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

Abstract

To provide a resist composition which has sufficient resistance to plating treatment and is capable of accurately forming a resist pattern, a method for producing a resist pattern using the resist composition, and a method for manufacturing a plated molded article using the resist pattern.SOLUTION: The present invention relates to: a resist composition which contains a compound (I) having a quinonediazidesulfonyl 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 producing a resist pattern using the resist composition; and a method for manufacturing a plated molded article using the resist pattern.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Patent Document 1 describes a resist composition that contains a compound having a naphthoquinone diazide sulfonyl group. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-101129 A Summary of the Invention [Problem to be solved by the invention]

[0004] When a plating process is performed using a resist pattern obtained using a conventional resist composition as described in Patent Document 1, there is still room for improvement in terms of forming a plated object with high accuracy. Therefore, an object of the present invention is to provide a resist composition that has sufficient resistance to plating treatment and is capable of forming a resist pattern with high precision, and also to provide a method for producing a resist pattern using the resist composition. [Means for solving the problem]

[0005] The present inventors have discovered that the above-mentioned problems can be solved by a resist composition that contains a compound having a quinone diazide sulfonyl group, a resin that includes a structural unit having an acid labile group, an alkali-soluble resin, and an acid generator. The present invention provides the following inventions. [1] A resist composition comprising a compound (I) having a quinone diazide sulfonyl group, a resin (A1) containing a structural unit having an acid labile group, an alkali-soluble resin (A2), and an acid generator (B). [2] The resist composition according to [1], wherein the compound (I) having a quinone diazide sulfonyl group is a compound having a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). TIFF0007645089000001.tif48167[In formula (a) and formula (b), * represents a bond.] TIFF0007645089000002.tif45167[In formula (c), * represents a bond.] [3] The resist composition according to [2], wherein the compound (I) having a quinone diazide sulfonyl group is at least one selected from the group consisting of a compound represented by formula (II), a compound represented by formula (III), a compound represented by formula (IV), and a compound represented by formula (V). TIFF0007645089000003.tif56167 [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 an oxygen atom, a carbonyl group or -NR d1 - may be replaced. R d1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 15 ~R 30 each independently represents a hydrogen atom, a hydroxy group, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). R 11 ~R 30 At least one of the formulas (a), (b), and (c) is a group represented by the formula (a), (b), or (c). TIFF0007645089000004.tif51168 [In formula (III), R 31 ~R 39 R each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). 31 ~R 39 At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c). P 1 ~P 5 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms is preferably an oxygen atom, a carbonyl group, or -NR d2 - may be replaced by P 1 and P 2 may be bonded to each other to form a ring together with the two carbon atoms to which they are attached. 4 and P 5 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. R d2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.] TIFF0007645089000005.tif30168 [In formula (IV), R 40 ~R 53 R each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). 40 ~R 53 At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c). n a represents an integer of 1 to 5. a If is an integer equal to or greater than 2, multiple R 49 ~R 52 may be the same or different.] TIFF0007645089000006.tif51168[In formula (V), R f1 , R f2 and R g1 ~Rg8 R each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). f1 , R f2 and R g1 ~R g8 At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c). P 6 represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The aromatic hydrocarbon group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms. P 7 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms is preferably an oxygen atom, a carbonyl group, or -NR d3 - may be replaced by P 6 and P 7 may be bonded to each other to form a ring. n v represents 1 or 2. R d3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.] [4] The resist composition according to any one of [1] to [3], wherein the resin (A1) containing a structural unit having an acid labile group is a resin containing a structural unit having a group represented by formula (10) or a group represented by formula (20). TIFF0007645089000007.tif22168[In formula (10), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.] TIFF0007645089000008.tif25168[In formula (20), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocycle having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.] [5] The resist composition according to any one of [1] to [4], wherein the resin (A1) containing a structural unit having an acid labile group is a resin containing a structural unit represented by formula (a1-1) or a structural unit represented by formula (a1-2). TIFF0007645089000009.tif53165[In formula (a1-1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R a4 represents a hydrogen atom or a methyl group. TIFF0007645089000010.tif50165[In formula (a1-2), R a1’ and R a2’each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocycle having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. R a5 represents a hydrogen atom or a methyl group. R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, a plurality of R a6 may be the same or different.] [6] The resist composition according to any one of [1] to [4], wherein the resin (A1) containing a structural unit having an acid labile group is a resin containing a structural unit represented by formula (a3A) or a structural unit represented by formula (a3B). TIFF0007645089000011.tif40165[In formula (a3A), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3 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 hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.] TIFF0007645089000012.tif37165[In formula (a3B), R a1’ and R a2’each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.] [7] The resist composition according to any one of [1] to [6], wherein the alkali-soluble resin (A2) is a resin that contains a structural unit having a carboxy group or a hydroxy group, but does not contain a structural unit having an acid labile group. [8] The resist composition according to any one of [1] to [7], further comprising a quencher (C). [9] A method for producing a resist pattern, comprising the steps of: (1) A step of applying the resist composition according to any one of the items [1] to [8] onto a metal surface of a substrate having a metal surface; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; and (4) A step of developing the composition layer after exposure A manufacturing method comprising:

[10] A method for manufacturing a plated object, comprising the steps of: (1) A step of applying the resist composition according to any one of the items [1] to [8] onto a metal surface of a substrate having a metal surface; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) developing the composition layer after exposure; (5) forming a plating object using the obtained resist pattern as a mold; and (6) Step of removing the resist pattern A manufacturing method comprising: Effect of the Invention

[0006] By using the resist composition of the present invention, a resist pattern can be formed with high precision, and further, the resist pattern can be used to form a plated object with high precision. [Brief description of the drawings]

[0007] [Figure 1] 1 is a diagram showing a schematic representation of a maximum value a and a minimum value b of a line width in a line and space pattern of a resist pattern. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In this specification, unless otherwise specified, in the explanation of the structural formula of a compound, "aliphatic hydrocarbon group" means a straight-chain or branched aliphatic hydrocarbon group, "alicyclic hydrocarbon group" means a group in which hydrogen atoms corresponding in number to the valence are removed from an alicyclic hydrocarbon ring. "Aromatic hydrocarbon group" also includes groups in which a hydrocarbon group is bonded to an aromatic ring. When stereoisomers exist, all stereoisomers are included. In this specification, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid", and "(meth)acrylate" means "at least one of acrylate and methacrylate". In the groups described herein, those which can have both a straight-chain structure and a branched structure are interpreted as including both. In this specification, the term "solids content of a resist composition" refers to the sum of the components excluding the solvent (E), which will be described later, from the total amount of the resist composition.

[0009] 1. Resist composition The resist composition of the present invention contains a compound having a quinonediazidesulfonyl group (hereinafter may be referred to as "compound (I)"), a resin including a structural unit having an acid labile group (hereinafter may be referred to as "resin (A1)"), an alkali-soluble resin (hereinafter may be referred to as "resin (A2)"), and an acid generator (hereinafter may be referred to as "acid generator (B)"). The resist composition of the present invention preferably contains, in addition to the compound (I), the resin (A1), the resin (A2) and the acid generator (B), a quencher (hereinafter, sometimes referred to as “quencher (C)”) and / or a solvent (hereinafter, sometimes referred to as “solvent (E)”).

[0010] <Compound (I)> The compound (I) of the present invention is a compound having a quinone diazide sulfonyl group. In the unexposed area, compound (I) interacts with the hydrophilic groups of resin (A2) to inhibit the dissolution of resin (A2) in a developer (alkaline aqueous solution), while in the exposed area, compound (I) decomposes the quinone diazide groups to generate carboxyl groups, generating carboxylic acids and promoting the dissolution of resin (A2) in a developer (alkaline aqueous solution). In the unexposed area, compound (I) crosslinks resin (A2) in the presence of developer (alkaline aqueous solution), making it resistant to developer (alkaline aqueous solution) and plating solution, thereby improving the accuracy of the plated object.

[0011] Compound (I) is not particularly limited as long as it has one or more quinone diazide sulfonyl groups in the molecule. The molecular weight of the compound obtained by replacing all quinone diazide sulfonyl 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.

[0012] The compound having a quinone diazide sulfonyl group includes a compound having a naphthoquinone diazide sulfonyl group, a compound having a benzoquinone diazide sulfonyl group, a compound having an anthraquinone diazide sulfonyl group, etc., and is preferably a compound having a naphthoquinone diazide sulfonyl group or a compound having a benzoquinone diazide sulfonyl group. The compound having a naphthoquinone diazide sulfonyl group is preferably a compound having a 1,2-naphthoquinone diazide sulfonyl group, more preferably a compound having a group represented by formula (a) or a group represented by formula (b), and even more preferably a compound having a group represented by formula (a). The compound having a benzoquinone diazide sulfonyl group is preferably a compound having a 1,2-benzoquinone diazide sulfonyl group, and more preferably a compound having a group represented by formula (c). TIFF0007645089000013.tif48167[In formula (a) and formula (b), * represents a bond.] TIFF0007645089000014.tif44167[In formula (c), * represents a bond.]

[0013] The compound obtained by replacing all quinone diazide sulfonyl groups present in the molecule of a compound having a quinone diazide sulfonyl group with hydrogen atoms is preferably an aromatic compound having a phenolic hydroxyl group. The compound having a quinone diazide sulfonyl group is preferably a compound obtained by converting an aromatic compound having a phenolic hydroxyl group into a quinone diazide sulfonate. The compound having a quinone diazide sulfonyl group is more preferably at least one selected from the group consisting of a compound represented by formula (II) (hereinafter sometimes referred to as "compound (II)"), a compound represented by formula (III) (hereinafter sometimes referred to as "compound (III)"), a compound represented by formula (IV) (hereinafter sometimes referred to as "compound (IV)"), and a compound represented by formula (V) (hereinafter sometimes referred to as "compound (V)"). TIFF0007645089000015.tif56167 [In formula (II), R11 ~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 an oxygen atom, a carbonyl group or -NR d1 - may be replaced. R d1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 15 ~R 30 each independently represents a hydrogen atom, a hydroxy group, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). R 11 ~R 30 At least one of the formulas (a), (b), and (c) is a group represented by the formula (a), (b), or (c). TIFF0007645089000016.tif53170[In formula (III), R 31 ~R 39 R each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). 31 ~R 39 At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c). P 1 ~P 5 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms is preferably an oxygen atom, a carbonyl group, or -NR d2 - may be replaced by P 1 and P 2 may be bonded to each other to form a ring together with the two carbon atoms to which they are attached. 4 and P 5 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. R d2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.] TIFF0007645089000017.tif29169 [In formula (IV), R 40 ~R 53 R each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). 40 ~R 53 At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c). n a represents an integer of 1 to 5. a If is an integer equal to or greater than 2, multiple R 49 ~R 52 may be the same or different.] TIFF0007645089000018.tif52169 [In formula (V), R f1 , R f2 and R g1 ~R g8 R each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). f1 , R f2 and R g1 ~R g8 At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c). P 6 represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The aromatic hydrocarbon group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms. P 7 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms is preferably an oxygen atom, a carbonyl group, or -NR d3 - may be replaced by P 6 and P 7 may be bonded to each other to form a ring. n vrepresents 1 or 2. R d3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0014] Examples of the hydrocarbon group having 1 to 18 carbon atoms include chain hydrocarbon groups having 1 to 18 carbon atoms (including linear or branched saturated chain hydrocarbon groups (alkyl groups) having 1 to 18 carbon atoms, and linear or branched unsaturated chain hydrocarbon groups having 2 to 18 carbon atoms (alkenyl groups, alkynyl groups), etc.), monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms (including saturated alicyclic hydrocarbon groups having 3 to 18 carbon atoms, unsaturated alicyclic hydrocarbon groups having 3 to 18 carbon atoms, etc.), and aromatic hydrocarbon groups having 6 to 18 carbon atoms, and may be a combination of two or more of these groups. The alkyl group having 1 to 18 carbon atoms may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t- or sec-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, etc. Among these, a linear alkyl group is preferable. The alkenyl group having 2 to 18 carbon atoms may be either linear or branched, and examples thereof include an ethenyl group, a propenyl group, an isopropenyl group, a methylpropenyl group, a methylbutenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, and a nonenyl group. The alkynyl group having 2 to 18 carbon atoms may be either linear or branched, and examples thereof include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. The chain hydrocarbon group having 1 to 18 carbon atoms preferably has 1 to 16 carbon atoms, more preferably has 1 to 12 carbon atoms, even more preferably has 1 to 8 carbon atoms, still more preferably has 1 to 6 carbon atoms, and even more preferably has 1 to 4 carbon atoms. Examples of the monocyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic saturated alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, and monocyclic unsaturated alicyclic hydrocarbon groups such as cyclopropenyl group and cyclobutenyl group. Examples of the polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms include polycyclic saturated alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, and norbornyl group. The alicyclic hydrocarbon group having 3 to 18 carbon atoms preferably has 3 to 16 carbon atoms, more preferably has 3 to 12 carbon atoms, and further preferably has 3 to 10 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, etc. The aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, and more preferably has 6 to 10 carbon atoms.

