Method for producing resin, active light-sensitive or radiation-sensitive resin composition, active light-sensitive or radiation-sensitive film, pattern forming method, and method for producing electronic device

Abstract

Provided are: a method for producing a resin, the method comprising (i) a step for polymerizing starting material monomers that include a specific monomer set forth in the description in the presence of a nitroxide radical or a dithioester-based compound set forth in the description, and (ii) a step for replacing the main chain terminal group of the polymer obtained in step (i) with a hydrogen atom or another substituent; an active light-sensitive or radiation-sensitive resin composition that contains a resin (A) which contains a specific repeating unit set forth in the description, and in which the terminal structure of the main chain is a group selected from among specific groups and the molecular weight distribution (Mw / Mn) is less than 1.40, a compound (B) which generates an acid upon irradiation with active light or radiation, and a solvent (S); an active light-sensitive or radiation-sensitive film which uses the active light-sensitive or radiation-sensitive resin composition; a pattern forming method; and a method for producing an electronic device.

Description

Method for producing resin, actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern forming method, and method for producing electronic device

[0001] The present invention relates to a method for producing a resin, an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device. More specifically, the present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, a method for producing an electronic device, and a method for producing a resin that can be used in an actinic ray- or radiation-sensitive resin composition, which can be suitably used in an ultra-microlithography process applicable to processes for producing VLSI (Large Scale Integration) and high-capacity microchips, a nanoimprint mold creation process, and a high-density information recording medium, as well as other photofabrication processes.

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), microfabrication is performed by lithography using resist compositions. In recent years, with the increasing integration density of integrated circuits, there has been a demand for ultrafine pattern formation in the submicron or quarter-micron range. Accordingly, there has been a trend toward shorter exposure wavelengths, from g-line to i-line and then to KrF excimer laser light, and currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as a light source have been developed. Furthermore, as a technique for further improving resolution, the so-called immersion method, in which a high refractive index liquid (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample, has been developed.

[0003] Currently, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is also being developed. Accordingly, various resist compositions that are effectively sensitive to various actinic rays or radiation have been developed.

[0004] Furthermore, various methods are known for producing resins used in resist compositions. For example, Patent Document 1 describes a method for producing a resin using a RAFT agent. Also, Patent Document 2 describes a method for producing a resin using a nitroxide radical.

[0005] Japanese Unexamined Patent Publication No. 2008-241737 Japanese Unexamined Patent Publication No. 10-288839

[0006] Recently, the performance required of resist compositions has become increasingly high. In particular, improvements in resolution, line width roughness (LWR) performance, and sensitivity are required when forming fine patterns. LWR performance refers to the ability to reduce the LWR of a pattern. Resist compositions containing the resins described in the above documents did not have sufficient sensitivity.

[0007] Therefore, an object of the present invention is to provide a method for producing a resin that can be suitably used for an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and sensitivity. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and sensitivity, an actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device.

[0008] The present inventors have found that the above problems can be solved by the following configuration.

[0009] [1] A method for producing a resin, comprising: (i) a step of polymerizing raw material monomers including at least one monomer selected from the group consisting of a monomer represented by the following general formula (a) and a monomer represented by the following general formula (aI), and a monomer represented by the following general formula (b), in the presence of a nitroxide radical represented by the following general formula (N) or a dithioester compound represented by the following general formula (Ra); and (ii) a step of substituting a main chain terminal group of the polymer obtained in the above step (i) with a hydrogen atom or another substituent.

[0010]

[0011] In general formula (a), L １ represents a divalent linking group. Ａ１ ~R Ａ３ R each independently represents a hydrogen atom or a monovalent substituent. Ａ４ represents a group that is decomposed and eliminated by the action of an acid. １ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ Rx each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. １ ~Rx ３ may be bonded to form a ring.

[0012]

[0013] In general formula (b), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ Is L ３ may be bonded to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group. ３ represents an (n+m+1)-valent aromatic ring group or an alicyclic group. Ｂ３ When R is bonded to form a ring, it represents an (n+m+2)-valent aromatic ring group or alicyclic group. ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group. Ｂ５ represents a halogen atom, m represents an integer of 1 or more, and n represents an integer of 0 or more.

[0014]

[0015] In general formula (N), R Ｎ１ Each of R independently represents an organic group. Ｎ１ may be bonded to form a ring.

[0016]

[0017] In the general formula (Ra), Ra １ and Ra ２ each independently represents an organic group.

[0018] [2] The method for producing a resin according to [1], wherein in the step (i), a reaction solution containing a solvent, 80% by mass or more of an initiator relative to the total amount of the initiator, and 90% by mass or more of a nitroxide radical or a dithioester-based compound relative to the total amount of the nitroxide radical or a dithioester-based compound is placed in a reaction vessel, and then at least a portion of the raw material monomers is added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator.

[0019] [3] The method for producing a resin according to [2], wherein in the step (i), a reaction solution containing a solvent, 80% by mass or more of an initiator relative to the total amount of the initiator, 90% by mass or more of a nitroxide radical or a dithioester compound relative to the total amount of the nitroxide radical or a dithioester compound, and a part of the raw material monomers is placed in a reaction vessel, and then the remaining raw material monomers are added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator.

[0020] [4] The method for producing a resin according to [2] or [3], wherein in the step (i), the raw material monomer in the reaction solution is 1 to 50 mol % based on the total amount of the raw material monomer. [5] The method for producing a resin according to any one of [2] to [4], wherein in the step (i), the raw material monomer is added dropwise for 1 to 24 hours.

[0021] [6] The method for producing a resin according to any one of [2] to [5], wherein in the step (i), the time for heating the reaction system after dropwise addition of the raw material monomer is less than 2 hours. [7] The method for producing a resin according to any one of [1] to [6], wherein the dithioester compound is represented by the following general formula (Ra-2):

[0022]

[0023] In general formula (Ra-2), Ra １ and Ra ３ each independently represents an organic group.

[0024] [8] The method for producing a resin according to any one of [1] to [7], wherein the monomer represented by the general formula (b) is represented by the following general formula (b-1):

[0025]

[0026] In general formula (b-1), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ may be bonded to Ar to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R Ｂ３ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. ｂ６ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5.

[0027] [9] R in the above general formula (b-1) ｂ６ is a group represented by any one of the following general formulas (3) to (7):

[0028]

[0029] In general formulas (3) to (7), R ３１ represents a hydrogen atom or an organic group. ４１ , R ５１ , R ６１ R each independently represents an organic group. ７１ , R ７２ R each independently represents a hydrogen atom or an organic group. ７３ represents an organic group. ７１ ~R ７３ may be linked to each other to form a ring. * indicates the bonding position to Ar.

[0030]

[10] The method for producing a resin according to [8] or [9], wherein, in the general formula (b-1), Ar is a benzene ring group.

[11] The method for producing a resin according to any one of [1] to

[10] , wherein, in the general formula (aI), T is an arylene group.

[0031]

[12] The production method according to any one of [1] to

[11] , wherein in the step (ii), the polymer obtained in the step (i) is reacted with a compound having hydrogen atom donating ability.

[13] The production method according to any one of [1] to

[11] , wherein in the step (ii), the polymer obtained in the step (i) is reacted with a compound having hydrogen atom donating ability and a free radical or a compound capable of generating a free radical.

[14] The production method according to any one of [1] to

[11] , wherein in the step (ii), the polymer obtained in the step (i) is reacted with a free radical or a compound capable of generating a free radical.

[0032]

[15] The production method according to any one of [1] to

[11] , wherein in the step (ii), the polymer obtained in the step (i) is reacted with a reducing agent.

[16] The production method according to any one of [1] to

[11] , wherein in the step (ii), the polymer obtained in the step (i) is reacted with an oxidizing agent.

[17] The production method according to any one of [1] to

[11] , wherein in the step (ii), the polymer obtained in the step (i) is heated in an inert solvent without adding any other reagent for 1 hour or more.

[0033]

[18] In the step (ii), the polymer obtained in the step (i) is reacted with a compound represented by the following general formula (M) or the following general formula (D):

[18] The method for producing a resin according to any one of the items [1] to

[11] .

[0034]

[0035] In general formula (M), R Ｍ１ R each independently represents a hydrogen atom or a monovalent substituent. Ｍ２ each independently represents a monovalent substituent, and may be bonded to each other to form a ring. Ｄ１R each independently represents a hydrogen atom or a monovalent substituent. Ｄ２ each independently represents a hydrogen atom or a monovalent substituent.

[0036]

[19] An actinic ray-sensitive or radiation-sensitive resin composition comprising: a resin (A) which contains at least one repeating unit selected from a repeating unit represented by the following general formula (A) and a repeating unit represented by the following general formula (AI) and a repeating unit represented by the following general formula (B), and which has a hydrogen atom or a group selected from —SH, —OH, a halogen atom, a heterocyclic group, a heterocyclic-S— group, and a hydrocarbon group at a terminal structure of the main chain and has a polydispersity (Mw / Mn) of less than 1.40; a compound (B) which generates an acid when irradiated with actinic rays or radiation; and a solvent (S).

[0037]

[0038] In general formula (A), L １ represents a divalent linking group. Ａ１ ~R Ａ３ R each independently represents a hydrogen atom or a monovalent substituent. Ａ４ represents a group that is decomposed and eliminated by the action of an acid. １ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ Rx each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. １ ~Rx ３ may be bonded to form a ring.

[0039]

[0040] In general formula (B), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ Is L ３ may be bonded to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２represents a single bond or a divalent linking group. ３ represents an (n+m+1)-valent aromatic ring group or an alicyclic group. Ｂ３ When R is bonded to form a ring, it represents an (n+m+2)-valent aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. Ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group. Ｂ５ represents a halogen atom, m represents an integer of 1 or more, and n represents an integer of 0 or more.

[0041]

[20] The actinic ray-sensitive or radiation-sensitive resin composition according to

[19] , wherein the repeating unit represented by the general formula (B) is represented by the following general formula (B-1):

[0042]

[0043] In general formula (B-1), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ may be bonded to Ar to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R Ｂ３ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. Ｂ６ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5.

[0044]

[21] R in the above general formula (B-1) Ｂ６ is a group represented by any one of the following general formulas (3) to (7):

[0045]

[0046] In general formulas (3) to (7), R ３１ represents a hydrogen atom or an organic group. ４１ , R ５１ , R ６１ R each independently represents an organic group.７１ , R ７２ R each independently represents a hydrogen atom or an organic group. ７３ represents an organic group. ７１ ~R ７３ may be linked to each other to form a ring. * indicates the bonding position to Ar.

[0047]

[22] The actinic ray-sensitive or radiation-sensitive resin composition according to

[20] or

[21] , wherein in general formula (B-1), Ar is a benzene ring group.

[23] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[19] to

[22] , wherein in general formula (AI), T is an arylene group.

[24] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[19] to

[23] .

[0048]

[25] A pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[19] to

[23] ; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.

[26] A method for producing an electronic device, comprising the pattern forming method according to

[25] .

