Resist composition and method for producing resist pattern

Abstract

To provide a resist composition which shows little temporal changes and can produce a resist pattern having a good pattern shape.SOLUTION: A resist composition comprises: a novolac resin having hydroxyl groups substituted with a group represented by formula (3), a resin having a group represented by formula (2), an acid generator, a quencher, and a solvent. [In the formula, Ra10 represents a C1-20 hydrocarbon group; Ra1' and Ra2' each independently represents a hydrogen atom or a C1-12 hydrocarbon group and Ra3' represents a C1-20 hydrocarbon group; or Ra1' represents a hydrogen atom or a C1-12 hydrocarbon group, and Ra2' and Ra3' are mutually bonded to form, together with a carbon atom and an oxygen atom to which they are bonded, a C2-20 heterocyclic group.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resist composition and a method for producing a resist pattern using the resist composition. Regarding. [Background technology]

[0002] Patent documents 1 and 2 disclose that the hydroxy group of cresol novolak is tert-butoxycarbonyl. A resist composition containing a carboxyl-protected resin is described. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 5-216244 [Patent Document 2] Japanese Patent Application Publication No. 9-6003 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention relates to a resist pattern which exhibits little change over time and has a good pattern shape. The object of the present invention is to provide a drug composition. [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A novolak resin in which a hydroxy group is substituted with a group represented by formula (3) and an acid generator A resist composition comprising a quencher and a solvent. TIFF0007675244000001.tif1859 [In formula (3), R a10 represents a hydrocarbon group having 1 to 20 carbon atoms. * represents a bond.] [2] The resist composition according to [1], wherein the novolak resin is a phenol novolak resin. thing. [3] The resin according to [1] or [2], further comprising a resin having a group represented by formula (2). Composition. TIFF0007675244000002.tif3259 [In formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a group having 1 to 12 carbon atoms R represents a hydrocarbon group. a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a1 ’ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a2’ and R a3’ are mutually They combine with the carbon and oxygen atoms to form a heterocyclic group having 2 to 20 carbon atoms. The hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms and the hydrocarbon group having 2 to 3 carbon atoms are preferably A methylene group contained in the heterocyclic group of 1 to 20 may be replaced by an oxygen atom or a sulfur atom. * represents a bond. [4] The resin having a group represented by formula (2) contains a structural unit represented by formula (a1-2): The resist composition according to [3], wherein the resin is a resin containing TIFF0007675244000003.tif4484[In formula (a1-2), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Represents R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a1’ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a2’ and R a3’ are combined with each other and forms a divalent heterocyclic group having 2 to 20 carbon atoms together with the carbon atom and oxygen atom to which it is bonded. The hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group having 2 to 20 carbon atoms. A methylene group contained in the heterocyclic group may be replaced by an oxygen atom or a sulfur atom. R a5 represents a hydrogen atom or a methyl group. R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, a plurality of R a6 are identical to each other But it can be different.] [5] The resin having a group represented by formula (2) is a novolak resin, The novolak resin is a novolak resin in which the hydroxyl group of the resin is substituted with a group represented by formula (2). A resist composition according to claim 1. [6] (1) A process for applying the resist composition according to any one of [1] to [5] onto a substrate. About (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; and (4) A method for producing a resist pattern, comprising the step of developing the composition layer after exposure. Effect of the Invention

[0006] The resist composition of the present invention provides a resist that exhibits little change over time and has a good pattern shape. The pattern can be manufactured. [Brief description of the drawings]

[0007] [Figure 1] The following are schematic diagrams of the cross-sectional shapes of line patterns. Figure 1(a) shows a good cross section with a top shape and bottom shape that are close to a rectangle, and Figure 1(b) shows a cross section with a poor top shape. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In this specification, unless otherwise specified, "(meth)acrylate" means "acrylate and methacrylates. The terms "acrylic acid" and "(meth)acryloyl" have the same meaning. Examples of structural units having "(CH3)-CO-" or "CH2=CH-CO-" are given. In the case where the structural unit has both groups, the structural unit having both groups is also exemplified. When stereoisomers exist, all stereoisomers are included. In this specification, the term "solid content of a resist composition" refers to the fraction of the total amount of the resist composition that is This refers to the total of the components excluding the solvent (D) described below.

[0009] [Resist Composition] The resist composition of the present invention comprises a resin (hereinafter sometimes referred to as “resin (A)”) and an acid generator (hereinafter sometimes referred to as "acid generator (B)") and a quencher (hereinafter sometimes referred to as "quencher (C Resist containing a solvent (hereinafter sometimes referred to as "solvent (D)") and a solvent (hereinafter sometimes referred to as "solvent (D)"). Resin (A) is a novolak resin having a hydroxy group represented by formula (3): The novolak resin (hereinafter sometimes referred to as “resin (A1)”) is substituted with a group. Resin (A) may further include a resin different from resin (A1) (hereinafter referred to as resin (A2) and resin (A 3) may also be included. The resist composition of the present invention may further contain an adhesion improver (hereinafter referred to as "adhesion improver (E)"). (In some cases)

[0010] <Resin (A1)> Resin (A1) is a novolak resin in which the hydroxy group is substituted with a group represented by formula (3). The hydroxyl groups of the novolak resin are partially substituted with groups represented by formula (3). This means a resin that has been TIFF0007675244000004.tif1963 [In formula (3), R a10 represents a hydrocarbon group having 1 to 20 carbon atoms. * represents a bond.]

[0011] R a10 The hydrocarbon group represented by the formula (I) is a chain hydrocarbon group (an alkyl group, an alkenyl group, and and alkynyl groups), alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. and the like. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples include a silyl group, a heptyl group, and an octyl group. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, and a butenyl group. isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples of the alkyl groups include an octenyl group, an isooctenyl group, and a nonenyl group. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, Examples thereof include a nonynyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the aryl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, Examples include a butyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond): It can be obtained. a10 The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms. TIFF0007675244000005.tif10167

[0012] Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group and the like. The group formed by the combination is a group formed by combining an alkyl group and an alicyclic hydrocarbon group. a group combining an alkyl group and an aromatic hydrocarbon group; and groups in which an alicyclic hydrocarbon group is combined. Examples of the group combining an alkyl group and an alicyclic hydrocarbon group include methylcyclohexane. alkylcycloalkyl groups such as alkyloxyl group, dimethylcyclohexyl group, methylnorbornyl group, etc. and cyclohexylmethyl, adamantylmethyl, adamantylethyl, Examples of cycloalkylalkyl groups include cycloalkyl groups such as a cycloalkylethyl group and a cyclobornylethyl group. Examples of the group consisting of an alkyl group and an aromatic hydrocarbon group include a benzyl group, phenylethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, p-Methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumene group Nyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and the like aralkyl groups. Examples of the group consisting of a combination of an aromatic hydrocarbon group and an alicyclic hydrocarbon group include phenyl Aryl-cycloalkyl groups such as cyclohexyl groups, fatty acids such as p-adamantylphenyl groups Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having a cyclic hydrocarbon group.

[0013] The group represented by formula (3) is preferably an acid labile group. An acid labile group is a group that has a leaving group and is released by contact with an acid to form a hydrophilic group (e.g. For example, a hydroxy group or a carboxy group. When the group represented by formula (3) is an acid labile group, it is a group represented by formula (3A). is preferred. TIFF0007675244000006.tif2567[In formula (3A), R a1 , R a2 and R a3 each independently represents an alkoxy group having 1 to 8 carbon atoms; represents an alkyl group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R a1 and R a2 are mutual and form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are attached. You may, R a3 is an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms * represents a bond.]

[0014] R a1 , R a2 and R a3 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, Examples of the alkyl group include a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, Examples of the cycloalkyl group include a cycloheptyl group and a cyclooctyl group. Examples of the hydrocarbon group include a decahydronaphthyl group, an adamantyl group, and a norbornyl group. groups, and the following groups (* represents a bond): TIFF0007675244000007.tif10167R a1 , R a2 and R a3 The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms.

[0015] R a1and R a2 When they are bonded to each other to form an alicyclic hydrocarbon group, -C(R a1 )(R a2 )(R a3 The alicyclic hydrocarbon group preferably has 3 carbon atoms. ~12. * represents a bond to -O-. TIFF0007675244000008.tif36159

[0016] Examples of the group represented by formula (3A) include an alkoxycarbonyloxy group (formula (3A ) in R a1 , R a2 and R a3 each of which is an alkyl group, preferably te rt-Butoxycarbonyloxy group), 1-alkylcyclopentan-1-yloxy group 1-alkylcyclohexyloxy and 1-alkylcyclohexyloxy (In formula (3A), R a1 and R a2 is bonded to a cyclopentyl or cyclohexyl group Formation, R a3 is an alkyl group) and 1-(cyclopentan-1-yl)-1-a alkylalkoxycarbonyloxy group and 1-(cyclohexyl)-1-yl alkylalkoxycarbonyloxy group (in formula (3A), R a1 and R a2 is an alkyl group R a3 is a cyclopentyl group or a cyclohexyl group). Specific examples of the group represented by formula (3A) include the following groups. TIFF0007675244000009.tif31167

[0017] Examples of the novolak resin in which the hydroxy group is substituted with a group represented by formula (3) include A dendritic cell comprising a structural unit represented by the formula (a3) ​​(hereinafter sometimes referred to as "structural unit (a3)"). Fat is one example. TIFF0007675244000010.tif3692[In formula (a3), R a10 represents a hydrocarbon group having 1 to 20 carbon atoms. R ab represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. . p represents an integer of 0 to 3. When p is 2 or more, a plurality of R ab are identical to each other may also be different.] R a10 Examples of the hydrocarbon group include the same groups as those mentioned above. R ab Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. group, hexyl group, etc. ab The alkyl group having 1 to 6 carbon atoms is preferably It is an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R ab Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a bromo group, and the like. R includes, for example, an alkoxy group, a pentyloxy group, and a hexyloxy group. ab Carbon number 1 to 6 The alkoxy group is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably a meth It is an oxy group. p is preferably 0 or 1.

[0018] Further, examples of the novolak resin in which the hydroxy group is substituted with a group represented by formula (3A) include: For example, a structural unit represented by the formula (a3A) (hereinafter referred to as "structural unit (a3A)") Examples of resins include those containing TIFF0007675244000011.tif36103[In formula (a3A), Ra1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R a1 and R a2 are combined with each other and may form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which it is bonded, and R a 3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R ab represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. . p represents an integer of 0 to 3. When p is 2 or more, a plurality of R ab are identical to each other may also be different.] R a1 , R a2 and R a3 The alkyl group and the alicyclic hydrocarbon group are the same as those mentioned above. Similar groups are mentioned. R a1 and R a2 When they are bonded to each other to form an alicyclic hydrocarbon group, -C(R a1 ) (R a1 )(R a3 ) includes the same groups as those mentioned above. R ab The alkyl group and alkoxy group include the same groups as those mentioned above.

[0019] The ratio of hydroxyl groups in the novolak resin substituted with the group represented by formula (3) is It is usually 3 to 80%, preferably 5 to 70%, and more preferably 8 to 60%. be.

[0020] Novolak resin is a resin obtained by condensing a phenolic compound and an aldehyde in the presence of a catalyst. The phenol compound is, for example, phenol; o-, m- or p-phenol. -Cresol; 2,3-, 2,5-, 3,4- or 3,5-xylenol; 2,3,5- Trimethylphenol; 2-, 3- or 4-tert-butylphenol; 2-tert -Butyl-4- or 5-methylphenol; 2-, 4- or 5-methylresorcinol; 2-, 3- or 4-Methoxyphenol; 2,3-, 2,5- or 3,5-dimethoxyphenol Enol;2-Methoxyresorcinol;4-tert-Butylcatechol;2-,3- or 4-ethylphenol; 2,5- or 3,5-diethylphenol; 2,3,5- Triethylphenol; 2-naphthol; 1,3-, 1,5- or 1,7-dihydroxynaphthalene Phthalene: A polyhydric compound obtained by condensation of xylenol with hydroxybenzaldehyde. These phenolic compounds include aryloxytriphenylmethane compounds. These may be used alone or in combination of two or more. The phenolic compounds that can be used are phenol, o-cresol, m-cresol, or p -Cresol is preferred, and phenol is more preferred.