[0015] As the alkyl group having 1 to 6 carbon atoms, a group corresponding to the alkyl group having 1 to 6 carbon atoms can be selected from the above-mentioned alkyl groups having 1 to 18 carbon atoms.

[0016] P 1 and P 2 are bonded together to form a ring together with the two carbon atoms to which they are attached, and P 4 and P 5 Examples of the rings formed by bonding to each other together with the carbon atoms to which they are bonded include monocyclic or polycyclic alicyclic hydrocarbon rings having 3 to 18 carbon atoms. Examples of these rings include cycloalkane rings such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; a decahydronaphthalene ring, an adamantane ring, and a norbornane ring. The alicyclic hydrocarbon ring having 3 to 18 carbon atoms preferably has 3 to 16 carbon atoms, more preferably has 3 to 12 carbon atoms, and further preferably has 3 to 10 carbon atoms.

[0017] P 7In the above formula, examples of the substituent on the hydrocarbon group having 1 to 18 carbon atoms include a halogen atom, a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, and an acyloxy group having 2 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group having 2 to 4 carbon atoms include an acetyl group, a propionyl group, and a butyryl group. Examples of the acyloxy group having 2 to 4 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group.

[0018] Specific examples of compound (II) include compounds represented by formulas (II-1) to (II-3). TIFF0007645089000019.tif56169, where R s2 R each independently represents a group represented by the above formula (a), a group represented by the formula (b), a group represented by the formula (c), or a hydroxy group. s2 At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c).

[0019] Specific examples of compound (III) include compounds represented by formulas (III-1-1) to (III-3-8). TIFF0007645089000020.tif46170

[0020] TIFF0007645089000021.tif100170

[0021] TIFF0007645089000022.tif99169, where R t1 R each independently represents a group represented by the above formula (a), a group represented by the formula (b), a group represented by the formula (c), or a hydroxy group.t1 At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c).

[0022] Specific examples of compound (IV) include compounds represented by formulas (IV-1-1) to (IV-5-2). TIFF0007645089000023.tif121169

[0023] TIFF0007645089000024.tif68169, where R t1 , R t3 , R t6 , R t7 , R t9 , R t10 and R t13 R each independently represents a group represented by the above formula (a), a group represented by the formula (b), a group represented by the formula (c), or a hydroxy group. t1 , R t3 , R t6 , R t7 , R t9 , R t10 and R t13 At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c).

[0024] Specific examples of compound (V) include compounds represented by formulas (V-1-1) to (V-3-1). TIFF0007645089000025.tif119169, where R v R each independently represents a group represented by the above formula (a), a group represented by the formula (b), a group represented by the formula (c), or a hydroxy group. v At least one of the above is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c).

[0025] Compound (I) can be produced, for example, according to the disclosures in JP-A-2-84650, JP-A-3-185447, JP-A-3-191351, JP-A-5-323597, JP-A-8-245461, JP-A-9-110762 and the like. Compound (I) can be produced, for example, by reacting an aromatic compound having a phenolic hydroxyl group (for example, a compound in which all of the quinone diazide sulfonyl groups in the molecule of the above-mentioned compounds (II) to (V) are replaced with hydrogen atoms, etc.) with a quinone diazide sulfonyl halide (for example, a quinone diazide sulfonyl chloride such as 1,2-naphthoquinone diazide sulfonyl chloride or 1,2-benzoquinone diazide sulfonyl chloride, a quinone diazide sulfonyl bromide such as 1,2-naphthoquinone diazide sulfonyl bromide or 1,2-benzoquinone diazide sulfonyl bromide, etc.) in the presence of a weak alkali, thereby completely or partially esterifying the compound. Aromatic compounds having a phenolic hydroxyl group are readily available on the market, and can be produced by known methods.

[0026] The content of compound (I) in the solid content of the resist composition is preferably 0.05 mass % or more and 25 mass % or less, more preferably 0.1 mass % or more and 20 mass % or less, even more preferably 0.5 mass % or more and 15 mass % or less, and even more preferably 1 mass % or more and 10 mass % or less. The content of compound (I) in the resist composition can be measured by known analytical means such as liquid chromatography or gas chromatography. As compound (I), compound (III) and compound (IV) are preferred, and compound (III) is more preferred.

[0027] <Resin (A1)> The resin (A1) contains a structural unit having an acid labile group (hereinafter, may be referred to as "structural unit (a1)"). The acid labile group refers to a group containing a group (sometimes called a leaving group) that can be eliminated by contact with an acid. When the resin (A1) comes into contact with an acid, the leaving group is eliminated from the acid labile group, forming a hydrophilic group (e.g., a hydroxy group (phenolic hydroxyl group, etc.) or a carboxy group). The solubility of the resin (A1) in an aqueous alkaline solution increases upon contact with an acid. In other words, it is preferable that the resin (A1) is insoluble or poorly soluble in an aqueous alkaline solution before contact with an acid, and becomes soluble in an aqueous alkaline solution after contact with an acid. Resin (A1) may contain, in addition to a structural unit having an acid labile group, structural units known in the art, such as a structural unit not having an acid labile group (hereinafter sometimes referred to as "structural unit (a2)"), so long as it has the above-mentioned properties.

[0028] Examples of the acid that eliminates the leaving group contained in the acid labile group include carboxylic acids, sulfonic acids, etc. In the composition of the present invention, examples of the acid that eliminates the leaving group include carboxylic acids and sulfonic acids that are generated by irradiating (exposing) the acid generator (B) described below with light in the photolithography process.

[0029] Examples of the acid labile group include a group represented by formula (10) and a group represented by formula (20). TIFF0007645089000026.tif24169 [In formula (10), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.]

[0030] TIFF0007645089000027.tif27170[In formula (20), R a1’and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocycle having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.]

[0031] R represented by equation (10) a1 ~R a3 The alkyl group having 1 to 8 carbon atoms may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. a1 ~R a3 The alkyl group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. R a1 ~R a3 The alicyclic hydrocarbon group having 3 to 20 carbon atoms may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond):

[0032] TIFF0007645089000028.tif25170R a1 ~R a3 The alicyclic hydrocarbon group having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably has 3 to 16 carbon atoms, and further preferably has 3 to 12 carbon atoms.

[0033] R a1 and Ra2 When they are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, -C(R a1 )(R a2 )(R a3 ) include, for example, the following groups. The ring having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and further preferably 3 to 12 carbon atoms. * represents a bond to -O-. TIFF0007645089000029.tif36170R a1 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a2 Combined with them is preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a2 and more preferably form a ring having 3 to 12 carbon atoms together with the carbon atom to which they are attached. R a2 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a1 and R are preferably bonded to each other to form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and are preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a1 and more preferably form a ring having 3 to 12 carbon atoms together with the carbon atom to which they are attached. R a3 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms. ma is preferably 0. na is preferably 1.

[0034] Examples of the group represented by formula (10) include R a1 , R a2 and R a3 are each independently an alkyl group having 1 to 3 carbon atoms (preferably a tert-butoxycarbonyl group); R a1and R a2 are each independently an alkyl group having 1 to 3 carbon atoms, and R a3 is a cyclopentyl group or a cyclohexyl group; R a1 and R a2 are bonded to each other to form a cyclopentane or cyclohexane ring together with the carbon atoms to which they are attached, and R a3 is an alkyl group having 1 to 3 carbon atoms. Specific examples of the group represented by formula (10) include the following groups. TIFF0007645089000030.tif90170

[0035] R of the group represented by formula (20) a1’ ~R a3’ Examples of the hydrocarbon group having 1 to 20 carbon atoms include chain hydrocarbon groups having 1 to 20 carbon atoms (such as alkyl groups, alkenyl groups, and alkynyl groups), alicyclic hydrocarbon groups having 3 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, and groups having 4 to 20 carbon atoms that are combinations of these. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl group. Examples of the alkenyl group having 2 to 20 carbon atoms include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, and a nonenyl group. Examples of the alkynyl group having 2 to 20 carbon atoms include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. The chain hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 18 carbon atoms, more preferably has 1 to 16 carbon atoms, even more preferably has 1 to 12 carbon atoms, still more preferably has 1 to 8 carbon atoms, and even more preferably has 1 to 6 carbon atoms. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group. The alicyclic hydrocarbon group having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably has 3 to 16 carbon atoms, and further preferably has 3 to 12 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may further have a substituent, and examples of the substituent include an aryloxy group having 6 to 10 carbon atoms. The aromatic hydrocarbon group having 6 to 20 carbon atoms preferably has 6 to 18 carbon atoms, more preferably has 6 to 14 carbon atoms, and further preferably has 6 to 10 carbon atoms. Among the groups having 4 to 20 carbon atoms in which the above groups are combined, examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined (groups having 4 to 20 carbon atoms) include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, an isobornyl group, a 2-alkyladamantan-2-yl group, and a 1-(adamantan-1-yl)alkane-1-yl group. Examples of the group in which an alkyl group and an aromatic hydrocarbon group are combined (groups having 7 to 20 carbon atoms) include an aralkyl group and an aromatic hydrocarbon group having an alkyl group. Specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of groups in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined (groups having 9 to 20 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group, and specific examples thereof include a p-cyclohexylphenyl group, a p-adamantylphenyl group, and a phenylcyclohexyl group. Ra2’ and R a3’ When they are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, -C(R a1’ )(R a2’ )-XR a3’ Examples of the heterocyclic ring include the following groups. The heterocyclic ring having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably has 3 to 16 carbon atoms, and further preferably has 3 to 12 carbon atoms. * represents a bond. TIFF0007645089000031.tif21170R a1’ is preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom. R a2' is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or R a3’ and X are preferably bonded to form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded and X, and R a3’ and more preferably bonded to each other to form a heterocycle having 3 to 12 carbon atoms together with the carbon atom to which they are bonded and X, still more preferably a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a methyl group or an ethyl group. R a3’ is a hydrocarbon group having 1 to 18 carbon atoms, or R a2' and R are preferably bonded to form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded and X, and R is preferably a hydrocarbon group having 1 to 12 carbon atoms. a2’ and more preferably, they are bonded to the carbon atom to which they are bonded and to X to form a heterocycle having 3 to 12 carbon atoms. Examples of the hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination of these groups having 4 to 18 carbon atoms. These groups can be arbitrarily selected from those listed above. X is preferably an oxygen atom. na' is preferably 0.

[0036] Specific examples of the group represented by formula (20) include the following groups. TIFF0007645089000032.tif100170

[0037] Specific examples of the group represented by formula (10) include a group represented by formula (1) and a group represented by formula (1'). TIFF0007645089000033.tif47170[In formula (1) and formula (1'), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. * represents a bond.] Specific examples of the group represented by formula (20) include a group represented by formula (2) and a group represented by formula (2'). TIFF0007645089000034.tif53170[In formula (2) and formula (2'), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocycle having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. * represents a bond.]

[0038] <Structural Unit (a1) Having an Acid Labile Group> The resin (A1) containing the structural unit (a1) having an acid labile group can be produced, for example, by polymerizing a monomer component containing an ethylenically unsaturated compound that leads to the structural unit (a1). The acid labile group contained in the structural unit (a1) is preferably a group represented by the above formula (10) and / or a group represented by the above formula (20). The resin (A1) may have only one type of structural unit (a1), or may have a plurality of types.

[0039] As the structural unit (a1), a structural unit represented by formula (a1-1) (hereinafter sometimes referred to as "structural unit (a1-1)") and a structural unit represented by formula (a1-2) (hereinafter sometimes referred to as "structural unit (a1-2)") are preferred.

[0040] TIFF0007645089000035.tif49170 [In formula (a1-1) and formula (a1-2), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocycle having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. R a4 and R a5each independently represents a hydrogen atom or a methyl group. R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, a plurality of R a6 may be the same or different.]