[0049] The present invention provides a method for producing a resin that can be suitably used for an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and sensitivity. The present invention also provides an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and sensitivity, an actinic ray-sensitive or radiation-sensitive film that uses the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for producing an electronic device.

[0050] The present invention will be described in detail below. The following description of the components will be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0051] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" refers to actinic rays or radiation. Unless otherwise specified, in this specification, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams. In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits.

[0052] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0053] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) using a GPC apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0054] In the description of groups (atomic groups) in this specification, unless contrary to the spirit of the present invention, notations that do not specify whether they are substituted or unsubstituted include groups that contain a substituent as well as groups that do not have a substituent. For example, the term "alkyl group" includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred as the substituent. Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen atoms, which can be selected, for example, from the following substituents T:

[0055] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; etc. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0056] In this specification, the bonding direction of a divalent group is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. The compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0057] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation using the following software package 1 based on a database of Hammett's substituent constants and known literature values. All pKa values ​​described in this specification are values ​​determined by calculation using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0058] The pKa can also be calculated by molecular orbital calculation. A specific method for this is to calculate the pKa of H in an aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, and Gaussian 16 is an example.

[0059] In this specification, pKa refers to a value calculated based on a database of Hammett's substituent constants and publicly known literature values ​​using software package 1, as described above, but if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be adopted.

[0060] In this specification, the term "solid content" refers to components that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component that forms an actinic ray-sensitive or radiation-sensitive film is considered to be a solid content even if it is in a liquid state.

[0061] [Method for producing resin] The present invention relates to a method for producing a resin, comprising: (i) a step of polymerizing raw material monomers including at least one monomer selected from a monomer represented by the following general formula (a) and a monomer represented by the following general formula (aI), and a monomer represented by the following general formula (b), in the presence of a nitroxide radical represented by the following general formula (N) or a dithioester compound represented by the following general formula (Ra); and (ii) a step of substituting a main chain terminal group of the polymer obtained in the above step (i) with a hydrogen atom or another substituent.

[0062]

[0063] In general formula (a), L １ represents a divalent linking group. Ａ１ ~R Ａ３ R each independently represents a hydrogen atom or a monovalent substituent. Ａ４ represents a group that is decomposed and eliminated by the action of an acid. １ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ Rx each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. １ ~Rx ３ may be bonded to form a ring.

[0064]

[0065] In general formula (b), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ Is L ３ may be bonded to form a ring, in which case R Ｂ３represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group. ３ represents an (n+m+1)-valent aromatic ring group or alicyclic group. Ｂ３ When R is bonded to form a ring, it represents an (n+m+2)-valent aromatic ring group or alicyclic group. ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group. Ｂ５ represents a halogen atom, m represents an integer of 1 or more, and n represents an integer of 0 or more.

[0066]

[0067] In general formula (N), R Ｎ１ Each of R independently represents an organic group. Ｎ１ may be bonded to form a ring.

[0068]

[0069] In the general formula (Ra), Ra １ and Ra ２ each independently represents an organic group.

[0070] The method for producing the resin (A) described below is not particularly limited, but it can be preferably produced by the resin production method of the present invention.

[0071] [Step (i) (Polymerization Step)] Step (i) in the present invention is a step of polymerizing raw material monomers including at least one monomer selected from the monomer represented by the general formula (a) above and the monomer represented by the general formula (aI) above, and the monomer represented by the general formula (b) above, in the presence of the nitroxide radical represented by the general formula (N) above or the dithioester compound represented by the general formula (Ra) above.

[0072] <At least one monomer selected from the group consisting of monomers represented by general formula (a) and monomers represented by general formula (aI)>

[0073]

[0074] In general formula (a), L １represents a divalent linking group. Ａ１ ~R Ａ３ R each independently represents a hydrogen atom or a monovalent substituent. Ａ４ represents a group that is decomposed and eliminated by the action of an acid. １ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ Rx each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. １ ~Rx ３ may be bonded to form a ring.

[0075] The monomer represented by the general formula (a) and the monomer represented by the general formula (aI) are preferably monomers having an acid-decomposable group as described below.

[0076] In general formula (a), L １ Examples of the divalent linking group represented by the formula (I) include an -Rta- group, a -COO-Rta- group, and an -O-Rta- group, with an -Rta- group being preferred. Rta represents a linear or branched alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. The aromatic ring group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic hydrocarbon group include an arylene group having 6 to 15 carbon atoms, and specific preferred examples include a phenylene group, a naphthylene group, and an anthrylene group. Examples of aromatic heterocyclic groups include heteroarylene groups having 2 to 15 carbon atoms, including 5- to 10-membered rings, and specific examples include groups in which any one hydrogen atom has been removed from a furyl group, thienyl group, thiazolyl group, pyrrolyl group, oxazolyl group, pyridyl group, benzofuranyl group, benzothienyl group, quinolinyl group, carbazolyl group, etc. The aromatic ring group may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group.

[0077] L １ is preferably an aromatic hydrocarbon group, more preferably a phenylene group.

[0078] R Ａ１ ~R Ａ３ Examples of the monovalent substituent represented by R include an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, and an alkoxycarbonyl group. Ａ１ ~R Ａ３ The alkyl group represented by R may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. Ａ１ ~R Ａ３ The cycloalkyl group represented by the formula (I) may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or may be a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. In the cycloalkyl group, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. Ａ１ ~R Ａ３ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. Ａ１ ~R Ａ３ The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0079] R Ａ１ ~R Ａ３ Preferably, each of represents a hydrogen atom.

[0080] R Ａ４ Examples of the group that is decomposed and eliminated by the action of an acid and is represented by the formula (Y1) to (Y4) described below include groups represented by the formula (Y3), among which the group represented by the formula (Y3) is preferred.

[0081] In general formula (aI), Xa １ Examples of the alkyl group represented by the formula include a methyl group or —CH ２ -R １１ Examples of the group include a group represented by the following formula: １１ represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. １ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. １ may be bonded to T to form a ring.

[0082] The divalent linking group represented by T includes an alkylene group, an aromatic ring group, a -COO-Rtb- group, a -O-Rtb- group, a -CONR １０４ -Rtb- group (R １０４ represents a hydrogen atom or an alkyl group). In the formula, Rtb represents a linear or branched alkylene group, a cycloalkylene group, or an aromatic ring group. Examples of the aromatic ring group include the aromatic ring groups described above as Rta, and preferred examples are also the same. The aromatic ring group may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group. Furthermore, these substituents may be substituted, if possible, with R Ｘ１ ~R Ｘ３ T may be bonded to any one of the following to form a ring. T is preferably a single bond or an aromatic ring group, and more preferably an arylene group.

[0083] Rx １ ~Rx ３ The alkyl group represented by the formula (I) may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.

[0084] Rx１ ~Rx ３ The cycloalkyl group represented by the formula (I) may be either a monocyclic or polycyclic group. １ ~Rx ３ The number of carbon atoms in the cycloalkyl group represented by Rx is preferably 6 to 15, and more preferably 6 to 10. １ ~Rx ３ Specific examples of the cycloalkyl group represented by the formula (I) include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

[0085] Rx １ ~Rx ３ The aryl group represented by the formula (I) is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

[0086] Rx １ ~Rx ３ The heteroaryl group represented by the formula (I) is preferably a heteroaryl group having 2 to 15 carbon atoms, and examples thereof include those having a 5- to 10-membered ring. Specific examples thereof include a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group.

[0087] Rx １ ~Rx ３ The alkenyl group represented by the formula (I) includes an alkenyl group having 2 to 10 carbon atoms.

[0088] Rx １ ~Rx ３ The alkynyl group represented by the formula (I) includes an alkynyl group having 2 to 10 carbon atoms.

[0089] Also, Rx １ ~Rx ３may be bonded to form a ring. The ring may be either a monocyclic or polycyclic ring. The ring is preferably a cycloalkyl group, more preferably a 5- or 6-membered monocyclic cycloalkyl group. Specific examples of the ring include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Rx １ ~Rx ３ In the cycloalkyl group formed by bonding these two, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

[0090] -C(Rx １ ) (Rx ２ ) (Rx ３ ) preferably represents a group that is decomposed and eliminated by the action of an acid.

[0091] Examples of the monomer represented by general formula (a) or general formula (aI) are shown below, but the present invention is not limited to these.

[0092]

[0093]

[0094]

[0095] The amount of at least one monomer selected from the group consisting of the monomer represented by general formula (a) and the monomer represented by general formula (aI) is not particularly limited, but is preferably 10 to 90 mol %, and more preferably 20 to 60 mol %, based on the total amount of raw material monomers. The at least one monomer selected from the group consisting of the monomer represented by general formula (a) and the monomer represented by general formula (aI) may be used alone or in combination of two or more.

[0096] <Monomer represented by formula (b)>

[0097]

[0098] In general formula (b), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ Is L ３ may be bonded to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group. ３ represents an (n+m+1)-valent aromatic ring group or alicyclic group. Ｂ３ When R is bonded to form a ring, it represents an (n+m+2)-valent aromatic ring group or alicyclic group. ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group. Ｂ５ represents a halogen atom, m represents an integer of 1 or more, and n represents an integer of 0 or more.

[0099] R in general formula (b) Ｂ１ ~R Ｂ３ R each independently represents a hydrogen atom, an organic group, or a halogen atom, and preferably represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ｂ１ ~R Ｂ３ The alkyl group in R may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Ｂ１ ~R Ｂ３ The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. １０１ , R １０２ and R １０３The cycloalkyl group of R is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Ｂ１ ~R Ｂ３ Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. Ｂ１ ~R Ｂ３ The alkyl group contained in the alkoxycarbonyl group may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. Ｂ２ represents Xa in the above general formula (aI). １ -CH as an alkyl group represented by ２ -R １１ It is also preferable that R Ｂ２ Is, L ２ may be bonded to form a ring.

[0100] R Ｂ１ , R Ｂ３ preferably represents a hydrogen atom. Ｂ２ preferably represents a hydrogen atom or a methyl group.

[0101] L in general formula (b) ２ represents a single bond or a divalent linking group. ２ The divalent linking group represented by is not particularly limited, but examples thereof include —COO—, —CONR １０４ -, an alkylene group, or a group formed by combining two or more of these groups. １０４ represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. R １０４When L represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups, and alkyl groups having 8 or less carbon atoms are preferred. ２ preferably represents a single bond.

[0102] In general formula (b), L ３ represents an (n+m+1)-valent aromatic ring group or alicyclic group. Ｂ３ When it bonds to form a ring, it represents an (n+m+2)-valent aromatic ring group or alicyclic group. When n+m is 1, the divalent aromatic ring group is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. The aromatic ring group may have a substituent. When n+m is 1, the divalent alicyclic group may be, for example, a monocyclic cycloalkylene group, such as a cyclopentylene group or a cyclohexylene group, or a group obtained by removing any one hydrogen atom from a polycyclic cycloalkyl group, such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The number of carbon atoms is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. In the cycloalkylene group, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

[0103] Specific examples of (n+m+1)-valent aromatic ring groups and alicyclic groups when n+m is an integer of 2 or greater include groups obtained by removing any (n+m-1) hydrogen atoms from the above-mentioned specific examples of divalent aromatic ring groups and alicyclic groups. The (n+m+1)-valent aromatic ring group or alicyclic group may further have a substituent. The substituent that the (n+m+1)-valent aromatic ring group or alicyclic group may have is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl; and halogen atoms.

