even more preferably 5 to 80 mol%, and particularly preferably 5 to 75 mol%.

[0308] When the resin (A1) contains structural unit (a2), the ratio of structural unit (a1) to structural unit (a2) [structural unit (a1): structural unit (a2)] is preferably 10:90 to 80:20 on a molar basis, more preferably 15:85 to 60:40, and even more preferably 15:85 to 45:55.

[0309] Examples of combinations of structural units contained in resin (A1) include those shown in formulas (A1-1) to (A1-46).

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317] In the above structural formula, with R a5 Structural units in which equivalent hydrogen atoms are replaced by methyl groups or methyl groups are replaced by hydrogen atoms can also be cited as specific examples of the aforementioned structural units. Furthermore, structural units containing both hydrogen atoms and methyl groups can coexist in a single resin.

[0318] The resin (A1) is preferably a resin containing structural unit (a1) and structural unit (a2), more preferably a resin containing structural unit (a1-1) and / or structural unit (a1-2) and structural unit (a2).

[0319] Resin (A1) may also be a resin obtained by reacting a resin having at least one of carboxyl and phenolic hydroxyl groups in its side chain with a compound having at least two ethylene oxy groups in one molecule (hereinafter sometimes referred to as "resin (A1b)").

[0320] The resin (A1b) is preferably a resin obtained by reacting a resin containing phenolic hydroxyl groups with a compound containing two or more ethylene oxygen groups per molecule. For example, such a resin can be obtained by reacting a resin containing the structural unit (a2-1) with a compound containing two or more ethylene oxygen groups per molecule. Alternatively, a linear phenolic resin (described later) can be used as the resin containing phenolic hydroxyl groups, and the linear phenolic resin can be reacted with the aforementioned compound containing ethylene oxygen groups. Furthermore, a resin can be obtained by mixing a resin containing the structural unit (a2-1) with a linear phenolic resin, and then reacting the aforementioned compound containing ethylene oxygen groups with the resulting resin mixture. Additionally, a resin obtained by reacting a resin containing the structural unit (a2-1) with the aforementioned compound containing ethylene oxygen groups, and a resin obtained by reacting a linear phenolic resin with the aforementioned compound containing ethylene oxygen groups, can be used in combination.

[0321] In the synthesis of resin (A1b), the ratio of compounds containing at least two ethylene oxide groups per molecule relative to carboxyl and phenolic hydroxyl groups [carboxyl and phenolic hydroxyl groups: ethylene oxide groups] on a molar basis is preferably 60:40 to 99:1, more preferably 70:30 to 95:5.

[0322] As for resins (A1b), examples include the resins described in Japanese Patent Application Publication No. 2008-134515 and Japanese Patent Application Publication No. 2008-46594.

[0323] Examples of compounds having at least two ethylene oxide groups in one molecule include 1,4-cyclohexanediethanol divinyl ether and ethylene glycol divinyl ether.

[0324] In the case where the resin (A1b) is obtained by mixing a resin containing structural unit (a2-1) with a linear phenolic resin and reacting a compound containing an ethylene oxide group with the resulting resin mixture, the content of the linear phenolic resin is 30 to 70% by mass relative to the total amount of resin (A1b).

[0325] The resin (A1) can be manufactured by polymerizing a monomeric component comprising an olefinic unsaturated compound corresponding to the above-described structural unit (a1) and an olefinic unsaturated compound corresponding to the structural unit (a2) as needed, using a known polymerization method (e.g., free radical polymerization).

[0326] The weight-average molecular weight of the resin (A1) is preferably 3,000 or more, more preferably 4,000 or more, more preferably 600,000 or less, and more preferably 500,000 or less. It should be noted that the weight-average molecular weight is a value obtained by conversion using gel permeation chromatography as a standard polystyrene reference. Detailed analytical conditions for this analysis are described in the embodiments of this application.

[0327] The content of resin (A1) relative to the total amount of resin contained in the resist composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 30% by mass or more, preferably 95% by mass or less, more preferably 85% by mass or less, and even more preferably 70% by mass or less.

[0328] Resin (A1) can also be a linear phenolic resin (hereinafter sometimes referred to as "resin (A1c)") that incorporates acid-labile groups containing groups capable of cleaving under acid. This resin refers to a resin in which part or all of the phenolic hydroxyl groups of the linear phenolic resin described below are protected with acid-labile groups containing groups capable of cleaving under acid, or a resin in which part or all of the phenolic hydroxyl groups of the linear phenolic resin described below are replaced with acid-labile groups containing groups capable of cleaving under acid. This resin also refers to a linear phenolic resin having acid-labile groups (including groups that can detach upon contact with acid).

[0329] Linear phenolic resins are resins obtained, for example, by adding and condensing an aromatic compound (hereinafter sometimes simply referred to as "phenolic compound") with an aldehyde under an acid catalyst.

[0330] Examples of phenolic compounds include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,5-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, 2-methylresorcinol, and 4-methylresorcinol. 5-Methylresorcinol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxyphenol, 2-methoxyresorcinol, hydroquinone, 4-tert-butylcatechol, hydroquinone monomethyl ether, pyrogallol, pyrogallol, hydroxybiphenyl, bisphenol A, gallic acid, gallic ester, α-naphthol, β-naphthol, 1,3-dihydroxynaphthol, 1,5-dihydroxynaphthol, 1,7-dihydroxynaphthol, and polyhydroxytriphenylmethane compounds obtained by the condensation of xylenol and hydroxybenzaldehyde, etc. These compounds can be used alone or in combination of two or more.

[0331] Among them, preferred phenolic compounds include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol.

[0332] Examples of aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acrolein, and crotonaldehyde; alicyclic aldehydes such as cyclohexylformaldehyde, cyclopentylformaldehyde, or furanylpropionaldehyde; aromatic aldehydes such as furanaldehyde, benzaldehyde, o-, m-, or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4-, or 3,5-dimethylbenzaldehyde, o-, m-, or p-hydroxybenzaldehyde, and o-, m-, or p-nitrobenzaldehyde; and aromatic aliphatic aldehydes such as phenylacetaldehyde or cinnamaldehyde. These can be used alone or in combination of two or more. Formaldehyde is preferred due to its ease of industrial availability.

[0333] Catalysts for addition condensation reactions include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid, and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid, and p-toluenesulfonic acid; and divalent metal salts such as zinc acetate, zinc chloride, and magnesium acetate. These can be used alone or in combination of two or more. The amount of catalyst used is typically 0.01 to 1 mole relative to 1 mole of aldehyde.

[0334] The condensation reaction can be carried out using conventional methods. For example, it can be conducted at a temperature ranging from 60 to 150°C for approximately 2 to 30 hours. The condensation reaction can be carried out in the presence of a solvent. Examples of such solvents include ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, and acetone. After the reaction is complete, for example, a water-insoluble solvent can be added to the reaction mixture as needed. The reaction mixture is then washed with water and concentrated to obtain the linear phenolic resin. Alternatively, after the reaction is complete, a basic compound can be added for neutralization to remove the acid catalyst, and the neutralized salt can be removed by washing with water.

[0335] In the linear phenolic resin, the weight-average molecular weight is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, even more preferably 9,000 or less, and even more preferably 8,000 or less.

[0336] In this application specification, the weight-average molecular weight is a value obtained by conversion using gel permeation chromatography as a standard polystyrene reference. Detailed analytical conditions for this analysis are described in the examples of this application.

[0337] The acid-insensitive group introduced into the linear phenolic resin is not particularly limited as long as it contains a group that can be cleaved by the action of an acid; known groups that are acid-insensitive can be cited as examples. The acid-insensitive group is introduced into part or all of the phenolic hydroxyl groups in the linear phenolic resin obtained by condensation as described above.

[0338] As the acid-labile groups introduced into the phenolic hydroxyl groups of the linear novolac resin, examples include the group represented by the above formula (10) or the group represented by the above formula (20), etc. A group represented by formula (1') or a group represented by formula (2) is preferred.

[0339] Specific examples of acid-labile groups include tert-butoxycarbonyloxy, 1-methylcyclopentan-1-yloxycarbonyloxy, 1-(cyclopentan-1-yl)-1-methylalkoxycarbonyloxy, butyloxyethoxy, ethoxypropoxy, ethoxybutoxy, tetrahydro-2-pyranyloxy, tetrahydro-2-furanyloxy, methoxyethoxy, 1-ethoxyethoxy, propyloxyethoxy, cyclohexyloxyethoxy, 1-(2-methylpropoxy)ethoxy, 1-(2-methoxyethoxy)ethoxy, 1-(2-acetoxyethoxy)ethoxy, 1-[2-(1-adamantyloxy)ethoxy]ethoxy, 1-[2-(1-adamantanecarbonyloxy)ethoxy]ethoxy, 3-oxocyclohexyloxy, 4-methyltetrahydro-2-pyrone-4-yloxy (original Japanese: 4-メチルテトラヒドロ-2-ピロン-4-イルオキシ基), and the like. Among these, at least one selected from the group consisting of ethoxyethoxy, ethoxypropoxy, ethoxybutoxy, isopropyloxyethoxy, cyclohexyloxyethoxy and 1-(2-methylpropoxy)ethoxy is preferred, at least one selected from the group consisting of ethoxyethoxy, isopropyloxyethoxy and cyclohexyloxyethoxy is more preferred, and 1-ethoxyethoxy is even more preferred.

[0340] As an embodiment of the linear novolac resin (A1c) having acid-labile groups, for example, a resin comprising 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)") can be mentioned.

[0341]

[0342] [In formula (a3A), R a1 , R a2 and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R 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 hydroxy group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2 or 3. When p is 2 or 3, R abChoose either the same or different.