[0041] In formula (a1-1), R a4 is preferably a methyl group. R a1 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a2 and R are preferably bonded to each other to form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and are preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a2 and more preferably form a ring having 3 to 12 carbon atoms together with the carbon atom to which they are attached. R a2 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a1 and R are preferably bonded to each other to form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and are preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a1 and more preferably form a ring having 3 to 12 carbon atoms together with the carbon atom to which they are attached. R a3 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms. In formula (a1-2), R a5 is preferably a hydrogen atom. R a1’ is preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom. R a2'is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or R a3’ and R form a heterocycle having 3 to 18 carbon atoms together with the carbon atom and oxygen atom to which they are bonded, and R is preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. a3’ and more preferably bonded to form a heterocycle having 3 to 12 carbon atoms together with the carbon atom and oxygen atom to which they are bonded, further preferably a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a methyl group or an ethyl group. R a3’ is a hydrocarbon group having 1 to 18 carbon atoms, or R a2' and R form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom and oxygen atom to which they are bonded, and preferably a hydrocarbon group having 1 to 12 carbon atoms or R a2’ and more preferably bonded to form a heterocycle having 3 to 12 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The above-mentioned hydrocarbon group includes an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group having 4 to 18 carbon atoms which is a combination of these. These groups can be arbitrarily selected from those listed above. The above-mentioned hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The above-mentioned alkyl group and the above-mentioned alicyclic hydrocarbon group are preferably unsubstituted. When the above-mentioned aromatic hydrocarbon group has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms. R a6 Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. R a6Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, etc. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. R a6 is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, even more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group. m is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0. In formula (a1-2), -OC(R a1’ )(R a2’ )-OR a3’ is preferably bonded to the 3- or 4-position of the benzene ring (m- or p-position with respect to the main chain bonded to the benzene ring), and more preferably bonded to the 4-position (p-position) of the benzene ring.

[0042] Examples of the structural unit (a1-1) include structural units represented by any of formulas (a1-1-1) to (a1-1-17). TIFF0007645089000036.tif40170

[0043] TIFF0007645089000037.tif71170

[0044] Examples of the structural unit (a1-2) include structural units represented by any of formulas (a1-2-1) to (a1-2-14). TIFF0007645089000038.tif126169

[0045] In the above structural unit, R a5A specific example of the structural unit (a1-2) is a structural unit in which a hydrogen atom corresponding to the following is replaced with a methyl group. The structural unit (a1-2) is preferably a structural unit represented by the formula (a1-2-2), (a1-2-3), (a1-2-4), (a1-2-9), or (a1-2-14), and more preferably a structural unit represented by the formula (a1-2-2), (a1-2-3), (a1-2-4), or (a1-2-9).

[0046] The resin (A1) containing a structural unit having an acid labile group is preferably a resin containing a structural unit (a1-2). When the resin (A1) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content of these structural units is preferably 3 to 80 mol %, more preferably 5 to 60 mol %, even more preferably 10 to 55 mol %, still more preferably 15 to 50 mol %, and even more preferably 20 to 45 mol %, based on all structural units in the resin (A1).

[0047] <Structural Unit (a2) Having No Acid Labile Group> Resin (A1) may contain structural unit (a1) having an acid labile group and structural unit (a2) not having an acid labile group as required. Resin (A1) containing structural unit (a1) and structural unit (a2) can be produced, for example, by polymerizing a monomer component containing an ethylenically unsaturated compound leading to structural unit (a1) and an ethylenically unsaturated compound leading to structural unit (a2). As the acid labile group contained in structural unit (a1), a group represented by the above formula (10) and / or a group represented by formula (20) is preferred. The resin (A1) may contain only one type of structural unit (a2) that does not have an acid labile group, or may contain multiple types.

[0048] Examples of the structural unit (a2) include structural units represented by any one of formulas (a2-1) to (a2-3) (hereinafter, sometimes referred to as "structural unit (a2-1)" depending on the formula number). TIFF0007645089000039.tif56169 [In formula (a2-1), formula (a2-2) and formula (a2-3), R a7 , R a8 and R a9 each independently represents a hydrogen atom or a methyl group. R a10 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m' represents an integer of 0 to 4. When m' is 2 or more, multiple R a10 may be the same or different from each other. R a11 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, except for groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. R a12 represents an alkyl group having 1 to 6 carbon atoms, except for groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. L a1 represents an alkanediyl group having 2 to 6 carbon atoms, except for groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. n represents an integer of 1 to 30. When n is 2 or more, multiple L a1 may be the same or different.]

[0049] R a10 Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. The alkyl group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms. R a10 Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, etc. The alkoxy group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms. R a11Examples of the hydrocarbon group having 1 to 12 carbon atoms include chain hydrocarbon groups having 1 to 12 carbon atoms (such as alkyl groups, alkenyl groups, and alkynyl groups), alicyclic hydrocarbon groups having 3 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 12 carbon atoms, and groups having 4 to 12 carbon atoms formed by combining these. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Examples of the alkenyl group having 2 to 12 carbon atoms include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, and a nonenyl group. Examples of the alkynyl group having 2 to 12 carbon atoms include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. The chain hydrocarbon group having 1 to 12 carbon atoms preferably has 1 to 10 carbon atoms, more preferably has 1 to 8 carbon atoms, and further preferably has 1 to 6 carbon atoms. The alicyclic hydrocarbon group having 3 to 12 carbon atoms may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond): TIFF0007645089000040.tif24169The alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and more preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms. Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, etc. The aromatic hydrocarbon group having 6 to 12 carbon atoms preferably has 6 to 10 carbon atoms. Examples of groups having 4 to 12 carbon atoms formed by combining the above groups, such as groups combining an alkyl group with an alicyclic hydrocarbon group (groups having 4 to 12 carbon atoms), include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, and a norbornylethyl group. Examples of groups combining an alkyl group and an aromatic hydrocarbon group (groups having 7 to 12 carbon atoms) include aralkyl groups and aromatic hydrocarbon groups having an alkyl group. Specific examples include benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, and 2-methyl-6-ethylphenyl group. Examples of groups combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (groups having 9 to 12 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group, and specific examples thereof include a p-cyclohexylphenyl group and a phenylcyclohexyl group.

[0050] R a12 Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, etc. The alkyl group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0051] L a1The alkanediyl group having 2 to 6 carbon atoms may be either linear or branched, and examples thereof include an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a propane-1,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. The alkanediyl group having 2 to 6 carbon atoms preferably has 2 to 4 carbon atoms, and more preferably has 2 to 3 carbon atoms.

[0052] R a7 is preferably a hydrogen atom. R a8 and R a9 are preferably, independently of each other, a methyl group. R a10 is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and is further preferably, for example, a methyl group, an ethyl group, a methoxy group or an ethoxy group, and further more preferably a methyl group or a methoxy group. m' is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0. R a11 is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and even more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 3 to 8 carbon atoms, except for groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. L a1is preferably an alkanediyl group having 2 to 4 carbon atoms (for example, an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, or a butane-1,4-diyl group), more preferably an alkanediyl group having 2 to 3 carbon atoms (for example, an ethane-1,2-diyl group, a propane-1,3-diyl group, or a propane-1,2-diyl group), and further preferably an ethane-1,2-diyl group. 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. R a12 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms, except for groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom.

[0053] The structural unit (a2-1) is preferably a structural unit represented by formula (a2-1-1), formula (a2-1-2), formula (a2-1-3) or formula (a2-1-4). Monomers from which the structural unit (a2-1) is derived are described, for example, in JP-A-2010-204634.

[0054] TIFF0007645089000041.tif39170

[0055] Examples of monomers from which the structural unit (a2-2) is derived include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and hexyl (meth)acrylate; monocyclic (meth)acrylic acid esters such as (meth)acrylic acid cycloalkyl esters such as cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate; Polycyclic (meth)acrylic acid esters such as adamantyl (meth)acrylate and norbornyl (meth)acrylate; Examples of the aryl (meth)acrylate include aryl (meth)acrylate esters such as phenyl (meth)acrylate and benzyl (meth)acrylate.

[0056] Examples of monomers that lead to the structural unit (a2-3) include (meth)acrylic acid esters such as (poly)ethylene glycol monomethyl ether (meth)acrylates ((poly)alkylene glycol monoalkyl ether (meth)acrylates), such as ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, pentaethylene glycol monomethyl ether (meth)acrylate, hexaethylene glycol monomethyl ether (meth)acrylate, heptaethylene glycol monomethyl ether (meth)acrylate, nonaethylene glycol monomethyl ether (meth)acrylate, and octaethylene glycol monomethyl ether (meth)acrylate.

[0057] Furthermore, examples of monomers that derive the structural unit (a2) include carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; and styrenes such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 4-isopropoxystyrene.

[0058] The structural unit (a2) may be, for example, a structural unit represented by formula (a2-4). TIFF0007645089000042.tif51170[In formula (a2-4), Ra13 represents a hydrogen atom or a methyl group. R a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R a15 represents a hydrocarbon group having 1 to 12 carbon atoms, except for groups in which the carbon atom bonded to an oxygen atom is a tertiary carbon atom. A methylene group contained in the hydrocarbon group having 1 to 12 carbon atoms may be substituted with an oxygen atom or a carbonyl group, however, a methylene group bonded to an oxygen atom and a methylene group bonded to the methylene group are not substituted with an oxygen atom. m" represents an integer of 0 to 4. When m" is 2 or more, multiple R a14 may be the same or different from each other. m''' represents an integer from 0 to 4. When m''' is 2 or more, multiple R a15 may be the same or different from each other. However, the sum of m" and m''' is 5 or less.

[0059] R a15 The hydrocarbon group in R is a group in which the bond to the oxygen atom is not a tertiary carbon atom, that is, a group in which the bond carbon is bonded to one or more atoms other than carbon atoms, such as a hydrogen atom. a15 Examples of the hydrocarbon group in the formula include a methylene group bonded to an oxygen atom and a group in which the methylene group bonded to the methylene group is not substituted with an oxygen atom, that is, a group not containing an acetal structure. Therefore, the structural unit represented by the formula (a2-4) does not include the structural unit (a1-2).

[0060] R a14 As the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms, R a10 The same groups as those shown below can be mentioned. R a15 As the hydrocarbon group having 1 to 12 carbon atoms, R a11 The same groups as those shown below can be mentioned.

[0061] R a13 is preferably a hydrogen atom. R a14 is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and is further preferably, for example, a methyl group, an ethyl group, a methoxy group or an ethoxy group, and further more preferably a methyl group or a methoxy group. R a15 is preferably a hydrocarbon group having 1 to 10 carbon atoms, or a group in which a methylene group contained in the hydrocarbon group is replaced with an oxygen atom or a carbonyl group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group formed by combining these and having 6 to 10 carbon atoms, or a group in which a methylene group contained in these groups is replaced with an oxygen atom or a carbonyl group, and even more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, a phenyl group, or a group formed by combining these and having 6 to 10 carbon atoms, or a group in which the methylene group adjacent to the oxygen atom of these groups is replaced with a carbonyl group. m'' is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0. m''' is preferably 0 to 3, more preferably 0 to 2, and further preferably 0 or 1. However, the sum of m" and m''' must be 5 or less.

[0062] Examples of the structural unit (a2-4) include structural units represented by formulas (a2-4-1) to (a2-4-10). TIFF0007645089000043.tif93170

[0063] In the structural units represented by formulas (a2-4-1) to (a2-4-10), R a13 A specific example of the structural unit (a2-4) is a structural unit in which a hydrogen atom corresponding to the following is replaced with a methyl group.

[0064] When the resin (A1) contains the structural unit (a2-1), the structural unit (a2-2), the structural unit (a2-3), and the structural unit (a2-4), the total content of these is preferably 1 to 90 mol %, more preferably 1 to 85 mol %, even more preferably 5 to 80 mol %, and particularly preferably 5 to 75 mol %, based on all structural units in the resin (A1).

[0065] When the resin (A1) contains the structural unit (a2), the content ratio of the structural unit (a1) to the structural unit (a2) [structural unit (a1):structural unit (a2)] is preferably 10:90 to 80:20, more preferably 15:85 to 60:40, and even more preferably 15:85 to 45:55, on a molar basis.

[0066] The combination of structural units contained in the resin (A1) includes those represented by formulas (A1-1) to (A1-46). TIFF0007645089000044.tif255170

[0067] TIFF0007645089000045.tif235167

[0068] TIFF0007645089000046.tif84169

[0069] TIFF0007645089000047.tif126169

[0070] TIFF0007645089000048.tif252168

[0071] TIFF0007645089000049.tif239170

[0072] TIFF0007645089000050.tif238169

[0073] TIFF0007645089000051.tif168169In the above structural formula, R a5Specific examples of the structural units include structural units in which a hydrogen atom corresponding to each of the above-mentioned groups is replaced with a methyl group or a methyl group is replaced with a hydrogen atom. In addition, structural units having a hydrogen atom and a methyl group may be present in a single resin.

[0074] The resin (A1) is preferably a resin containing the structural unit (a1) and the structural unit (a2), and more preferably a resin containing the structural unit (a1-1) and / or the structural unit (a1-2) and the structural unit (a2).