[0021] Examples of aldehydes include formaldehyde, acetaldehyde, and propionaldehyde. aldehyde, n-butyraldehyde, isobutyraldehyde, acrolein or crotonaldehyde Aliphatic aldehydes such as cyclohexane aldehyde, cyclopentane aldehyde, etc. Alicyclic aldehydes such as furyl acrolein, furfural, benzaldehyde , o-, m- or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2, 4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde or o- or m- or aromatic aldehydes such as p-hydroxybenzaldehyde; and aromatic aliphatic aldehydes such as cinnamaldehyde or cinnamic aldehyde. The aldehydes may be used alone or in combination of two or more. Among the aldehydes, formaldehyde is preferred because it is easily available industrially.

[0022] Examples of catalysts used in the condensation of phenol compounds with aldehydes include hydrochloric acid, sulfuric acid, Inorganic acids such as perchloric acid or phosphoric acid; formic acid, acetic acid, oxalic acid, trichloroacetic acid or p-toluene Organic acids such as sulfonic acids; divalent metals such as zinc acetate, zinc chloride or magnesium acetate These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is, for example, 0.01 to 1 mole per mole of aldehyde. It is.

[0023] The condensation reaction between a phenol compound and an aldehyde can be carried out according to a conventional method. The polymerization reaction is carried out, for example, by mixing a phenolic compound with an aldehyde and then heating at a temperature of 60 to 120°C. The condensation reaction can be carried out at 30° C. for about 2 to 30 hours. The condensation reaction may be carried out in the presence of methyl ethyl ketone, methyl isobutyl ketone, acetone, etc. After the reaction is completed, for example, the reaction mixture may be A water-insoluble solvent was added to the mixture, and the reaction mixture was washed with water and then concentrated to give Novoisopropyl alcohol. The rack resin can be removed.

[0024] Examples of the novolak resin in which the hydroxy group is substituted with a group represented by formula (3) include Examples of the resin include those containing structural units represented by formulae (A1-1) to (A1-6). TIFF0007675244000012.tif99155

[0025] The resin (A1) has a mass average molecular weight of 3,000 to 12,000, preferably 4,000. It is preferably from 5,000 to 10,000. The content of the resin (A1) relative to the total amount of resins contained in the resist composition is preferably It is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. Preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. The following is the result.

[0026] <Resin (A2)> The resin (A2) is a resin having a group represented by formula (2). TIFF0007675244000013.tif3259 [In formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a group having 1 to 12 carbon atoms R represents a hydrocarbon group. a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a1 ’ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a2’ and R a3’ are mutually They combine with the carbon and oxygen atoms to form a heterocyclic group having 2 to 20 carbon atoms. The hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms and the hydrocarbon group having 2 to 3 carbon atoms are preferably A methylene group contained in the heterocyclic group of 1 to 20 may be replaced by an oxygen atom or a sulfur atom. * represents a bond. The group represented by formula (2) acts as an acid labile group.

[0027] R a1’ , R a2’ and R a3’ The hydrocarbon group represented by the formula (I) is a chain hydrocarbon group (a alkyl groups, alkenyl groups and alkynyl groups), alicyclic hydrocarbon groups and aromatic hydrocarbon groups, etc. and groups formed by combining these. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples of the alkyl group include a silyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl group. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, and a butenyl group. isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples of the alkyl groups include an octenyl group, an isooctenyl group, and a nonenyl group. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, Examples thereof include a nonynyl group. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. cycloalkyl groups such as cyclooctyl group, decahydronaphthyl group, adamantyl group, etc. and polycyclic alicyclic hydrocarbon groups such as a norbornyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group and the like. The group formed by the combination is a group formed by combining an alkyl group and an alicyclic hydrocarbon group. a group combining an alkyl group and an aromatic hydrocarbon group; and groups in which an alicyclic hydrocarbon group is combined. Examples of the group combining an alkyl group and an alicyclic hydrocarbon group include methylcyclohexane. xyl group, dimethylcyclohexyl group, methylnorbornyl group, isobornyl group, and -alkyladamantan-2-yl group and the like. An example of a group that combines an alkyl group with an aromatic hydrocarbon group is an aralkyl group. Specifically, benzyl, phenethyl, phenylpropyl, trityl, naphthyl, methyl group, naphthylethyl group, p-methylphenyl group, p-tert-butylphenyl group group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2 -methyl-6-ethylphenyl group. Examples of the group consisting of a combination of an aromatic hydrocarbon group and an alicyclic hydrocarbon group include phenyl Aryl-cycloalkyl groups such as cyclohexyl groups, fatty acids such as p-adamantylphenyl groups Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having a cyclic hydrocarbon group. R a2’ and R a3’ are bonded to each other together with the carbon and oxygen atoms to which they are bonded. When a heterocyclic group is formed in -C(R a1’ )(R a2’ )-OR a3’ The following groups are used as examples: etc. * represents a bond. TIFF0007675244000014.tif22153R a1’ is preferably a hydrogen atom. R a2' is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a methyl group. and an ethyl group. R a3’ The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, An alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. More preferably, the alkyl group has 1 to 18 carbon atoms, and the alicyclic aliphatic hydrocarbon group has 3 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group are each an aryl group or an aralkyl group having 7 to 18 carbon atoms. When the aromatic hydrocarbon group has a substituent, the substituent is preferably is preferably an aryloxy group having 6 to 10 carbon atoms.

[0028] Specific examples of the group represented by formula (2) include the following groups. TIFF0007675244000015.tif63167

[0029] The resin having a group represented by formula (2) is a resin having a structural unit represented by formula (a1-2) (hereinafter Examples of the structural unit include a resin containing the structural unit (a1-2) below. TIFF0007675244000016.tif4485[In formula (a1-2), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Represents R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a1’ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a2’ and R a3’ are combined with each other and forms a divalent heterocyclic group having 2 to 20 carbon atoms together with the carbon atom and oxygen atom to which it is bonded. The hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group having 2 to 20 carbon atoms. A methylene group contained in the heterocyclic group may be replaced by an oxygen atom or a sulfur atom. R a5 represents a hydrogen atom or a methyl group. R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, a plurality of Ra6 are identical to each other But it can be different.]

[0030] In formula (a1-2), R a1’ is preferably a hydrogen atom. R a2' is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a methyl group. and an ethyl group. R a3’ The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, An alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. More preferably, the alkyl group has 1 to 18 carbon atoms, and the alicyclic aliphatic hydrocarbon group has 3 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group are each an aryl group or an aralkyl group having 7 to 18 carbon atoms. When the aromatic hydrocarbon group has a substituent, the substituent is preferably is preferably an aryloxy group having 6 to 10 carbon atoms. R a5 is preferably a hydrogen atom. R a6 is preferably an alkoxy group having 1 to 4 carbon atoms, and is preferably a methoxy group or an ethoxy group. A silyl group is more preferred, and a methoxy group is even more preferred. m is preferably 0 or 1, and more preferably 0.

[0031] Examples of monomers from which the structural unit (a1-2) is derived include those represented by the formulae (a1-2-1) to (a 1-2-14) can be mentioned. TIFF0007675244000017.tif127162

[0032] In the above monomer, R a5 A monomer in which the hydrogen atom corresponding to is replaced by a methyl group. can also be mentioned as a specific example of the monomer. Among them, formula (a1-2-2), formula (a1-2-3), (a1-2-4), (a1-2 -9), (a1-2-14) is preferred, and the structural unit derived from a monomer represented by the formula Represented by (a1-2-2), (a1-2-3), (a1-2-4), and (a1-2-9) Structural units derived from monomers are more preferred.

[0033] In the resin containing the structural unit (a1-2), the content of the structural unit (a1-2) is A2) is preferably from 10 to 80 mol %, more preferably from 20 to 70 mol %, based on the total structural units. It is preferably 30 to 60 mol %, and more preferably 30 to 60 mol %.

[0034] The resin containing the structural unit (a1-2) further contains, in addition to the structural unit (a1-2), an acid labile In the art, a structural unit having no group (hereinafter sometimes referred to as "structural unit (a2)") It may contain known structural units. The structural unit (a2) having no acid labile group is, in the resin containing the structural unit (a1-2), It may have only one type or a plurality of types.

[0035] The structural unit (a2) is, for example, a structural unit represented by any one of formulas (a2-1) to (a2-3). The structural unit (hereinafter, may be referred to as "structural unit (a2-1)" etc. depending on the formula number) ) are mentioned. TIFF0007675244000018.tif54125 [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 are identical to each other may be different. R a11 represents a hydrogen atom or a primary or secondary hydrocarbon group having 1 to 10 carbon atoms. R a12 represents a primary or secondary alkyl group having 1 to 6 carbon atoms. L a1 represents an alkanediyl group having 2 to 6 carbon atoms. The atoms are primary or secondary carbon atoms. n represents an integer of 1 to 30. When n is 2 or more, multiple L a1 are identical to each other may also be different.]

[0036] R a10 or R a12 The alkyl group represented by the formula (I) is a methyl group, an ethyl group, a propyl group, Examples of the alkyl group include an aryl group, a butyl group, a pentyl group, and a hexyl group. R a10 Examples of the alkoxy group represented by the formula (I) include a methoxy group, an ethoxy group, a propoxy group, Examples thereof include a butoxy group, a pentyloxy group, and a hexyloxy group. R a11 As the hydrocarbon group represented by the formula (I), an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, groups and groups formed by combining these groups. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples of the alkyl group include a silyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the aryl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include, for example, For example, decahydronaphthyl, adamantyl, norbornyl and the following groups (* indicates a bond): It represents the following: TIFF0007675244000019.tif11164 Examples of groups combining an alkyl group and an alicyclic hydrocarbon group include methylcyclohexyl. cyclohexyl, dimethylcyclohexyl, methylnorbornyl, cyclohexylmethyl, Examples thereof include a damantylmethyl group and a norbornylethyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the group formed by combining an alkyl group with an aromatic hydrocarbon group include an aralkyl group such as a benzyl group. Examples include:

[0037] L a1 The alkanediyl group is an ethylene group, a propane-1,3-diyl group, a proline group, Pan-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, heptane-1,6-diyl group, xanthane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group and and propane-2,2-diyl; propane-1,2-diyl, pentane-2,4-diyl 2-methylpropane-1,3-diyl group, pentane-1,4-diyl group, 2-methyl branched alkanediyl groups such as lobutan-1,4-diyl group; and the like.

[0038] 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 alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group. An oxy group is more preferable, and a methoxy group is even more preferable. m' is preferably 0 or 1, and more preferably 0. R a11 is preferably a primary or secondary alkyl group having 1 to 6 carbon atoms. L a1 is preferably an alkanediyl group having 2 to 4 carbon atoms, and ethane-1,2- Diyl group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4 More preferably, it is an ethane-1,2-diyl group, and even more preferably, it is an ethane-1,2-diyl group. I wish. It is preferable that n is an integer of 1-10. R a12 is preferably a primary or secondary alkyl group having 1 to 3 carbon atoms.

[0039] The structural unit (a2-1) may be any of the following: The structural unit represented by formula (a-1-3) or formula (a2-1-4) is preferred. Monomers from which 2-1) can be derived are described, for example, in JP-A-2010-204634. do. TIFF0007675244000020.tif39125

[0040] Examples of the monomer from which the structural unit (a2-2) is derived include methyl (meth)acrylate. , ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate (meth)acrylic acid alkyl esters such as hexyl (meth)acrylate and hexyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. p) acrylic acid cycloalkyl ester; Polycyclic (meth)acrylic acid esters such as adamantyl (meth)acrylate; (Meth)acrylics such as phenyl (meth)acrylate and benzyl (meth)acrylate Acid aryl esters are included.