[0104] L ３ preferably represents an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group, and even more preferably a benzene ring group.

[0105] R in general formula (b) ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group.

[0106] R ｂ４ Specifically, the group represented by the formula (3) that decomposes with an acid or a base to produce an —OH group is preferably a group represented by any one of the following general formulas (3) to (7). The groups represented by the general formulas (3) to (6) are base-decomposable groups, and the group represented by the general formula (7) is an acid-decomposable group.

[0107]

[0108] In general formulas (3) to (7), R ３１ represents a hydrogen atom or an organic group. ４１ , R ５１ , R ６１ R each independently represents an organic group. ７１ , R ７２ R each independently represents a hydrogen atom or an organic group. ７３ represents an organic group. ７１ ~R７３ may be linked to each other to form a ring. ３ represents the bonding position with

[0109] R ３１ , R ４１ , R ５１ , and R ６１ Examples of the organic group represented by include an alkyl group, a cycloalkyl group, and an aryl group. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group.

[0110] R ３１ , R ４１ , R ５１ , and R ６１ The organic group represented by may further have a substituent, and the substituent is preferably a halogen atom such as a fluorine atom.

[0111] R ３１ , R ４１ , R ５１ , and R ６１ is preferably an alkyl group having 1 to 3 carbon atoms, a trifluoromethyl group, or a phenyl group.

[0112] R ７１ , R ７２ , and R ７３ Examples of the organic group represented by R include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group. ７１ , R ７２ , and R ７３ The alkyl group, cycloalkyl group, and aryl group represented by R ３１ , R ４１ , R ５１ , and R ６１Examples of the alkyl group, cycloalkyl group, and aryl group represented by R ７１ , R ７２ , and R ７３ The heteroaryl group represented by is preferably a heteroaryl group having 2 to 15 carbon atoms, and examples thereof include those having 5 to 10 membered rings, and specific examples thereof include a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group. ７１ , R ７２ , and R ７３ The alkenyl group represented by R is an alkenyl group having 2 to 10 carbon atoms. ７１ , R ７２ , and R ７３ The alkynyl group represented by R is an alkynyl group having 2 to 10 carbon atoms. ７１ , R ７２ , and R ７３ The above group represented by may further have a substituent.

[0113] R ７１ represents a hydrogen atom, and R ７２ , and R ７３ It is preferred that represents an alkyl group having 1 to 3 carbon atoms.

[0114] R ｂ４ The fluorinated alcohol group represented by the formula (I) is preferably a hexafluoroisopropanol group.

[0115] R ｂ４ is preferably a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and more preferably a hydroxyl group or a group represented by general formula (3), (4) or (7). ｂ４ is a hydroxyl group or a group that generates an —OH group when decomposed by an acid or a base, ３ is particularly preferably an aromatic hydrocarbon ring group.

[0116] In general formula (b), R Ｂ５ represents a halogen atom. Ｂ５Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0117] In formula (b), m represents an integer of 1 or more, preferably an integer of 1 to 3, and more preferably 1 or 2. n represents an integer of 0 or more, preferably an integer of 0 to 5, and more preferably 0.

[0118] The monomer represented by the above general formula (b) is preferably a monomer represented by the following general formula (b-1):

[0119]

[0120] In general formula (b-1), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ may be bonded to Ar to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R Ｂ３ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. ｂ６ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5.

[0121] R in general formula (b-1) Ｂ１ ~R Ｂ３ , L ２ represents R in the general formula (b). Ｂ１ ~R Ｂ３ , L ２ The same applies to preferred examples.

[0122] In the general formula (b-1), the (k+1)-valent aromatic ring group represented by Ar is L in the above general formula (b). ３ and an (n+m+1)-valent aromatic ring group as the aromatic ring group, where n+m is to be read as k.

[0123] Ar preferably represents an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group, and even more preferably a benzene ring group.

[0124] R in general formula (b-1) ｂ６ and a group which decomposes with an acid or a base to form an —OH group, such as R in the above general formula (b). ｂ４ and groups that decompose with an acid or a base to form an —OH group, and preferred examples are also the same. However, in the above general formulas (3) to (7), * should be read as the bonding position with Ar.

[0125] In formula (b-1), k represents an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0126] Examples of the monomer represented by formula (b) are shown below, but the invention is not limited to these.

[0127]

[0128]

[0129]

[0130] The amount of the monomer represented by formula (b) used is not particularly limited, but is preferably 10 to 90 mol %, more preferably 50 to 80 mol %, based on the total amount of raw material monomers. The monomer represented by formula (b) may be used alone or in combination of two or more.

[0131] In step (i), a monomer other than the monomer represented by general formula (a), the monomer represented by general formula (aI), and the monomer represented by general formula (b) may be used depending on the desired polymer structure. The amount of each monomer to be added may be determined depending on the desired polymer structure.

[0132] <Radical Polymerization Initiator> The reaction in the above step (i) uses a radical polymerization initiator. As the radical polymerization initiator, for example, azo-based initiators and peroxides are used to initiate polymerization. As the radical initiator, azo-based initiators are preferred, and azo-based initiators having an ester group, a cyano group, or a carboxyl group are preferred. Preferred initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), etc.

[0133] <Nitroxide Radical> The reaction in the above step (i) can be carried out in the presence of a nitroxide radical represented by the following general formula (N): The nitroxide radical used in the production method of the present invention is a compound that exists stably in the form of a free radical, and is formed as a radical on an oxygen atom bonded to a nitrogen atom.

[0134]

[0135] In general formula (N), R Ｎ１ Each of R independently represents an organic group. Ｎ１ may be bonded to form a ring.

[0136] R Ｎ１ Examples of the organic group represented by R include organic groups having 1 to 30 carbon atoms, preferably organic groups having 1 to 20 carbon atoms, and more preferably organic groups having 1 to 10 carbon atoms. Ｎ１ The organic group represented by is not particularly limited, but examples thereof include an alkyl group and an aryl group.

[0137] The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and the aryl group is preferably a phenyl group or naphthyl group having 6 to 10 carbon atoms.

[0138] R Ｎ１ The organic group represented by may further have a substituent, such as an alkyl group, an aryl group, an ester group, a hydroxyl group, a carbonyl group, a phosphate ester, or a carboxyalkyl group.

[0139] Two R's Ｎ１may be bonded to form a ring. Ｎ１ Examples of the ring formed by bonding include a piperidine ring and a pyrrolidine ring. A methylene group forming the ring may be substituted with a carbonyl group. In a preferred embodiment, two or more nitroxide radicals represented by general formula (N) may be bonded via a single bond or a linking group.

[0140] Specific examples of the nitroxide radical represented by general formula (N) include 2,2,6,6-tetramethyl-1-piperidinyloxy radical (N-1 below), 2,2,6,6-tetraethyl-1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-pyrrolidinyloxy radical (N-2 below), 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical, and N,N-di-t-butylamineoxy radical. The 2,2,6,6-tetramethyl-1-piperidinyloxy radical (N-1 below) is preferably used in the present invention. Other examples include the following compounds N-3 to N-9.

[0141]

[0142] The ratio of the raw material monomer to the nitroxide radical is preferably 0.001 to 0.1 mol, more preferably 0.01 to 0.05 mol, of the nitroxide radical per 1 mol of the raw material monomer. When the ratio of the two is within the above range, the molecular weight and molecular weight distribution of the resin can be appropriately controlled, and the resin can be produced at an appropriate polymerization rate, which is preferable.

[0143] The ratio of the two to be used in combination is not particularly limited, but can be selected from the range of 0.1 to 2 moles, preferably 0.5 to 1.5 moles, and more preferably 0.8 to 1.2 moles of radical polymerization initiator per mole of nitroxide radical. It is preferable that the nitroxide radical does not also function as a polymerization initiator. Specifically, it is preferable that the nitroxide radical does not combine with the polymerization initiator and function as a polymerization initiator together.

[0144] <Dithioester Compound> The reaction in the above step (i) can be carried out in the presence of a dithioester compound represented by the following general formula (Ra): In the present invention, the dithioester compound refers to a compound having —S—C(═S)— in its structure.

[0145] In the general formula (Ra), Ra １ and Ra ２ each independently represents an organic group.

[0146] Ra １ Examples of the organic group represented by Ra include organic groups having 1 to 30 carbon atoms, preferably organic groups having 1 to 20 carbon atoms, and more preferably organic groups having 1 to 10 carbon atoms. １ The organic group represented by is not particularly limited, but examples thereof include an alkyl group, an aryl group, and a heteroaryl group.

[0147] The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. The aryl group is preferably a phenyl group or naphthyl group having 6 to 10 carbon atoms. The heteroaryl group is preferably a heteroaryl group having 2 to 15 carbon atoms, and examples thereof include those having 5 to 10 membered rings, such as a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, a pyrazole group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group.

[0148] Ra １ The organic group represented by may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, an amino group, a cyano group, a carboxyl group, —CO—, —O—, and —NR １０４ - (R １０４ represents a hydrogen atom or an alkyl group), -S-, -SC(=S)-, and groups formed by combining these groups.

[0149] Ra ２ Examples of the organic group represented by Ra include organic groups having 1 to 30 carbon atoms, preferably organic groups having 1 to 20 carbon atoms, and more preferably organic groups having 1 to 10 carbon atoms. ２The organic group represented by is not particularly limited, but examples thereof include an alkyl group, an aryl group, a heteroaryl group, an -S-alkyl group, an -S-aryl group, and an -S-heteroaryl group.

[0150] The alkyl group and the alkyl group in the -S-alkyl group are the same as those described above in Ra １ The aryl group and the aryl group in the -S-aryl group include the alkyl groups represented by the above-mentioned Ra １ Examples of the heteroaryl group and the heteroaryl group in the -S-heteroaryl group include the aryl groups represented by the above-mentioned Ra １ Examples of heteroaryl groups include:

[0151] The dithioester compound represented by general formula (Ra) is preferably represented by the following general formula (Ra-2).

[0152]

[0153] In general formula (Ra-2), Ra １ and Ra ３ Each of Ra in general formula (Ra-2) independently represents an organic group. １ is Ra in the above general formula (Ra). １ The same applies to preferred examples of Ra in general formula (Ra-2). ３ The organic group represented by the general formula (Ra) is １ The preferred examples are also the same.