[0075] Resin (A1) may be a resin obtained by reacting a resin containing at least one group selected from a carboxy group and a phenolic hydroxyl group in a side chain with a compound containing at least two vinyloxy groups in one molecule (hereinafter sometimes referred to as "resin (A1b)"). The resin (A1b) is preferably a resin obtained by reacting a resin containing a phenolic hydroxyl group with a compound containing two or more vinyloxy groups in one molecule. Such a resin can be obtained, for example, by reacting a resin containing the structural unit (a2-1) with a compound containing two or more vinyloxy groups in one molecule. In addition, the resin containing a phenolic hydroxyl group may be a novolak resin described below, which is reacted with the vinyloxy group-containing compound described above. Furthermore, the resin may be a resin obtained by mixing a resin containing the structural unit (a2-1) with a novolak resin and reacting the resulting resin mixture with the vinyloxy group-containing compound described above. In addition, a resin obtained by reacting a resin containing the structural unit (a2-1) with the vinyloxy group-containing compound described above and a resin obtained by reacting a novolak resin with the vinyloxy group-containing compound described above may be used in combination.

[0076] In the synthesis of the resin (A1b), the ratio of the amount of the compound containing at least two or more vinyloxy groups in one molecule to the amount of the carboxy group and the phenolic hydroxyl group [carboxy group and phenolic hydroxyl group:vinyloxy group] used is preferably 60:40 to 99:1, and more preferably 70:30 to 95:5, on a molar basis.

[0077] Examples of the resin (A1b) include the resins described in JP-A-2008-134515 and JP-A-2008-46594.

[0078] Examples of the compound having at least two vinyloxy groups in one molecule include 1,4-cyclohexanedimethanol divinyl ether and ethylene glycol divinyl ether.

[0079] When the resin (A1b) is a resin obtained by mixing a resin containing the structural unit (a2-1) with a novolak resin and reacting the resulting resin mixture with a vinyloxy group-containing compound, the content of the novolak resin is 30 to 70 mass % based on the total amount of the resin (A1b).

[0080] The resin (A1) can be produced by polymerizing a monomer component containing an ethylenically unsaturated compound corresponding to the structural unit (a1) described above and, if necessary, an ethylenically unsaturated compound corresponding to the structural unit (a2) by a known polymerization method (e.g., a radical polymerization method). The weight average molecular weight of the resin (A1) is preferably 3,000 or more, more preferably 4,000 or more, and preferably 600,000 or less, more preferably 500,000 or less. The weight average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. The detailed analysis conditions are described in the examples of the present application.

[0081] The content of resin (A1) relative to the total amount of resins contained in the resist composition is preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 30 mass% or more, and is preferably 95 mass% or less, more preferably 85 mass% or less, and even more preferably 70 mass% or less.

[0082] Resin (A1) may be a novolak resin (hereinafter sometimes referred to as "resin (A1c)") into which an acid labile group containing a group that can be cleaved by the action of an acid has been introduced. This resin refers to a novolak resin described below in which some or all of the phenolic hydroxyl groups have been protected with acid labile groups containing a group that can be cleaved by the action of an acid, or a novolak resin described below in which some or all of the phenolic hydroxyl groups have been substituted with acid labile groups containing a group that can be cleaved by the action of an acid. This resin is also called a novolak resin having an acid labile group (a group containing a group that can be cleaved by contact with an acid). Novolak resins are resins obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as a "phenol compound") and an aldehyde in the presence of an acid catalyst. Examples of the phenol compound include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,5-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, 2-methylresorcinol, 4-methylresorcinol, and 5-methylresorcinol. , 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxyphenol, 2-methoxyresorcinol, hydroquinone, 4-tert-butylcatechol, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid esters, α-naphthol, β-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, polyhydroxytriphenylmethane compounds obtained by condensation of xylenol and hydroxybenzaldehyde, etc. These may be used alone or in combination of two or more. Among these, preferred phenol compounds include, for example, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol.

[0083] Examples of the aldehyde include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acrolein, and crotonaldehyde; alicyclic aldehydes such as cyclohexane aldehyde, cyclopentanaldehyde, and furyl acrolein; aromatic aldehydes such as furfural, benzaldehyde, o-, m-, or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4-, or 3,5-dimethylbenzaldehyde, o-, m-, or p-hydroxybenzaldehyde, and o-, m-, or p-nitrobenzaldehyde; and aromatic aliphatic aldehydes such as phenylacetaldehyde and cinnamic aldehyde. These may be used alone or in combination of two or more. Among these, formaldehyde is preferred because it is easily available industrially.

[0084] Examples of catalysts for addition condensation include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid, and phosphoric acid, organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid, and p-toluenesulfonic acid, and divalent metal salts such as zinc acetate, zinc chloride, and magnesium acetate. These may be used alone or in combination of two or more. The amount of catalyst used is usually 0.01 to 1 mole per mole of aldehyde.

[0085] The condensation reaction can be carried out according to a conventional method. For example, it can be carried out at a temperature in the range of 60 to 150°C for about 2 to 30 hours. The condensation reaction can be carried out in the presence of a solvent. Examples of the solvent include ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, and acetone. After the reaction is completed, for example, a water-insoluble solvent can be added to the reaction mixture as necessary, the reaction mixture can be washed with water, and then concentrated to extract the novolac resin. After the reaction is completed, a basic compound can be added to neutralize the acid catalyst, and the neutralized salt can be removed by washing with water.

[0086] The weight average molecular weight of the novolak resin is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, still more preferably 9,000 or less, and even more preferably 8,000 or less. In the present specification, the weight average molecular weight is determined by gel permeation chromatography analysis, converted into a standard polystyrene standard. Detailed analysis conditions for this analysis are described in the Examples of the present application.

[0087] The acid labile groups introduced into the novolak resin are not particularly limited as long as they contain a group that can be cleaved by the action of an acid, and examples of the acid labile groups include those known in the art. The acid labile groups are introduced into some or all of the phenolic hydroxyl groups in the novolak resin obtained by condensation as described above.

[0088] Examples of the acid labile group introduced into the phenolic hydroxyl group of the novolac resin include the group represented by the above formula (10) or the group represented by the formula (20). Preferred is the group represented by the formula (1') or the group represented by the formula (2). Specific examples of the acid labile group include a tert-butoxycarbonyloxy group, a 1-methylcyclopentan-1-yloxycarbonyloxy group, a 1-(cyclopentan-1-yl)-1-methylalkoxycarbonyloxy group, a butyloxyethoxy group, an ethoxypropyloxy group, an ethoxybutyloxy group, a tetrahydro-2-pyranyloxy group, a tetrahydro-2-furyloxy group, a methoxyethoxy group, a 1-ethoxyethoxy group, a propyl ...butyloxyethoxy group, an ethoxypropyloxy group, a butyloxyethoxy group, an ethoxypropyloxy group, a butyloxyethoxy group, an ethoxypropyloxy group, a butyloxyethoxy group, an ethoxypropyloxy group, a butyloxyethoxy group, an ethoxypropyloxy group, a butyloxyethoxy group, an ethoxypropyloxy group, a butyloxyethoxy group, an ethoxypropyloxy group, a butyloxyethoxy group, an ethoxypropyloxy group, a butyloxyeth Examples of such groups include an aryloxyethoxy group, a cyclohexyloxyethoxy group, a 1-(2-methylpropoxy)ethoxy group, a 1-(2-methoxyethoxy)ethoxy group, a 1-(2-acetoxyethoxy)ethoxy group, a 1-[2-(1-adamantyloxy)ethoxy]ethoxy group, a 1-[2-(1-adamantanecarbonyloxy)ethoxy]ethoxy group, a 3-oxocyclohexyloxy group, and a 4-methyltetrahydro-2-pyron-4-yloxy group. Among these, at least one selected from the group consisting of an ethoxyethoxy group, an ethoxypropyloxy group, an ethoxybutyloxy group, an isopropyloxyethoxy group, a cyclohexyloxyethoxy group, and a 1-(2-methylpropoxy)ethoxy group is preferred, at least one selected from the group consisting of an ethoxyethoxy group, an isopropyloxyethoxy group, and a cyclohexyloxyethoxy group is more preferred, and a 1-ethoxyethoxy group is even more preferred.

[0089] An example of the novolak resin (A1c) having an acid labile group is a resin containing a structural unit represented by formula (a3A) (hereinafter sometimes referred to as "structural unit (a3A)") or a structural unit represented by formula (a3B) (hereinafter sometimes referred to as "structural unit (a3B)"). TIFF0007645089000052.tif40169[In formula (a3A), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3R represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.] TIFF0007645089000053.tif37169 [In formula (a3B), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms. a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.]

[0090] R ab Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group. R ab Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, etc. 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. R abis preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, even more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group. p is preferably 0 to 2, and more preferably 0 or 1.

[0091] Examples of the combination of structural units contained in the novolak resin (A1c) having an acid labile group include those represented by formulae (A1c-1) to (A1c-12). TIFF0007645089000054.tif197169

[0092] The introduction ratio (introduction rate) of the acid labile group is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, based on the phenolic hydroxyl group of the novolak resin of the resin (A1c). Also, it is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. Furthermore, there is an optimal introduction rate depending on the acid labile group. When the resin (A1) has an acid labile group (2), the introduction ratio of the acid labile group (2) is preferably 20 mol % or more, more preferably 30 mol % or more, based on the above-mentioned phenolic hydroxyl group. When the resin (A1) has an ethoxyethoxy group as the acid labile group, it is more preferably 30 to 60 mol %, when it has a propyloxyethoxy group, it is more preferably 20 to 60 mol %, and when it has a cyclohexyloxyethoxy group, it is more preferably 20 to 60 mol %. By setting it in this range, it is possible to effectively ensure the resolution, remaining film rate, and heat resistance after pattern formation with a resist composition using this resin. The introduction ratio of the acid labile group is, for example, 1 It can be measured by H-NMR.

[0093] The method of introducing an acid labile group into a phenolic hydroxyl group of a novolac resin may be a method known in the art. For example, when an ethoxyethoxy group is introduced as an acid labile group, a method of adding a predetermined amount of ethyl vinyl ether to a novolac resin in the presence of an acid catalyst at room temperature, reacting for a predetermined time in the presence of an acid catalyst, and then adding diethyl ether and washing with water may be used.

[0094] The weight average molecular weight of the resin (A1c) is preferably 3,000 or more, more preferably 4,000 or more, and preferably 200,000 or less, more preferably 100,000 or less. The weight average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. The detailed analysis conditions are described in the examples of the present application.

[0095] The content of resin (A1c) relative to the total amount of resins contained in the resist composition is preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 30 mass% or more, and is preferably 95 mass% or less, more preferably 85 mass% or less, and even more preferably 70 mass% or less.

[0096] <Resin (A2)> Resin (A2) is preferably an alkali-soluble resin. An alkali-soluble resin is a resin that has an acidic group (sometimes called a hydrophilic group) and is soluble in an alkaline developer. Examples of the acidic group include a carboxy group, a sulfo group, and a hydroxy group (such as a phenolic hydroxy group). The alkali-soluble resin may be any known alkali-soluble resin in the resist field, such as a novolac resin, a resin containing the structural unit (a2-1) but not containing the structural unit (a1), such as a resin containing a structural unit derived from hydroxystyrene, a resin containing a structural unit derived from (meth)acrylic acid ester, and polyalkylene glycol. A novolac resin is preferred. The alkali-soluble resin is preferably free of acid labile groups. In other words, the alkali-soluble resin is preferably a resin containing a structural unit having an acidic group and not containing a structural unit having an acid labile group. The alkali-soluble resin is preferably one that does not change in solubility in an aqueous alkaline solution upon contact with an acid. The alkali-soluble resin may be used alone or in combination of two or more. In the resin (A2), the total content of structural units having an acidic group is preferably 3 to 100 mol%, more preferably 5 to 100 mol%, even more preferably 10 to 100 mol%, still more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%, still more preferably 60 to 100 mol%, particularly preferably 70 to 100 mol%, and particularly preferably 80 to 100 mol%, based on all structural units in the resin (A2). The resin (A2) may contain only one type of structural unit having an acidic group, or may contain a plurality of types.

[0097] The alkali-soluble resin may be, for example, a resin that has a residual film ratio of 0% to 90% when developed with an alkali developer under practical use conditions. The residual film ratio is preferably 0% to 85%, and more preferably 0% to 80%.

[0098] The remaining film ratio can be measured, for example, as follows. After dissolving the resin in an organic solvent, if necessary, filtration is performed using a filter, and then the solution is applied onto a substrate using a spin coater or the like, followed by heating to remove the organic solvent. The obtained organic film on the substrate is measured using a thickness meter, developed with a 2.38% by mass alkaline aqueous solution, and the thickness after development is measured again using a thickness meter. The remaining film ratio can be obtained by dividing the thickness after development by the thickness before development for the measured value thus obtained. The development conditions are actual use conditions. For example, the development temperature can be 5 to 60°C, and the development time can be 5 to 600 seconds. The alkaline developer can be various alkaline aqueous solutions used in this field, such as aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline).