[0041] Examples of monomers from which the structural unit (a2-3) is derived include ethylene glycol monomethyl ether. Ethylene glycol monoethyl ether (meth)acrylate acrylate, ethylene glycol monopropyl ether (meth)acrylate, ethylene glycol Liquor monobutyl ether (meth)acrylate, diethylene glycol monomethyl ether Triethylene glycol monomethyl ether (meth)acrylate acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, penta Ethylene glycol monomethyl ether (meth)acrylate, hexaethylene glycol Monomethyl ether (meth)acrylate, nonaethylene glycol monomethyl ether Octaethylene glycol monomethyl ether (meth)acrylate Examples of suitable methacrylate esters include (meth)acrylates.

[0042] Further, examples of the monomer from which the structural unit (a2) is derived include acrylic acid, methacrylic acid, chloroform, and the like. Acid, 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate Acrylates, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene , 3-methylstyrene, 4-methoxystyrene, 4-isopropoxystyrene, etc. can be.

[0043] The structural unit (a2) may be, for example, a structural unit represented by formula (a2-4). TIFF0007675244000021.tif5146[In formula (a2-4), R a13 represents a hydrogen atom or a methyl group. R a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R a15 represents a primary or secondary hydrocarbon group having 1 to 12 carbon atoms, The methylene group may be substituted with an oxygen atom or a carbonyl group. The bonding methylene group is not replaced by an oxygen atom. m" represents an integer of 0 to 4. When m" is 2 or more, multiple R a14 are identical to each other may be different. m''' represents an integer from 0 to 4. When m''' is 2 or more, multiple R a15 are identical to each other may be the same or different. However, the sum of m" and m''' is 5 or less.

[0044] In other words, R a15 In the above, the bond to the oxygen atom must not be a tertiary carbon atom. A group that has one or more atoms other than carbon atoms, such as hydrogen atoms, bonded to its carbon bond. Examples of the groups include Therefore, the structural unit represented by the formula (a2-4) is a structural unit (I) and a structural unit (a1- 2) is not included.

[0045] R a14 The alkyl and alkoxy groups of R a10 The same groups as those shown below can be mentioned. R a15 As the hydrocarbon group of R a11 The same groups as those shown below can be mentioned. R a15 Among them, straight or branched alkyl groups having 1 to 5 carbon atoms, An alicyclic hydrocarbon group, a phenyl group, or a group formed by combining these groups, Preferably, the carbon atom adjacent to the oxygen atom of the above group is replaced with a carbonyl group.

[0046] Examples of the structural unit (a2-4) include those represented by the formulae (a2-4-1) to (a2-4-10): Examples of the structural unit include those represented by the following formula: TIFF0007675244000022.tif91153

[0047] In the structural units represented by formulas (a2-4-1) to (a2-4-10), R a13 The structural unit in which the hydrogen atom corresponding to the structural unit (a2-4) is replaced by a methyl group is also called the structural unit (a2-4). The following can be given as a specific example.

[0048] The resin containing the structural unit (a1-2) is a resin containing a structural unit (a2-1), a structural unit (a2-2), When the structural unit (a2-3) and the structural unit (a2-4) are present, the total content of these is The content is preferably 20 to 90 mol %, more preferably 30 to 80 mol %, based on the total structural units of the resin (A2). It is more preferable that the content is 40 to 60 mol %, and further more preferable that the content is 40 to 60 mol %.

[0049] When the resin containing the structural unit (a1-2) has the structural unit (a2), The content ratio of structural unit (a1-2) to structural unit (a2) [structural unit (a1-2):structural unit (a2)] is On a per-unit basis, the ratio is preferably 10:90 to 80:20, and more preferably 20:80 to 70 :30, and more preferably 30:70 to 60:40.

[0050] Examples of the resin containing the structural unit (a1-2) include those represented by the formulae (A2-1) to (A2-22) ) is included. TIFF0007675244000023.tif57136

[0051] TIFF0007675244000024.tif119159

[0052] TIFF0007675244000025.tif91158

[0053] TIFF0007675244000026.tif137123

[0054] In the above structural formula, R a5 The hydrogen atom corresponding to the above is a methyl group or the methyl group is a hydrogen A structural unit in which an atom is substituted can also be given as a specific example of the structural unit. In one resin, structural units having a hydrogen atom and a methyl group may be present together.

[0055] The resin containing the structural unit (a1-2) preferably contains the structural unit (a1-2) and the structural unit (a 2), and more preferably, a resin having the structural unit (a1-2) and the structural unit (a2- 1) A resin having the above properties.

[0056] In addition, the resin having a group represented by formula (2) is a novolak resin having a hydroxy group represented by formula (2) Also included are resins substituted with a group represented by formula (2). In a novolak resin in which the hydroxy group is substituted with a group represented by formula (2), The volac resin is a novolac resin similar to the novolac resin exemplified above as resin (A1). Examples include:

[0057] Examples of novolak resins in which the hydroxyl groups are substituted with groups represented by formula (2) include For example, a structural unit represented by formula (a4) (hereinafter sometimes referred to as "structural unit (a4)") Examples of resins include those containing TIFF0007675244000027.tif3485[In formula (a4), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Represents R a3’represents a hydrocarbon group having 1 to 20 carbon atoms, or R a1’ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a2’ and R a3’ are combined with each other and forms a divalent heterocyclic group having 2 to 20 carbon atoms together with the carbon atom and oxygen atom to which it is bonded. The hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group having 2 to 20 carbon atoms. A methylene group contained in the heterocyclic group may be replaced by an oxygen atom or a sulfur atom. R ab represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. . p represents an integer of 0 to 3. When p is 2 or more, a plurality of R ab are identical to each other may also be different.] R a1’ , R a2’ and R a3’ Examples of the hydrocarbon group include the same groups as those described above. can be done. R a2’ and R a3’ are bonded to each other together with the carbon and oxygen atoms to which they are bonded. When a heterocyclic group is formed in -C(R a1’ )(R a2’ )-OR a3’ As mentioned above, The same groups as those in the group can be mentioned. R ab Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. group, hexyl group, etc. ab The alkyl group having 1 to 6 carbon atoms is preferably It is an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R ab Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a bromo group, and the like. R includes, for example, an alkoxy group, a pentyloxy group, and a hexyloxy group.ab Carbon number 1 to 6 The alkoxy group is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably a meth It is an oxy group. p is preferably 0 or 1.

[0058] Examples of novolak resins in which the hydroxyl groups are substituted with groups represented by formula (2) include For example, resins containing structural units represented by formulas (A2-23) to (A2-28) can be mentioned. do. TIFF0007675244000028.tif94153

[0059] A specific example of a resin having a group represented by formula (2) is polyhydroxystyrene. A resin in which the hydroxy group is substituted with a group represented by formula (2), or a novolak resin having a hydroxy group represented by formula (3): Examples of the resin include a resin in which a silyl group is substituted with a group represented by formula (2).

[0060] The hydroxy group in the polyhydroxystyrene is substituted with a group represented by formula (2) The ratio is usually 10 to 80%, preferably 20 to 70%, and more preferably It is 30 to 60%. The ratio of the group represented by formula (2) introduced relative to the hydroxyl group of the novolak resin is It is usually 10 to 80%, preferably 20 to 70%, and more preferably 30 to 60%. The probability is 0%. The resin (A2) has a mass average molecular weight of 3,000 to 80,000, preferably 4,000. It is preferably from 5,000 to 20,000.

[0061] When the resin (A) contains the resin (A2), the content of the resin (A2) in the resist composition is Preferably, the content is 5% by mass or more, more preferably 10% by mass or more, based on the total amount of resin. It is preferably 70% by mass or less, and more preferably 65% ​​by mass or less.

[0062] <Resin (A3)> The resin (A3) is preferably an alkali-soluble resin. The resin contains an acidic group and is soluble in an alkaline developer. group, a sulfo group, and a phenolic hydroxy group. Examples of the alkali-soluble resin include alkali-soluble resins known in the resist field. For example, novolac resins, resins having polymerization units derived from hydroxystyrene, (meth)styrene Examples include resins having polymerization units derived from acrylic esters and polyalkylene glycols. The novolak resin is preferable. The alkali-soluble resin may be used alone. Two or more of them may be used in combination.

[0063] As mentioned above, novolak resin is a compound obtained by reacting a phenol compound with an aldehyde in the presence of a catalyst. The phenol compound is, for example, phenol; o-, m- or p-cresol; 2,3-, 2,5-, 3,4- or 3,5-xylenol 2,3,5-trimethylphenol; 2-, 3- or 4-tert-butylphenol 2-tert-butyl-4- or 5-methylphenol; 2-, 4- or 5-methyl Resorcinol; 2-, 3- or 4-methoxyphenol; 2,3-, 2,5- or 3, 5-Dimethoxyphenol;2-Methoxyresorcinol;4-tert-Butylcatechol 2-, 3- or 4-ethylphenol; 2,5- or 3,5-diethylphenol ;2,3,5-triethylphenol;2-naphthol;1,3-, 1,5- or 1,7 -Dihydroxynaphthalene; by condensation of xylenol with hydroxybenzaldehyde The polyhydroxytriphenylmethane compounds obtained from these phenols include The compounds may be used alone or in combination of two or more. The phenol compounds used in (A3) include o-cresol, m-cresol, p -Cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-Xylenol, 2,3,5-Trimethylphenol, 2-tert-Butylphenol phenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butylphenol rt-Butyl-4-methylphenol or 2-tert-butyl-5-methylphenol Ru is preferred. Examples of aldehydes include formaldehyde, acetaldehyde, and propionaldehyde. aldehyde, n-butyraldehyde, isobutyraldehyde, acrolein or crotonaldehyde Aliphatic aldehydes such as cyclohexane aldehyde, cyclopentane aldehyde, etc. Alicyclic aldehydes such as furyl acrolein, furfural, benzaldehyde , o-, m- or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2, 4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde or o- or m- or aromatic aldehydes such as p-hydroxybenzaldehyde; and aromatic aliphatic aldehydes such as cinnamaldehyde or cinnamic aldehyde. The aldehydes may be used alone or in combination of two or more. Among the aldehydes, formaldehyde is preferred because it is easily available industrially. Examples of catalysts used in the condensation of phenol compounds with aldehydes include hydrochloric acid, sulfuric acid, Inorganic acids such as perchloric acid or phosphoric acid; formic acid, acetic acid, oxalic acid, trichloroacetic acid or p-toluene Organic acids such as sulfonic acids; divalent metals such as zinc acetate, zinc chloride or magnesium acetate These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is, for example, 0.01 to 1 mole per mole of aldehyde. It is. The condensation reaction between a phenol compound and an aldehyde can be carried out according to a conventional method. The polymerization reaction is carried out, for example, by mixing a phenolic compound with an aldehyde and then heating at a temperature of 60 to 120°C. The condensation reaction can be carried out at 30° C. for about 2 to 30 hours. The condensation reaction may be carried out in the presence of methyl ethyl ketone, methyl isobutyl ketone, acetone, etc. After the reaction is completed, for example, the reaction mixture may be A water-insoluble solvent was added to the mixture, and the reaction mixture was washed with water and then concentrated to give Novoisopropyl alcohol. The rack resin can be removed.

[0064] The resin (A3) has a mass average molecular weight of 3,000 to 10,000, preferably 4,000. The range is preferably from 5,000 to 9,000, and more preferably from 5,000 to 8,000. This makes it possible to effectively prevent thinning and residue remaining after development.