[0154] Examples of the dithioester compound represented by general formula (Ra) include, but are not limited to, the following:

[0155]

[0156]

[0157] The ratio of the raw material monomer to the dithioester compound is preferably 0.001 to 0.1 mol, more preferably 0.01 to 0.05 mol, of the dithioester compound per 1 mol of the raw material monomer. When the ratio of the two is within the above range, the molecular weight and molecular weight distribution of the resin can be appropriately controlled, and the resin can be produced at an appropriate polymerization rate, which is preferable.

[0158] The ratio of the two to be used in combination is not particularly limited, but can be selected from the range of 0.1 to 2 moles, preferably 0.5 to 1.5 moles, and more preferably 0.8 to 1.2 moles of radical polymerization initiator per mole of dithioester compound.

[0159] <Solvent> The reaction in step (i) above is typically carried out in a liquid phase. That is, the reaction system above typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, but examples thereof include alcohol-based solvents, ether-based solvents, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, dialkylene glycol dialkyl ethers, cyclic lactones, linear or cyclic ketones, alkylene carbonates, alkyl carboxylates, alkyl alkoxyacetates, alkyl pyruvates, and hydrocarbon-based solvents. Other usable solvents include, for example, the solvents described in U.S. Patent Application Publication No. 2008 / 0248425 A1, paragraphs

[0244] and thereafter.

[0160] The alcohol solvent is not particularly limited as long as it contains —OH, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 1-methoxy-2-propanol, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, and diacetone alcohol.

[0161] The ether solvent is not particularly limited as long as it contains —O—, and may be either chain or cyclic. Examples of the ether solvent include tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane.

[0162] Preferred examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

[0163] Preferred examples of alkylene glycol monoalkyl ethers include propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Preferred examples of dialkylene glycol monoalkyl ethers include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether. Note that alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers are included in the alcohol-based solvents.

[0164] Examples of dialkylene glycol dialkyl ethers include diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether, etc. Dialkylene glycol dialkyl ethers are included in the ether solvents.

[0165] Preferred examples of cyclic lactones include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone.

[0166] Examples of chain or cyclic ketones include 2-butanone (methyl ethyl ketone), 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, and 2-nonane. Preferred examples of the cyclohexane-1,1-dione include cyclohexane, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, and 3-methylcycloheptanone.

[0167] Preferred examples of alkylene carbonates include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate. Preferred examples of alkyl carboxylates include butyl acetate and acetic anhydride.

[0168] Preferred examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-2-propyl acetate. Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

[0169] Examples of hydrocarbon solvents include toluene, dichlorobenzene, and chlorobenzene.

[0170] These solvents may be used alone or in combination of two or more.

[0171] <Polymerization Reaction> The polymerization reaction in step (i) is carried out in the presence of a nitroxide radical or a dithioester compound. By carrying out radical polymerization via these compounds, the polydispersity (Mw / Mn) of the resulting polymer can be kept low. In the polymerization reaction in step (i), the raw material monomers may be added all at once to the reaction system. However, from the viewpoints of the polydispersity of the polymer obtained in step (i) (hereinafter referred to as polymer (X1)), the uniformity of the composition between each polymer, safety, etc., it is preferable to carry out dropwise polymerization.

[0172] In step (i), it is preferable to place a reaction solution containing a solvent, an initiator in an amount of 80 mass% or more based on the total amount of the initiator, and a nitroxide radical or dithioester-based compound in an amount of 90 mass% or more based on the total amount of the nitroxide radical or dithioester-based compound in a reaction vessel, and then dropwise add at least a portion of the raw material monomers to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator.

[0173] The reaction solution may be charged into a reaction vessel and then heated to a temperature equal to or higher than the decomposition temperature of the initiator, or the heated reaction solution may be added dropwise to the reaction vessel.

[0174] From the viewpoint of uniformity of the polymer composition, the reaction solution preferably contains 80% by mass or more of the initiator used, more preferably 90% by mass or more, even more preferably 95% by mass or more, still more preferably 99% by mass or more, and particularly preferably 100% by mass, based on the total amount of the initiator.

[0175] From the viewpoint of uniformity of the polymer composition, the reaction solution preferably contains 90% by mass or more of the nitroxide radical or dithioester compound used, more preferably 95% by mass or more, still more preferably 99% by mass or more, and particularly preferably 100% by mass, of the total amount of the nitroxide radical or dithioester compound contained in the reaction solution.

[0176] It is also preferable that the reaction solution contains some of the raw material monomers. That is, in step (i), it is also preferable to place a reaction solution containing a solvent, 80% by mass or more of an initiator based on the total amount of initiators, 90% by mass or more of a nitroxide radical or dithioester compound based on the total amount of nitroxide radicals or dithioester compounds, and some of the raw material monomers in a reaction vessel, and then dropwise add the remaining raw material monomers to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator. The amount of raw material monomers in the reaction solution is preferably 1 to 50 mol %, more preferably 1 to 30 mol %, and even more preferably 1 to 10 mol %, based on the total amount of raw material monomers.

[0177] The raw material monomers to be dropped into the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator are typically dropped as a raw material monomer solution containing a solvent. The raw material monomer solution may contain 10% by mass or less of the initiator, 10% by mass or less of the nitroxide radical or dithioester compound, but it is preferable that the raw material monomer solution does not contain these.

[0178] When the raw material monomer is dropped into the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator, it is preferable that the reaction solution is heated to at least the decomposition temperature of the initiator or higher. The upper limit of the heating temperature is, for example, 150°C.

[0179] The dropping time of the raw material monomers to be dropped into the reaction solution is preferably 1 to 24 hours. By setting the dropping time within this range, thermal decomposition of the polymer can be suppressed.

[0180] Furthermore, the time for heating the reaction system after dropping the raw material monomers into the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator is preferably less than 2 hours. By setting the heating time to less than 2 hours, the uniformity of the polymer composition can be improved. The heating time is preferably 0 to 1 hour, more preferably 0 to 30 minutes.

[0181] The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and may be carried out in the presence of a chain transfer agent (e.g., alkyl mercaptan) as needed.

[0182] The monomer concentration in the reaction system is preferably 20 to 80% by mass, more preferably 25 to 70% by mass.

[0183] <Polymer (X1)> The polymer (X1) obtained by the above step (i) will be described. The polymer (X1) contains at least one repeating unit selected from the repeating unit represented by the following general formula (A) and the repeating unit represented by the following general formula (AI), and a repeating unit represented by the following general formula (BX), and has a nitroxide radical residue or a dithioester compound residue as a terminal structure of the main chain.

[0184]

[0185] In general formula (A), L １ , R Ａ１ ~R Ａ３ , and R Ａ４ represents L in the above general formula (a). １ , R Ａ１ ~R Ａ３ , and R Ａ４ In general formula (AI), Xa １ , T, Rx １ ~Rx ３ represents Xa in the above general formula (aI). １ , T, Rx １ ~Rx３ The same applies to preferred examples.

[0186]

[0187] In general formula (BX), R Ｂ１ ~R Ｂ３ , L ２ , L ３ , R ｂ４ , R Ｂ５ , m and n are R in the above general formula (b). Ｂ１ ~R Ｂ３ , L ２ , L ３ , R ｂ４ , R Ｂ５ , m and n have the same meanings, and preferred examples are also the same.

[0188] The polymer (X1) has a nitroxide radical residue or a dithioester compound residue as a terminal structure of the main chain. Specifically, —O—N(R Ｎ１ ) ２ , or -S-C(=S)-R ａ２ (R Ｎ１ and R ａ２ represents an organic group. Ｎ１ may be bonded to form a ring) (hereinafter, these may be collectively referred to as "specific structure"). Ｎ１ represents R in the above general formula (N). Ｎ１ and preferred examples are also the same, or represent an organic group containing another polymer segment. ａ２ represents R in the above general formula (Ra). ａ２ and preferred examples thereof are also the same, or represent an organic group containing another polymer segment.

[0189] The term "terminal structure of the main chain of polymer (X1)" refers to a terminal structure other than the structure corresponding to the repeating unit of polymer (X1). The term "polymer (X1) having the above-mentioned specific structure at the terminal structure of the main chain" means that polymer (X1) has the above-mentioned specific structure at at least one of the terminal structures of the main chain structure.

[0190] The terminal structure of the main chain is １ H-NMR, １３ This can be confirmed by C-NMR or the like.

[0191] The polymer (X1) may be a linear polymer, a star polymer, or a branched polymer. The main chain structure of the resin (X1) refers to the main chain structure of a polymer segment in the case of a star polymer or a branched polymer. Furthermore, at least one of the terminal structures of the main chain structures of the multiple polymer segments may have the specific structure. The polydispersity (Mw / Mn) of the polymer (X1) is preferably less than 1.40.

[0192] [Step (ii) (End Group Treatment Step)] Step (ii) is a step of substituting the main chain end groups of the polymer obtained in step (i) above with hydrogen atoms or other substituents. Here, the main chain end groups of the polymer obtained in step (i) are the portions of the polymer whose ends are protected by the nitroxide radical or dithioester compound used in step (i), and specifically, the above-mentioned -O-N(R Ｎ１ ) ２ , or -S-C(=S)-R ａ２ (R Ｎ１ and R ａ２ represents an organic group. Ｎ１ may be bonded to form a ring). The main chain terminal group may be present in at least one of the terminal structures of the main chain structure in the polymer.

[0193] The method for substituting the main chain end group is not particularly limited, and examples thereof include a method of reacting the polymer obtained in (i) with the following compounds: (1) a compound having hydrogen atom donating properties (2) a compound having hydrogen atom donating properties and a free radical or a compound that generates free radicals (3) a free radical or a compound that generates free radicals (4) a reducing agent (5) an oxidizing agent (6) a compound represented by the following general formula (M) or the following general formula (D) Other methods for substituting the main chain end group include, for example, (7) a method of heating the polymer obtained in (i) in an inert solvent without adding any other reagents for 1 hour or more.

[0194] <(1) Method of Reacting the Polymer Obtained in (i) with a Compound Having Hydrogen Atom Donating Property> Examples of the compound having hydrogen atom donating property that can be used in method (1) include amine compounds such as piperidine, inorganic bases such as hydrazine and hydroxide, and boron hydrides.

[0195] The amount of the hydrogen atom donating compound used may be, for example, 1 to 20 molar equivalents, preferably 3 to 8 molar equivalents, relative to the main chain terminal group of the polymer.

[0196] The reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents listed in step (i), amine solvents, amide solvents, and chloroform.

[0197] The reaction temperature is usually 50° C. to 150° C., preferably 70° C. to 120° C. The reaction time is usually 1 to 24 hours, preferably 1 to 6 hours.

[0198] As a result of the above reaction, the terminal groups of the main chain become hydrogen atoms.

[0199] <(2) Method of reacting the polymer obtained in (i) with a compound having hydrogen atom donating ability and a free radical or a compound capable of generating free radicals> (Compound having hydrogen atom donating ability) Examples of the compound having hydrogen atom donating ability to be used in method (2) include the compounds having hydrogen atom donating ability that can be used in the above-mentioned method (1).