[0099] The novolak resin is a resin obtained by condensing a phenol compound with an aldehyde in the presence of a catalyst, and can be selected from, for example, those described above as the resin (A1c). An example of the novolac resin is a resin containing a structural unit represented by formula (a4) (hereinafter, sometimes referred to as "structural unit (a4)"). TIFF0007645089000055.tif29169 [In formula (a4), R ac represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p1 represents 0, 1, 2, or 3. When p1 is 2 or 3, R ac may be the same or different. q1 represents 1, 2 or 3. However, the sum of p1 and q1 is 4 or less.] R ac As the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms, R ab The same groups as those shown below can be mentioned. R acis preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, even more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group. p1 is preferably 0 to 2, and more preferably 1 or 2. q1 is preferably 1 or 2, and more preferably 1. The weight average molecular weight of the novolac resin is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and even more preferably 6,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, even more preferably 9,000 or less, and even more preferably 8,000 or less. By setting it within this range, it is possible to effectively prevent thinning and residue remaining after development. The weight average molecular weight is determined as a converted value based on standard polystyrene by gel permeation chromatography analysis. Detailed analysis conditions for this analysis are described in the examples of this application.

[0100] Examples of resins containing structural units derived from hydroxystyrene include resins containing structural units derived from monomers having phenolic hydroxyl groups, such as hydroxystyrenes such as hydroxystyrenes (p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene) and isopropenylphenol (p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol), and specifically include resins containing structural units represented by formula (a2-1). The resins containing structural units derived from hydroxystyrene may contain structural units derived from monomers exemplified below in the resins containing structural units derived from (meth)acrylic acid esters, in addition to the structural units derived from the above monomers. The resin containing a structural unit derived from hydroxystyrene is typically poly(vinylphenol) (poly(hydroxystyrene)), and preferably poly(p-vinylphenol) (poly(p-hydroxystyrene)). Specifically, a resin consisting of a structural unit represented by formula (a2-1) can be mentioned. Such a poly(vinylphenol) can be obtained, for example, by polymerizing a monomer described in JP-A-2010-204634.

[0101] Examples of resins containing structural units derived from (meth)acrylic acid esters include those obtained by using the following compounds as monomers and polymerizing one or more of these monomers in combination by a conventional method. In other words, examples of resins containing structural units derived from (meth)acrylic acid esters include resins containing structural units derived from the following monomers. Monomers having a carboxy group, such as (meth)acrylic acid; Monomers having a hydroxy group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Monomers having a plurality of ether bonds, such as polyethylene glycol monomethyl ether (meth)acrylates (polyalkylene glycol monoalkyl ether (meth)acrylates), 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.

[0102] The above-mentioned monomers may be used in combination with (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, tert-butyl (meth)acrylate, and hexyl (meth)acrylate; (meth)acrylic acid cycloalkyl esters such as cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate; monocyclic (meth)acrylic acid esters such as adamantyl (meth)acrylate and norbornyl (meth)acrylate; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; and ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, and ethylene glycol monobutyl ether (meth)acrylate. In addition to the above monomers, styrenes 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, mesaconic acid, and itaconic acid; and hydroxystyrenes exemplified in the resin containing the structural unit derived from hydroxystyrene described above may be used in combination. Examples of structural units derived from such monomers include structural units represented by formulae (a2-1) to (a2-4). Polyalkylene glycol is a polymer obtained by addition polymerization of alkylene oxide to alcohol. Examples of alcohol include butanol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, etc. Examples of alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc. Examples of polyalkylene glycol include polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.

[0103] The content of resin (A2) relative to the total amount of resins contained in the resist composition is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 20 mass% or more, and is preferably 90 mass% or less, more preferably 80 mass% or less, even more preferably 70 mass% or less, and even more preferably 65 mass% or less.

[0104] The resist composition of the present invention further contains a resin (A2) in addition to the resist composition containing the compound (I), the resin (A1) and the acid generator (B). The resin (A2) can adjust the solubility of the resist in a developer (alkaline aqueous solution) by interacting with the compound (I), and also has resistance to the developer (alkaline aqueous solution) and plating solution by crosslinking with the compound (I), thereby improving the accuracy of the plated object.

[0105] The mass ratio ((A1):(A2)) of the resin (A1) and the resin (A2) contained in the resist composition is usually 20:80 to 80:20, and preferably 30:70 to 70:30. Setting the mass ratio within this range is preferable because it can further improve the accuracy of the plated object.

[0106] In the resist composition of the present invention, the content of resin (A1) and resin (A2) is preferably 80% by mass or more and 99% by mass or less based on the total amount of solids 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, based on the total amount of solids 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, based on the total amount of solids in the resist composition. The solids and the content of each component contained in the resist composition of the present invention can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0107] <Acid Generator (B)> The acid generator (B) is a compound that can generate an acid by decomposition upon irradiation with light (exposure). The generated acid can eliminate the leaving group contained in the acid labile group of the resin (A1), and convert the acid labile group into a hydrophilic group (e.g., a carboxy group, a hydroxy group (phenolic hydroxyl group, etc.)). In other words, by exposing the resist composition containing the resin (A1) to light, the resist can be made soluble in a developer (an alkaline aqueous solution). The acid generator (B) may be either a nonionic or ionic type. Examples of nonionic acid generators include organic halides, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), and sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane). Representative examples of ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts). Examples of anions of onium salts include sulfonate anions, sulfonylimide anions, and sulfonylmethide anions.

[0108] As the acid generator (B), compounds that generate acid by radiation, such as those described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, and European Patent No. 126,712, can be used. Compounds produced by known methods can also be used. The acid generator (B) can be used alone or in combination of two or more.

[0109] As the nonionic acid generator, a compound having a group represented by formula (B1) (* represents a bond) is preferable. TIFF0007645089000056.tif23169 [In formula (B1), R b1 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom or a carbonyl group.] The nitrogen atom may have a double bond.

[0110] R b1 Examples of the hydrocarbon group having 1 to 18 carbon atoms in the hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom include linear or branched chain hydrocarbon groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, and groups having 4 to 18 carbon atoms which are combinations of these groups. As the linear or branched chain hydrocarbon group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms is preferred, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. Among these, linear groups are preferred. Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group. The aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably an aryl group having 6 to 18 carbon atoms, and examples thereof include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Among the groups having 4 to 18 carbon atoms formed by combining the above groups, examples of the group (group having 4 to 18 carbon atoms) in which a chain hydrocarbon group and an alicyclic hydrocarbon group are combined include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, an isobornyl group, a 2-alkyladamantan-2-yl group, and a 1-(adamantan-1-yl)alkane-1-yl group. Examples of groups in which a chain hydrocarbon group and an aromatic hydrocarbon group are combined (groups having 7 to 18 carbon atoms) include aralkyl groups and aromatic hydrocarbon groups having an alkyl group, and specific examples thereof include benzyl groups, phenethyl groups, phenylpropyl groups, trityl groups, naphthylmethyl groups, naphthylethyl groups, p-methylphenyl groups, p-tert-butylphenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, 2,6-diethylphenyl groups, and 2-methyl-6-ethylphenyl groups. Examples of groups in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined (groups having 9 to 18 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group, and specific examples thereof include a p-cyclohexylphenyl group, a p-adamantylphenyl group, and a phenylcyclohexyl group. R b1 Of the hydrocarbon groups having 1 to 18 carbon atoms represented by the formula (I), preferably, they are alkyl groups having 1 to 10 carbon atoms or aromatic hydrocarbon groups having 6 to 10 carbon atoms, more preferably, they are alkyl groups having 1 to 8 carbon atoms, and even more preferably, they are alkyl groups having 1 to 4 carbon atoms.

[0111] R b1 Examples of the group in which a methylene group contained in an alicyclic hydrocarbon group having 3 to 18 carbon atoms is substituted with an oxygen atom or a carbonyl group include groups represented by formulae (Y1) to (Y12). Preferred are groups represented by formulae (Y7) to (Y9), and more preferred is a group represented by formula (Y9). TIFF0007645089000057.tif57169

[0112] The hydrocarbon group having 1 to 18 carbon atoms and containing a fluorine atom is a group in which one or more hydrogen atoms contained in the above-mentioned hydrocarbon group having 1 to 18 carbon atoms are substituted with a fluorine atom, and specific examples thereof include fluoroalkyl groups such as a fluoromethyl group, a fluoroethyl group, a fluoropropyl group, a fluorobutyl group, a fluoropentyl group, a fluorohexyl group, a fluoroheptyl group, a fluorooctyl group, a fluorononyl group, and a fluorodecyl group; fluorocycloalkyl groups such as a fluorocyclopropyl group, a fluorocyclobutyl group, a fluorocyclopentyl group, a fluorocyclohexyl group, a fluorocycloheptyl group, a fluorocyclooctyl group, and a fluoroadamantyl group; and fluoroaryl groups such as a fluorophenyl group, a fluoronaphthyl group, and a fluoroanthryl group.

[0113] The hydrocarbon group having 1 to 18 carbon atoms and containing a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom, or an aromatic hydrocarbon group having 6 to 10 carbon atoms and containing a fluorine atom, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0114] Examples of the compound having a group represented by formula (B1) include compounds represented by formulas (b1) to (b3). Preferred are compounds represented by formula (b1) and formula (b2), and more preferred is a compound represented by formula (b1). TIFF0007645089000058.tif36169 [In formula (b1) to formula (b3), R b1 has the same meaning as above. R b2’ , R b3 and R b4 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Ring W b1 represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms or an aromatic heterocycle having 6 to 14 carbon atoms. x represents an integer of 0 to 2. When x is 2, multiple R b2’may be the same or different.]

[0115] Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and a methyl group is preferred. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group, and preferably a methoxy group.

[0116] Examples of the aromatic hydrocarbon ring having 6 to 14 carbon atoms include a benzene ring, a naphthalene ring, and an anthracene ring. The aromatic heterocycle having 6 to 14 carbon atoms is an aromatic heterocycle having 6 to 14 ring atoms. Of these, the following rings are preferable. TIFF0007645089000059.tif21169 Ring W b1 is preferably a naphthalene ring.

[0117] The compound represented by formula (b1) is preferably a compound represented by any one of formulas (b4) to (b7), and more preferably a compound represented by formula (b4). TIFF0007645089000060.tif58169 [In formulas (b4) to (b7), R b1 has the same meaning as above. R b2 , R b5 , R b6 and R b7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.]

[0118] Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and a methyl group is preferred.

[0119] Examples of the compound represented by formula (b1) include compounds represented by formulas (b1-1) to (b1-14), etc. Preferred are compounds represented by formula (b1-6) or formula (b1-7). TIFF0007645089000061.tif100169

[0120] TIFF0007645089000062.tif27169

[0121] Examples of the compound represented by formula (b2) include compounds represented by the following formulas. TIFF0007645089000063.tif56170

[0122] Examples of the compound represented by formula (b3) include compounds represented by the following formulas: TIFF0007645089000064.tif17170

[0123] The ionic acid generator is preferably a compound represented by formula (b8) or formula (b9). TIFF0007645089000065.tif37170[In formula (b8) and formula (b9), A b1 and A b2 represent each independently an oxygen atom or a sulfur atom. R b8 , R b9 , R b10 and R b11 each independently represents an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. X1 ― and X2 - represents an organic anion.

[0124] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of aromatic hydrocarbon groups having 6 to 12 carbon atoms include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl. The aromatic hydrocarbon group may further have a substituent, and examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. R b8 , R b9 , R b10 and R b11 are each preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a phenyl group.

[0125] X1 - and X2 - Examples of the organic anion represented by the formula (b10) include a sulfonate anion, a bis(alkylsulfonyl)amide anion, and a tris(alkylsulfonyl)methide anion. Of these, a sulfonate anion is preferred, and a sulfonate anion represented by the formula (b10) is more preferred. TIFF0007645089000066.tif21170[In formula (b10), R b12 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and a methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.] R b12 As the R in formula (B1), b1 The same groups as those shown below can be mentioned.

[0126] Examples of the compound represented by formula (b8) include the following compounds. TIFF0007645089000067.tif102169

[0127] Examples of the compound represented by formula (b9) include the following compounds. TIFF0007645089000068.tif63169

[0128] In the resist composition of the present invention, the content of the acid generator is preferably from 0.1 to 40 parts by mass, more preferably from 0.5 to 30 parts by mass, even more preferably from 1 to 20 parts by mass, and even more preferably from 1 to 5 parts by mass, relative to 100 parts by mass of the resin (A). The resist composition of the present invention may contain one type of acid generator (B) alone, or may contain multiple types.

[0129] <Solvent (D)> The content of the solvent (D) in the resist composition is usually 45% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass or less, more preferably 90% by mass or less. The content of the solvent (E) can be measured by a known analytical method such as liquid chromatography or gas chromatography.