[0065] The resin having a polymerization unit derived from hydroxystyrene is typically polyhydroxystyrene. The preferred polyhydrogen is poly-p-hydroxystyrene. Xystyrene is a monomer described in, for example, JP-A-2010-204634. can be obtained by polymerizing

[0066] Examples of the resin having a polymerization unit derived from a (meth)acrylic acid ester include the following: Such compounds are used as monomers, and one or more of these monomers are combined and reacted in a conventional manner. Examples of the copolymer include those obtained by polymerization of the above-mentioned copolymer. those with carboxy groups, such as (meth)acrylic acid; 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate those with hydroxy groups such as carboxylates; Diethylene glycol monomethyl ether (meth)acrylate, triethylene glycol Tetraethylene glycol monomethyl ether (meth)acrylate Pentaethylene glycol monomethyl ether (meth)acrylate Acrylate, Hexaethylene glycol monomethyl ether (meth)acrylate, Hep Octaethylene glycol monomethyl ether (meth)acrylate, Octaethylene glycol Monomethyl ether (meth)acrylate, nonaethylene glycol monomethyl ether Polyethylene glycol monomethyl ether (meth)acrylate, etc. Those with multiple ether bonds, such as acrylates.

[0067] The above monomers and methyl (meth)acrylate, ethyl (meth)acrylate, te (Meth)acrylic acid alkyl esters such as rt-butyl (meth)acrylate, cyclohexane (Meth)acrylates such as cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate Cycloalkyl acrylates; polycyclic acrylates such as adamantyl (meth)acrylate (Meth)acrylic acid esters; Ethylene glycol monomethyl ether (meth)acrylic acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol Ethylene glycol monopropyl ether (meth)acrylate, Ethylene glycol monobutyl ether ethylene glycol monoalkyl ether (meth)acrylate, It is also possible to use a combination of the above.

[0068] When the resin (A) contains the resin (A3), the content of the resin (A3) in the resist composition is It is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total amount of resin. , preferably 70% by mass or less, and more preferably 65% ​​by mass or less.

[0069] The content of the resin (A) in the resist composition is 8 to 100% based on the solid content of the resist composition. The content is preferably 0% by mass or more and 99% by mass or less, and more preferably 90 to 99% by mass. The solid content of the resist composition and the resin content therein were measured by liquid chromatography or The measurement can be performed by a known analytical method such as gas chromatography.

[0070] <Acid Generator (B)> The acid generator (B) may be either a nonionic or ionic acid generator. Biocides include sulfonate esters (e.g., 2-nitrobenzyl esters, aromatic sulfonates, etc.). sulfonates, oximesulfonates, N-sulfonyloxyimides, sulfonyloxyketones ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g. disulfone, ketone Examples of ionic acid generators include oni Onium salts containing ion cations (e.g. diazonium salts, phosphonium salts, sulfonium salts) The anion of the onium salt is typically a sulfonate anion. ion, sulfonylimide anion, sulfonylmethide anion, etc. Examples of the acid generator (B) include those described in JP-A-63-26653 and 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, European Patent No. Compounds that generate an acid when exposed to radiation, such as those described in US Pat. No. 5,312,712, can be used. In addition, a compound produced by a known method may be used. The acid generator (B) may be a compound containing two or more kinds of compounds. They may also be used in combination.

[0071] The nonionic acid generator is a compound having a group represented by formula (B1) (* represents a bond). Compounds are preferred. TIFF0007675244000029.tif2257[In formula (B1), R b1 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, The methylene group contained in the group may be substituted with an oxygen atom or a carbonyl group. The nitrogen atom may have a double bond.

[0072] Examples of the hydrocarbon group having 1 to 18 carbon atoms include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Hydrogen groups and combinations thereof are also included. The chain hydrocarbon group is preferably an alkyl group, for example, a methyl group, an ethyl group, a proline group, Pyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and An example of such a group is a decyl group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, Examples include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group. can be. The aromatic hydrocarbon group is preferably an aryl group having 6 to 18 carbon atoms, for example, phenyl. Examples of aryl groups include aryl groups such as aryl, naphthyl, anthryl, biphenyl, and phenanthryl groups. Can be obtained. The combined group may be a group that combines a chain hydrocarbon group with an alicyclic hydrocarbon group (e.g. For example, cycloalkylalkyl groups, aralkyl groups such as benzyl groups, and alkyl groups having chain hydrocarbon groups. Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, triphenylphenyl, etc.) phenyl, xylyl, cumenyl, mesityl, 2,6-diethylphenyl, 2-methyl -6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclo phenylcyclohexyl group, p-adamantylphenyl group, etc. Examples include aryl-cycloalkyl groups. R b1 The hydrocarbon group represented by the formula (I) is preferably an alkyl group or a hydrocarbon group having 1 to 10 carbon atoms. It is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. More preferably, it is an alkyl group having 1 to 4 carbon atoms.

[0073] R b1 is an alicyclic hydrocarbon group or an alicyclic hydrocarbon group having a chain hydrocarbon group, Alicyclic hydrocarbon groups in which a methylene group is substituted with an oxygen atom or a carbonyl group. Examples of the groups include those represented by the formulae (Y1) to (Y12). A group represented by the formula (Y9) is preferable, and a group represented by the formula (Y9) is more preferable. TIFF0007675244000030.tif64161

[0074] Examples of the hydrocarbon group having a fluorine atom include a fluoromethyl group, a fluoroethyl group, and a fluoromethyl group. Fluoropropyl group, fluorobutyl group, fluoropentyl group, fluorohexyl group, fluoro fluoro groups such as fluoroheptyl group, fluorooctyl group, fluorononyl group, and fluorodecyl group Alkyl group; fluorocyclopropyl group, fluorocyclobutyl group, fluorocyclopentene group Fluorocyclohexyl, fluorocycloheptyl, fluorocyclooctyl fluorocycloalkyl groups such as fluorophenyl groups, fluoroadamantyl groups, etc.; Examples of the fluoroaryl group include a fluoronaphthyl group and a fluoroanthryl group.

[0075] The hydrocarbon group having a fluorine atom is preferably a hydrocarbon group having 1 to 1 carbon atoms and a fluorine atom. an aromatic hydrocarbon group having 6 to 10 carbon atoms and having an alkyl group having 0 or a fluorine atom, Preferably, it is a perfluoroalkyl group having 1 to 8 carbon atoms, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms. 4 is a perfluoroalkyl group.

[0076] The compound having a group represented by formula (B1) includes compounds represented by formulas (b1) to (b3). Compounds represented by formula (b1) and formula (b2) are preferred, and more preferably A compound represented by formula (b1) is preferred. TIFF0007675244000031.tif38159 [In formula (b1) to formula (b3), R b1 has the same meaning as above. R b2’ , R b3 and R b4 are each independently a hydrogen atom or 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. represent. x represents an integer of 0 to 2. When x is 2, multiple R b2’ are the same may also be different.]

[0077] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Of these, a methyl group is preferred. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group. Examples of the aryl group include a methoxy group.

[0078] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring. do. The aromatic heterocycle may be a ring having 6 to 14 atoms constituting the ring, and preferably has the following structure: Examples of such rings include: TIFF0007675244000032.tif21129 Ring W b1 The substituent that may be present in the alkyl group includes an alkyl group having 1 to 5 carbon atoms. do. Ring W b1 is preferably a naphthalene ring.

[0079] The compound represented by formula (b1) is represented by any one of formulas (b4) to (b7). A compound represented by formula (b4) is preferred, and a compound represented by formula (b5) is more preferred. TIFF0007675244000033.tif59138 [In formulas (b4) to (b7), R b1 has the same meaning as above. R b2 , R b5 , R b6 and R b7are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. represents an alkyl group.

[0080] The compound represented by formula (b1) includes compounds represented by formulas (b1-1) to (b1-14). Compounds represented by formula (b1-6) or (b1-7) are preferred. It is an object. TIFF0007675244000034.tif102155

[0081] TIFF0007675244000035.tif27155

[0082] Examples of the compound represented by formula (b2) include compounds represented by the following formula: TIFF0007675244000036.tif55145

[0083] Examples of the compound represented by formula (b3) include compounds represented by the following formula: TIFF0007675244000037.tif16155

[0084] The ionic acid generator is preferably a compound represented by formula (b8) or formula (b9). TIFF0007675244000038.tif38127[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 are each independently an alkyl group having 1 to 10 carbon atoms. group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. X1 ― and X2 - represents an organic anion.

[0085] The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples include a silyl group, a heptyl group, and an octyl group. The aromatic hydrocarbon group includes a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, nyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, Silyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethyl Examples of the aryl group include an aryl group such as a phenyl group and a 2-methyl-6-ethylphenyl group. R b8 , R b9 , R b10 and R b11 Each of the aromatic rings preferably has 6 to 12 carbon atoms. It is an aromatic compound, more preferably a phenyl group.

[0086] X1 - and X2 - As the organic anion represented by the formula, a sulfonate anion, a bis(alanine) tris(alkylsulfonyl)amide anion, and tris(alkylsulfonyl)methide anion A sulfonate anion is preferred, and a sulfonate anion is more preferred, which is represented by the formula (b10). It is a sulfonate anion. TIFF0007675244000039.tif1953[In formula (b10), R b12 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, The methylene group contained in the alkyl 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.

[0087] Examples of the compound represented by formula (b8) include the following compounds. TIFF0007675244000040.tif102124

[0088] Examples of the compound represented by formula (b9) include the following compounds. TIFF0007675244000041.tif61147

[0089] In the resist composition of the present invention, the content of the acid generator is On the other hand, the amount is preferably 0.5 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less. The resist of the present invention is preferably 1 part by mass or more and more preferably 5 parts by mass or less. The composition may contain one type of acid generator (B) alone or a plurality of types.

[0090] <Quencher (C)> The quencher (C) is a compound having a function of capturing the acid generated from the acid generator upon exposure to light. The quencher (C) may be a basic nitrogen-containing organic compound. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of amines include aliphatic and aromatic amines; primary, secondary and tertiary amines. Examples include:

[0091] The amine may, for example, be a compound represented by formula (C1) or formula (C2). TIFF0007675244000042.tif2261[In formula (C1), R c1 , R c2 and R c3 are each independently a hydrogen atom, a carbon atom having 1 to 1 an alkyl group having 5 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms The hydrogen atoms contained in the alkyl group and the alicyclic hydrocarbon group are each independently selected from the group consisting of a hydroxyl group and a cycloaliphatic hydrocarbon group. The aromatic hydrocarbon may be substituted with an amino group or an alkoxy group having 1 to 6 carbon atoms. The hydrogen atom contained in the group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or It may be substituted with an alicyclic hydrocarbon group having 5 to 10 carbon atoms.]

[0092] The alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and alkoxy group in formula (C1) The alkanediyl group includes the same groups as those mentioned above.

[0093] The compound represented by formula (C1) includes 1-naphthylamine, 2-naphthylamine, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline Phosphorus, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine amine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine , dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine diamine, didecylamine, triethylamine, trimethylamine, tripropylamine , tributylamine, tripentylamine, trihexylamine, triheptylamine, Trioctylamine, trinonylamine, tridecylamine, dibutylmethylamine, Dipentylamine, Dihexylmethylamine, Dicyclohexylmethylamine, Dihe Butylmethylamine, Methyldioctylamine, Methyldinonylamine, Didecylmethyl Amine, Ethyldibutylamine, Ethyldipentylamine, Ethyldihexylamine, Ethyl Ethyldiheptylamine, Ethyldioctylamine, Ethyldinonylamine, Ethyldidecylamine Aminopropylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanol Aminopropylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4, 4'-Diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyl diphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, etc. Of these, diisopropylaniline is preferred, and 2,6-diisopropylaniline is particularly preferred. Examples of such aniline include propyl aniline.

[0094] TIFF0007675244000043.tif1978[In formula (C2), Ring W 1 is a heterocyclic ring containing a nitrogen atom as an atom constituting the ring, or a substituted or unsubstituted a The heterocycle and the benzene ring are each independently a hydroxyl group and a carbon atom. It may have at least one selected from the group consisting of alkyl groups 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 1 may be the same or different.]

[0095] The substituted or unsubstituted amino group is -N(R 4 )(R 5 ) and R 4 and R 5 teeth , each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, It represents a hydrocarbon group or an aromatic hydrocarbon group having 6 to 14 carbon atoms. Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Examples of alkyl groups include hexyl, heptyl, and octyl groups. The alicyclic hydrocarbon group is R a1 ~R a3 The same groups as in Examples of the aromatic hydrocarbon group include R a1’ ~R a3’ In The same groups as those shown below can be mentioned.