[0343]

[0344] In formula (a3B), R a1’ and R a2’ R represents a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms, which can be independently represented by each other. a3’ This indicates a hydrocarbon group with 1 to 20 carbon atoms. Alternatively, R... a1’ Represents a hydrocarbon group with 1 to 20 hydrogen or carbon atoms, and R a2’ and R a3’ They bond to each other and together with the carbon and oxygen atoms they are bonded to form a heterocycle with 3 to 20 carbon atoms. The hydrocarbon group with 1 to 20 carbon atoms and the methylene group in the heterocycle with 3 to 20 carbon atoms may be optionally replaced by an oxygen or sulfur atom. R ab This indicates a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R... ab Choose either the same or different.

[0345] As R ab Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl. These alkyl groups having 1 to 6 carbon atoms are preferably alkyl groups having 1 to 4 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms, and even more preferably methyl.

[0346] As R ab Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy. 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 even more preferably a methoxy group.

[0347] R ab Preferably, it is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms, further preferably methyl, ethyl, methoxy or ethoxy, and even more preferably methyl or methoxy.

[0348] p is preferably 0 to 2, more preferably 0 or 1.

[0349] As a combination of structural units contained in a linear phenolic resin (A1c) having groups that are unstable to acid, examples of combinations shown in formulas (A1c-1) to (A1c-12) can be cited.

[0350]

[0351]

[0352] Regarding the proportion (introduction rate) of acid-labile groups, the phenolic hydroxyl groups in the linear phenolic resin (Alc) are preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more. Furthermore, it is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. Moreover, there exists an optimal introduction rate depending on the acid-labile groups.

[0353] When the resin (A1) has an acid-labile group (2), the proportion of the acid-labile group (2) introduced is preferably 20 mol% or more, more preferably 30 mol% or more, relative to the phenolic hydroxyl group described above. When the resin (A1) has an ethoxy group as an acid-labile group, it is further preferably 30 to 60 mol%, when it has a propyloxyethoxy group, it is further preferably 20 to 60 mol%, and when it has a cyclohexyloxyethoxy group, it is further preferably 20 to 60 mol%. By setting it within this range, the resolution, residual film rate, and heat resistance of the resist composition using this resin after pattern formation can be effectively ensured.

[0354] The proportion of groups introduced that are unstable in acid can be, for example, utilized... 1 The measurements were performed using H-NMR.

[0355] For methods of introducing acid-labile groups into the phenolic hydroxyl groups of a linear phenolic resin, methods known in the art can be cited. For example, in the case of introducing ethoxyethoxy groups as acid-labile groups, methods such as adding a predetermined amount of ethyl vinyl ether to a linear phenolic resin at room temperature under an acid catalyst, reacting for a predetermined time under an acid catalyst, and then adding diethyl ether and washing with water can be cited.

[0356] The weight-average molecular weight of the resin (A1c) is preferably 3,000 or more, more preferably 4,000 or more, more preferably 200,000 or less, and more preferably 100,000 or less. It should be noted that the weight-average molecular weight is a value obtained by conversion using gel permeation chromatography as a standard polystyrene reference. Detailed analytical conditions for this analysis are described in the embodiments of this application.

[0357] The content of resin (A1c) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 30% by mass or more, preferably 95% by mass or less, more preferably 85% by mass or less, and even more preferably 70% by mass or less, relative to the total amount of resin contained in the resist composition.

[0358] <Resin (A2)>

[0359] The resin (A2) is preferably an alkali-soluble resin. An alkali-soluble resin is a resin that has acidic groups (sometimes also called hydrophilic groups) and is soluble in alkaline developing solutions. Examples of acidic groups include carboxyl groups, sulfonyl groups, and hydroxyl groups (phenolic hydroxyl groups, etc.).

[0360] Examples of alkali-soluble resins include those known in the field of photoresists, such as linear phenolic resins, resins containing structural units (a2-1) but not structural units (a1), resins containing structural units derived from hydroxystyrene, resins containing structural units derived from (meth)acrylates, and polyalkylene glycols. Linear phenolic resins are preferred. The alkali-soluble resin preferably does not have groups unstable to acids. That is, the alkali-soluble resin is preferably a resin containing structural units with acidic groups but not structural units with groups unstable to acids. The solubility of the alkali-soluble resin in an alkaline aqueous solution preferably does not change upon contact with an acid. Alkali-soluble resins can be used alone or in combination of two or more.

[0361] In resin (A2), the total content of structural units having acidic groups, relative to all structural units of resin (A2), is preferably 3 to 100 mol%, more preferably 5 to 100 mol%, even more preferably 10 to 100 mol%, even more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%, even more preferably 60 to 100 mol%, particularly preferably 70 to 100 mol%, especially preferably 80 to 100 mol%.

[0362] The resin (A2) may contain only one type of structural unit with an acidic group, or it may contain multiple types.

[0363] Examples of alkali-soluble resins include those with a residual film rate of 0% or more and 90% or less when developed with an alkaline developer under actual usage conditions. This residual film rate is preferably 0% or more and 85% or less, and more preferably 0% or more and 80% or less.

[0364] The residual film rate can be determined, for example, as follows. The resin is dissolved in an organic solvent, filtered as needed, and then coated onto a substrate using a spin coater or similar method. Heating is then applied to remove the organic solvent. The organic film on the substrate is measured using a thickness gauge, and developed with a 2.38% by mass alkaline aqueous solution. The film thickness after development is measured again using a thickness gauge. The residual film rate is obtained by dividing the developed film thickness by the undeveloped film thickness. The development conditions are those used in actual applications. For example, the development temperature can be 5–60°C, and the development time can be 5–600 seconds. Various alkaline aqueous solutions used in this field can be used as alkaline developing solutions, such as aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline).

[0365] Linear phenolic resin is a resin obtained by condensing phenolic compounds and aldehydes in the presence of a catalyst, and can be selected from the resins described in Resin (A1c).

[0366] As a type of linear phenolic resin, examples include resins containing the structural unit shown in formula (a4) (hereinafter sometimes referred to as "structural unit (a4)").

[0367]

[0368] In formula (a4), R ac This indicates a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. p1 indicates 0, 1, 2, or 3. When p1 is 2 or 3, R ac Choose either the same or different. q1 represents 1, 2, or 3. The sum of p1 and q1 is 4 or less.

[0369] As R ac Alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms can be exemplified by those related to R. ab Same group.

[0370] R ac Preferably, it is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms, further preferably methyl, ethyl, methoxy or ethoxy, and even more preferably methyl or methoxy.

[0371] p1 is preferably 0 to 2, more preferably 1 or 2.

[0372] q1 is preferably 1 or 2, and more preferably 1.

[0373] The weight-average molecular weight of the linear phenolic resin is preferably 3000 or more, more preferably 4000 or more, further preferably 5000 or more, even more preferably 6000 or more, preferably 100000 or less, more preferably 50000 or less, even more preferably 10000 or less, even more preferably 9000 or less, and even more preferably 8000 or less. By setting it within this range, film formation and residue retention can be effectively prevented after development. The weight-average molecular weight is a value obtained by conversion using gel permeation chromatography as a standard polystyrene reference. Detailed analytical conditions for this analysis are described in the embodiments of this application.

[0374] Resins containing structural units derived from hydroxystyrene can include, for example, resins containing structural units from monomers with phenolic hydroxyl groups, such as hydroxystyrene (p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene) and isopropenylphenol (p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol). Specifically, resins containing structural units shown in formula (a2-1) can be cited as examples. Resins containing structural units derived from hydroxystyrene may, in addition to structural units from the aforementioned monomers, also contain structural units from monomers such as those exemplified later in the resins containing structural units derived from (meth)acrylates.

[0375] The resin containing structural units derived from hydroxystyrene is typically poly(vinylphenol)(poly(hydroxystyrene)), preferably poly(p-vinylphenol)(poly(p-hydroxystyrene)). Specifically, resins containing structural units shown in formula (a2-1) can be cited as examples. Such poly(vinylphenol) can be obtained, for example, by polymerizing the monomers described in Japanese Patent Application Publication No. 2010-204634.

[0376] Examples of resins containing structural units derived from (meth)acrylates include resins obtained by polymerizing one or more of the following compounds as monomers using conventional methods. Specifically, examples of resins containing structural units derived from (meth)acrylates include resins containing structural units derived from monomers described below.

[0377] Monomers containing carboxyl groups, such as (meth)acrylic acid;

[0378] Monomers containing hydroxyl groups, such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate;

[0379] Monomers containing multiple ether bonds, 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, and nonaethylene glycol monomethyl ether (meth) acrylate, are polyethylene glycol monomethyl ether (meth) acrylates (polyalkylene glycol monoalkyl ether (meth) acrylates).

[0380] The monomers mentioned above can also be used in combination with alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, tert-butyl methacrylate, and hexyl methacrylate; monocyclic methacrylates such as cyclopentyl methacrylate and cyclohexyl methacrylate; polycyclic methacrylates such as adamantyl methacrylate and norbornyl methacrylate; aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; and ethylene glycol monoalkyl ether methacrylates such as ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether methacrylate, ethylene glycol monopropyl ether methacrylate, and ethylene glycol monobutyl ether methacrylate (alkylene glycol monoalkyl ether methacrylates). In addition to the monomers mentioned above, styrene derivatives such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 4-isopropoxystyrene; carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, zeaxanthinic acid, and itaconic acid; and hydroxystyrene derivatives exemplified in the resins containing structural units derived from hydroxystyrene, etc., may also be used in combination. Structural units derived from the monomers described above may also include those shown in formulas (a2-1) to (a2-4).

[0381] Polyalkylene glycols are polymers obtained by the addition polymerization of epoxides from alcohols. Examples of alcohols include butanol, ethylene glycol, propylene glycol, glycerol, and pentaerythritol. Examples of epoxides include ethylene oxide, propylene oxide, and butane oxide. Examples of polyalkylene glycols include polyethylene glycol, polypropylene glycol, and polybutane glycol.