[0200] (Free radicals and compounds capable of generating free radicals) Examples of the free radicals used in method (2) include azo initiators and peroxide initiators. Examples of compounds capable of generating free radicals include compounds that generate free radicals by light or heat. Examples include known radical polymerization initiators, and among these, azo initiators are preferred.

[0201] The amount of the hydrogen atom-donating compound used may be, for example, 1 to 20 molar equivalents, preferably 3 to 10 molar equivalents, relative to the main chain terminal group of the polymer. The amount of the free radical or the compound that generates a free radical used may be, for example, 1 to 20 molar equivalents, preferably 3 to 8 molar equivalents, relative to the main chain terminal group of the polymer.

[0202] The reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents that can be used in the method (1) above.

[0203] The reaction temperature is usually 50° C. to 150° C., preferably 70° C. to 120° C. The reaction time is usually 1 to 24 hours, preferably 1 to 6 hours.

[0204] As a result of the above reaction, the terminal groups of the main chain become hydrogen atoms.

[0205] <(3) Method of Reacting the Polymer Obtained in (i) with Free Radicals or a Compound Capable of Generating Free Radicals> (Free Radicals and Compounds Capable of Generating Free Radicals) Examples of the free radicals and compounds capable of generating free radicals that can be used in the method (3) include the free radicals and compounds capable of generating free radicals that can be used in the method (2) described above.

[0206] The amount of the free radical or the compound that generates the free radical to be used may be, for example, 1 to 20 molar equivalents, preferably 3 to 8 molar equivalents, relative to the main chain terminal group of the polymer.

[0207] The reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents that can be used in the method (1) above.

[0208] The reaction temperature is usually 50° C. to 150° C., preferably 70° C. to 120° C. The reaction time is usually 1 to 24 hours, preferably 1 to 6 hours.

[0209] By the above reaction, the main chain terminal group is converted into a residue of the initiator used.

[0210] <(4) Method of Reacting the Polymer Obtained in (i) with a Reducing Agent> (Reducing Agent) Examples of reducing agents that can be used in method (4) include alkanethiols such as 1-dodecanethiol, alcohols such as isopropanol, silane compounds such as triethylsilane, phosphine reducing agents such as triethylamine hypophosphite, and metal reducing agents such as zinc.

[0211] The amount of the reducing agent used may be, for example, 1 to 20 molar equivalents, preferably 3 to 8 molar equivalents, relative to the main chain terminal group of the polymer.

[0212] The reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents that can be used in the method (1) above.

[0213] The reaction may be carried out under acidic conditions as needed. The reaction may also be carried out in the presence of a radical polymerization initiator as needed. The reaction temperature is usually 50°C to 150°C, and preferably 70°C to 120°C. The reaction time is usually 1 to 24 hours, and preferably 1 to 6 hours.

[0214] As a result of the above reaction, the terminal groups of the main chain become hydrogen atoms.

[0215] <(5) Method of Reacting the Polymer Obtained in (i) with an Oxidizing Agent> (Oxidizing Agent) Examples of the oxidizing agent that can be used in method (5) include peracids such as m-chloroperbenzoic acid, and inorganic oxidizing agents such as ammonium hexanitratocerate(IV).

[0216] The amount of the reducing agent used may be, for example, 1 to 20 molar equivalents, preferably 3 to 8 molar equivalents, relative to the main chain terminal group of the polymer.

[0217] The reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents that can be used in the method (1) above.

[0218] The reaction temperature is usually −20° C. to 100° C., preferably −20° C. to 80° C. The reaction time is usually 1 to 24 hours, preferably 1 to 6 hours.

[0219] By the above reaction, the terminal group of the main chain is cleaved, generating a —C(═O)— or a hydroxyl group in the adjacent repeating unit.

[0220] <(6) A method of reacting the polymer obtained in (i), an oxidizing agent, and a compound represented by the following general formula (M) or the following general formula (D)>

[0221]

[0222] In general formula (M), R Ｍ１ R each independently represents a hydrogen atom or a monovalent substituent. Ｍ２ each independently represents a monovalent substituent, and may be bonded to each other to form a ring. Ｄ１ R each independently represents a hydrogen atom or a monovalent substituent. Ｄ２ each independently represents a hydrogen atom or a monovalent substituent.

[0223] R in general formula (M) Ｍ１ , R Ｍ２ The monovalent substituent represented by is not particularly limited, but is preferably an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an arylcarbonyl group, an arylcarbonyloxy group, an aryloxycarbonyl group, an alkylamino group, an arylamino group, and a group formed by combining two or more of these. The organic group may further have a substituent (for example, the above-mentioned substituent T, etc.).

[0224] The compound represented by the above general formula (M) is preferably a compound represented by the following general formula (M1).

[0225]

[0226] In general formula (M1), R Ｍ１ R each independently represents a hydrogen atom or a monovalent substituent. Ｍ３ represents a monovalent substituent.

[0227] R in general formula (M1) Ｍ１ is R in general formula (M) Ｍ１ It is synonymous with R Ｍ１ are preferably all hydrogen atoms.

[0228] R in general formula (M1) Ｍ３ Examples of the monovalent substituent represented by the formula (M) include R Ｍ１ , R Ｍ２ The substituent is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.

[0229] R in general formula (D) Ｄ１ , R Ｄ２ The monovalent substituent represented by is not particularly limited, but is preferably an organic group. Examples of the organic group include alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkyloxy groups, aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, arylthio groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkoxycarbonyl groups, arylcarbonyl groups, arylcarbonyloxy groups, aryloxycarbonyl groups, alkylamino groups, arylamino groups, and groups formed by combining two or more of these, among which alkyl groups are preferred. The organic group may further have a substituent (for example, the above-mentioned substituent T, etc.).

[0230] The amount of the compound represented by the general formula (M) or the general formula (D) used may be, for example, 1.0 to 10 molar equivalents, and preferably 1.2 to 3 molar equivalents, relative to the main chain terminal group of the polymer.

[0231] The reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents that can be used in the method (1) above.

[0232] The above reaction may be carried out in the presence of a Lewis acid such as zinc chloride, if necessary. The above reaction may also be carried out in the presence of a radical polymerization initiator, if necessary. The reaction temperature is usually 50°C to 150°C, preferably 70°C to 120°C. The reaction time is usually 1 to 24 hours, preferably 1 to 6 hours.

[0233] By the above reaction, the main chain terminal group becomes a group containing a structure derived from the compound represented by the above general formula (M) or general formula (D).

[0234] <(7) A Method of Heating the Polymer Obtained in (i) in an Inert Solvent without Adding Other Reagents for 1 Hour or More> (Inert Solvent) Examples of inert solvents that can be used in the method (7) include ketone solvents such as cyclohexanone, and hydrocarbon solvents such as toluene and mesitylene.

[0235] The reaction is preferably carried out at reflux at the boiling point for a period of usually 1 to 24 hours, preferably 1 to 6 hours.

[0236] By the above reaction, the terminal group of the main chain is cleaved, and a carbon-carbon double bond is generated in the adjacent repeating unit.

[0237] In step (ii), the main chain terminal groups of the polymer obtained in step (i) above are substituted with hydrogen atoms or other substituents. Examples of such other substituents include —SH, —OH, halogen atoms, groups containing a structure derived from the compound represented by general formula (M) or general formula (D) above, and groups selected from hydrocarbon groups. This also includes embodiments in which the main chain terminal groups are cleaved to generate carbon-carbon double bonds or —C(═O)— in adjacent repeating units, thereby forming other substituents.

[0238] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a bromine atom being preferred.

[0239] Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, alkenyl groups, and aryl groups. Examples of alkyl groups include linear or branched alkyl groups having 1 to 10 carbon atoms. Examples of cycloalkyl groups include cycloalkyl groups having 6 to 15 carbon atoms, which may be either monocyclic or polycyclic. Examples of alkenyl groups include vinyl groups. Examples of aryl groups include aryl groups having 6 to 10 carbon atoms, which may be either monocyclic or polycyclic.

[0240] The hydrocarbon group may further have a substituent, and examples of the substituent include the above-mentioned substituent (T).

[0241] The group containing a structure derived from the compound represented by general formula (M) or general formula (D) may contain a part of the dithioester compound residue or a part of the nitroxide radical residue. However, it does not include —S—C(═S)— or —O—NR— (wherein R represents a hydrogen atom or a substituent). Specific examples include a heterocyclic group and a heterocyclic-S— group.

[0242] <Polymer (X2)> When the method for producing a resin of the present invention does not include the step (iii) or the step (iv) described below, the polymer (X2) obtained by the step (ii) contains at least one repeating unit selected from the repeating unit represented by the general formula (A) and the repeating unit represented by the general formula (AI), and a repeating unit represented by the general formula (BX), and has, at a terminal structure of the main chain, a hydrogen atom or a group selected from —SH, —OH, a halogen atom, a heterocyclic group, a heterocyclic-S— group, and a hydrocarbon group (hereinafter collectively referred to as “specific structure A”), and has a polydispersity (Mw / Mn) of less than 1.40.

[0243] The term "terminal structure of the main chain of polymer (X2)" refers to a terminal structure other than the structure corresponding to the repeating unit of polymer (X2). The term "polymer (X2) having the specific structure A at the terminal structure of the main chain" means that polymer (X2) has the specific structure A at least in one of the terminal structures of the main chain structure.

[0244] When the resin production method of the present invention does not include the following steps (iii) and (iv), the polymer (X2) can be the resin (A) described below. That is, the repeating unit represented by the general formula (BX) can be the repeating unit corresponding to the repeating unit represented by the general formula (B) in the resin (A) described below.

[0245] The resin production method of the present invention may include steps other than the above steps (i) and (ii), such as step (iii) a deprotection step and step (iv) a reprotection step.

[0246] [Step (iii) (Deprotection Step)] Step (iii) is a step of deprotecting a group that may be contained in the polymer (X1) or the polymer (X2) and that generates an —OH group upon decomposition with an acid or a base, to form an —OH group. Step (iii) may be performed after step (i) and before step (ii), or may be performed after step (ii).

[0247] <Decomposition Reaction of Base-Decomposable Group> R in the repeating unit represented by the above general formula (BX) in the polymer (X1) or the polymer (X2) ｂ４ is a base-decomposable group, in step (iii), R ｂ４ can be decomposed with a base to form a repeating unit represented by the following general formula (BX2).

[0248]

[0249] In general formula (BX2), R Ｂ１ ~R Ｂ３ , L ２ , L ３ , R Ｂ５ , m and n are R in the above general formula (b). Ｂ１ ~R Ｂ３ , L ２ , L ３ , R Ｂ５ , m and n have the same meanings, and preferred examples are also the same.

[0250] (Base) Examples of the base that can be used include triethylamine, tetra-n-butylammonium fluoride, pyridine, diazabicycloundecene, etc. The amount of the base is preferably 1 to 5 molar equivalents, more preferably 1.2 to 3 molar equivalents, relative to the base-decomposable groups in the resin.