[0096] The heterocycle containing a nitrogen atom as an atom constituting the ring may be an aromatic ring or a non-aromatic ring. In addition, the heterocycle may have another heteroatom (for example, an oxygen atom or a sulfur atom). The number of nitrogen atoms contained in the heterocycle is, for example, 1 to 3. Examples of the heterocycle include those represented by the formula (Y 13) to (Y28). One of the hydrogen atoms contained in the ring is a ring represented by any one of the following formulas: The pair is separated, A 1 It becomes a combination with. TIFF0007675244000044.tif66151

[0097] Ring W 1 is preferably a heterocycle containing a nitrogen atom as an atom constituting the ring, and more preferably is a 5- or 6-membered aromatic heterocycle containing a nitrogen atom as an atom constituting the ring, Preferably, it is a ring represented by any one of formulae (Y20) to (Y25).

[0098] The compound represented by formula (C2) is any one of formulas (C2-1) to (C2-11). The compounds represented by the formula (C2-2) to (C2-8) are preferable. It is a compound represented by the formula: TIFF0007675244000045.tif102167

[0099] The content of the quencher (C) in the solid content of the resist composition is preferably 0.0001 The concentration is preferably 0.0001 to 5% by mass, more preferably 0.0001 to 4% by mass, and even more preferably 0. 0.001 to 3 mass %, more preferably 0.01 to 1.0 mass %, and particularly The content is preferably 0.1 to 0.7 mass %.

[0100] <Solvent (D)> The content of the solvent (D) in the resist composition is usually 45% by mass or more and 99.9% by mass or less. It is preferably 50% by mass or more and 99% by mass or less, and more preferably 55% by mass or more. The content of the solvent (D) is 90% by mass or less. The content of the solvent (D) is, for example, measured by liquid chromatography or gas chromatography. This can be measured by known analytical means such as chromatography. The solvent (D) may be ethyl cellosolve acetate, methyl cellosolve acetate, or Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, acetic acid esters such as butyl acetate, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; cyclic esters; etc. One type of solvent (D) may be used alone, Two or more types may be used.

[0101] <Adhesion improver (E)> The adhesion improver (E) prevents corrosion of metals used in substrates or wiring, etc. There are no particular limitations on the type of material as long as it can improve the adhesion and / or the adhesion of the material to metals. In addition to these effects, it also has a strong anti-rust effect on the substrate or metal and resist. The adhesion to the composition can be improved. Examples of the adhesion improver (E) include sulfur-containing compounds, aromatic hydroxy compounds, benzene compounds, and the like. Examples of the compounds include isotriazole-based compounds, triazine-based compounds, and silicon-containing compounds. These can be used alone or in combination of two or more.

[0102] 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. It may also be a mixture. An example of a chain compound is dithiodiglycerol [S(CHCH(OH)CH(OH ))2], bis(2,3-dihydroxypropylthio)ethylene [CH2CH2(SCH 2CH(OH)CH2(OH))2], 3-(2,3-dihydroxypropylthio)-2 -Methyl-propylsulfonic acid sodium salt [CH2(OH)CH(OH)CH2SCH2 CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)C H2(OH)], sodium 3-mercapto-1-propanesulfonate [HSCH2CH 2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], thio Glycolic acid [HSCH2CO2H], 3-mercapto-1-propanol [HSCH2 CH2CH2] etc.

[0103] The sulfur-containing compound is preferably a compound having a sulfide bond and a mercapto group. More preferably, the heterocyclic compound is a heterocyclic compound having a sulfide bond and a mercapto group. The heterocyclic compound is more preferably a heterocyclic compound having a sulfide bond in the ring structure. In the sulfur-containing compound, the number of sulfide bonds and mercapto groups is not particularly limited. , each of which may be 1 or greater. The heterocyclic compound having a sulfide bond in the ring structure may be either a monocyclic or polycyclic ring. The ring may be either saturated or unsaturated. The compound preferably further contains a heteroatom other than a sulfur atom. Examples of the alkyl group include a hydrogen atom and a nitrogen atom, and a nitrogen atom is preferable. As the heterocyclic compound having a sulfide bond in the ring structure, a heterocyclic compound having 2 to 12 carbon atoms is Heterocyclic compounds having 2 to 6 carbon atoms are preferred, and heterocyclic compounds having 2 to 6 carbon atoms are more preferred. It is preferable that the heterocyclic compound having a sulfide bond in the ring structure is unsaturated. It is preferable that the heterocyclic compound having a sulfide bond in the ring structure is unsaturated and monocyclic. is preferred.

[0104] Examples of heterocyclic compounds having a sulfide bond in the ring structure include the following heterocyclic compounds: can be. TIFF0007675244000046.tif36145

[0105] The sulfur-containing compound may be a polymer. The polymer may have a sulfide bond and a mercapto group. It is preferable that the structure has a sulfide bond and a mercapto group in the side chain. The structure having the unit (hereinafter sometimes referred to as unit (1)) and the main chain are connected by an amide bond, an amide bond, an amide bond, and an amide bond. It is preferable that the linkage is via a linking group such as a ter bond, a thioether bond, or an ester bond.

[0106] The polymer may be a homopolymer or a copolymer. When the polymer is a copolymer, the structural unit having an acid labile group, It may contain structural units that are not included. The weight average molecular weight of the homopolymer and copolymer is usually 3000 or more, preferably is 5000 or more, and usually 100,000 or less, preferably 50,000 or less. When the sulfur-containing compound is a polymer, it is preferable that the polymer has a structural unit having a sulfide bond and a mercapto group. The content of the sulfur-containing compound is usually 0.1 to 50 mol% based on the total structural units of the polymer of the sulfur-containing compound. %, preferably 0.5 to 30 mol %, and more preferably 1 to 20 mol %.

[0107] The sulfur-containing compound is, for example, a compound represented by formula (IA) or a compound represented by formula (IB) It is preferably a polymer having units. TIFF0007675244000047.tif2668[In formula (IA), R i11 is a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, Hydrocarbon group, alicyclic hydrocarbon group having 3 to 18 carbon atoms, -SR 11 or a group represented by -NR 12 R 13 It represents a group represented by the following formula: R 11 , R 12 and R 13 are each independently a hydrogen atom, a chain hydrocarbon having 1 to 10 carbon atoms, a hydrocarbon group having 3 to 10 carbon atoms, an alicyclic hydrocarbon group having 6 to 14 carbon atoms, or a carbon represents an alkylcarbonyl group having a number of 1 to 12, and these chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic The hydrogen atoms of the aromatic hydrocarbon group and the alkylcarbonyl group are replaced by hydroxy groups. This is also fine. R i12 and R i13 are each independently a hydrogen atom or 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, and B is a nitrogen atom; m1 represents 0, and when B is a carbon atom, m1 represents 1.

[0108] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Examples of alkyl groups include hexyl, heptyl, and octyl groups. The aromatic hydrocarbon group includes a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, nyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, Silyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethyl Examples of the aryl group include an aryl group such as a phenyl group and a 2-methyl-6-ethylphenyl group. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups, cyclooctyl groups, and decahydronaphthalene groups; Examples of the polycyclic alicyclic hydrocarbon groups include a naphthyl group, an adamantyl group, and a norbornyl group. can be.

[0109] R 11 is preferably a chain hydrocarbon group or an alkylcarbonyl group, and R 12 Reach BiR 13 are each independently a hydrogen atom, a chain hydrocarbon group, an aromatic hydrocarbon group, or an alkyl A carbonyl group is preferred. The alkylcarbonyl group includes an acetyl group, a propionyl group, a butyryl group, and a valeryl group. group, hexylcarbonyl group, heptylcarbonyl group, octylcarbonyl group, decylcarbonyl group Examples of the alkyl group include dodecylcarbonyl and benzoyl groups.

[0110] R i11 is more preferably a hydrogen atom or a mercapto group. R i12 and R i13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferable that the aryl group is a hydrogen atom, and more preferable that the aryl group is a hydrogen atom. At least one of A and B is preferably a nitrogen atom, and both are preferably nitrogen atoms. It is more preferable that

[0111] TIFF0007675244000048.tif5478[In formula (IB), R i21 and R i31 are each independently a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms. represents 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 is a nitrogen atom, n2 represents 0, A 1 is a carbon atom, n2 represents 1, B 1 When is a nitrogen atom, In this case, m2 represents 0, and B 1 is a carbon atom, m2 represents 1. R i4 It represents a hydrogen atom or a methyl group. X i1 represents a sulfur atom or an NH group. L i1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. The aryl group may be substituted with an oxygen atom or a carbonyl group.

[0112] R i21 and R i31 Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, Examples of alkyl groups include butyl, pentyl, hexyl, heptyl, and octyl groups. Of these, preferred is an alkyl group having 1 to 4 carbon atoms. R i21 and R i31Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an aryl group, and an aryl group. p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group Phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthrene group Aryl groups, 2,6-diethylphenyl groups, and 2-methyl-6-ethylphenyl groups. An aryl group having 6 to 10 carbon atoms is preferable. R i21 and R i31 Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, and Monocyclic alicyclic carbonyl groups such as cycloalkyl groups, cyclohexyl groups, cycloheptyl groups, and cyclooctyl groups. Hydrogen radicals; and polycyclic radicals such as decahydronaphthyl radicals, adamantyl radicals, and norbornyl radicals. Alicyclic hydrocarbon groups are preferred, and preferably, alicyclic hydrocarbon groups having 5 to 10 carbon atoms are preferred. do. R i21 and R i31 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferable that

[0113] L i1 Examples of the divalent hydrocarbon group represented by the formula include a methylene group, an ethylene group, a propane-1 ,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane -1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, Dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1, 14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1, 1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane- 2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1, 2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Alkanediyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as cyclohexene-1,4-diyl group and cyclooctane-1,5-diyl group a monocyclic divalent alicyclic saturated hydrocarbon group, Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen radicals, etc.; 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 It is a group formed by combining an arylene group having 6 to 10 carbon atoms and an alkanediyl group having 1 to 11 carbon atoms.

[0114] The structural unit represented by formula (IB) is preferably a structural unit represented by formula (IB-1) or It is a structural unit represented by formula (IB-2). TIFF0007675244000049.tif80119 [In formula (IB-1), R i22 and R i32 are each independently a hydrogen atom or 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. 2 represent each independently a nitrogen atom or a carbon atom. n3 and m3 each independently represent 0 or 1. 2is a nitrogen atom, n3 represents 0, A 2 is a carbon atom, n3 represents 1, B 2 When is a nitrogen atom, In this case, m3 represents 0, and B 2 When is a carbon atom, m3 represents 1. X i11 represents a sulfur atom or an NH group. L i2 represents a divalent hydrocarbon group having 1 to 18 carbon atoms. The aryl group may be substituted with an oxygen atom or a carbonyl group. R i5 represents a hydrogen atom or a methyl group. In formula (IB-2), R i23 and R i33 are each independently a hydrogen atom or 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, A 3 is a carbon atom, n4 represents 1, B 3 When is a nitrogen atom, In this case, m4 represents 0, and B 3 is a carbon atom, m4 represents 1. X i12 represents a sulfur atom or an NH group. L i3 represents a divalent hydrocarbon group having 1 to 14 carbon atoms. The aryl 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.

[0115] R i22 , R i32 , R i23 and R i33 A chain hydrocarbon with 1 to 10 carbon atoms represented by The group is R i21 and R i31 The same as the chain hydrocarbon group having 1 to 10 carbon atoms represented by The following are some of the reasons. R i22 , R i32 , R i23 and R i33 Aromatic hydrocarbons with carbon numbers of 6 to 14, represented by The basic group is R i21 and R i31 The same as the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by the formula: Examples include the following. R i22 , R i32 , R i23 and R i33 Alicyclic hydrocarbons with 3 to 18 carbon atoms, represented by The basic group is R i21 and R i31 The same as the alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by the formula: Examples include the following.