[0130] Examples of the solvent (D) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; and cyclic esters such as γ-butyrolactone. The solvent (D) may be contained alone or in combination of two or more.

[0131] <Quencher (C)> The resist composition of the present invention may contain a quencher (hereinafter sometimes referred to as "quencher (C)"). The quencher (C) is a compound that has the effect of capturing the acid generated from the acid generator upon exposure to light. The quencher (C) may be a basic nitrogen-containing organic compound. The basic nitrogen-containing organic compound may be an amine or an ammonium salt. The amine may be an aliphatic amine (including a primary amine, a secondary amine, and a tertiary amine), an aromatic amine, etc.

[0132] The amine may, for example, be a compound represented by formula (C1) or formula (C2). TIFF0007645089000069.tif22169 [In formula (C1), R c1 , R c2 and R c3 represent each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, the alkyl group having 1 to 6 carbon atoms and the alicyclic hydrocarbon group having 3 to 10 carbon atoms may have at least one group selected from the group consisting of a hydroxy group, an amino group, and an alkoxy group having 1 to 6 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms may have at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alicyclic hydrocarbon group having 3 to 10 carbon atoms.]

[0133] In formula (C1), examples of the alkyl group having 1 to 6 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms, the aromatic hydrocarbon group having 6 to 10 carbon atoms, and the alkoxy group having 1 to 6 carbon atoms are the same as those mentioned above.

[0134] Examples of the compound represented by formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, dibutylmethylamine, Examples of the amines include ethyl dipentylamine, dihexylmethylamine, dicyclohexylmethylamine, diheptylmethylamine, methyl dioctylamine, methyl dinonylamine, didecylmethylamine, ethyl dibutylamine, ethyl dipentylamine, ethyl dihexylamine, ethyl diheptylamine, ethyl dioctylamine, ethyl dinonylamine, ethyl didecylamine, 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.

[0135] TIFF0007645089000070.tif18169[In formula (C2), Ring W 1 represents a heterocycle containing a nitrogen atom as an atom constituting the ring, or a benzene ring having a substituted or unsubstituted amino group, and the heterocycle and the benzene ring may have at least one group selected from the group consisting of a hydroxy group and an alkyl group having 1 to 4 carbon atoms. A 1 represents a phenyl group or a naphthyl group. nc represents 2 or 3, and a plurality of A 1may be the same or different.]

[0136] The substituted or unsubstituted amino group is -N(R 4 )(R 5 ) and R 4 and R 5 each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group having 3 to 10 carbon atoms is R a1 ~R a3 The groups include the same as those in the above. As the aromatic hydrocarbon group having 6 to 14 carbon atoms, R a1’ ~R a3’ The groups include the same as those in the above.

[0137] The heterocycle containing a nitrogen atom as an atom constituting the ring may be an aromatic ring or a non-aromatic ring, and may have other heteroatoms (e.g., oxygen atoms, sulfur atoms) in addition to the nitrogen atom. The number of nitrogen atoms in the heterocycle is, for example, 1 to 3. Examples of the heterocycle include rings represented by any of formulae (Y13) to (Y28). When one of the hydrogen atoms in the ring is removed, A 1 It becomes a combination with. TIFF0007645089000071.tif67169

[0138] Ring W 1 is preferably a heterocycle containing a nitrogen atom as an atom constituting the ring, more preferably a 5- or 6-membered aromatic heterocycle containing a nitrogen atom as an atom constituting the ring, and further preferably a ring represented by any of formulae (Y20) to (Y25).

[0139] Examples of the compound represented by formula (C2) include compounds represented by any of formulas (C2-1) to (C2-11). Preferred are compounds represented by any of formulas (C2-2) to (C2-8). TIFF0007645089000072.tif98170

[0140] The content of the quencher (C) in the solid content of the resist composition is preferably 0.0001 to 5 mass%, more preferably 0.0001 to 4 mass%, even more preferably 0.001 to 3 mass%, still more preferably 0.01 to 1.0 mass%, and even more preferably 0.1 to 0.7 mass%.

[0141] <Adhesion improver (E)> The adhesion improver (E) is not particularly limited as long as it can prevent corrosion and / or improve adhesion to metals used in substrates or wiring. By preventing metal corrosion, it exerts a rust-preventing effect. In addition to these effects, it can also improve the adhesion between the substrate or metal and the resist composition. Examples of the adhesion improver (E) include sulfur-containing compounds, aromatic hydroxy compounds, benzotriazole-based compounds, triazine-based compounds, and silicon-containing compounds, which can be used alone or in combination of two or more.

[0142] The sulfur-containing compound may be, for example, a compound having a sulfide bond and / or a mercapto group. The sulfur-containing compound may be a chain compound or a compound having a cyclic structure. Examples of chain compounds include dithiodiglycerol [S(CH2CH(OH)CH2(OH))2], bis(2,3-dihydroxypropylthio)ethylene [CH2CH2(SCH2CH(OH)CH2(OH))2], sodium 3-(2,3-dihydroxypropylthio)-2-methyl-propylsulfonate [CH2(OH)CH(OH)CH2SCH2CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)CH2(OH)], sodium 3-mercapto-1-propanesulfonate [HSCH2CH2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], thioglycolic acid [HSCH2CO2H], and 3-mercapto-1-propanol [HSCH2CH2CH2].

[0143] The sulfur-containing compound is preferably a compound having a sulfide bond and a mercapto group, more preferably a heterocyclic compound having a sulfide bond and a mercapto group.The heterocyclic compound is more preferably a heterocyclic compound having a sulfide bond in a ring structure.In the sulfur-containing compound, the number of sulfide bonds and mercapto groups is not particularly limited, and each may be 1 or more. The heterocyclic ring in the heterocyclic compound may be either a monocyclic ring or a polycyclic ring, and may be either a saturated or unsaturated ring. The heterocyclic ring preferably further contains a heteroatom other than a sulfur atom. Examples of the heteroatom include an oxygen atom and a nitrogen atom, and preferably a nitrogen atom. The heterocycle is preferably a heterocycle having 2 to 12 carbon atoms, more preferably a heterocycle having 2 to 6 carbon atoms. The heterocycle is preferably a monocycle. The heterocycle is preferably an unsaturated ring. The heterocycle is preferably an unsaturated and monocycle.

[0144] Examples of the heterocycle include the following heterocycles. TIFF0007645089000073.tif36170

[0145] The sulfur-containing compound may be a polymer. The polymer preferably contains a structure having a sulfide bond and a mercapto group in a side chain. The structure having a sulfide bond and a mercapto group (hereinafter, sometimes referred to as unit (1)) is preferably bonded to the main chain via a linking group such as an amide bond, an ether bond, a thioether bond, or an ester bond.

[0146] The polymer may be a homopolymer or a copolymer. When the polymer is a copolymer, it may contain the above-mentioned structural unit (a1) having an acid labile group and structural unit (a2) having no acid labile group. The weight average molecular weight of the homopolymer and copolymer is usually at least 3000, preferably at least 5000, and usually at most 100,000, preferably at most 50,000. The weight average molecular weight is determined by gel permeation chromatography analysis using standard polystyrene as the converted value. When the sulfur-containing compound is a polymer, the content of the structural unit having a sulfide bond and a mercapto group is usually 0.1 to 50 mol %, preferably 0.5 to 30 mol %, and more preferably 1 to 20 mol %, based on the total structural units of the polymer of the sulfur-containing compound.

[0147] The sulfur-containing compound is preferably, for example, a compound represented by formula (IA) or a polymer having a structural unit represented by formula (IB). TIFF0007645089000074.tif25170[In formula (IA), R i11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, -SR 11 or -NR 12 R 13 It represents a group represented by the following formula: R 11 , R 12 and R 13each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an acyl group having 2 to 12 carbon atoms, and these chain hydrocarbon groups, aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and acyl groups may have a hydroxy group. R i12 and R i13 each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. A and B each independently represent a nitrogen atom or a carbon atom. n1 and m1 each independently represent 0 or 1. However, when A is a nitrogen atom, n1 represents 0, when A is a carbon atom, n1 represents 1, when B is a nitrogen atom, m1 represents 0, and when B is a carbon atom, m1 represents 1.

[0148] Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms include aryl groups having 6 to 14 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may further have a substituent, and examples of aromatic hydrocarbon groups having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group.

[0149] R 11 is preferably a chain hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 2 to 12 carbon atoms, and R 12 and R 13 are preferably, independently, a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an acyl group having 2 to 12 carbon atoms. Examples of the acyl group having 2 to 12 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, a hexylcarbonyl group, a heptylcarbonyl group, an octylcarbonyl group, a decylcarbonyl group, a dodecylcarbonyl group, and a benzoyl group.

[0150] R i11 is more preferably a hydrogen atom or a mercapto group. R i12 and R i13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom. At least one of A and B is preferably a nitrogen atom, and more preferably both are nitrogen atoms.

[0151] TIFF0007645089000075.tif51168[In formula (IB), R i21 and R i31 each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. A 1 and B. 1 represent, independently of each other, a nitrogen atom or a carbon atom. n2 and m2 each independently represent 0 or 1. 1 When is a nitrogen atom, n2 represents 0, and A 1 is a carbon atom, n2 represents 1, B 1 When is a nitrogen atom, m2 represents 0; B 1 is a carbon atom, m2 represents 1. Ri4 It represents a hydrogen atom or a methyl group. X i1 represents a sulfur atom and an NH group. L i1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. A methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

[0152] R i21 and R i31 Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and preferably an alkyl group having 1 to 4 carbon atoms. R i21 and R i31 Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include aryl groups having 6 to 14 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group, and preferably an aryl group having 6 to 10 carbon atoms. The aromatic hydrocarbon group may further have a substituent, and examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. R i21 and R i31 Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups such as a cycloalkyl group having 3 to 18 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group, and preferably an alicyclic hydrocarbon group having 5 to 10 carbon atoms. R i21 and R i31are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0153] L i1 Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1, alkanediyl groups such as a 1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group; Examples of the aryl group include arylene groups such as a phenylene group, a tolylene group, and a naphthylene group. L i1 is preferably an alkanediyl group having 2 to 14 carbon atoms containing an ester bond or a group formed by combining an arylene group having 6 to 10 carbon atoms with an alkanediyl group having 1 to 11 carbon atoms.

[0154] The structural unit represented by formula (IB) is preferably a structural unit represented by formula (IB-1) or a structural unit represented by formula (IB-2). TIFF0007645089000076.tif79168 [In formula (IB-1), R i22 and R i32 each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. A 2 and B. 3 represent each independently a nitrogen atom or a carbon atom. n3 and m3 each independently represent 0 or 1. 2 When is a nitrogen atom, n3 represents 0, and A 2 is a carbon atom, n3 represents 1, B 2 is a nitrogen atom, m3 represents 0, B 2 When is a carbon atom, m3 represents 1. X i11 represents a sulfur atom and an NH group. L i2 represents a divalent hydrocarbon group having 1 to 18 carbon atoms. A methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. R i5 represents a hydrogen atom or a methyl group. In formula (IB-2), R i23 and R i33 each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. A 3 and B. 3 represent, independently of each other, a nitrogen atom or a carbon atom. n4 and m4 each independently represent 0 or 1. 3 is a nitrogen atom, n4 represents 0, and A 3 is a carbon atom, n4 represents 1, B 3 is a nitrogen atom, m4 represents 0, B 3 is a carbon atom, m4 represents 1. X i12 represents a sulfur atom and an NH group. L i3represents a divalent hydrocarbon group having 1 to 14 carbon atoms. A methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. R i7 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R i6 represents a hydrogen atom or a methyl group. mx represents an integer from 0 to 4.

[0155] R i22 , R i32 , R i23 and R i33 As the chain hydrocarbon group having 1 to 10 carbon atoms represented by the formula: i21 and R i31 Examples of the alkyl group include the chain hydrocarbon group having 1 to 10 carbon atoms represented by the following formula: R i22 , R i32 , R i23 and R i33 As the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by the formula: i21 and R i31 Examples of the aromatic hydrocarbon group include those having 6 to 14 carbon atoms represented by the following formula: R i22 , R i32 , R i23 and R i33 As the alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by the formula i21 and R i31 Examples of the alicyclic hydrocarbon group include the same as the alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by the following formula:

[0156] L i2Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1, alkanediyl groups such as 14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group; Examples of the aryl group include arylene groups such as a phenylene group, a tolylene group, and a naphthylene group. L i2 is preferably an alkanediyl group having 1 to 14 carbon atoms, and more preferably an alkanediyl group having 1 to 11 carbon atoms.

[0157] L i3Examples of the divalent hydrocarbon group having 1 to 14 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, and an undecane-1,11-diyl group. alkanediyl groups such as a dodecane-1,12-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples of the polycyclic divalent alicyclic saturated hydrocarbon groups include norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. L i3 is preferably an alkanediyl group having 1 to 14 carbon atoms, and more preferably an alkanediyl group having 1 to 11 carbon atoms. Based on the position of the phenyl group that is bonded to the main chain, L i3 is preferably attached at the p-position.