[0382] The content of resin (A2) relative to the total amount of resin contained in the resist composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less.

[0383] The resist composition of the present invention further comprises resin (A2) in a resist composition comprising compound (I), resin (A1), and acid generating agent (B). Resin (A2) can adjust the solubility of the resist in the developer (alkaline aqueous solution) by interacting with compound (I). Furthermore, by crosslinking with compound (I), it becomes a resin resistant to the developer (alkaline aqueous solution) and plating solution, thereby improving the precision of the plated model.

[0384] The mass ratio ((A1):(A2)) of resin (A1):(A2) in the resist composition is typically 20:80 to 80:20, preferably 30:70 to 70:30. Setting it to this range can further improve the precision of the plated model, and is therefore suitable.

[0385] The content of resin (A1) and resin (A2) in the resist composition of the present invention is preferably 80% by mass or more and 99% by mass or less, relative to the total amount of solid components in the resist composition. The content of resin (A1) is preferably 1% by mass or more and 98% by mass or less, more preferably 5% by mass or more and 90% by mass or less, relative to the total amount of solid components in the resist composition. The content of resin (A2) is preferably 1% by mass or more and 98% by mass or less, more preferably 5% by mass or more and 90% by mass or less, relative to the total amount of solid components in the resist composition. The solid components and the content of each component contained in the resist composition of the present invention can be determined, for example, using known analytical methods such as liquid chromatography or gas chromatography.

[0386] <Acid Generator (B)>

[0387] The acid generator (B) is a compound that can decompose upon exposure to light to produce acid. The produced acid causes the leaving groups in the acid-labile groups of the resin (A1) to detach, converting the acid-labile groups into hydrophilic groups (e.g., carboxyl groups, hydroxyl groups (phenolic hydroxyl groups, etc.)). That is, by exposing the photoresist composition containing the resin (A1), the photoresist can be made soluble relative to the developer (alkaline aqueous solution).

[0388] Acid generator (B) can be either nonionic or ionic.

[0389] Examples of nonionic acid generators include organohalides, sulfonates (e.g., 2-nitrobenzoyl esters, aromatic sulfonates, oxime sulfonates, N-sulfonyloxyimides, sulfonyloxy ketones, diazonoquinone 4-sulfonates), and sulfones (e.g., disulfones, ketone sulfones, sulfonyldiazomethanes). Examples of ionic acid generators include ononium salts containing ononium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodoonium salts). Examples of ononium salt anions include sulfonate anions, sulfonylimide anions, and sulfonylmethyl anions.

[0390] As the acid generating agent (B), compounds that generate acid using radiation, as described in Japanese Patent Application Publication Nos. 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853, 63-146029, US Patent Nos. 3,779,778 and 3,849,137, German Patent No. 3,914,407, and European Patent No. 126,712, can be used. Alternatively, compounds manufactured using known methods can also be used. The acid generating agent (B) can be used alone or in combination of two or more.

[0391] As a nonionic acid generator, a compound having a group (* indicates a bonding end) as shown in formula (B1) is preferred.

[0392]

[0393] In formula (B1),

[0394] R b1 This indicates a hydrocarbon group with 1 to 18 carbon atoms, optionally containing a fluorine atom, wherein the methylene group is optionally replaced by an oxygen atom or a carbonyl group.

[0395] It should be noted that nitrogen atoms can have double bonds.

[0396] As R b1 The hydrocarbon groups with 1 to 18 carbon atoms that are optionally containing fluorine atoms can include linear or branched chain hydrocarbon groups with 1 to 18 carbon atoms, alicyclic hydrocarbon groups with 3 to 18 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, and groups with 4 to 18 carbon atoms obtained by combining these groups.

[0397] As a linear or branched chain hydrocarbon group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms is preferred, and examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. Among them, a linear group is preferred.

[0398] Examples of alicyclic hydrocarbon groups with 3 to 18 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl.

[0399] As an aromatic hydrocarbon group with 6 to 18 carbon atoms, aryl groups with 6 to 18 carbon atoms are preferred, such as phenyl, naphthyl, anthracene, biphenyl, phenanthrene and other aryl groups.

[0400] Among the groups with 4 to 18 carbon atoms obtained by combining the above-mentioned groups, groups with 4 to 18 carbon atoms obtained by combining chain hydrocarbon groups and alicyclic hydrocarbon groups include, for example, methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, isobornyl, 2-alkyladamantane-2-yl, 1-(adamantane-1-yl)alkane-1-yl, etc.

[0401] A group (a group with 7 to 18 carbon atoms) obtained by combining a chain hydrocarbon group and an aromatic hydrocarbon group, for example, an aralkyl group or an aromatic hydrocarbon group having an alkyl group. 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.

[0402] As a group obtained by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (a group with 9 to 18 carbon atoms), for example, an aromatic hydrocarbon group having an alicyclic hydrocarbon group or an alicyclic hydrocarbon group having an aromatic hydrocarbon group, specifically, p-cyclohexylphenyl, p-adamantylphenyl, phenylcyclohexyl, etc.

[0403] 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.

[0404] As R b1 The methylene group in the alicyclic hydrocarbon group with 3 to 18 carbon atoms is a group in which the methylene group is replaced by an oxygen atom or a carbonyl group, for example, the groups shown in formulas (Y1) to (Y12). Preferably, the groups shown in formulas (Y7) to (Y9) are preferred, and more preferably the group shown in formula (Y9).

[0405]

[0406] A hydrocarbon group having 1 to 18 carbon atoms and containing fluorine atoms is a group in which one or more hydrogen atoms in the aforementioned hydrocarbon group having 1 to 18 carbon atoms are replaced by fluorine atoms. Specifically, examples include fluoroalkyl groups such as fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl, fluorohexyl, fluoroheptyl, fluorooctyl, fluorononyl, and fluorodecyl; fluorocycloalkyl groups such as fluorocyclopropyl, fluorocyclobutyl, fluorocyclopentyl, fluorocyclohexyl, fluorocycloheptyl, and fluorocyclooctyl; and fluoroaryl groups such as fluorophenyl, fluoronaphthyl, and fluoroanthrayl.

[0407] The hydrocarbon group having 1 to 18 carbon atoms and containing fluorine atoms is preferably an alkyl group having 1 to 10 carbon atoms and containing fluorine atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms and containing fluorine atoms, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0408] Examples of compounds having the group shown in formula (B1) include compounds shown in formulas (b1) to (b3). Compounds shown in formulas (b1) and (b2) are preferred, and compounds shown in formula (b1) are more preferred.

[0409]

[0410] In equations (b1) to (b3),

[0411] R b1 It indicates the same meaning as the text above.

[0412] R b2’ R b3 and R b4 They can be used to represent hydrogen atoms, alkyl groups with 1 to 8 carbon atoms, or alkoxy groups with 1 to 8 carbon atoms, independently of each other.

[0413] Ring W b1 It represents an aromatic hydrocarbon ring with 6 to 14 carbon atoms, or an aromatic heterocycle with 6 to 14 carbon atoms.

[0414] x represents any integer from 0 to 2. When x is 2, multiple R... b2’ Choose either the same or different.

[0415] Examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, and pentyl, with methyl being preferred.

[0416] Examples of alkoxy groups having 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentoxy, with methoxy being preferred.

[0417] Examples of aromatic hydrocarbon rings with 6 to 14 carbon atoms include benzene rings, naphthalene rings, and anthracene rings.

[0418] As aromatic heterocycles with 6 to 14 carbon atoms, examples of rings with 6 to 14 constituent atoms can be given, and the following rings are preferred.

[0419]

[0420] Ring W b1 Naphthalene rings are preferred.

[0421] As the compound shown in formula (b1), the compound shown in any of formulas (b4) to (b7) is preferred, and the compound shown in formula (b4) is more preferred.

[0422]

[0423] In equations (b4) to (b7),

[0424] R b1 It indicates the same meaning as the text above.

[0425] R b2 R b5 R b6 and R b7 Alkyl groups, which can be independently represented by 1 to 8 hydrogen atoms or carbon atoms.

[0426] Examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, and pentyl, with methyl being preferred.

[0427] Examples of compounds represented by formula (b1) include those represented by formulas (b1-1) to (b1-14). Compounds represented by formulas (b1-6) or (b1-7) are preferred.

[0428]

[0429] Examples of compounds represented by formula (b2) include compounds represented by the following formula.

[0430]

[0431] Examples of compounds represented by formula (b3) include compounds represented by the following formula.

[0432]

[0433] As an ionic acid generator, the compound shown in formula (b8) or formula (b9) is preferred.

[0434]

[0435] In equations (b8) and (b9),

[0436] A b1 and A b2 They can be represented independently of each other, representing oxygen or sulfur atoms.

[0437] R b8 R b9 R b10 and R b11 Alkyl groups having 1 to 10 carbon atoms or aromatic hydrocarbon groups having 6 to 12 carbon atoms can be represented independently of each other.

[0438] X1 - and X2 - This indicates an organic anion.

[0439] Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0440] Examples of aromatic hydrocarbon groups with 6 to 12 carbon atoms include aryl groups such as phenyl, naphthyl, anthraceneyl, biphenyl, and phenanthrene. These aromatic hydrocarbon groups may optionally have substituents. Examples of substituent-containing aromatic hydrocarbon groups include aralkyl groups and aromatic hydrocarbon groups containing alkyl groups. Specifically, examples include benzyl, phenethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, isopropylphenyl, mesitylene, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl.

[0441] R b8 R b9 R b10 and R b11 The preferred groups are aromatic hydrocarbon groups with 6 to 12 carbon atoms, and more preferably phenyl groups.

[0442] As X1 - and X2 - The organic anion shown can be, for example, a sulfonate anion, a bis(alkylsulfonyl)amide anion, a tri(alkylsulfonyl)methyl anion, etc., preferably a sulfonate anion, more preferably a sulfonate anion shown in formula (b10).