[0116] L i2 Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group Hexane-1,6-diyl group, Heptane-1,7-diyl group, Octane-1,8-diyl group diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1, 11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, Toradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane- 1,16-diyl group, heptadecane-1,17-diyl group, ethane-1,1-diyl group , propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group 2-methylpropane-1,3-diyl group, 2-methylpropane-2,4-diyl group, propane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1, Alkanediyl groups such as 4-diyl groups; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as cyclohexene-1,4-diyl group and cyclooctane-1,5-diyl group a monocyclic divalent alicyclic saturated hydrocarbon group, Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like. L i2 is preferably an alkanediyl group having 1 to 14 carbon atoms, more preferably It is an alkanediyl group having a number of 1 to 11.

[0117] L i3 Examples of the divalent hydrocarbon group having 1 to 14 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group Hexane-1,6-diyl group, Heptane-1,7-diyl group, Octane-1,8-diyl group diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1, 11-diyl group, dodecane-1,12-diyl group, ethane-1,1-diyl group, propane -1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentaerythritol group, Tan-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane -1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group Alkanediyl groups such as the group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as cyclohexene-1,4-diyl group and cyclooctane-1,5-diyl group a monocyclic divalent alicyclic saturated hydrocarbon group, Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like. L i3 is preferably an alkanediyl group having 1 to 14 carbon atoms, more preferably It is an alkanediyl group having a number of 1 to 11. L i3 is preferably bonded at the p-position relative to the main chain bonded to the phenyl group.

[0118] The sulfur-containing compound includes compounds represented by formula (I-1) to compounds represented by formula (I-26). Among them, the compound represented by the formula (I-1) is preferable. The compound represented by the formula (I-13) is preferably a compound represented by the formula (I-1). A compound represented by formula (I-4) and a compound represented by formula (I-11) be. TIFF0007675244000050.tif79162

[0119] TIFF0007675244000051.tif99148

[0120] The sulfur-containing compound may be any of the structural units represented by formulae (I-27) to (I-38). A homopolymer consisting of any one of the structural units or a copolymer containing one or more of these structural units. Rimmer is mentioned. Preferably, the copolymer contains one or more structural units represented by formulas (I-27) to (I-36). It is preferably a copolymer having a structural unit represented by formula (I-33). do. TIFF0007675244000052.tif149149

[0121] Such copolymers include those having structural units represented by formulae (I-39) to (I-48). Among them, copolymers consisting of the formula (I-39) to the formula (I-4 A polymer having a structural unit represented by 4) is preferred.

[0122] TIFF0007675244000053.tif242117

[0123] TIFF0007675244000054.tif160149

[0124] The sulfur-containing compound is synthesized by a known method (for example, JP 2010-79081 A). The polymer containing a sulfur-containing compound may be a commercially available product ( For example, Bismuthiol (manufactured by Tokyo Chemical Industry Co., Ltd., etc.) may be used, or a known method (e.g., It may also be one synthesized according to the method disclosed in JP-A-2001-75277.

[0125] Aromatic hydroxy compounds include phenol, cresol, xylenol, pyrocate Chole (=1,2-dihydroxybenzene), tert-butylcatechol, resorcino , hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicylalcohol , p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p- Hydroxyphenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol Nophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoin Acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxy Examples of such an acid include benzoic acid, 3,5-dihydroxybenzoic acid, and gallic acid.

[0126] Benzotriazole compounds include compounds represented by formula (IX). TIFF0007675244000055.tif2858[In formula (IX), R 1 and R 2 each independently represents a hydrogen atom or a C1 to C10 Hydrocarbon groups, carboxy groups, amino groups, hydroxy groups, cyano groups, formyl groups, sulfo groups represents an arylalkyl group or a sulfo group. Q is a hydrogen atom, a hydroxyl group, or a hydrocarbon having 1 to 10 carbon atoms which may have a substituent. group, aryl group or **-R 3x -N(R 4x )(R 5x ), wherein the hydrocarbon group represents The structure may contain an amide bond or an ester bond. R 3x represents an alkanediyl group having 1 to 6 carbon atoms. ** represents a nitrogen atom and Represents a bond in . R 4x and R 5x are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, and an alkoxyalkyl group having 1 to 6 carbon atoms. vinegar.]

[0127] R 1 , R 2 and the hydrocarbon group of Q may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. It may have saturated and / or unsaturated bonds. The aliphatic hydrocarbon group is preferably an alkyl group, and the alkyl group is preferably a methyl group. , ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, te rt-Butyl group, n-pentyl group, methylpentyl group, n-hexyl group, n-heptyl group etc. The aromatic hydrocarbon group is preferably an aryl group, and the aryl group is preferably a phenyl group. group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, Phenyl, phenanthryl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl. Examples of the alkyl group include a phenyl group and a phenyl group. R 3x Examples of the alkanediyl group are as described above. The substituents which the hydrocarbon group may have include hydroxyalkyl groups, alkoxy groups, Examples of such groups include alkyl groups. Hydroxyalkyl groups include hydroxymethyl, hydroxyethyl, and dihydro. Examples of the aryl group include an oxyethyl group. Examples of the alkoxyalkyl include a methoxymethyl group, a methoxyethyl group, a dimethoxyethyl group, and a Examples thereof include a ethyl group.

[0128] 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 benzotriazol Although the oleyl compounds are poorly water-soluble, there are other components that can dissolve these compounds. When present, it is preferably used.

[0129] The resist composition of the present invention may also be used to form an inorganic material layer (e.g., a polysilicon film, an amorphous When the compound is applied to a substrate having a silicon film, Q in formula (IX) is a water-soluble group. Specifically, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, Hydroxyalkyl groups, hydroxy groups, etc. of 3 are preferred. This improves the corrosion resistance of the substrate. This can be achieved more effectively.

[0130] Benzotriazole compounds include benzotriazole, 5,6-dimethylbenzo Triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1 -Aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethyl Benzotriazole, 1-benzotriazole methyl carboxylate, 5-benzotriazole carboxylic acid, 1-methoxy-benzotriazole, 1-(2,2-dihydroxyethyl )-benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, or the "Ilgamet (registered trademark)" series available from BASF. 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-benzotriazo 2,2'-{[(4-methyl-1-yl)methyl]imino}bisethane, H-benzotriazol-1-yl)methyl]imino}bispropane and the like.

[0131] An example of the triazine compound is a compound represented by the formula (II). TIFF0007675244000056.tif2548 [In formula (II), R 6 , R 7 and R 8 are each independently a halogen atom, a hydrogen atom, a hydroxyl group, an amino group, , a mercapto group, a hydrocarbon group having 1 to 10 carbon atoms which may be substituted, An alkyloxy group having 1 to 10 carbon atoms, or an amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms. represents.] Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. . Examples of the hydrocarbon group and alkyloxy group include the same as those mentioned above.

[0132] Examples of triazine compounds include 1,3,5-triazine-2,4,6-triazine. Examples include oars.

[0133] An example of the silicon-containing compound is a compound represented by formula (IIA). TIFF0007675244000057.tif2984[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 Represents. R j2 ~R j4 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, R represents an alkoxy group, a mercapto group, or a mercaptoalkyl group having 1 to 5 carbon atoms. j2 ~ R j4 At least one of the above is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms. It is. t irepresents an integer from 1 to 10.

[0134] The aliphatic hydrocarbon group includes a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the alkyl group include an alkyl group such as an alkyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. The mercaptoalkyl group includes a methyl mercapto group, an ethyl mercapto group, and a proline group. A pyrimercapto group and the like are exemplified.

[0135] R j1 is an aliphatic hydrocarbon group having 1 or 2 carbon atoms, or a mercaptoalkyl group having 1 to 3 carbon atoms. A methyl group or a mercaptopropyl group is preferable, and a methyl group or a mercaptopropyl group is more preferable. It is nice. R j2 ~R j4 each independently represents an aliphatic hydrocarbon group having 1 or 2 carbon atoms, or or 2 is preferably an alkoxy group, more preferably a methyl group or a methoxy group. However, at least one of them is a mercapto group or a group having 1 to 3 carbon atoms. is preferably a mercaptoalkyl group represented by the formula: It is more preferable that: R j2 and R j3 may be the same or different, but from the viewpoint of productivity, It is preferable that it is one.

[0136] The compound represented by formula (IIA) includes the compounds represented by the following formulas (II-1) to (II-7). Examples of compounds that can be used include: TIFF0007675244000058.tif193125 Among them, 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyl Triethoxysilane and the like are preferred.

[0137] The content of the adhesion improver (E) is preferably 100% by weight based on the total amount of solids in the resist composition. 0.001% by mass or more, more preferably 0.002% by mass or more, and even more preferably 0.0 05% by mass or more, and preferably 20% by mass or less, and more preferably 10% by mass or less. % by weight or less, more preferably 4% by weight or less, and even more preferably 3% by weight or less. The content is particularly preferably 1 mass % or less. By setting the content in this range, a highly accurate resist can be obtained. The resist composition can be used to form a resist pattern. Therefore, the adhesion between the film and the substrate can be ensured.

[0138] <Other Ingredients> The resist composition of the present invention may further contain components other than the above-mentioned components (hereinafter referred to as “other components”) as necessary. (F)) may be contained. There are no particular limitations on other components (F). However, additives known in the resist art, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc., may be used. Agents, dyes, etc. can be used.

[0139] Preparation of Resist Composition The resist composition of the present invention comprises the resin (A1) of the present invention, an acid generator (B), a quencher ( C), solvent (D), and, if necessary, resin (A2), resin (A3), adhesion improver The composition can be prepared by mixing (E) and the other component (F). The order of mixing is arbitrary. The temperature during mixing is from 10 to 40°C, and the resin An appropriate temperature can be selected depending on the type of resin, the solubility of resin in the solvent (D), etc. 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, etc. can be used. After mixing the components, filter using a filter with a pore size of approximately 0.1 to 50 μm. is preferred.

[0140] <Method for Producing Resist Pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) applying a resist composition of the present invention to a substrate; (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. To apply the resist composition onto a substrate, a commonly used device such as a spin coater is used. The substrate may be an inorganic substrate such as a silicon wafer. A semiconductor element (e.g., a transistor, a diode, etc.) may be formed on the substrate in advance. When the resist composition of the present invention is used for forming a bump, the substrate further includes a conductive material. The conductive material is preferably gold, copper, nickel, tin, palladium, or the like. At least one metal selected from the group consisting of aluminum and silver, or at least one metal selected from the group consisting of aluminum and silver The metal may be an alloy containing at least one metal, 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. It may be possible. The composition after coating is dried to remove the solvent and form a composition layer. For example, the solvent can be evaporated using a heating device such as a hot plate (prebaking). The heating temperature is 50 to 200°C. It is preferable that the heating time is 30 to 600 seconds. The pressure during the process is 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 3 to 150 μm, more preferably is 4 to 100 μm. The obtained composition layer is usually exposed using an exposure device. A light source that emits light of ~436 nm (g-line (wavelength: 436 nm), h-line (wavelength: 405 nm) ), i-line (wavelength: 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser Ultraviolet lasers such as F2 excimer laser (wavelength 193 nm) and F2 excimer laser (wavelength 157 nm) Those that emit laser light in the range, lasers from solid-state laser light sources (YAG or semiconductor lasers, etc.) those that convert the wavelength of laser light to emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range; electron beams Various types of light sources can be used, such as those that emit ultraviolet light (EUV) or those that emit extreme ultraviolet light (EUV). In the specification, the irradiation of these types of radiation may be collectively referred to as "exposure". When exposed to light, exposure is usually carried out through a mask that corresponds to the desired pattern. In the case of electron beams, exposure may be performed by direct writing without using a mask. The composition layer after exposure is subjected to a heat treatment (so-called heat treatment) in order to promote the deprotection reaction of the acid labile group. Post-exposure bake may be added. The heating temperature is usually around 50 to 200°C. The heating temperature is usually 40 to 400 seconds, preferably about 70 to 150°C. The time is preferably 50 to 350 seconds. The composition layer after heating is usually developed using a developing device and a developing solution. Examples of the method include the dip method, the paddle method, the spray method, and the dynamic dispense method. The development temperature is preferably, for example, 5 to 60° C., and the development time is, for example, 5 The time is preferably 600 seconds or less. By selecting the type of developer as follows: Either a positive resist pattern or a negative resist pattern can be produced.