[0158] R i7 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R i7 Examples of the alkoxy group having 1 to 6 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0159] Examples of the sulfur-containing compound include compounds represented by any of the formulae (I-1) to (I-26). Among them, preferred are the compounds represented by the formulae (I-1) to (I-13), and more preferred are the compounds represented by the formulae (I-1), (I-4) and (I-11). TIFF0007645089000077.tif80169

[0160] TIFF0007645089000078.tif98168

[0161] Examples of the sulfur-containing compound include homopolymers consisting of any one of the structural units represented by formulae (I-27) to (I-38) and copolymers containing one or more of these structural units. A copolymer containing one or more of the structural units represented by formulae (I-27) to (I-36) is preferable, and a copolymer containing a structural unit represented by formula (I-33) is more preferable. TIFF0007645089000079.tif146170

[0162] Examples of such copolymers include copolymers having structural units represented by formulae (I-39) to (I-48). Among them, polymers having structural units represented by formulae (I-39) to (I-44) are preferred.

[0163] TIFF0007645089000080.tif242168

[0164] TIFF0007645089000081.tif158169

[0165] The sulfur-containing compound may be synthesized by a known method (e.g., JP 2010-79081 A) or may be a commercially available product. The polymer containing a sulfur-containing compound may be a commercially available product (e.g., bismuthiol (manufactured by Tokyo Chemical Industry Co., Ltd., etc.) or may be synthesized by a known method (e.g., JP 2001-75277 A).

[0166] Examples of aromatic hydroxy compounds include phenol, cresol, xylenol, pyrocatechol (=1,2-dihydroxybenzene), tert-butylcatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and gallic acid.

[0167] An example of the benzotriazole compound is a compound represented by the formula (IX). TIFF0007645089000082.tif27169 [In formula (IX), R 1 and R 2 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a carboxy group, an amino group, a hydroxy group, a cyano group, a formyl group, a sulfonylalkyl group, or a sulfo group. Q is a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aryl group, or **-R 3X -N(R 4X )(R 5X ) wherein the hydrocarbon group may have an amide bond or an ester bond in the structure. R 3X represents an alkanediyl group having 1 to 6 carbon atoms. ** represents a bond to a nitrogen atom contained in the ring. R 4X and R 5X each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms.]

[0168] R 1 , R 2 The hydrocarbon group having 1 to 10 carbon atoms for Q may be either an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and may have saturated and / or unsaturated bonds. The aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a methylpentyl group, an n-hexyl group, and an n-heptyl group. carbon The aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably an aryl group, and examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may further have a substituent, and examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples of the aromatic hydrocarbon group having a substituent include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the substituent that the hydrocarbon group having 1 to 10 carbon atoms may have include a hydroxyalkyl group and an alkoxyalkyl group. R 3X The alkanediyl group having 1 to 6 carbon atoms may be either linear or branched, and examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, and a propane-1,2-diyl group. R 4X and R 5XExamples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R 4X and R 5X Examples of the hydroxyalkyl group having 1 to 6 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a dihydroxyethyl group. R 4X and R 5X Examples of the alkoxyalkyl group having 2 to 6 carbon atoms include a methoxymethyl group, a methoxyethyl group, and a dimethoxyethyl group.

[0169] When the resist composition of the present invention is applied to a substrate on which Cu is formed, Q in formula (IX) is **-R 3X -N(R 4X )(R 5X Among them, the compound represented by R 4X and R 5X When at least one of the groups is an alkyl group having 1 to 6 carbon atoms, the benzotriazole compound has poor water solubility, but is preferably used when other components capable of dissolving this compound are present.

[0170] Furthermore, when the resist composition of the present invention is applied to a substrate having an inorganic material layer (e.g., a polysilicon film, an amorphous silicon film, etc.), Q in formula (IX) is preferably a water-soluble group. Specifically, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a hydroxy group, etc. are preferred. This allows the substrate to exhibit corrosion resistance more effectively.

[0171] Examples of the benzotriazole-based compounds include benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethylbenzotriazole, 1-methylbenzotriazole, 5-benzotriazolecarboxylic acid, 1-methoxy-benzotriazole, 1-(2,2-dihydroxyethyl)-benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethane, and 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bispropane.

[0172] An example of the triazine compound is a compound represented by the formula (II). TIFF0007645089000083.tif24169 [In formula (II), R 6 , R 7 and R 8 each independently represents a halogen atom, a hydrogen atom, a hydroxyl group, an amino group, a mercapto group, an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, or an amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms.] Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include the same as those mentioned above. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

[0173] An example of the triazine compound is 1,3,5-triazine-2,4,6-trithiol.

[0174] An example of the silicon-containing compound is a compound represented by formula (IIA). TIFF0007645089000084.tif29170[In formula (IIA), R j1 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a mercaptoalkyl group having 1 to 5 carbon atoms. R j2 ~R j4 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a mercapto group, or a mercaptoalkyl group having 1 to 5 carbon atoms; R j2 ~R j4 At least one of them is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms. t i represents an integer from 1 to 10.

[0175] Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group and an ethoxy group. Examples of the mercaptoalkyl group having 1 to 5 carbon atoms include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group.

[0176] R j1 is preferably a methyl group, an ethyl group, or a mercaptoalkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or a mercaptopropyl group (particularly, a 3-mercaptopropyl group). R j2 ~R j4 are preferably each independently a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more preferably a methyl group or a methoxy group, provided that at least one of these is preferably a mercapto group or a mercaptoalkyl group having 1 to 3 carbon atoms, and more preferably a mercapto group or a mercaptopropyl group. R j2 and Rj3 may be the same or different, but are preferably the same from the viewpoint of productivity.

[0177] Examples of the compound of formula (IIA) include compounds represented by the following formulae (II-1) to (II-7). TIFF0007645089000085.tif189170Of these, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like are preferred.

[0178] The content of the adhesion improver (E) 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 also 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 particularly preferably 0.1% by mass or less, based on the total amount of solids in the resist composition. By setting the content within this range, a resist composition capable of forming a highly accurate resist pattern can be obtained, and adhesion between the resist pattern and the substrate can be ensured.

[0179] <Other ingredients> The resist composition of the present invention may contain components other than the above-mentioned components (hereinafter, sometimes referred to as "other components (F)") as necessary. There are no particular limitations on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc., can be used. When other component (F) is used, the content thereof is appropriately selected depending on the type of other component (F).

[0180] 2. Preparation of resist composition The resist composition of the present invention can be prepared by mixing the compound (I), the resin (A1), the resin (A2), and the acid generator (B), and, if necessary, the resin other than the resin (A1) and the resin (A2), the quencher (C), the solvent (D), the adhesion improver (E), and other components (F). The order of mixing is arbitrary and is not particularly limited. The temperature during mixing can be selected from 10 to 40°C depending on the type of resin, the solubility of the resin in the solvent (D), and the like. The mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used. After mixing the components, it is preferable to filter the mixture using a filter having a pore size of about 0.003 to 50 μm.

[0181] 3. Method for manufacturing resist patterns The method for producing a resist pattern of the present invention comprises the steps of: (1) applying the resist composition of the present invention onto a metal surface of a substrate having a metal surface; (2) A step of drying the applied resist composition to form a composition layer; (3) exposing the composition layer to light; and (4) A step of developing the composition layer after exposure.

[0182] The resist composition can be applied onto a substrate by a commonly used device such as a spin coater. The substrate may be an inorganic substrate such as a silicon wafer, on which a semiconductor element (e.g., a transistor, a diode, etc.) may be formed in advance. When the resist composition of the present invention is used for bump formation, the substrate is preferably one on which a conductive material is further laminated. The conductive material may be at least one metal selected from the group consisting of gold, copper, nickel, tin, palladium, and silver, or an alloy containing at least one metal selected from the group, and preferably copper or an alloy containing copper. Before applying the resist composition, the substrate may be washed, and an anti-reflective film or the like may be formed on the substrate. The composition after coating is dried to remove the solvent and form a composition layer. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a vacuum device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 30 to 600 seconds. The pressure during drying under reduced pressure is preferably 1 to 1.0×10 5 It is preferable that the pressure is about Pa. After drying, the film thickness of the resulting composition is preferably 1 to 150 μm, and more preferably 1.5 to 100 μm. The obtained composition layer is usually exposed using an exposure machine. As the exposure light source, various types can be used, such as a light source that emits light with a wavelength of 345 to 436 nm (g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), i-line (wavelength: 365 nm)), a light source that emits ultraviolet laser light such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and F2 excimer laser (wavelength 157 nm), a light source that converts the wavelength of laser light from a solid laser light source (YAG or semiconductor laser, etc.) to emit a harmonic laser light in the far ultraviolet or vacuum ultraviolet range, and a light source that irradiates electron beams or extreme ultraviolet light (EUV). In this specification, irradiation with these types of radiation may be collectively referred to as "exposure". During exposure, exposure is usually performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. The composition layer after exposure may be subjected to a heat treatment (so-called post-exposure bake) in order to promote the elimination reaction of the acid labile group of the resin (A1). The heating temperature is usually about 50 to 200° C., preferably about 70 to 150° C. The heating time is usually 40 to 400 seconds, preferably 50 to 350 seconds.

[0183] The composition layer after heating is usually developed using a developing device and a developer. Examples of the developing method include a dip method, a paddle method, a spray method, and a dynamic dispense method. The developing temperature is preferably, for example, 5 to 60° C., and the developing time is preferably, for example, 5 to 600 seconds. By selecting the type of developer as follows, a positive resist pattern or a negative resist pattern can be produced.

[0184] When a positive resist pattern is produced from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline) may be used. The alkaline developer may contain a surfactant. After development, the resist pattern is preferably washed with ultrapure water, and then water remaining on the substrate and the pattern is removed. When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used as the developer. Examples of organic solvents contained in organic developers include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole. The content of the organic solvent in the organic developer is preferably from 90% by mass to 100% by mass, more preferably from 95% by mass to 100% by mass, and further preferably consists essentially of the organic solvent. Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant and may contain a small amount of water. During development, the development may be stopped by replacing the organic developer with a different type of solvent. The resist pattern after development is preferably washed with a rinse solution. There are no particular limitations on the rinse solution as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove any rinsing liquid remaining on the substrate and the pattern.

[0185] By exposing a resist obtained using the resist composition of the present invention, a resist pattern with a highly accurate shape can be formed.

[0186] 4. Manufacturing method for plated objects The resist pattern formed by the above method is used as a mold to deposit an electrode material by plating, and the resist pattern is then peeled off to form a plated object such as a bump or rewiring. The method for producing a plated object of the present invention comprises the steps of: (5) forming a plating object using the resist pattern as a mold; and (6) A step of stripping off the resist pattern is included. A resist pattern formed on a substrate having a conductive layer or the like is used as a template to deposit a conductive material using a plating solution by a known method, thereby forming a plated object. Examples of the plating solution include a copper plating solution, a gold plating solution, a nickel plating solution, a solder plating solution, and a silver-tin plating solution. After the plating object is formed, the resist pattern is removed using a stripping solution by a known method. Examples of the stripping solution include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Examples of the propylene glycol alkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These may be used alone or in combination of two or more. By the above method, plated objects such as bumps and rewirings can be formed. When forming a plated object, the surface of the conductive layer may be subjected to an ashing process or the like in order to improve adhesion between the conductive layer and the plated object. Examples of the ashing process include a method using oxygen plasma.

[0187] A plated object obtained by using the resist pattern of the present invention swells little in a plating bath, and therefore the plated object can be formed with high precision.