[0443]

[0444] In formula (b10),

[0445] R b12 This indicates a hydrocarbon group with 1 to 18 carbon atoms, optionally containing a fluorine atom, wherein the methylene group is optionally replaced by an oxygen atom or a carbonyl group.

[0446] As R b12 Examples of R in equation (B1) can be cited.b1 Same group.

[0447] Examples of compounds represented by formula (b8) include the following compounds.

[0448]

[0449] Examples of compounds represented by formula (b9) include the following compounds.

[0450]

[0451] In the resist composition of the present invention, the content of the acid generating agent relative to 100 parts by weight of resin (A) is preferably 0.1 parts by weight or more and 40 parts by weight or less, more preferably 0.5 parts by weight or more and 30 parts by weight or less, further preferably 1 part by weight or more and 20 parts by weight or less, and even more preferably 1 part by weight or more and 5 parts by weight or less. The resist composition of the present invention may contain only one type of acid generating agent (B), or it may contain multiple types.

[0452] <Solvent (D)>

[0453] The content of solvent (D) in the resist composition is typically 45% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more, typically 99.9% by mass or less, preferably 99% by mass or less, more preferably 90% by mass or less. The content of solvent (E) can be determined, for example, using known analytical methods such as liquid chromatography or gas chromatography.

[0454] Examples of solvents (D) include glycol ether esters such as ethyl cellolytic acetate, methyl cellolytic acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; and cyclic esters such as γ-butyrolactone. A solvent (D) may be present alone or in combination with two or more solvents.

[0455] <Quencher (C)>

[0456] The resist composition of the present invention may contain a quencher (hereinafter sometimes referred to as "quencher (C)").

[0457] Quencher (C) is a compound that captures acid generated from an acid-generating agent upon exposure. Examples of quenchers (C) include basic nitrogen-containing organic compounds.

[0458] Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of amines include aliphatic amines (including primary, secondary, and tertiary amines) and aromatic amines.

[0459] Examples of amines include compounds represented by formula (C1) or formula (C2).

[0460]

[0461] In formula (C1), R c1 R c2 and R c3 The groups independently 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 may optionally have at least one selected from hydroxyl, amino, and alkoxy groups having 1 to 6 carbon atoms. The aromatic hydrocarbon group having 6 to 10 carbon atoms may optionally have at least one selected from alkyl, alkoxy, and alicyclic hydrocarbon groups having 1 to 6 carbon atoms.

[0462] Examples of alkyl groups with 1 to 6 carbon atoms, alicyclic hydrocarbon groups with 3 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 10 carbon atoms, and alkoxy groups with 1 to 6 carbon atoms in formula (C1) can be the same as those mentioned above.

[0463] Examples of compounds represented by formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3-, or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, dibutylmethylamine, and methyldipentylamine. Dihexylmethylamine, dicyclohexylmethylamine, diheptylmethylamine, methyldioctylamine, methyldinonylamine, didecylmethylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, etc. Diisopropylaniline is preferred, and 2,6-diisopropylaniline is particularly preferred.

[0464]

[0465] In formula (C2),

[0466] Ring W1 This refers to a heterocycle containing a nitrogen atom in the atoms constituting the ring, or a benzene ring having a substituted or unsubstituted amino group, wherein the heterocycle and the benzene ring optionally have at least one selected from hydroxyl groups and alkyl groups having 1 to 4 carbon atoms.

[0467] A 1 It indicates phenyl or naphthyl.

[0468] nc represents 2 or 3, multiple A's 1 Choose either the same or different.

[0469] The substituted or unsubstituted amino group is in the form of -N(R) 4 (R) 5 ) indicates that R 4 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.

[0470] 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.

[0471] As an alicyclic hydrocarbon group with 3 to 10 carbon atoms, examples can be given of R in formula (10). a1 ~R a3 The same group as the alicyclic hydrocarbon group in it.

[0472] As aromatic hydrocarbon groups with 6 to 14 carbon atoms, examples can be given that R in formula (20) is similar to R. a1’ ~R a3’ The same group as the aromatic hydrocarbon group in it.

[0473] A heterocycle containing nitrogen atoms in its ring can be an aromatic ring, a non-aromatic ring, or it may 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 any of the rings shown in formulas (Y13) to (Y28). Removing one hydrogen atom from the ring results in a ring with nitrogen atoms... 1 The bonding ends.

[0474]

[0475] 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 of formulas (Y20) to (Y25).

[0476] Examples of compounds represented by formula (C2) include compounds represented by any of formulas (C2-1) to (C2-11). Compounds represented by any of formulas (C2-2) to (C2-8) are preferred.

[0477]

[0478] The content of quencher (C) in the solid component of the resist composition is preferably 0.0001 to 5% by mass, more preferably 0.0001 to 4% by mass, even more preferably 0.001 to 3% by mass, even more preferably 0.01 to 1.0% by mass, and even more preferably 0.1 to 0.7% by mass.

[0479] <Seam-Adhesive Enhancer (E)>

[0480] Adhesion enhancer (E) is not particularly limited to any substance that can prevent corrosion and / or improve adhesion to metals used in substrates or wiring. It functions as a rust preventer by preventing metal corrosion. Furthermore, it can improve the adhesion between the substrate or metal and the resist composition while performing these functions.

[0481] Examples of sealing enhancers (E) include sulfur-containing compounds, aromatic hydroxyl compounds, benzotriazole compounds, triazine compounds, and silicon-containing compounds. They can be used alone or in combination of two or more.

[0482] As a sulfur-containing compound, it can be any compound having a thioether bond and / or a thiol group. Sulfur-containing compounds can be chain-like or have a cyclic structure.

[0483] Examples of chain-like compounds include dithiodiglycerol [S(CH2CH(OH)CH2(OH))2], bis(2,3-dihydroxypropylthio)ethylene [CH2CH2(SCH2CH(OH)CH2(OH))2], sodium 3-(2,3-dihydroxypropylthio)-2-methyl-propylsulfonate [CH2(OH)CH(OH)CH2SCH2CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)CH2(OH)], sodium 3-mercapto-1-propanesulfonate [HSCH2CH2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], mercaptoacetic acid [HSCH2CO2H], and 3-mercapto-1-propanol [HSCH2CH2CH2].

[0484] The sulfur-containing compound is preferably a compound having a thioether bond and a thiol group, more preferably a heterocyclic compound having both a thioether bond and a thiol group. The heterocyclic compound is more preferably a heterocyclic compound having a thioether bond in its ring structure. In the sulfur-containing compound, the number of thioether bonds and thiol groups is not particularly limited, as long as there is one or more of each.

[0485] The heterocycle in a heterocyclic compound can be any monocyclic or polycyclic ring, and can be any saturated or unsaturated ring. Preferably, the heterocycle also contains heteroatoms other than sulfur atoms. Examples of heteroatoms include oxygen atoms and nitrogen atoms, with nitrogen atoms being preferred.

[0486] The heterocycle is preferably a heterocycle with 2 to 12 carbon atoms, more preferably a heterocycle with 2 to 6 carbon atoms. The heterocycle is preferably a monocyclic ring. The heterocycle is preferably unsaturated. The heterocycle is preferably unsaturated and monocyclic.

[0487] Examples of heterocycles include the following heterocycles.

[0488]

[0489] The sulfur-containing compound can be a polymer. The polymer preferably contains a structure with thioether bonds and thiol groups in the side chain. Preferably, the structure with thioether bonds and thiol groups (hereinafter sometimes referred to as unit (1)) is bonded to the main chain using linking groups such as amide bonds, ether bonds, thioether bonds, and ester bonds.

[0490] The polymer can be a homopolymer or a copolymer.

[0491] When the polymer is a copolymer, it may include the above-mentioned structural units (a1) having groups that are unstable to acid, structural units (a2) not having groups that are unstable to acid, etc.

[0492] The weight-average molecular weight of the homopolymers and copolymers is typically above 3000, preferably above 5000, and typically below 100000, preferably below 50000. The weight-average molecular weight is determined using gel permeation chromatography as a standard reference for polystyrene.

[0493] When the sulfur-containing compound is a polymer, the content of structural units having thioether bonds and thiol groups, relative to all structural units of the sulfur-containing compound polymer, is typically 0.1 to 50 mol%, preferably 0.5 to 30 mol%, and more preferably 1 to 20 mol%.

[0494] Sulfur-containing compounds are preferably, for example, compounds represented by formula (IA) or polymers having structural units represented by formula (IB).

[0495]

[0496] In formula (IA),

[0497] R i11 Represents hydrogen atoms, chain hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, alicyclic hydrocarbon groups with 3 to 18 carbon atoms, and -SR. 11 The indicated group, or -NR 12 R 13 The group shown.

[0498] R 11 R 12 and R 13 The groups can be independently represented by hydrogen atoms, chain hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, alicyclic hydrocarbon groups with 3 to 10 carbon atoms, or acyl groups with 2 to 12 carbon atoms, and these chain hydrocarbon groups, aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and acyl groups may optionally have hydroxyl groups.

[0499] R i12 and R i13 They can be used to represent hydrogen atoms, chain hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, or alicyclic hydrocarbon groups with 3 to 18 carbon atoms, independently of each other.

[0500] A and B represent nitrogen or carbon atoms independently.

[0501] n1 and m1 independently represent 0 or 1. Specifically, when A is a nitrogen atom, n1 represents 0; when A is a carbon atom, n1 represents 1. When B is a nitrogen atom, m1 represents 0; when B is a carbon atom, m1 represents 1.

[0502] 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.

[0503] Examples of aromatic hydrocarbon groups with 6 to 14 carbon atoms include phenyl, naphthyl, anthraceneyl, biphenyl, and phenanthrene aryl groups. The aromatic hydrocarbon group may optionally have substituents. Examples of substituent-containing aromatic hydrocarbon groups include aralkyl groups and aromatic hydrocarbon groups containing alkyl groups. Specifically, examples include benzyl, phenethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, isopropylphenyl, mesitylene, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl.