[0251] (Solvent) The base decomposition reaction is typically carried out in a liquid phase. That is, the above reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents listed in step (i).

[0252] These solvents may be used alone or in combination of two or more.

[0253] The reaction temperature is usually 10° C. to 100° C., preferably 20° C. to 80° C., and more preferably 40° C. to 80° C. The reaction time is usually 3 to 48 hours, preferably 3 to 24 hours, and more preferably 6 to 12 hours.

[0254] <Decomposition Reaction of Acid-Decomposable Group> R in the repeating unit represented by the general formula (BX) in the polymer (X1) or the polymer (X2) ｂ４ is an acid-decomposable group, in step (iii), R ｂ４ can be decomposed with an acid to give the compound represented by the above general formula (BX2).

[0255] (Acid) Examples of the acid that can be used include hydrochloric acid, p-toluenesulfonic acid, hydrobromic acid, etc. The amount of the acid is preferably 1 to 5 molar equivalents, more preferably 1.2 to 3 molar equivalents, relative to the acid-decomposable groups in the resin.

[0256] (Solvent) The acidolysis reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents listed in step (i).

[0257] These solvents may be used alone or in combination of two or more.

[0258] The reaction temperature is usually 10° C. to 100° C., preferably 20° C. to 80° C., and more preferably 40° C. to 80° C. The reaction time is usually 3 to 48 hours, preferably 3 to 24 hours, and more preferably 6 to 12 hours.

[0259] When the resin production method of the present invention includes the above step (iii) but does not include the following step (iv), the polymer obtained by steps (i) to (iii) can be the resin (A) described below. That is, the repeating unit represented by the general formula (BX2) can be a repeating unit corresponding to the repeating unit represented by the general formula (B) in the resin (A) described below.

[0260] [Step (iv) (reprotection step)] The resin production method of the present invention may further include a step of protecting —OH groups in the repeating units represented by general formula (BX2) contained in the polymer obtained in step (iii). Step (iv) may be carried out after step (iii). When step (ii) is carried out after step (iii), step (iv) may be carried out before or after step (ii).

[0261] In step (iv), the polymer obtained in step (iii) is reacted with a halogenated compound represented by X-Rc to reprotect the —OH group in the repeating unit represented by general formula (BX2) above, thereby converting it into a repeating unit represented by general formula (BX3) below.

[0262]

[0263] In the compound represented by X-Rc, X represents a halogen atom, preferably a chlorine atom. Rc represents a group that is eliminated by the action of an acid. Specific examples of the elimination group include the elimination groups described below.

[0264] In general formula (BX3), R Ｂ１ ~R Ｂ３ , L ２ , L ３ , R Ｂ５ , m and n are R in the above general formula (b). Ｂ１ ~R Ｂ３ , L ２ , L ３ , R Ｂ５, m and n have the same meanings, and preferred examples are also the same.

[0265] In this way, by the step (iv), a repeating unit having a group that is decomposed by a desired acid to generate an --OH group can be introduced into the polymer.

[0266] The amount of the compound represented by X-Rc to be added is not particularly limited, and may be adjusted appropriately depending on the desired polymer structure.

[0267] (Base) The protection reaction can be carried out in the presence of a base. Examples of the base that can be used include triethylamine, pyridine, and potassium carbonate. The amount of the base used can be, for example, 1 to 5 moles per mole of the compound represented by X-Rc.

[0268] (Solvent) The reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents listed in step (i).

[0269] These solvents may be used alone or in combination of two or more.

[0270] The reaction temperature is usually −10° C. to 30° C., preferably −10° C. to 20° C., and more preferably 0° C. to 20° C. The reaction time is usually 1 to 6 hours, preferably 1 to 4 hours, and more preferably 1 to 2 hours.

[0271] When the resin production method of the present invention includes the above steps (iii) and (iv), the polymer obtained by steps (i) to (iv) can be the resin (A) described below. That is, the repeating unit represented by the general formula (BX2) and the repeating unit represented by the general formula (BX3) can be the repeating unit corresponding to the repeating unit represented by the general formula (B) in the resin (A) described below.

[0272] [Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition] The actinic ray- or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") contains a resin (A) that contains at least one repeating unit selected from a repeating unit represented by general formula (A) below and a repeating unit represented by general formula (AI) below, and a repeating unit represented by general formula (B) below, and that has a hydrogen atom or a group selected from -SH, -OH, a halogen atom, a heterocyclic group, a heterocyclic-S- group, and a hydrocarbon group at a terminal structure of the main chain and has a polydispersity (Mw / Mn) of less than 1.40; a compound (B) that generates an acid upon irradiation with actinic rays or radiation; and a solvent (S).

[0273]

[0274] In general formula (A), L １ represents a divalent linking group. Ａ１ ~R Ａ３ R each independently represents a hydrogen atom or a monovalent substituent. Ａ４ represents a group that is decomposed and eliminated by the action of an acid. １ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ Rx each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. １ ~Rx ３ may be bonded to form a ring.

[0275]

[0276] In general formula (B), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ Is L ３ may be bonded to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group. ３ represents an (n+m+1)-valent aromatic ring group or an alicyclic group. Ｂ３When R is bonded to form a ring, it represents an (n+m+2)-valent aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. Ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group. Ｂ５ represents a halogen atom, m represents an integer of 1 or more, and n represents 0 or an integer of 1 or more.

[0277] Although the mechanism by which the above-mentioned effects are obtained by applying the resin obtained by the above-described resin production method of the present invention to an actinic ray-sensitive or radiation-sensitive resin composition and by the composition of the present invention is not fully understood, the present inventors speculate as follows. By using step (i) in the resin production method of the present invention, the polydispersity of the obtained resin can be narrowed (specifically, less than 1.40). Since the difference in molecular weight between resins is small, it is believed that the resolution and roughness performance are excellent. The polymer obtained by step (i) has main chain terminal groups consisting of nitroxide radical residues or dithioester residues. However, it has been found that, in an actinic ray-sensitive or radiation-sensitive film obtained from the actinic ray-sensitive or radiation-sensitive resin composition, these residues in the main chain terminal groups react with acids generated from compounds that generate acids upon exposure to actinic rays or radiation (hereinafter also referred to as photoacid generator (B)) or absorb secondary electrons, which may result in a decrease in sensitivity. As a result of extensive research by the present inventors, it is believed that the above-mentioned decrease in sensitivity can be suppressed by removing the main chain terminal group in step (ii) of the resin production method of the present invention. Furthermore, the resin (A) contained in the composition of the present invention has a narrow polydispersity of less than 1.40 and a small difference in molecular weight between resins, and therefore is believed to have excellent resolution and roughness performance. Furthermore, the specific group in the terminal structure of the main chain of the resin (A) does not react with an acid generated from a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as photoacid generator (B)) during exposure in an actinic ray- or radiation-sensitive film obtained from the actinic ray- or radiation-sensitive resin composition, and does not absorb secondary electrons generated upon irradiation with actinic rays or radiation. Therefore, it is believed that the decrease in sensitivity caused by the terminal structure of the main chain can be suppressed.

[0278] The composition of the present invention is typically a resist composition, and may be either a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention is typically a chemically amplified resist composition. An actinic ray-sensitive or radiation-sensitive film can be formed using the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film. First, the various components of the composition of the present invention will be described in detail below.

[0279] [Resin (A)] The resin (A) contained in the composition of the present invention contains at least one repeating unit selected from the repeating unit represented by the general formula (A) above and the repeating unit represented by the general formula (AI) above, and a repeating unit represented by the general formula (B) above.

[0280] <At least one repeating unit selected from the repeating unit represented by general formula (A) and the repeating unit represented by general formula (AI)>

[0281]

[0282] In general formula (A), L １ represents a divalent linking group. Ａ１ ~R Ａ３ R each independently represents a hydrogen atom or a monovalent substituent. Ａ４ represents a group that is decomposed and eliminated by the action of an acid. １ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ Rx each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. １ ~Rx ３ may be bonded to form a ring.

[0283] In general formula (A), L １, R Ａ１ ~R Ａ３ , and R Ａ４ represents L in the above general formula (a). １ , R Ａ１ ~R Ａ３ , and R Ａ４ In general formula (AI), Xa １ , T, Rx １ ~Rx ３ represents Xa in the above general formula (aI). １ , T, Rx １ ~Rx ３ The same applies to preferred examples.

[0284] The repeating unit represented by general formula (A) and the repeating unit represented by general formula (AI) are preferably repeating units having an acid-decomposable group as described below. Ａ４ Similarly, -C(Rx １ ) (Rx ２ ) (Rx ３ ) is preferably a group that is decomposed and eliminated by the action of an acid.

[0285] The at least one repeating unit selected from the repeating unit represented by general formula (A) and the repeating unit represented by general formula (AI) contained in the resin (A) may be one type or two or more types.

[0286] The content of at least one repeating unit selected from the repeating units represented by general formula (A) and the repeating units represented by general formula (AI) relative to all repeating units in resin (A) is not particularly limited, but can be, for example, 5 to 70 mol %, preferably 10 to 60 mol %, more preferably 15 to 50 mol %.

[0287] <Repeating unit represented by formula (B)>

[0288]

[0289] In general formula (B), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ Is L３ may be bonded to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group. ３ represents an (n+m+1)-valent aromatic ring group or alicyclic group. Ｂ３ When R is bonded to form a ring, it represents an (n+m+2)-valent aromatic ring group or alicyclic group. Ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group. Ｂ５ represents a halogen atom, m represents an integer of 1 or more, and n represents 0 or an integer of 1 or more.

[0290] In general formula (B), R Ｂ１ ~R Ｂ３ , L ２ , L ３ , R Ｂ５ , m and n are R in the above general formula (b). Ｂ１ ~R Ｂ３ , L ２ , L ３ , R Ｂ５ , m and n have the same meanings, and preferred examples are also the same.

[0291] R in general formula (B) Ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group. Ｂ４ The group which is decomposed by an acid or a base to form an —OH group and the fluorinated alcohol group are R ｂ４ Examples of the alkyl group include a group that generates an —OH group upon decomposition with an acid or base, and a fluorinated alcohol group, and preferred examples are also the same.

[0292] The repeating unit represented by the above general formula (B) is preferably a repeating unit represented by the following general formula (B-1):

[0293]

[0294] In general formula (B-1), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom.Ｂ３ may be bonded to Ar to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R Ｂ３ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. Ｂ６ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5.

[0295] R in general formula (B-1) Ｂ１ ~R Ｂ３ , L ２ represents R in the above general formula (B). Ｂ１ ~R Ｂ３ , L ２ The same applies to preferred examples.

[0296] In the general formula (B-1), the (k+1)-valent aromatic ring group represented by Ar is L in the above general formula (B). ３ and an (n+m+1)-valent aromatic ring group as the aromatic ring group, where n+m is to be read as k.

[0297] Ar preferably represents an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group, and even more preferably a benzene ring group.