[0188] 5.Applications The resist composition of the present invention is useful for producing a thick resist film, for example, a resist film with a thickness of 1 to 150 μm. The resist composition of the present invention is also useful for producing bumps and rewiring by a plating process. When producing bumps and rewiring using the resist composition, they can usually be formed by the following procedure. This allows the production of a resist pattern with a particularly excellent pattern shape. First, a conductive material (seed metal) is laminated on a wafer on which semiconductor elements and the like are formed to form a conductive layer. Then, a resist pattern is formed on the conductive layer using the resist composition of the present invention. Next, an electrode material (e.g., Cu, Ni, solder, etc.) is deposited by plating using the resist pattern as a mold, and the resist pattern and the conductive layer remaining under the resist pattern are removed by etching or the like to form bumps and rewiring. After removing the conductive layer, the electrode material may be melted by heat treatment to form a bump, if necessary. EXAMPLES

[0189] The present invention will be described in more detail with reference to examples. In the examples, "%" and "parts" expressing the content or amount used are based on mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions. Equipment: HLC-8120GPC model (Tosoh Corporation) Column: TSKgel Multipore H XL -M x 3 + guard column (Tosoh) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation)

[0190] Synthesis Example 1 [Synthesis of Resin (A1)-1] 20 parts of poly-p-hydroxystyrene (S-4P; Maruzen Petrochemical Co., Ltd.) was dissolved in 240 parts of methyl isobutyl ketone at room temperature and concentrated with an evaporator. The concentrated resin solution and 0.003 parts of p-toluenesulfonic acid dihydrate were added to a four-neck flask equipped with a reflux condenser, a stirrer, and a thermometer. While the mixture was kept at 20 to 25°C, 5.05 parts of ethyl vinyl ether was added dropwise to the mixture over 10 minutes. The mixture was stirred at 20 to 25°C for 2 hours. The reaction mixture was diluted with 200 parts of methyl isobutyl ketone, washed with ion-exchanged water, and separated five times. The organic layer was concentrated to 45 parts using an evaporator, and then 150 parts of propylene glycol monomethyl ether acetate was added and concentrated again to obtain 78 parts of a propylene glycol monomethyl ether acetate solution of resin (A1)-1 (solid content 29%). Resin (A1)-1 is a resin having the following structural unit. The weight average molecular weight of resin (A1)-1 is 1.16×10 4 The ratio of hydroxy groups in poly-p-hydroxystyrene that were replaced with ethoxyethoxy groups was 40.9%. TIFF0007645089000086.tif38169

[0191] Synthesis Example 2 [Synthesis of Resin (A1)-2] In a flask, 120 parts of phenol novolac resin (PSM-4326 manufactured by Gun-ei Chemical Co., Ltd.) and 960 parts of methyl isobutyl ketone were added and dissolved. The obtained phenol novolac resin solution was washed five times with ion-exchanged water and separated. The obtained organic layer was concentrated to 327.3 parts. The resin content in the obtained resin solution was 35.2%. The resulting resin solution (56.8 parts), methyl isobutyl ketone (76.52 parts) and p-toluenesulfonic acid monohydrate (0.0036 parts) were added to a flask. Ethyl vinyl ether (8.81 parts) was added dropwise to this mixture and reacted at room temperature for 3 hours. Ion-exchanged water was added to this reaction solution, the mixture was stirred, allowed to stand, and the organic layer was separated to remove the organic layer. This washing with ion-exchanged water was repeated four more times, for a total of five washings. The organic layer was then removed and concentrated. Then, propylene glycol monomethyl ether acetate was added to remove water and methyl isobutyl ketone by azeotropy, and the mixture was further concentrated to obtain 57.44 parts of a resin solution. The resulting resin solution was a resin solution in which the hydroxyl groups of the phenol novolac resin were partially 1-ethoxyethylated, and this resin was 1 Analysis by H-NMR revealed that 53.0% of the hydroxyl groups of the phenol novolac resin were replaced with 1-ethoxyethyl ether. The concentration of the resin solution was measured using a dry weight loss method and found to be 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 3 It was. TIFF0007645089000087.tif31169

[0192] Synthesis Example 3 [Synthesis of Resin (A2)-1] In a four-neck flask equipped with a stirrer, a reflux condenser, and a thermometer, 413.5 parts of 2,5-xylenol, 103.4 parts of salicylaldehyde, 20.1 parts of p-toluenesulfonic acid, and 826.9 parts of methanol were added, and the temperature was raised to reflux and kept at that temperature for 4 hours. After cooling, 1320 parts of methyl isobutyl ketone was added, and 1075 parts of the solvent were distilled off at normal pressure. 762.7 parts of m-cresol and 29.0 parts of 2-tert-butyl-5-methylphenol were added thereto, and the temperature was raised to 65°C, and 678 parts of 37% aqueous formalin solution were dropped over 1.5 hours while adjusting the temperature so that the temperature was 87°C at the end of the dropwise addition. The resulting mixture was kept at 87°C for 10 hours, 1115 parts of methyl isobutyl ketone was added, and the mixture was washed by separating the liquid three times with ion-exchanged water. 500 parts of methyl isobutyl ketone was added to the resulting mixture, and the mixture was concentrated under reduced pressure until the total amount was 3435 parts. 3796 parts of methyl isobutyl ketone and 4990 parts of n-heptane were added to the obtained mixture, and the mixture was heated to 60° C. and stirred for 1 hour. After that, the liquid was separated and the lower layer containing the resin was taken out, diluted with 3500 parts of propylene glycol monomethyl ether acetate, and concentrated to obtain 1690 parts of a propylene glycol monomethyl ether acetate solution of resin (A2)-1 (solid content 43%). The weight average molecular weight of novolac resin (A2)-1 was 7×10 3 The residual film ratio when developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was 74%. The residual film ratio was measured by the method described in the section <Resin (A2)> of the Detailed Description of the Invention.

[0193] <Preparation of resist composition> The components shown in Table 1 were mixed and dissolved to obtain a mixture, which was then filtered through a fluororesin filter having a pore size of 0.5 μm to prepare a resist composition.

[0194] [Table 1]

[0195] <Resin> (A1)-1: Resin (A1)-1 (A1)-2: Resin (A1)-2 (A2)-1: Resin (A2)-1

[0196] <Acid Generator (B)> (B)-1: N-hydroxynaphthalimide triflate (NAI-105; Midori Chemical Co., Ltd.) TIFF0007645089000089.tif24168(B)-2: Compound represented by the following formula (PAG-103; manufactured by BASF) TIFF0007645089000090.tif33169

[0197] <Compound (I)> (I)-1: Synthesized by the method described in JP-A-3-185447 TIFF0007645089000091.tif41169(I)-2: Synthesized by the method described in JP-A-9-110762 In addition, R t1 , R t6 , R t7 , R t9 , R t10 For every mole of the following compound, where R is a hydroxy group, 2 moles of sulfonyl chloride reacted, and the reaction proceeded to almost 100%. t1 , R t6 , R t7 , R t9 , R t10 It was confirmed that the hydrogen atoms in two of the hydroxyl groups were replaced by 1,2-naphthoquinone diazide sulfonyl groups (MS: M+: 1080). TIFF0007645089000092.tif35170(I)-3: Synthesized by the method described in JP-A-8-245461 In addition, R t1 , R t7 , R t9 , R t10 For every mole of the following compound, where R is a hydroxy group, 2 moles of sulfonyl chloride reacted, and the reaction proceeded to almost 100%. t1 , R t7 , R t9 , R t10It was confirmed that the hydrogen atoms in two of the hydroxyl groups were replaced by 1,2-naphthoquinone diazide sulfonyl groups (MS: M+: 960). TIFF0007645089000093.tif36170<Quencher(C)> (C)-1: 2,4,5-triphenylimidazole (Tokyo Chemical Industry Co., Ltd.) <Solvent (D)> (D)-1: Propylene glycol monomethyl ether acetate

[0198] Examples 1 to 6, Comparative Examples 1 and 2 (i-line exposure evaluation of resist composition) The above resist composition was spin-coated onto a 4-inch silicon wafer on which copper had been evaporated, so that the film thickness after pre-baking would be 1.5 μm. Thereafter, the coating was prebaked on a direct hot plate at 100° C. for 180 seconds to form a composition layer. Next, the composition layer formed on the wafer was exposed to light through a mask using an i-line stepper (NSR-2005i9C; manufactured by Nikon Corporation, NA=0.5) to form a 1:1 line and space pattern (line width 1 μm) by gradually changing the exposure dose. After exposure, post-exposure baking was performed on a hot plate at 90° C. for 60 seconds, and then paddle development was performed with a 2.38 mass % aqueous solution of tetramethylammonium hydroxide for 180 seconds to obtain a resist pattern. The resist pattern obtained after development was observed under a scanning electron microscope, and the exposure dose at which a line and space pattern with a line width of 1 μm was obtained was taken as the effective sensitivity.

[0199] <Resolution evaluation> The resist pattern obtained at the effective sensitivity was observed under a scanning electron microscope, and the minimum line width of the resolved line and space pattern was measured.

[0200] <Roughness evaluation due to standing wave effect> The cross-sectional shape of a line and space pattern with a line width of 0.6 μm obtained at the effective sensitivity was observed with a scanning electron microscope, and the line widths of a and b shown in Figure 1 were measured. If the calculated value derived from b / a was less than 0.8, it was rated as "C", if it was 0.8 or more but less than 0.9, it was rated as "B", and if it was 0.9 or more, it was rated as "A". a is the line width of the longest part of a given line (maximum line width) (μm), and b is the line width of the shortest part of a given line (minimum line width) (μm). The results shown in the table are for the line with the smallest b / a value among those observed.

[0201] <Plating resistance evaluation> After preparing a patterned wafer using the effective sensitivity obtained in the above i-line exposure evaluation, the wafer was immersed in a Cu plating solution for 5 minutes, 15 minutes, and 30 minutes. After immersion, the patterned wafer was observed under an optical microscope to observe a line and space pattern with a line width of 1 μm. Those that showed pattern collapse after 15 minutes of immersion were rated "C", those that showed no pattern collapse after 15 minutes of immersion but showed pattern collapse after 30 minutes were rated "B", and those that showed no pattern collapse after 30 minutes of immersion were rated "A".

[0202] [Table 2] [Industrial Applicability]

[0203] INDUSTRIAL APPLICABILITY The resist composition of the present invention is capable of producing a resist pattern having a good shape and plating resistance, and is suitable for semiconductor microfabrication and therefore extremely useful industrially.

Claims

1. A resist composition comprising a compound (I) having a quinone diazide sulfonyl group, a resin (A1) including a structural unit having an acid labile group, an alkali-soluble resin (A2), and an acid generator (B), the compound (I) having a quinone diazide sulfonyl group is at least one selected from the group consisting of a compound represented by formula (II), a compound represented by formula (III), a compound represented by formula (IV), and a compound represented by formula (V), [In formula (II), R 11 to R 14 each independently represent 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 may be replaced by an oxygen atom, a carbonyl group, or -NR d1 -. R d1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 15 to R 30 each independently represent 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). At least one of R 11 to R 30 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 to R 39 each independently represent 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). At least one of R 31 to R 39 is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). P 1 to P 5 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be replaced with an oxygen atom, a carbonyl group, or -NR d2 -, P 1 and P 2 may be bonded to each other to form a ring together with the two carbon atoms to which they are bonded, and P 4 and P 5 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. R d2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.] [In formula (IV), R 40 to R 53 each independently represent 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). At least one of R 40 to R 53 is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). n a represents an integer of 1 to 5. When n a is an integer of 2 or more, R 49 to R 52 may be the same or different.] [In formula (V), R f1 , R f2 and R g1 to R g8 each independently represent 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). At least one of R f1 , R f2 and R g1 to R g8 is a group represented by formula (a), a group represented by formula (b) or a group represented by formula (c). P 6 represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The aromatic hydrocarbon group may be substituted with at least one group selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms. P 7 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be replaced by an oxygen atom, a carbonyl group or -NR d3 -. P 6 and P 7 may bond to each other to form a ring. n v represents 1 or 2. R d3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.] [In formula (a) and formula (b), * represents a bond.] [In formula (c), * represents a bond.] The resist composition, wherein the resin (A1) containing a structural unit having an acid labile group is a resin containing a structural unit represented by formula (a1-1) or a structural unit represented by formula (a1-2), or a resin containing a structural unit represented by formula (a3A) or a structural unit represented by formula (a3B). [In formula (a1-1), R a1 , R a2 and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alternatively, R a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R a4 represents a hydrogen atom or a methyl group. [In formula (a1-2), R a1' and R a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3' represents a hydrocarbon group having 1 to 20 carbon atoms. Alternatively, R a1' represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2' and R a3' are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. A methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocycle having 3 to 20 carbon atoms may be replaced with an oxygen atom or a sulfur atom. R a5 represents a hydrogen atom or a methyl group. R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, multiple R a6 may be the same or different. [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 atom to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2 or 3. When p is 2 or 3, R ab may be the same or different.] [In formula (a3B), R a1' and R a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3' represents a hydrocarbon group having 1 to 20 carbon atoms. Alternatively, R a1' represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2' and R a3' are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocycle having 3 to 20 carbon atoms may be replaced by an oxygen atom or a sulfur atom. R ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.]

2. 2. The resist composition according to claim 1, wherein the alkali-soluble resin (A2) is a resin that contains a structural unit having a carboxy group or a hydroxy group, but does not contain a structural unit having an acid labile group.

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

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

5. A method for manufacturing a plated object, comprising the steps of: (1) A step of applying the resist composition according to any one of claims 1 to 3 onto a metal surface of a substrate having a metal surface; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) developing the composition layer after exposure; (5) forming a plating object using the obtained resist pattern as a mold; and (6) Step of removing the resist pattern A manufacturing method comprising:

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