[0504] Examples of alicyclic hydrocarbon groups with 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, as well as polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornel.

[0505] R 11 Preferably, it is a chain hydrocarbon group with 1 to 10 carbon atoms or an acyl group with 2 to 12 carbon atoms, R 12 and R 13 The preferred groups are hydrogen atoms, chain hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, or acyl groups with 2 to 12 carbon atoms, which are independent of each other.

[0506] Examples of acyl groups with 2 to 12 carbon atoms include acetyl, propionyl, butyryl, valeryl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, decylcarbonyl, dodecylcarbonyl, and benzoyl.

[0507] R i11 More preferably, it is a hydrogen atom or a thiol group.

[0508] R i12 and R i13 The preferred components are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and more preferably hydrogen atoms.

[0509] Preferably, at least one of A and B is a nitrogen atom, and more preferably both are nitrogen atoms.

[0510]

[0511] In formula (IB),

[0512] R i21 and R i31 They can be used to represent hydrogen atoms, chain hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, or alicyclic hydrocarbon groups with 3 to 18 carbon atoms, independently of each other.

[0513] A 1 and B 1 They can represent nitrogen or carbon atoms independently.

[0514] n² and m² represent 0 or 1 independently. Where, in A... 1 In the case of nitrogen atoms, n2 represents 0, and in A 1 In the case of carbon atoms, n2 represents 1, in B 1 In the case of nitrogen atoms, m2 represents 0, and in B 1 In the case of carbon atoms, m2 represents 1.

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

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

[0517] L i1This indicates a divalent hydrocarbon group with 1 to 20 carbon atoms. The methylene group in this hydrocarbon group may be replaced by either an oxygen atom or a carbonyl group.

[0518] As R i21 and R i31 The chain hydrocarbon group having 1 to 10 carbon atoms includes, for example, alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with alkyl groups having 1 to 4 carbon atoms being preferred.

[0519] As R i21 and R i31 The aromatic hydrocarbon group has 6 to 14 carbon atoms. Examples of aryl groups with 6 to 14 carbon atoms include phenyl, naphthyl, anthraceneyl, biphenyl, and phenanthrene, with aryl groups having 6 to 10 carbon atoms being preferred. The aromatic hydrocarbon group may optionally have substituents. Examples of substituent-containing aromatic hydrocarbon groups 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, and 2-methyl-6-ethylphenyl.

[0520] As R i21 and R i31 Alicyclic hydrocarbon groups with 3 to 18 carbon atoms, such as monocyclic alicyclic hydrocarbon groups with cycloalkyl groups having 3 to 18 carbon atoms, including cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, etc., with alicyclic hydrocarbon groups having 5 to 10 carbon atoms being preferred.

[0521] R i21 and R i31 The preferred components are alkyl groups having 1 to 4 hydrogen atoms or carbon atoms, which are independent of each other.

[0522] As L i1Examples of divalent hydrocarbon groups with 1 to 20 carbon atoms 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. Alkyl-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, etc. alkyldiyl groups;

[0523] 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;

[0524] Norbornene-1,4-diyl, norbornene-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, and other polycyclic divalent alicyclic saturated hydrocarbon groups;

[0525] Aryl groups such as phenylene, tolyl, and naphthylene.

[0526] L i1 Preferably, it is a group obtained by combining an alkyldiyl group containing an ester bond with 2 to 14 carbon atoms or an arylene group containing 6 to 10 carbon atoms with an alkyldiyl group containing 1 to 11 carbon atoms.

[0527] The structural unit shown in formula (IB) is preferably the structural unit shown in formula (IB-1) or the structural unit shown in formula (IB-2).

[0528]

[0529] In formula (IB-1),

[0530] R i22 and R i32 They can be used to represent hydrogen atoms, chain hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, or alicyclic hydrocarbon groups with 3 to 18 carbon atoms, independently of each other.

[0531] A 2 and B 3 They can represent nitrogen or carbon atoms independently.

[0532] n3 and m3 independently represent 0 or 1. Wherein, in A...2 In the case of nitrogen atoms, n3 represents 0, and in A 2 In the case of carbon atoms, n3 represents 1, and in B 2 In the case of nitrogen atoms, m3 represents 0, and in B 2 In the case of carbon atoms, m3 represents 1.

[0533] X i11 It represents a sulfur atom and an NH group.

[0534] L i2 This indicates a divalent hydrocarbon group with 1 to 18 carbon atoms. The methylene group contained in this hydrocarbon group may be replaced by an oxygen atom or a carbonyl group.

[0535] R i5 It represents a hydrogen atom or a methyl group.

[0536] In equation (IB-2),

[0537] R i23 and R i33 They can be used to represent hydrogen atoms, chain hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, or alicyclic hydrocarbon groups with 3 to 18 carbon atoms, independently of each other.

[0538] A 3 and B 3 They can represent nitrogen or carbon atoms independently.

[0539] n4 and m4 independently represent 0 or 1. Wherein, in A... 3 In the case of nitrogen atoms, n4 represents 0, and in A 3 In the case of carbon atoms, n4 represents 1, and in B 3 In the case of nitrogen atoms, m4 represents 0, and in B 3 In the case of carbon atoms, m4 represents 1.

[0540] X i12 It represents a sulfur atom and an NH group.

[0541] L i3 This indicates a divalent hydrocarbon group with 1 to 14 carbon atoms. The methylene group contained in this hydrocarbon group may be replaced by an oxygen atom or a carbonyl group.

[0542] R i7 It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms.

[0543] R i6 It represents a hydrogen atom or a methyl group.

[0544] mx represents an integer from 0 to 4.

[0545] As R i22 Ri32 R i23 and R i33 The chain hydrocarbon groups with 1 to 10 carbon atoms shown can be exemplified by those related to R. i21 and R i31 The groups shown are chain hydrocarbon groups with the same number of carbon atoms from 1 to 10.

[0546] As R i22 R i32 R i23 and R i33 The aromatic hydrocarbon groups with 6 to 14 carbon atoms shown can be exemplified by those related to R. i21 and R i31 The groups shown are the same as aromatic hydrocarbon groups with 6 to 14 carbon atoms.

[0547] As R i22 R i32 R i23 and R i33 The alicyclic hydrocarbon groups with 3 to 18 carbon atoms shown can be exemplified by those related to R. i21 and R i31 The groups shown are the same as the alicyclic hydrocarbon groups with 3 to 18 carbon atoms.

[0548] As L i2 Examples of divalent hydrocarbon groups with 1 to 18 carbon atoms 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. Alkyl-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, etc. alkyldiyl groups;

[0549] 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;

[0550] Norbornene-1,4-diyl, norbornene-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, and other polycyclic divalent alicyclic saturated hydrocarbon groups;

[0551] Aryl groups such as phenylene, tolyl, and naphthylene.

[0552] 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.

[0553] As L i3 Examples of divalent hydrocarbon groups with 1 to 14 carbon atoms 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.

[0554] 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;

[0555] Norbornene-1,4-diyl, norbornene-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, and other polycyclic divalent alicyclic saturated hydrocarbon groups.

[0556] L i3 Preferably, it is an alkyldiyl group with 1 to 14 carbon atoms, and more preferably an alkyldiyl group with 1 to 11 carbon atoms.

[0557] Based on the position of the phenyl group bonded to the main chain, L i3 Preferred bonding is at the correct position.

[0558] As R i7 Alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and isopropyl, can be given examples.

[0559] As R i7 Examples of alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, and butoxy.

[0560] Examples of sulfur-containing compounds include, for example, any of the compounds shown in formula (I-1) to formula (I-26). Among these, compounds shown in formula (I-1) to formula (I-13) are preferred, and compounds shown in formula (I-1), formula (I-4), and formula (I-11) are more preferred.

[0561]

[0562]

[0563] Examples of sulfur-containing compounds include homopolymers containing any one of the structural units shown in formulas (I-27) to (I-38) or copolymers containing one or more of these structural units.

[0564] Preferably, it is a copolymer containing one or more structural units shown in formulas (I-27) to (I-36), and more preferably a copolymer containing structural units shown in formula (I-33).

[0565]

[0566] Examples of such copolymers include copolymers comprising structural units shown in formulas (I-39) to (I-48). Among these, polymers having structural units shown in formulas (I-39) to (I-44) are preferred.

[0567]

[0568]

[0569] The sulfur-containing compound can be a compound synthesized using known methods (e.g., Japanese Patent Application Publication No. 2010-79081) or a commercially available product. The polymer containing the sulfur-containing compound can be a commercially available product (e.g., bismuthiol (manufactured by Tokyo Chemical Industry Co., Ltd.), or a polymer synthesized using known methods (e.g., Japanese Patent Application Publication No. 2001-75277).

[0570] Examples of aromatic hydroxyl compounds include phenol, cresol, xylenol, catechol (=1,2-dihydroxybenzene), tert-butylcatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-pyrogallol, salicylol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenylethanol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, etc.

[0571] Examples of benzotriazole compounds include, for instance, compounds represented by formula (IX).

[0572]

[0573] In formula (IX),

[0574] R 1 and R 2 The groups that independently represent hydrogen atoms and optionally have 1 to 10 carbon atoms, including hydrocarbon, carboxyl, amino, hydroxyl, cyano, formyl, sulfonylalkyl, or sulfonyl groups.

[0575] Q represents a hydrogen atom, a hydroxyl group, an optional hydrocarbon group with 1 to 10 carbon atoms having substituents, an aryl group, or **-R. 3X -N(R 4X (R) 5X The hydrocarbon group may optionally have an amide bond or an ester bond in its structure.

[0576] R 3X This indicates an alkyldiyl group with 1 to 6 carbon atoms. ** indicates a bond end with a nitrogen atom contained in the ring.