[0298] R in general formula (B-1) Ｂ６ and a group which generates an —OH group by decomposition with an acid or a base, such as R in the above general formula (B). Ｂ４ and groups that decompose with an acid or a base to form an —OH group, and preferred examples are also the same. However, in the above general formulas (3) to (7), * should be read as the bonding position with Ar.

[0299] In formula (B-1), k represents an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0300] The repeating unit represented by general formula (B) contained in the resin (A) may be of one type or of two or more types.

[0301] The content ratio of the repeating unit represented by general formula (B) relative to all repeating units in resin (A) is preferably 40 to 90 mol %, more preferably 45 to 80 mol %, and even more preferably 50 to 75 mol %.

[0302] <Repeating unit having an acid-decomposable group> The resin (A) preferably has an acid-decomposable group. The resin (A) preferably contains a repeating unit having an acid-decomposable group. When the resin (A) is an acid-decomposable resin, in a pattern forming method using the composition of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0303] The acid-decomposable group is a group that decomposes under the action of an acid to increase its polarity. The acid-decomposable group is typically a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a group that leaves under the action of an acid (leaving group). Typically, the polarity of the resin (A) increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent. The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxyl groups.

[0304] Examples of the leaving group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1): —C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx１ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (R ３７ ) (OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0305] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), a heteroaryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), an alkenyl group (linear or branched), or an alkynyl group (linear or branched). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to each other to form a ring (which may be either a monocyclic or polycyclic ring). １ ~Rx ３ The alkyl group of Rx is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group of Rx is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. １ ~Rx ３The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The heteroaryl group in Rx is preferably a heteroaryl group having 2 to 15 carbon atoms, and examples thereof include a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group. １ ~Rx ３ The aralkyl group of Rx １ ~Rx ３ A group in which one hydrogen atom in the alkyl group is substituted with an aryl group (preferably a phenyl group) having 6 to 10 carbon atoms is preferred, and examples thereof include a benzyl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ Examples of the alkynyl group of Rx include an ethynyl group. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by combining the two is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. １ ~Rx ３ In the cycloalkyl group formed by bonding these two, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The group represented by formula (Y1) or formula (Y2) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３and are preferably bonded to form the above-mentioned cycloalkyl group.

[0306] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. ３６ is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. For example, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have one or more methylene groups replaced with a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. In addition, R ３８ may bond with another substituent on the main chain of the repeating unit to form a ring. ３８ The group formed by bonding together the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0307] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0308] The content of the repeating units having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on the total repeating units in the resin (A), and the content of the repeating units having an acid-decomposable group is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, based on the total repeating units in the resin (A).

[0309] The repeating unit having an acid-decomposable group contained in the resin (A) may be a repeating unit represented by the above-mentioned general formula (A), a repeating unit represented by the general formula (AI), a repeating unit represented by the general formula (B), or another repeating unit. The repeating unit having an acid-decomposable group contained in the resin (A) may be one type or two or more types. When the resin (A) contains two or more types of repeating units having an acid-decomposable group, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0310] Resin (A) may contain other repeating units in addition to the repeating units represented by the above-mentioned general formula (A), the repeating units represented by the general formula (AI), the repeating units represented by the general formula (B), and the repeating units having an acid-decomposable group. For the other repeating units, the contents of paragraphs

[0079] to

[0172] of WO 2022 / 024928 are incorporated by reference.

[0311] The total content of the repeating units represented by the general formula (A), the repeating units represented by the general formula (AI), and the repeating units represented by the general formula (B) in the resin (A) is not particularly limited, but is preferably 70 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more.

[0312] <Terminal Structure of Main Chain> The resin (A) has, at the terminal structure of the main chain, a hydrogen atom or a group selected from —SH, —OH, a halogen atom, a heterocyclic group, a heterocyclic-S— group, and a hydrocarbon group (specific structure A).

[0313] The term "terminal structure of the main chain of resin (A)" refers to a terminal structure other than the structure corresponding to the repeating unit of resin (A). The term "resin (A) has the specific structure A" in the terminal structure of the main chain means that resin (A) has the specific structure A in at least one of the terminal structures of the main chain structure.

[0314] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a bromine atom being preferred.

[0315] Examples of heterocyclic groups include 5- to 10-membered heterocyclic groups having a heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom as a ring member. In the heterocyclic group, for example, one of the methylene groups constituting the ring may be replaced with a group having a heteroatom such as a carbonyl group or a vinylidene group. Furthermore, one or more ethylene groups constituting the ring may be replaced with a vinylene group. The same groups can also be used as the heterocyclic group in the heterocyclic group -S- group.

[0316] Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, alkenyl groups, and aryl groups. Examples of alkyl groups include linear or branched alkyl groups having 1 to 10 carbon atoms. Examples of cycloalkyl groups include cycloalkyl groups having 6 to 15 carbon atoms, which may be either monocyclic or polycyclic. Examples of alkenyl groups include vinyl groups. Examples of aryl groups include aryl groups having 6 to 10 carbon atoms, which may be either monocyclic or polycyclic. The hydrocarbon group may have a carbonyl bond between two adjacent carbon atoms.

[0317] The heterocyclic group, heterocyclic-S- group, and hydrocarbon group may further have a substituent, and examples of the substituent include the above-mentioned substituent (T).

[0318] As described above, the terminal structure of the main chain of the resin (A) does not include -S-C(=S)- or -O-NR- (wherein R represents a hydrogen atom or a substituent). １ H-NMR, １３ This can be confirmed by C-NMR, UV / vis spectrometry, etc. The specific structure A typically constitutes the main chain of the resin (A) and is directly bonded to a carbon atom located at the end of the main chain.

[0319] The method for synthesizing resin (A) is not particularly limited, but from the viewpoint of narrowing the molecular weight distribution of resin (A), it is preferable to synthesize resin (A) using the above-mentioned method for producing a resin of the present invention.

[0320] The weight average molecular weight (Mw) of the resin (A), as a polystyrene equivalent value measured by the GPC method, is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000 or more, and is preferably 30,000 or less, more preferably 15,000 or less.

[0321] The polydispersity (molecular weight distribution, Pd, Mw / Mn) of resin (A) is less than 1.40, preferably greater than 1.00 to 1.35, more preferably greater than 1.00 to 1.30, even more preferably greater than 1.00 to 1.25, and particularly preferably greater than 1.00 to 1.20. The smaller the polydispersity, the better the resolution and resist shape, and further the smoother the sidewalls of the resist pattern and the better the roughness.

[0322] In the composition of the present invention, the content of resin (A) is preferably 40.0 to 99.9 mass% and more preferably 60.0 to 90.0 mass% based on the total solid content of the composition of the present invention. Resin (A) may be used alone or in combination of two or more. When two or more resins (A) are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0323] [Compound (B) that generates an acid upon irradiation with actinic rays or radiation] The composition of the present invention contains a compound (B) that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as photoacid generator (B)). The photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. There is no particular restriction on the lower limit, but 100 or more is preferred. When the photoacid generator is in the form of being incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). The photoacid generator is preferably in the form of a low molecular weight compound. The photoacid generator is preferably a compound that generates an acid having a pKa of −2.0 or more upon irradiation with actinic rays or radiation, and more preferably a compound that generates an acid having a pKa of −2.0 or more and 1.0 or less.

[0324] Examples of the photoacid generator (B) include "M ＋ X － ", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0325] "M ＋ X － In the compound represented by the formula ", M ＋ represents an organic cation. As the organic cation, a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0326]

[0327] In formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples.

[0328] R ２０１ , R ２０２ , and R ２０３The organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 5. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The heteroaryl group is preferably a heteroaryl group having 3 to 20 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.

[0329] In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５ The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. ２０４ and R ２０５ The aryl group in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0330] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0331] "M ＋ X － In the compound represented by the formula "X － represents an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0332] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0333] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0334] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0335] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0336] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0337] An example of the sulfonylimide anion is a saccharin anion.

[0338] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0339] Other non-nucleophilic anions include, for example, phosphorus fluorides (e.g., PF ６ － ), boron fluorides (e.g., BF ４ － ), and antimony fluorides (e.g., SbF ６ － ) are listed.

[0340] Preferred non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, and tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom. Among these, perfluoroaliphatic sulfonate anions (preferably having 4 to 8 carbon atoms) and benzenesulfonate anions having a fluorine atom are more preferred, and nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluorobenzenesulfonate anions, and 3,5-bis(trifluoromethyl)benzenesulfonate anions are even more preferred.

[0341] "M ＋ X － For the compound represented by the formula "", the contents of

[0114] to

[0144] of JP-A No. 2005-2236 can be cited.

[0342] The photoacid generator (B) may be at least one selected from the group consisting of the following compounds (I) to (II):

[0343] (Compound (I)) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing the first acidic moiety derived from the structural moiety X and the second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation. Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and by irradiation with actinic rays or radiation, HA １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and by irradiation with actinic rays or radiation, HA ２ The compound (I) satisfies the following condition I:

[0344] Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cation moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by ２ and an acid dissociation constant a2 derived from the acidic moiety represented by the following formula (1): At least one of the acid dissociation constants a1 is less than 0.

[0345] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y, compound PI is "HA １ and H.A. ２ The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." More specifically, when the acid dissociation constant of the compound PI is calculated, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." １ － and H.A. ２ The pKa at which the compound becomes "a compound having the above formula (A)" is the acid dissociation constant a1, １ － and H.A. ２ "A compound having １ － and A ２ － The pKa at which the compound becomes "a compound having the above formula (I)" is the acid dissociation constant a2.

[0346] For example, when compound (I) is an acid-generating compound having two of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y, compound PI is a compound having two HAs. １ and one HA ２ When the acid dissociation constant of compound PI is calculated, compound PI corresponds to "a compound having one A １ － and one HA １ and one HA ２ and the acid dissociation constant when "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ The acid dissociation constant when the compound is a compound having two A's corresponds to the acid dissociation constant a1 described above. １ － and one HA ２ "Compound having two A １ － and A ２－ In other words, in the case of compound PI, the acid dissociation constant when the compound becomes a compound having the cation moiety M in the structural moiety X corresponds to the acid dissociation constant a2. １ ＋ H ＋ HA is replaced by １ When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by the formula (I), the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1. １ － and one HA １ and one HA ２ The acid dissociation constant when the compound is aa is defined as "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ When the acid dissociation constant when the compound becomes "a compound having the formula (I)" is ab, the relationship between aa and ab satisfies aa<ab.

[0347] The acid dissociation constants a1 and a2 are determined by the above-mentioned method for measuring an acid dissociation constant. The compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation. When compound (I) has two or more structural moieties X, the structural moieties X may be the same or different. In addition, when two or more of the above A １ － and two or more of the above M １ ＋ In compound (I), the above A １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0348] (Compound (II)) Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0349] For example, when compound (II) is an acid-generating compound having two of the first acidic sites derived from the structural site X and the structural site Z, compound PII is "two HA １ When the acid dissociation constant of this compound PII was calculated, it was found that the compound PII has "one A １ － and one HA １ and the acid dissociation constant when "a compound having one A １ － and one HA １ "Compound having two A １ － The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0350] The acid dissociation constant a1 is determined by the above-mentioned method for measuring an acid dissociation constant. At least one of the acid dissociation constants a1 is less than 0. The compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. The two or more A １ － and two or more of the above M １ ＋ may be the same or different.