[0141] When a positive resist pattern is produced from the resist composition of the present invention, a developer An alkaline developer is used. The alkaline developer is any of the various alkaline solutions used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples of the aqueous solution ... ethyl)trimethylammonium hydroxide (commonly known as choline) include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is It is preferable to remove it. When a negative resist pattern is produced from the resist composition of the present invention, A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers are ketones such as 2-hexanone and 2-heptanone. Solvents; glycol ether ethers such as propylene glycol monomethyl ether acetate Steryl solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and the like aromatic hydrocarbon solvents. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, The content is preferably from 95% by mass to 100% by mass, and more preferably substantially only an organic solvent. More preferred. Among them, organic developers include those containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass. Preferably, the content is 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the components are qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 10%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too. It is preferable to wash the resist pattern after development with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and any solvent containing a general organic solvent may be used. Any suitable solvent may be used, preferably an alcohol or ester solvent. After cleaning, it is preferable to remove any rinsing liquid remaining on the substrate and the pattern.

[0142] <Application> The resist composition of the present invention is useful for producing a thick resist film. It is useful for producing resist films 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 a bump and a rewiring are manufactured using a resist composition, the following steps are usually performed: This makes it possible to manufacture a resist pattern with an excellent pattern shape. can. First, a conductive material (seed metal) is layered on a wafer on which semiconductor elements and other components are formed. Thereafter, a resist pattern is formed on the conductive layer using the resist composition of the present invention. Next, the resist pattern is used as a template to form an electrode material (e.g., C The resist pattern and the metal remaining under the resist pattern are then deposited. The conductive layer is then removed by etching or the like to form bumps and rewiring. After removing the conductive layer, the electrode material is melted by heat treatment as necessary. may be used as a bump. EXAMPLES

[0143] The present invention will be described in more detail with reference to examples. "%" and "parts" are by weight unless otherwise specified. The weight average molecular weight was determined by gel permeation chromatography under the following conditions: value. 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)

[0144] Synthesis Example 1 [Synthesis of Resin A1-1] In a flask, 33.0 parts of phenol novolac resin (PSM-4326 manufactured by Gun-ei Chemical Co., Ltd.) and 198.0 parts of propylene glycol monomethyl ether acetate were added, and the temperature was raised to 60°C. The temperature was raised, and after dissolution, it was cooled to 40°C. To the resulting mixture, 20.0 parts of acetonitrile and N,N-dimethyl-4-aminopyridinium The mixture was then cooled to room temperature. After adding dropwise 9.77 parts of di-tert-butyl acetate, the mixture was stirred at room temperature and reacted for 24 hours. The reaction solution was then diluted with 99 parts of methyl isobutyl ketone, and 183 parts of a 2% aqueous oxalic acid solution was added. After separation, 183 parts of ion-exchanged water was added to the organic layer, and washing and separation were repeated five times. The organic layer was concentrated. The resulting liquid was mixed with phenol and concentrated to give 61.24 parts of resin solution. The hydroxyl groups of the polyol novolac resin are partially tert-butoxycarbonylated. This resin is a fatty solution. 13 C-NMR analysis revealed that phenol novolac resin 10.5% of the hydroxy groups were replaced by tert-butoxycarbonyloxy groups. The concentration of the resin liquid was measured by the dry weight loss method and was found to be 40.5%. This resin is referred to as Resin A1-1. The weight average molecular weight of Resin A1-1 is 6.3×10 3 Yes Ta. TIFF0007675244000059.tif4092

[0145] Synthesis Example 2 [Synthesis of Resin A1-2] In a flask, 33.0 parts of phenol novolac resin (PSM-4326 manufactured by Gun-ei Chemical Co., Ltd.) and 198.0 parts of propylene glycol monomethyl ether acetate were added, and the temperature was raised to 60°C. The temperature was raised, and after dissolution, it was cooled to 40°C. To the resulting mixture, 20.0 parts of acetonitrile and N,N-dimethyl-4-aminopyridinium After adding 6.71 parts of ethanol dropwise at 40° C. for 20 minutes, the mixture was cooled to room temperature. After 14.98 parts of di-tert-butyl was added dropwise, the mixture was stirred at room temperature and reacted for 24 hours. The reaction solution was then diluted with 99 parts of methyl isobutyl ketone, and 183 parts of a 2% aqueous oxalic acid solution was added. After separation, 183 parts of ion-exchanged water was added to the organic layer, and washing and separation were repeated five times. The organic layer was concentrated. The resulting liquid was mixed with phenol and concentrated to give 83.50 parts of resin solution. The hydroxyl groups of the polyol novolac resin are partially tert-butoxycarbonylated. This resin is a fatty solution. 13 C-NMR analysis revealed that phenol novolac resin 15.3% of the hydroxy groups were replaced by tert-butoxycarbonyloxy groups. The concentration of the resin liquid was measured using a dry weight loss method and was found to be 38.2%. This resin is referred to as Resin A1-2. The weight average molecular weight of Resin A1-2 is 6.5×10 3 Yes Ta. TIFF0007675244000060.tif3894

[0146] Synthesis Example 3 [Synthesis of Resin A1-3] In a flask, 33.0 parts of phenol novolac resin (PSM-4326 manufactured by Gun-ei Chemical Co., Ltd.) and 198.0 parts of propylene glycol monomethyl ether acetate were added, and the temperature was raised to 60°C. The temperature was raised, and after dissolution, it was cooled to 40°C. To the resulting mixture, 20.0 parts of acetonitrile and N,N-dimethyl-4-aminopyridinium After adding 6.71 parts of ethanol dropwise at 40° C. for 20 minutes, the mixture was cooled to room temperature. After 17.98 parts of di-tert-butyl was added dropwise, the mixture was stirred at room temperature and reacted for 24 hours. The reaction solution was then diluted with 99 parts of methyl isobutyl ketone, and 183 parts of a 2% aqueous oxalic acid solution was added. After separation, 183 parts of ion-exchanged water was added to the organic layer, and washing and separation were repeated five times. The organic layer was concentrated. The resulting liquid was mixed with phenol and concentrated to give 79.76 parts of resin solution. The hydroxyl groups of the polyol novolac resin are partially tert-butoxycarbonylated. This resin is a fatty solution. 13 C-NMR analysis revealed that phenol novolac resin 20.1% of the hydroxy groups were replaced by tert-butoxycarbonyloxy groups. The concentration of the resin liquid was measured using a dry weight loss method and was found to be 37.9%. This resin is referred to as Resin A1-3. The weight average molecular weight of Resin A1-3 is 7.1×10 3 Yes Ta. TIFF0007675244000061.tif3998

[0147] Synthesis Example 4 [Synthesis of Resin A1-4] In a flask, 33.0 parts of phenol novolac resin (PSM-4326 manufactured by Gun-ei Chemical Co., Ltd.) and 198.0 parts of propylene glycol monomethyl ether acetate were added, and the temperature was raised to 60°C. The temperature was raised, and after dissolution, it was cooled to 40°C. The resulting mixture was mixed with 15.28 parts of triethylamine and N,N-dimethyl-4-aminopyridine. Lysine (8.39 parts) was added dropwise at 40° C. for 20 minutes, and then cooled to room temperature. After 38.96 parts of di-tert-butyl carbonate was added dropwise at room temperature, the mixture was heated to 60°C and stirred. The mixture was reacted for 8 hours, and then cooled, and 9.06 parts of acetic acid and 183 parts of ion-exchanged water were added thereto. The reaction solution was then diluted with 99 parts of methyl isobutyl ketone, and 183 parts of a 2% aqueous oxalic acid solution was added. After separation, 183 parts of ion-exchanged water was added to the organic layer, and washing and separation were repeated five times. The organic layer was concentrated. The resulting liquid was concentrated to give 87.0 parts of a resin solution. A resin in which the hydroxyl groups of a polynovolac resin have been partially tert-butoxycarbonylated. This resin is a solution. 13 C-NMR analysis revealed that the phenol novolac resin 35.1% of the hydroxyl groups were replaced by tert-butoxycarbonyloxy groups. The concentration of the resin solution was measured using the dry weight loss method and found to be 35.3%. The resin is designated as Resin A1-4. The weight average molecular weight of Resin A1-4 is 8.9 × 10 3 Was . TIFF0007675244000062.tif3798

[0148] Synthesis Example 5 [Synthesis of Resin A2-1] In a flask, 120 parts of phenol novolac resin (PSM-4326 manufactured by Gun-ei Chemical Co., Ltd.) and The resulting phenol novolak resin was dissolved in 960 parts of methyl isobutyl ketone. The solution was washed five times with ion-exchanged water and separated. The obtained organic layer was diluted to 327.3 parts. The resin concentration in the resulting resin solution was 35.2%. Into a flask, 56.8 parts of the obtained resin solution, 76.52 parts of methyl isobutyl ketone, and 0.0036 parts of p-toluenesulfonic acid monohydrate was added to the mixture. 8.81 parts of ether was added dropwise and the mixture was reacted at room temperature for 3 hours. The mixture was stirred, allowed to stand, and the organic layer was separated. This was repeated four more times for a total of five washings, after which the organic layer was removed and concentrated. Then, in order to remove water and methyl isobutyl ketone by azeotropy, propylene glycol Add diethyl ether acetate and further concentrate to obtain 57.44 parts of resin solution. The resin solution obtained had some of the hydroxyl groups of the phenol novolac resin converted to 1-ethoxy groups. The resin is a solution of hydroxyethylated resin. 1 H-NMR analysis revealed that 53.0% of the hydroxyl groups in the nol novolac resin are replaced by 1-ethoxyethyl ether. The concentration of the resin solution was measured using the dry weight loss method and found to be 45.0 This resin is designated as Resin A2-1. The weight average molecular weight of Resin A2-1 was 7.2× 10 3 It was. TIFF0007675244000063.tif2997

[0149] Synthesis Example 6 [Synthesis of Resin A2-2] 20 parts of poly-p-hydroxystyrene (S-4P; Maruzen Petrochemical Co., Ltd.) was dissolved in methyl isopropanol. The mixture was dissolved in 240 parts of isobutyl ketone at room temperature and concentrated in an evaporator. In a four-neck flask equipped with a thermometer and a condensed resin solution and 2 ml of p-toluenesulfonic acid The resulting mixture was kept at 20 to 25°C and the resulting 5.05 parts of ethyl vinyl ether was added dropwise to the mixture over 10 minutes. The mixture was stirred at 25° C. for 2 hours. The resulting reaction mixture was diluted with 200 parts of methyl isobutyl ketone. The organic layer was separated five times using an evaporator. After concentrating the mixture to 45 parts, 15 parts of propylene glycol monomethyl ether acetate was added. 100 parts of propylene glycol monomethyl ether of resin A2-2 was added and concentrated again. The weight average molecular weight of Resin A2-2 was 1. 16×104 The hydroxy group in poly-p-hydroxystyrene was ethoxylated. The proportion of ethoxy groups substituted was 40.9%. TIFF0007675244000064.tif3897

[0150] Synthesis Example 7 [Synthesis of Resin A3-1] In a four-neck flask equipped with a stirrer, reflux condenser, and thermometer, add 2,5-xylenol 413 0.5 parts, salicylaldehyde 103.4 parts, p-toluenesulfonic acid 20.1 parts, and methacrylic acid 10.5 parts. 826.9 parts of ethanol was added, the temperature was raised to reflux, and the temperature was maintained for 4 hours. 1,320 parts of butyl ketone was added, and 1,075 parts of the solvent was distilled off under normal pressure. Add 762.7 parts of tert-butyl-5-methylphenol and 29.0 parts of 2-tert-butyl-5-methylphenol and mix for 65 minutes. ℃, add 678 parts of 37% aqueous formalin solution, and heat the mixture until it reaches 87℃ when the drop is complete. The mixture was added dropwise over 1.5 hours while adjusting the temperature. The resulting mixture was kept at 87°C for 10 hours. 1,115 parts of methyl isobutyl ketone was added, and the mixture was washed three times with ion-exchanged water. 500 parts of methyl isobutyl ketone was added to the resulting mixture until the total amount reached 3,435 parts. The mixture was concentrated under reduced pressure. 3,796 parts of methyl isobutyl ketone and n-heptane were added to the resulting mixture. The mixture was heated to 60°C and stirred for 1 hour. The layer containing the compound was removed and washed with 3,500 parts of propylene glycol monomethyl ether acetate. Dilute and concentrate to obtain propylene glycol monomethyl ether acetate of resin A3-1. The weight average molecular weight of the novolak resin A3-1 was 1,690 parts (solid content 43%). 7×10 3 It was.