[0577] R 4X and R 5X These can be used independently to represent hydrogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, hydroxyalkyl groups with 1 to 6 carbon atoms, and alkoxyalkyl groups with 2 to 6 carbon atoms.

[0578] R 1 R 2 The hydrocarbon group of Q with 1 to 10 carbon atoms can be any aliphatic hydrocarbon group with 1 to 10 carbon atoms or aromatic hydrocarbon group with 6 to 10 carbon atoms, and can have saturated and / or unsaturated bonds.

[0579] As an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkyl group is preferred. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, methylpentyl, n-hexyl, and n-heptyl.

[0580] As an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aryl group is preferred. Examples of such an aryl group include phenyl, naphthyl, anthraceneyl, biphenyl, and phenanthrene. The aromatic hydrocarbon group may optionally have substituents. Examples of substituent-containing aromatic hydrocarbon groups include aralkyl groups and aromatic hydrocarbon groups containing alkyl groups. Specifically, examples include benzyl, phenethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, isopropylphenyl, mesitylene, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl.

[0581] Substituents that can be optionally present in a hydrocarbon group having 1 to 10 carbon atoms include, for example, hydroxyalkyl, alkoxyalkyl, etc.

[0582] As R 3X Alkyl groups having 1 to 6 carbon atoms can be either straight-chain or branched, and examples include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, etc.

[0583] As R 4X and R 5X Alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and isopropyl.

[0584] As R 4X and R 5X Hydroxyalkyl groups having 1 to 6 carbon atoms, such as hydroxymethyl, hydroxyethyl, and dihydroxyethyl.

[0585] As R 4X and R 5X Alkoxyalkyl groups having 2 to 6 carbon atoms, such as methoxymethyl, methoxyethyl, and dimethoxyethyl.

[0586] When the resist composition of the present invention is applied to a substrate on which Cu is formed, in formula (IX), Q is preferably in the form of **-R 3X -N(R 4X (R) 5X Compounds represented by ) . Where, in R 4X and R 5X When at least one of the components is an alkyl group having 1 to 6 carbon atoms, benzotriazole compounds lack water solubility; however, they are preferred when other components capable of dissolving the compound are present.

[0587] Furthermore, when the resist composition of the present invention is applied to a substrate having an inorganic material layer (e.g., a polycrystalline silicon film, an amorphous silicon film, etc.), in formula (IX), Q preferably represents a water-soluble group. Specifically, hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, hydroxyalkyl groups having 1 to 3 carbon atoms, hydroxyl groups, etc., are preferred. This allows for more effective corrosion resistance of the substrate.

[0588] Examples of benzotriazole compounds include benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethylbenzotriazole, methyl 1-benzotriazole formate, 5-benzotriazole formate, 1-methoxy-benzotriazole, 1-(2,2-dihydroxyethyl)-benzotriazole, and 1-(2,3-dihydroxypropyl)benzotriazole. Alkyl, or 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}diethane, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}dipropane, etc.

[0589] Examples of triazine compounds include those represented by formula (II).

[0590]

[0591] In formula (II),

[0592] R 6 R 7 and R 8 The groups that can be represented independently are halogen, hydrogen atom, hydroxyl group, amino group, mercapto group, alkyl group with 1 to 10 optional substituted carbon atoms, alkoxy group with 1 to 10 optional substituted carbon atoms, and amino group with 1 to 10 carbon atoms substituted by an alkyl group.

[0593] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0594] Hydrocarbon groups with 1 to 10 carbon atoms can be the same as those mentioned above.

[0595] Examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, and propoxy.

[0596] Examples of triazine compounds include 1,3,5-triazine-2,4,6-trithiol.

[0597] Examples of silicon-containing compounds include those represented by formula (IIA).

[0598]

[0599] In formula (IIA),

[0600] R j1 It represents an aliphatic hydrocarbon group with 1 to 5 carbon atoms or a mercaptoalkyl group with 1 to 5 carbon atoms.

[0601] R j2 ~R j4 Independently representing aliphatic hydrocarbon groups, alkoxy groups, mercapto groups, or mercaptoalkyl groups with 1 to 5 carbon atoms, R j2 ~R j4 At least one of them is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms.

[0602] t i Represents integers from 1 to 10.

[0603] Examples of aliphatic hydrocarbon groups with 1 to 5 carbon atoms include alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, propyl, butyl, and pentyl.

[0604] Examples of alkoxy groups with 1 to 5 carbon atoms include methoxy and ethoxy.

[0605] Examples of mercaptoalkyl groups having 1 to 5 carbon atoms include methyl mercapto, ethyl mercapto, and propyl mercapto.

[0606] R j1 Preferably, it is methyl, ethyl, or a mercaptoalkyl group having 1 to 3 carbon atoms, more preferably methyl or mercaptopropyl (especially 3-mercaptopropyl).

[0607] R j2 ~R j4 The preferred groups are methyl, ethyl, methoxy, and ethoxy, with methyl and methoxy being more preferred. At least one of these groups is preferably a mercapto group or a mercaptoalkyl group having 1 to 3 carbon atoms, with mercapto or mercaptopropyl being more preferred.

[0608] R j2 and R j3 They can be chosen to be the same or different from each other, but from a productivity point of view, they are preferred to be the same.

[0609] Examples of compounds of formula (IIA) include those shown in formulas (II-1) to (II-7).

[0610]

[0611] Among them, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane are preferred.

[0612] The content of the adhesion enhancer (E) relative to the total amount of solid components in the resist composition is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, even more preferably 0.005% by mass or more, particularly preferably 0.008% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 4% by mass or less, even more preferably 3% by mass or less, particularly preferably 1% by mass or less, and especially preferably 0.1% by mass or less. By setting it within this range, a resist composition capable of forming highly precise resist patterns can be produced, ensuring the adhesion between the resist pattern and the substrate.

[0613] <Other Ingredients>

[0614] The resist composition of the present invention may contain components other than those described above (hereinafter sometimes referred to as "other components (F)"). There are no particular limitations on other components (F), and additives known in the field of resists, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc., may be used.

[0615] When using other ingredients (F), their content should be appropriately selected according to the type of other ingredients (F).

[0616] 2. Preparation of the resist composition

[0617] The resist composition of the present invention can be prepared by mixing compound (I), resin (A1), resin (A2), acid generating agent (B), and resin other than resin (A1) and resin (A2) as needed, quencher (C), solvent (D), adhesion enhancer (E), and other components (F). The mixing order is optional and not particularly limited. The mixing temperature can be selected from 10 to 40°C depending on the type of resin, the solubility of the resin in the solvent (D), etc. The mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. It should be noted that the mixing method is not particularly limited, and stirring or similar methods can be used.

[0618] After mixing the components, it is preferable to use a filter with a pore size of about 0.003 to 50 μm for filtration.

[0619] 3. Method for manufacturing resist patterns

[0620] The method for manufacturing the resist pattern of the present invention includes:

[0621] (1) The process of coating the resist composition of the present invention onto the metal surface of a substrate having a metal surface;

[0622] (2) The process of drying the coated resist composition to form a composition layer.

[0623] (3) The process of exposing the composite layer, and

[0624] (4) The process of developing the exposed composite layer.

[0625] When applying the resist composition to a substrate, it can be done using a conventional apparatus such as a spin coater. Examples of substrates include inorganic substrates such as silicon wafers, on which semiconductor elements (e.g., transistors, diodes, etc.) can be pre-formed. When using the resist composition of the present invention for bump formation, it is preferable that a substrate further laminated with a conductive material is also used as the substrate. Examples of conductive materials include at least one metal selected from gold, copper, nickel, tin, palladium, and silver, or an alloy containing at least one metal selected from this group; copper or an alloy containing copper is preferred.

[0626] The substrate can be washed before applying the resist composition, or an anti-reflective film can be formed on the substrate.

[0627] The coated composition is dried to remove the solvent, forming a composition layer. Drying can be performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-drying), or by using a depressurization device. The heating temperature is preferably 50–200°C, and the heating time is preferably 30–600 seconds. Furthermore, the pressure during depressurization drying is preferably 1–1.0 × 10⁻⁶. 5 Approximately Pa.

[0628] After drying, the film thickness of the resulting composition is preferably 1 to 150 μm, more preferably 1.5 to 100 μm.

[0629] The resulting composite layer is typically exposed using an exposure machine. As the exposure light source, various devices can be used, such as those emitting light in the ultraviolet region (g-line (wavelength: 436nm), h-line (wavelength: 405nm), i-line (wavelength: 365nm)), KrF excimer lasers (wavelength: 248nm), ArF excimer lasers (wavelength: 193nm), F2 excimer lasers (wavelength: 157nm), high-frequency lasers emitting far-ultraviolet or vacuum ultraviolet regions by wavelength conversion of laser light from solid-state laser sources (YAG or semiconductor lasers, etc.), electron beam irradiation, and ultraviolet (EUV) light irradiation devices. It should be noted that in this specification, the operation of emitting these radiations is sometimes collectively referred to as "exposure." During exposure, exposure is usually performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure can be performed directly using the pattern without a mask.

[0630] To promote the desorption reaction of acid-labile groups in the resin (Al), the exposed composition layer may be subjected to heat treatment (so-called post-exposure baking). The heating temperature is typically around 50–200°C, preferably around 70–150°C. The heating time is typically 40–400 seconds, preferably 50–350 seconds.

[0631] A developing apparatus is typically used to develop the heated composite layer using a developing solution. Examples of developing methods include immersion, paddle, spray, and dynamic coating. The developing temperature is preferably 5–60°C, and the developing time is preferably 5–600 seconds. By selecting the type of developing solution as shown below, positive or negative resist patterns can be produced.

[0632] When manufacturing positive resist patterns using the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer can be any alkaline aqueous solution used in this field. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may also contain a surfactant.

[0633] Preferably, the resist pattern after development is washed with ultrapure water, and then the water remaining on the substrate and the pattern is removed.

[0634] In the case of manufacturing a negative resist pattern using the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used as the developer.

[0635] Organic solvents contained in organic-based developers include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole.

[0636] In organic-based developing solutions, the content of organic solvents is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only organic solvents.

[0637] Among them, the organic developer preferably contains butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2-heptanone.

[0638] Organic-based developers may also contain surfactants. Additionally, organic-based developers may contain trace amounts of water.

[0639] During development, development can be stopped by replacing the solvent with a different type of solvent than that used in organic developers.

[0640] The developed resist pattern is preferably washed with a rinsing solution. There are no particular limitations on the rinsing solution, as long as it does not dissolve the resist pattern; a solution containing a common organic solvent can be used, preferably an alcohol or ester solvent.

[0641] It is preferable to remove the rinsing solution remaining on the substrate and pattern after washing.

[0642] By exposing the resist obtained using the resist composition of the present invention, a resist pattern with high precision can be formed.

[0643] 4. Manufacturing method of plated shapes

[0644] Using the resist pattern formed by the above method as a mold, the resist pattern is peeled off by depositing electrode material, thereby forming plated shapes such as bumps and redistribution lines.

[0645] The method for manufacturing plated molded objects of the present invention includes:

[0646] (5) The process of forming a plated object using a resist pattern as a mold, and

[0647] (6) The process of peeling off the resist pattern.

[0648] Using a resist pattern formed on a substrate having a conductive layer as a mold, a conductive material is deposited using a plating solution using a known method to form a plated shape.

[0649] Examples of plating solutions include copper plating solution, gold plating solution, nickel plating solution, solder plating solution, and silver-tin plating solution.

[0650] After the plated shape is formed, the resist pattern is removed using a stripping solution by a known method.

[0651] As the stripping solution, examples include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate. One of these may be used alone, or two or more of them may be used in combination.

[0652] By means of the above method, plated shaped articles such as bumps and rewiring can be formed.

[0653] It should be noted that, when forming the plated shaped article, in order to improve the adhesion between the conductive layer and the plated shaped article, the surface of the conductive layer may be subjected to ashing treatment (original Japanese text: アッシング処理) or the like. Examples of the ashing treatment method include a method using oxygen plasma.

[0654] The plated shaped article obtained by using the resist pattern of the present invention has less swelling in a plating bath, so the plated shaped article can be formed with excellent precision.

[0655] 5. Applications

[0656] The resist composition of the present invention is useful for producing thick resist films. For example, it is useful for producing a resist film having a film thickness of 1 to 150 μm.

[0657] In addition, the resist composition of the present invention is useful for manufacturing bumps and rewiring through a plating process. When the resist composition is used to manufacture bumps and rewiring, they can generally be formed by the following steps. Thereby, a resist pattern with a particularly excellent pattern shape can be manufactured.

[0658] First, a conductive layer is formed by laminating a conductive material (seed metal) on a wafer on which semiconductor elements are formed. Then, a resist pattern is formed on the conductive layer using the resist composition of the present invention. Next, using the resist pattern as a mold, electrode material (e.g., Cu, Ni, solder, etc.) is deposited by plating. The resist pattern and the conductive layer remaining under the resist pattern are removed by etching or the like, thereby forming bumps and rewiring. After removing the conductive layer, the electrode material can be melted by heat treatment if necessary, and the resulting material can be used as bumps.

[0659] [Example]

[0660] The invention will be further described in detail by way of examples. In these examples, unless otherwise specified, "%" and "parts" indicating content or amount used are quality standards.

[0661] The weight-average molecular weight is a value obtained by gel permeation chromatography under the following conditions.

[0662] Device: HLC-8120GPC (manufactured by Tosoh Corporation)

[0663] Column: TSKgel Multipore H XL -M×3+ Protective Posts (Made by Tosoh)

[0664] Eluent: Tetrahydrofuran

[0665] Flow rate: 1.0 mL / min

[0666] Detector: RI detector

[0667] Column temperature: 40℃

[0668] Injection volume: 100 μl

[0669] Molecular weight standard: Standard polystyrene (manufactured by Tosoh).

[0670] Synthesis Example 1 [Synthesis of Resin (A1)-1]

[0671] 20 parts of poly(p-hydroxystyrene) (S-4P; manufactured by Maruzen Petrochemical Co., Ltd.) were dissolved in 240 parts of methyl isobutyl ketone at room temperature and concentrated using an evaporator. The concentrated resin solution and 0.003 parts of p-toluenesulfonic acid dihydrate were added to a four-necked flask equipped with a reflux condenser, stirrer, and thermometer. While maintaining the resulting mixture at 20–25°C, 5.05 parts of ethyl vinyl ether were added dropwise over 10 minutes. The mixture was stirred at 20–25°C for 2 hours. The resulting reaction mixture was diluted with 200 parts of methyl isobutyl ketone, washed with deionized water, and separated five times. The resulting organic layer was concentrated to 45 parts using an evaporator, and then 150 parts of propylene glycol monomethyl ether acetate were added, followed by further concentration to obtain 78 parts of a propylene glycol monomethyl ether acetate solution of resin (A1)-1 (29% solids). Resin (A1)-1 is a resin having the following structural units. The weight-average molecular weight of resin (A1)-1 is 1.16 × 10⁻⁶. 4 The proportion of ethoxylated hydroxyl groups in poly-p-hydroxystyrene is 40.9%.

[0672]

[0673] Synthesis Example 2 [Synthesis of Resin (A1)-2]

[0674] 120 parts of linear phenolic resin (PSM-4326 manufactured by Chung Yung Chemical Co., Ltd.) and 960 parts of methyl isobutyl ketone were added to a flask and dissolved. The resulting linear phenolic resin solution was washed five times with deionized water and separated. The resulting organic layer was concentrated to 327.3 parts. The resin concentration in the resulting resin solution was 35.2%.

[0675] Add 56.8 parts of the obtained resin solution, 76.52 parts of methyl isobutyl ketone, and 0.0036 parts of p-toluenesulfonic acid monohydrate to a flask. Add 8.81 parts of ethyl vinyl ether dropwise to the mixture and react at room temperature for 3 hours. Add deion-exchanged water to the reaction solution and stir, allow to stand, and remove the organic layer by separation. Repeat the washing with deion-exchanged water four times, for a total of five washings. Then, remove the organic layer and concentrate it. Subsequently, to remove water and methyl isobutyl ketone through azeotropic extraction, add propylene glycol monomethyl ether acetate and further concentrate to obtain 57.44 parts of resin solution. The obtained resin solution is a solution of phenol linear phenolic resin in which the hydroxyl groups are partially 1-ethoxyethylated. This resin is used... 1¹H-NMR analysis revealed that 53.0% of the hydroxyl groups in the linear phenolic resin were replaced with 1-ethoxyethyl ether. Furthermore, the concentration of the resin solution was determined using the dry weight reduction method, yielding a result of 45.0%. This resin is designated as resin (A1)-2. Resin (A1)-2 is a resin having the following structural units. The weight-average molecular weight of resin (A1)-2 is 7.2 × 10⁻⁶. 3 .

[0676]

[0677] Synthesis Example 3 [Synthesis of Resin (A2)-1]

[0678] To a four-necked flask equipped with a stirrer, reflux condenser, and thermometer, add 413.5 parts of 2,5-xylenol, 103.4 parts of salicylaldehyde, 20.1 parts of p-toluenesulfonic acid, and 826.9 parts of methanol. Heat to reflux and maintain this temperature for 4 hours. After cooling, add 1320 parts of methyl isobutyl ketone and distill off 1075 parts of solvent under normal pressure. Add 762.7 parts of m-cresol and 29.0 parts of 2-tert-butyl-5-methylphenol and heat to 65°C. While adjusting the temperature to 87°C at the end of the addition, add 678 parts of a 37% formalin aqueous solution dropwise over 1.5 hours. Maintain the resulting mixture at 87°C for 10 hours, add 1115 parts of methyl isobutyl ketone, and wash three times with ion-exchange water. Add 500 parts of methyl isobutyl ketone to the resulting mixture and concentrate under reduced pressure to a total volume of 3435 parts. 3796 parts of methyl isobutyl ketone and 4990 parts of n-heptane were added to the resulting mixture, and the mixture was heated to 60°C and stirred for 1 hour. Subsequently, the mixture was separated, and the lower layer containing the resin was collected and diluted with 3500 parts of propylene glycol monomethyl ether acetate. The solution was then concentrated to obtain 1690 parts of a propylene glycol monomethyl ether acetate solution of resin (A2)-1 (43% solids). The weight-average molecular weight of linear phenolic resin (A2)-1 is 7 × 10⁻⁶. 3 Furthermore, the residual film rate was 74% when developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution. This residual film rate was determined using the method described in the <Resin (A2)> section of the detailed description of the invention.

[0679] <Preparation of the resist composition>

[0680] The resist composition was prepared by filtering the mixture obtained by mixing and dissolving the components shown in Table 1 through a fluoropolymer filter with a pore size of 0.5 μm.

[0681] [Table 1]

[0682]

[0683] <Resin>

[0684] (A1)-1: Resin (A1)-1

[0685] (A1)-2: Resin (A1)-2

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

[0687] <Acid Generator (B)>

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

[0689]

[0690] (B)-2: The compound shown in the following formula (PAG-103; manufactured by BASF)

[0691]

[0692] <Compound (I)>

[0693] (I)-1: Synthesized using the method described in Japanese Patent Application Publication No. 3-185447

[0694]

[0695] (I)-2: Synthesized using the method described in Japanese Patent Application Publication No. 9-110762

[0696] It should be noted that, relative to R t1 R t6 R t7 R t9 R t10 For every 1 mole of the following compounds with a hydroxyl group, 2 moles of sulfonyl chloride react, resulting in almost 100% propagation of the reaction. Therefore, it is confirmed that the reaction is primarily driven by R. t1 R t6 R t7 R t9 R t10 The hydrogen atom in the two hydroxyl groups is replaced by a 1,2-naphthoquinone diazidosulfonyl group, which is a disubstituted derivative (MS: M+: 1080).