[0151] Synthesis Example 8 [Synthesis of Resin A4-1] Poly-p-hydroxystyrene (S-4P; Maruzen Petrochemical Co., Ltd.) 33.0 parts and Add 198.0 parts of pyrene glycol monomethyl ether acetate and heat to 60°C. After dissolution, the mixture was cooled to 40°C. To the resulting mixture, 20.0 parts of acetonitrile and N,N-dimethyl-4-aminopyridinium After adding 6.71 g of ethanol dropwise at 40° C. for 20 minutes, the mixture was cooled to room temperature. After 29.97 parts of di-tert-butyl was added dropwise, the mixture was stirred at room temperature and reacted for 24 hours. The reaction solution was then diluted with 99 parts of methyl isobutyl ketone, and 183 parts of a 2% aqueous oxalic acid solution was added. After separation, 183 parts of ion-exchanged water was added to the organic layer, and washing and separation were repeated five times. The organic layer was concentrated. The resulting liquid was mixed with polytetrafluoroethylene and concentrated to give 106.7 parts of a resin solution. The hydroxyl groups of p-hydroxystyrene are partially tert-butoxycarbonylated. This resin is a resin solution. 13 C-NMR analysis revealed that poly-p-hydroxys 36.0% of the hydroxyl groups of ethylene are replaced by tert-butoxycarbonyloxy groups. The concentration of the resin solution was measured using the dry weight loss method and found to be 40.2%. This resin is called Resin A4-1. The weight average molecular weight of Resin A4-1 is 1.33×1 0 4 It was. TIFF0007675244000065.tif4097

[0152] <Preparation of resist composition> Mix each component in the parts by weight shown in Table 1 (the parts by weight of resin indicate the parts by weight of solid content). , dissolved in a solvent (the parts by mass of the solvent shown in Table 1 represent the parts by mass of the solvent contained in the entire composition). The mixture obtained by this was filtered through a fluororesin filter with a pore size of 5 μm, and the resist was removed. A composition was prepared. [Table 1]

[0153] <Resin> A1-1: Resin A1-1 A1-2: Resin A1-2 A1-3: Resin A1-3 A1-4: Resin A1-4 A2-1: Resin A2-1 A2-2: Resin A2-2 A3-1: Resin A3-1 A4-1: Resin A4-1 <Acid Generator (B)> B1: N-hydroxynaphthalimide triflate (NAI-105; Midori Chemical Co., Ltd.) (Manufacturer) TIFF0007675244000067.tif2649<Quencher(C)> C1: 2,4,5-triphenylimidazole (Tokyo Chemical Industry Co., Ltd.) <Adhesion improver> E1: Bismuthiol (Tokyo Chemical Industry Co., Ltd.) <Solvent> Propylene glycol monomethyl ether acetate

[0154] Examples 1 to 7, Comparative Examples 1 to 3 (i-line exposure evaluation of resist composition) The above resist composition was applied to a 4-inch silicon wafer on which copper was evaporated. The film was spin-coated so that the thickness after coating was 1.5 μm. Then, the composition layer was pre-baked on a direct hot plate at 110°C for 180 seconds. The composition layer formed on the wafer was then subjected to an i-line stepper (NSR-2005i 9C (Nikon Corporation, NA = 0.5) was used, and the exposure amount was changed stepwise to obtain a 1:1 light. The film was exposed to light through a mask for forming a line-and-space pattern (line width: 1 μm). After exposure, post-exposure bake was performed on a hot plate at 120°C for 60 seconds. Then, it was washed with 2.38% by mass tetramethylammonium hydroxide aqueous solution for 180 seconds. A resist pattern was obtained by puddle development. The resist pattern obtained after development was observed with a scanning electron microscope, and a line width of 1 μm was The exposure amount at which an and-space pattern was obtained was defined as the effective sensitivity.

[0155] <Pattern shape evaluation> Pattern shape evaluation: A 1 μm-wide line pattern obtained at the effective sensitivity was Observe under a microscope at 10,000 times magnification and check that the top and bottom shapes are close to rectangular and in good condition. The shape of the top [Fig. 1(a)] is marked with an O, and the shape of the top [Fig. 1(b)] or a tapered shape is marked with an X. The results are shown in Table 2. <Changes over time> The prepared resist composition was stored at -5°C and 40°C for 2 weeks. The above i-line exposure evaluation was performed, and the effective sensitivity of the sample stored at 40°C was 90% of that of the sample stored at -5°C. % to 110% was rated as good, and less than 90% or more than 110% was rated as bad. <Plating resistance evaluation> Using the effective sensitivity obtained in the above i-line exposure evaluation, a patterned wafer was prepared, and then the Cu plating solution was The samples were immersed in the solution for 10, 30, and 60 minutes. After immersion, the patterned wafer was observed with an optical microscope to determine the 1 μm line and space pattern. I observed the turn. Pattern collapse occurs after immersion for 10 minutes, and pattern collapse occurs after immersion for 30 minutes. The ones with pattern collapse after 60 minutes of immersion are marked △, the ones with pattern collapse after 60 minutes of immersion are marked 〇, and the ones with pattern collapse after 60 minutes of immersion are marked 100%. Those without defects were marked with ◎. [Table 2]

[0156] Example 8, Comparative Examples 4-5 (i-line exposure evaluation of resist composition) The above resist composition was applied to a 4-inch silicon wafer on which copper was evaporated. The film was spin-coated so that the thickness after coating was 6 μm. Then, the composition was pre-baked on a direct hot plate at 110°C for 180 seconds. The composition layer formed on the wafer was then subjected to an i-line stepper (NSR-2005 i9C (Nikon Corporation, NA = 0.5) was used to change the exposure amount stepwise to obtain a 1:1 laser. Exposure was performed through a mask for forming an in-and-space pattern (line width: 2 μm). After exposure, post-exposure bake was performed on a hot plate at 120°C for 60 seconds. Then, it was washed with 2.38% by mass tetramethylammonium hydroxide aqueous solution for 180 seconds. A resist pattern was obtained by puddle development. The resist pattern obtained after development was observed with a scanning electron microscope, and a line width of 2 μm was The exposure amount at which an and-space pattern was obtained was defined as the effective sensitivity.

[0157] <Pattern shape evaluation> Pattern shape evaluation: A 2 μm-wide line pattern obtained at the effective sensitivity was Observe under a microscope at 10,000 times magnification and check that the top and bottom shapes are close to rectangular and in good condition. The shape of the top [Fig. 1(a)] is marked with an O, and the shape of the top [Fig. 1(b)] or a tapered shape is marked with an X. This was the decision that was made. <Changes over time> The prepared resist composition was stored at -5°C and 40°C for 2 weeks. The above i-line exposure evaluation was performed, and the effective sensitivity of the sample stored at 40°C was 90% of that of the sample stored at -5°C. % to 110% was rated as good, and less than 90% or more than 110% was rated as bad. <Plating resistance evaluation> Using the effective sensitivity obtained in the above i-line exposure evaluation, a patterned wafer was prepared, and then the Cu plating solution was The samples were immersed in the solution for 10, 30, and 60 minutes. After immersion, the patterned wafer was observed with an optical microscope to determine the 2 μm line and space pattern. I observed the turn. Pattern collapse occurs after immersion for 10 minutes, and pattern collapse occurs after immersion for 30 minutes. The ones with pattern collapse after 60 minutes of immersion are marked △, the ones with pattern collapse after 60 minutes of immersion are marked 〇, and the ones with pattern collapse after 60 minutes of immersion are marked 100%. Those without defects were marked with ◎. [Table 3] [Industrial Applicability]

[0158] The resist composition of the present invention exhibits little change over time and can form an excellent pattern shape. Turns can be produced.

Claims

1. a novolak resin in which a hydroxy group is substituted with a group represented by formula (3); A resin having a group represented by formula (2), An acid generator; A quencher, and a solvent. [In formula (3), R ａ10 represents a hydrocarbon group having 1 to 20 carbon atoms. * represents a bond. [In formula (2), R ａ１’ and R ａ２’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R ａ３’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R ａ１’ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R ａ２’ and R ａ３’ are bonded to each other to form a heterocyclic group having 2 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 12 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. * represents a bond.]

2. 2. The resist composition according to claim 1, wherein the novolak resin is a phenol novolak resin.

3. 3. The resist composition according to claim 1, wherein the resin having a group represented by formula (2) is a resin containing a structural unit represented by formula (a1-2). [In formula (a1-2), R ａ１’ and R ａ２’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R ａ３’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R ａ１’ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R ａ２’ and R ａ３’ are bonded to each other to form, together with the carbon atom and oxygen atom to which they are bonded, a divalent heterocyclic group having 2 to 20 carbon atoms. A methylene group contained in the hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon group having 1 to 20 carbon atoms, and the heterocyclic group having 2 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.

4. 4. The resist composition according to claim 1, wherein the resin having a group represented by formula (2) is a novolak resin in which a hydroxy group of the novolak resin is substituted with a group represented by formula (2).

5. 5. The resist composition according to claim 1, wherein the group represented by formula (3) is a group represented by formula (3A). [In formula (3A), 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, or R ａ１ and R ａ2 may be bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, 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.]

6. 6. The resist composition according to claim 1, wherein the novolak resin in which a hydroxy group is substituted with a group represented by formula (3) is a resin containing a structural unit represented by formula (a3). [In formula (a3), R ａ10 represents a hydrocarbon group having 1 to 20 carbon atoms. R ａｂ represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents an integer of 0 to 3. When p is 2 or more, a plurality of R ａｂ may be the same or different.

7. 7. The resist composition according to claim 1, wherein the novolak resin in which a hydroxy group is substituted with a group represented by formula (3) is a resin containing a structural unit represented by formula (a3A). [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, or R ａ１ and R ａ2 may be bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, R ａ３ represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R ａｂ represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents an integer of 0 to 3. When p is 2 or more, a plurality of R ａｂ may be the same or different.

8. 8. The resist composition according to claim 1, wherein the acid generator is a compound having a group represented by formula (B1). [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 may be substituted with an oxygen atom or a carbonyl group.

9. 9. The resist composition according to claim 1, wherein the acid generator is a compound represented by any one of formulas (b1) to (b3). [In formulas (b1) to (b3), R ｂ１ represents a hydrocarbon group having 1 to 18 carbon atoms which may contain a fluorine atom, and a methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. 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, a plurality of R ｂ２’ may be the same or different.

10. 10. The resist composition according to claim 1, wherein the quencher is a compound represented by formula (C1) or formula (C2). [In formula (C1), R ｃ１ , R ｃ２ and R ｃ３ represent, independently of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the alkyl group and the alicyclic hydrocarbon group may be substituted with a hydroxy group, an amino group, or an alkoxy group having 1 to 6 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 5 to 10 carbon atoms.] [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. n c represents 2 or 3, and a plurality of A １ may be the same or different.

11. (1) A step of applying a resist composition according to any one of claims 1 to 10 onto a substrate; (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 method for producing a resist pattern comprising the steps of:

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