[0697]

[0698] (I)-3: Synthesized using the method described in Japanese Patent Application Publication No. 8-245461

[0699] It should be noted that, relative to R t1 R t7 R t9 Rt10 For every 1 mole of the following compounds with a hydroxyl group, 2 moles of sulfonyl chloride react, resulting in almost 100% propagation of the reaction. Therefore, it is confirmed that the reaction is primarily driven by R. t1 R t7 R t9 R t10 The hydrogen atom in the two hydroxyl groups is replaced by a 2-substituted product of 1,2-naphthoquinone diazidosulfonyl group (MS: M+: 960).

[0700]

[0701] <Quencher (C)>

[0702] (C)-1: 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0703] <Solvent (D)>

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

[0705] Examples 1-6, Comparative Examples 1 and 2

[0706] (i-line exposure evaluation of the resist composition)

[0707] The above-mentioned resist composition was spin-coated onto a substrate on a 4-inch silicon wafer in such a way that the pre-baked film thickness was 1.5 μm.

[0708] Subsequently, the composite layer is pre-baked at 100°C for 180 seconds on a direct hot plate.

[0709] Then, the composite layer formed on the wafer is exposed using an i-line stepper lithography machine (NSR-2005i9C; Nikon Corporation, NA=0.5) with the exposure amount varying in stages through a mask used to form 1:1 lines and spacing patterns (1 μm linewidth).

[0710] After exposure, the image is baked on a hot plate at 90°C for 60 seconds, followed by paddle development for 180 seconds using a 2.38% by mass tetramethylammonium hydroxide aqueous solution, thus obtaining the resist pattern.

[0711] The resist pattern obtained after development was observed using a scanning electron microscope, and the exposure amount of the line and spacing pattern with a line width of 1 μm was set as the effective sensitivity.

[0712] <Resolution Evaluation>

[0713] The resist pattern obtained at effective sensitivity was observed using a scanning electron microscope, and the minimum line width of the resolvable lines and spacing patterns was determined.

[0714] Roughness Evaluation Based on Standing Wave Effect

[0715] The cross-sectional shape of a line and spacing pattern with a linewidth of 0.6 μm obtained at effective sensitivity was observed using a scanning electron microscope, and the determination was performed. Figure 1 The line widths 'a' and 'b' shown are categorized as follows: 'C' represents a calculated value of b / a less than 0.8; 'B' represents a value greater than 0.8 but less than 0.9; and 'A' represents a value greater than 0.9. 'a' is the line width of the longest segment of the specified line (maximum line width) (μm), and 'b' is the line width of the shortest segment of the specified line (minimum line width) (μm). The results shown in the table are for the line with the smallest observed b / a value.

[0716] <Evaluation of plating resistance>

[0717] After fabricating patterned wafers at the effective sensitivity obtained in the above i-line exposure evaluation, they were immersed in Cu plating solution for 5 minutes, 15 minutes, and 30 minutes.

[0718] The patterned wafer after impregnation was observed using an optical microscope, and the lines and spacing patterns with a line width of 1 μm were observed.

[0719] The case where the pattern is skewed after 15 minutes of soaking is designated as "C", the case where the pattern is not skewed after 15 minutes of soaking but is skewed after 30 minutes is designated as "B", and the case where the pattern is not skewed after 30 minutes of soaking is designated as "A".

[0720] [Table 2]

[0721] Example 1 Composition 1 0.4 A A Example 2 Composition 2 0.375 B A Example 3 Composition 3 0.375 A A Example 4 Composition 4 0.375 B A Example 5 Composition 5 0.375 A A Example 6 Composition 6 0.375 A A Comparative Example 1 Comparative Composition 1 0.475 C C Comparative Example 2 Comparative Composition 2 0.475 C C

[0722] Industrial availability

[0723] The resist composition of the present invention can produce resist patterns with good shape and plating resistance, which is suitable for the microfabrication of semiconductors and is extremely useful in industry.

Claims

1. A resist composition comprising: The compound having a quinone diazidosulfonyl group (I), a resin containing a structural unit having a group that is unstable to acid (A1), an alkali-soluble resin (A2), and an acid generating agent (B). The compound (I) having a quinone diazidosulfonyl group is selected from at least one of the compounds shown in formula (II), formula (III), formula (IV), and formula (V); In formula (II), R 11 ~R 14 each 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); a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms is optionally replaced with an oxygen atom, a carbonyl group, or -NR d1 -; R d1 Indicates an alkyl group having 1 to 6 hydrogen atoms or carbon atoms; R 15 ~R 30 Each of these independently represents a hydrogen atom, a hydroxyl group, a group shown in formula (a), a group shown in formula (b), or a group shown in formula (c); 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); In formula (III), 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); R 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); P 1 ~P 5 Each of these groups independently represents a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms, wherein the methylene group in the hydrocarbon group having 1 to 18 carbon atoms may optionally be replaced by an oxygen atom, a carbonyl group, or -NR. d2 -, P 1 and P 2 The two carbon atoms that are arbitrarily bonded to each other can form a ring together; P 4 and P 5 They can be arbitrarily bonded together and form rings with the carbon atoms they are bonded to; R d2 Indicates an alkyl group having 1 to 6 hydrogen atoms or carbon atoms; In equation (IV), R 40 ~R 53 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); R 40 ~R 53 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); n a Represents any integer from 1 to 5; in n a In the case of any integer greater than 2, multiple R 49 ~R 52 Choose either the same as or different from each other; In equation (V), R f1 R f2 and R g1 ~R g8 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); R f1 R f2 and R g1 ~R g8 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); P 6 It represents an aromatic hydrocarbon group with 6 to 12 carbon atoms in a monovalent state or an aromatic hydrocarbon group with 6 to 12 carbon atoms in a divalent state; the aromatic hydrocarbon group may be optionally substituted by at least one of a hydroxyl group and an alkyl group having 1 to 6 carbon atoms; P 7 Represents a hydrogen atom, and optionally a hydrocarbon group having 1 to 18 carbon atoms with substituents, wherein the methylene group containing 1 to 18 carbon atoms is optionally replaced by an oxygen atom, a carbonyl group, or -NR. d3 -;P 6 and P 7 They can be selectively bonded together to form a ring; n v Indicates 1 or 2; R d3 Indicates an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. In equations (a), (b), and (c), * denotes the bonding end; The resin (A1) containing structural units having groups that are unstable to acid is a resin containing structural units shown in formula (a1-1), formula (a1-2), formula (a3A), or formula (a3B). In equation (a1-1), R a1 R a2 and R a3 Independently representing alkyl groups having 1 to 8 carbon atoms or alicyclic hydrocarbon groups having 3 to 20 carbon atoms; or, R a1 and R a2 They bond to each other and together with the carbon atoms they are bonded to form rings with 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 Indicates a hydrogen atom or a methyl group; In equation (a1-2), R a1’ and R a2’ R represents a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms, which can be independently represented by each other. a3’ Represents a hydrocarbon group with 1 to 20 carbon atoms; or, R a1’ Represents a hydrocarbon group with 1 to 20 hydrogen or carbon atoms, and R a2’ and R a3’ They bond to each other and together with the carbon and oxygen atoms they bond to form a heterocycle with 3 to 20 carbon atoms; the hydrocarbon group with 1 to 20 carbon atoms and the methylene group contained in the heterocycle with 3 to 20 carbon atoms may be optionally replaced by an oxygen atom or a sulfur atom. R a5 Indicates a hydrogen atom or a methyl group; R a6 Indicates an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; m represents an integer from 0 to 4; when m is greater than 2, multiple R... a6 Choose either the same as or different from each other; In formula (a3A), R a1 R a2 and R a3 Independently representing alkyl groups having 1 to 8 carbon atoms or alicyclic hydrocarbon groups having 3 to 20 carbon atoms; or, R a1 and R a2 They bond to each other and together with the carbon atoms they are bonded to form rings with 3 to 20 carbon atoms, and R a3 R represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; 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 Choose either the same or different; In equation (a3B), R a1’ and R a2’ R represents a hydrocarbon group consisting of 1 to 20 hydrogen atoms or carbon atoms, which can be independently represented by each other. a3’ Represents a hydrocarbon group with 1 to 20 carbon atoms; or, R a1’ Represents a hydrocarbon group with 1 to 20 hydrogen or carbon atoms, and R a2’ and R a3’ They bond to each other and together with the carbon and oxygen atoms they are bonded to form a heterocycle with 3 to 20 carbon atoms; the hydrocarbon group with 1 to 20 carbon atoms and the methylene group contained in the heterocycle with 3 to 20 carbon atoms are optionally replaced by oxygen or sulfur 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 Choose either the same or different.

2. The resist composition according to claim 1, wherein, Alkali-soluble resin (A2) is a resin containing structural units having carboxyl or hydroxyl groups and not containing structural units having groups that are unstable to acids.

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

4. A method for manufacturing a resist pattern, the method comprising: (1) The process of coating the resist composition of claim 1 onto the metal surface of a substrate having a metal surface; (2) The process of drying the coated composition to form a composition layer. (3) The process of exposing the composite layer, and (4) The process of developing the exposed composite layer.

5. A method for manufacturing a plated molded object, the method comprising: (1) The process of coating the resist composition of claim 1 onto the metal surface of a substrate having a metal surface; (2) The process of drying the coated composition to form a composition layer. (3) The process of exposing the composite layer; (4) The process of developing the exposed composite layer; (5) The process of forming a plated object using the obtained resist pattern as a mold, and (6) The process of peeling off the resist pattern.

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