[0351] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having electrons. Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0352]

[0353] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Of these, a primary amine structure, a secondary amine structure, a tertiary amine structure, and a tertiary amine structure are preferred.

[0354] With regard to the cation, compound (I) and compound (II), the contents of paragraphs

[0207] to

[0278] of WO 2022 / 024928 can be cited.

[0355] The content of the photoacid generator (B) in the composition of the present invention is preferably 1.0 mass% or more, more preferably 3.0 mass% or more, and even more preferably 5.0 mass% or more, based on the total solid content of the composition of the present invention. The content of the photoacid generator (B) is preferably 30.0 mass% or less, more preferably 25.0 mass% or less, and even more preferably 20.0 mass% or less, based on the total solid content of the composition of the present invention. The photoacid generator (B) may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

[0356] [Acid Diffusion Controller (C)] The acid diffusion controller (C) traps the acid generated from, for example, the photoacid generator (B) during exposure, and acts as a quencher to suppress the reaction of the acid-decomposable resin in unexposed areas due to excess generated acid. The type of acid diffusion controller (C) is not particularly limited, and examples thereof include a basic compound (CA), a low-molecular-weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. Examples of the compound (CC) include an onium salt compound (CD) of an acid that is weaker in acid than the acid generated from the photoacid generator (B), and a basic compound (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. Specific examples of the basic compound (CA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, and specific examples of the basic compound (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

[0155] of WO 2020 / 066824, and those described in paragraph

[0164] of WO 2020 / 066824. Specific examples of the low molecular weight compound (CB) having a nitrogen atom and having a group that leaves under the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824. For example, specific examples of the onium salt compound (CD) that is a weaker acid than the acid generated from the photoacid generator (B) or the like include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0357] In addition to the above, for example, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458A1 can be suitably used as the acid diffusion controller.

[0358] When the composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller (the total content if multiple types are present) is preferably 0.1 to 15.0 mass %, more preferably 1.0 to 15.0 mass %, based on the total solid content of the composition of the present invention. In the composition of the present invention, the acid diffusion controller may be used alone or in combination of two or more types.

[0359] [Hydrophobic Resin (Resin (D))] The composition of the present invention may further contain a hydrophobic resin (also referred to as "Resin (D)") different from Resin (A). The hydrophobic resin is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of the polar substance and the non-polar substance.

[0360] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0361] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass% and more preferably 0.1 to 15.0 mass% based on the total solid content of the composition of the present invention. One type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0362] [Surfactant] The composition of the present invention may contain a surfactant. When a surfactant is contained, a pattern with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0363] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the composition of the present invention. One type of surfactant may be used, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0364] [Solvent (S)] The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0365] Combining the above-mentioned solvent with the above-mentioned resin is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern. The above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, and therefore can suppress unevenness in the film thickness of the resist film and the occurrence of precipitates during spin coating. Details of component (M1) and component (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference.

[0366] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0367] The content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass, which further improves the coatability of the composition of the present invention.

[0368] [Other Additives] The composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0369] The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less, which is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0370] [Method for producing actinic ray-sensitive or radiation-sensitive resin composition] The present invention also relates to a method for producing an actinic ray-sensitive or radiation-sensitive resin composition, including the method for producing the resin described above.

[0371] The actinic ray- or radiation-sensitive resin composition obtained by the above-mentioned production method includes a resin obtained by the above-mentioned resin production method. The resin is not particularly limited as long as it is a polymer obtained through the above-mentioned steps (i) and (ii), and examples thereof include the above-mentioned polymer (X2). Further examples include the resin (A) contained in the composition of the present invention.

[0372] Components other than the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition obtained by the above production methods include components other than the resin (A) described in the section on actinic ray-sensitive or radiation-sensitive resin compositions above (e.g., compound (B) that generates an acid upon irradiation with actinic rays or radiation, solvent (S), etc.). The actinic ray-sensitive or radiation-sensitive resin composition obtained by each of the above production methods can be produced by mixing the resin obtained by the above-mentioned resin production method and, if necessary, other components. The mixing step is not particularly limited.

[0373] [Actinic ray- or radiation-sensitive film, pattern forming method] The present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention. The actinic ray- or radiation-sensitive film of the present invention is preferably a resist film. The present invention also relates to a pattern forming method. The pattern forming method of the present invention is preferably a pattern forming method comprising the steps of forming an actinic ray- or radiation-sensitive film (typically a resist film) on a substrate using the composition of the present invention, exposing the actinic ray- or radiation-sensitive film, and developing the exposed actinic ray- or radiation-sensitive film using a developer. The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but preferably comprises the following steps: Step 1: Forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention; Step 2: Exposing the actinic ray- or radiation-sensitive film; Step 3: Developing the exposed actinic ray- or radiation-sensitive film using a developer. The procedure of each of the above steps is described in detail below.

[0374] (Step 1: Actinic Ray- or Radiation-Sensitive Film Forming Step) Step 1 is a step of forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention.

[0375] An example of a method for forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention is to coat the composition of the present invention on the substrate. It is preferable to filter the composition of the present invention as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0376] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed during spin application using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After application of the composition of the present invention, the substrate may be dried to form an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed under the actinic ray-sensitive or radiation-sensitive film.

[0377] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, and may also be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0378] The thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0379] A top coat may be formed on top of the actinic ray-sensitive or radiation-sensitive film using a top coat composition. It is preferable that the top coat composition does not mix with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the actinic ray-sensitive or radiation-sensitive film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP 2014-059543 A. For example, a top coat containing a basic compound such as that described in JP 2013-61648 A is preferably formed on the actinic ray-sensitive or radiation-sensitive film. Specific examples of basic compounds that may be contained in the top coat include the basic compounds that may be contained in the composition of the present invention. It is also preferable that the top coat contain a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0380] (Step 2: Exposure Step) Step 2 is a step of exposing the actinic ray-sensitive or radiation-sensitive film. Examples of the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, and include far ultraviolet light with a wavelength of preferably 250 nm or less, more preferably 220 nm or less, and 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Excimer laser (157 nm), EUV (13.5 nm), X-ray, and electron beam are particularly preferred.

[0381] After exposure, it is preferable to bake (heat) the film before developing. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like. This process is also called post-exposure baking.

[0382] (Step 3: Development Step) Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0383] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispense nozzle is scanned at a constant speed (dynamic dispense method). Furthermore, after the development step, a step of stopping development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0384] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a quaternary ammonium salt, such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0385] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0386] The above-mentioned solvents may be mixed in plural, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0387] The pattern forming method of the present invention is preferably a positive pattern forming method using an alkaline developer.

[0388] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0389] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0390] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0391] The method for the rinsing step is not particularly limited, and examples include a method in which a rinsing solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dipping method), and a method in which the rinsing solution is sprayed onto the substrate surface (spray method). The pattern formation method may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern by baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0392] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching is preferably oxygen plasma etching.

[0393] The composition of the present invention and various materials used in the pattern formation method (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, top coat compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0394] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0395] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0396] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and a content of 0 ppt by mass or more is preferred.

[0397] A conductive compound may be added to an organic processing liquid such as a rinse solution to prevent breakdown of the chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular lower limit, but 0.01% by mass or more is preferred. For the chemical solution piping, for example, stainless steel (SUS), or various piping coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used. Similarly, for the filters and O-rings, antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used.

[0398] [Method for Manufacturing an Electronic Device] The present specification also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of the present specification include those installed in electrical and electronic devices (such as home appliances, office automation (OA), media-related devices, optical devices, and communication devices).

[0399] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0400] [Resin Synthesis Examples] <Synthesis Example 1: Synthesis of Resin P-1>

[0401]

[0402] Monomers (a-5), (b-1), (c-1), and (d-5) were used, and the monomers were mixed in a molar ratio of (a-1) / (b-1) / (c-1) / (d-5) = 64 / 28 / 5 / 3. PGMEA (propylene glycol monomethyl ether acetate) was added to a solution with a monomer concentration of 65% by mass to prepare a monomer solution. This solution was divided into two portions at a mass ratio of 30:70, designated as Monomer Solution A and Monomer Solution B, respectively. To Monomer Solution A, 0.030 molar equivalents (0.03 eq) of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) was added as an initiator relative to the total amount of monomers, and 0.03 eq of compound (RA-1) was added as a dithiocarbonyl compound relative to the total amount of monomers. Under a nitrogen atmosphere, Monomer Solution A was added dropwise to a reaction vessel at 85°C over one hour, and then heated at 85°C for an additional one hour. The solution was heated to 85°C, the temperature at which polymerization proceeds, and then Monomer Solution B (25°C) was added dropwise over 3 hours, followed by an additional 1 hour of reaction at 85°C. The resulting resin solution was added dropwise to a mixed solvent of ethyl acetate and n-heptane at a mass ratio of 1:9 to precipitate the resin. The resin was filtered, recovered, and then vacuum-dried to obtain Resin (P-1) in a yield of 75%. The introduction ratio (molar ratio) of (a-5) / (b-1) / (c-1) / (d-5) was 62 / 30 / 5 / 3, with an Mw of 7980 and an Mw / Mn of 1.22.

[0403] Resins PA-2, P-3, P-4, PA-5, P-6 to P-8, P-12, and PA-38 were synthesized in the same manner as for Resin (P-1), except that the monomers used and their ratios, solvent, monomer concentration, initiator, dithioester compound and its molar equivalent, dropwise addition time of Monomer Solution B, and reaction temperature at that time were changed as shown in Table 1.

[0404] The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). １３ Measurement was performed by C-NMR (nuclear magnetic resonance). In Table 1, PGME represents propylene glycol monomethyl ether, and DAA represents diacetone alcohol.

[0405]

[0406] In P-1, PA-2, P-3, P-4, PA-5, P-6 to P-8, P-12, and PA-38 in Table 1, the raw material monomers are as follows: a-9, c-1 to c-3, c-7, c-8, d-1, d-2, d-5 to d-9, and d-12 are described as repeating units derived from the raw material monomers.

[0407]

[0408]

[0409]

[0410]

[0411]

[0412]

[0413]

[0414] The compounds used as initiators in Table 1 above are as follows: (I-1), (I-2), and (I-3) have decomposition temperatures of 66°C, 65°C, and 51°C, respectively.

[0415]

[0416] The compounds used as dithioester compounds in Table 1 above are as follows:

[0417]

[0418] <Synthesis Example 2: Synthesis of Resin PA-1> Deprotection Condition A

[0419]

[0420] To 10 g of resin (P-1), 100 ml of a 1 mol% tetra-n-butylammonium fluoride THF solution was added, heated to 50 ° C, and reacted for 6 hours. After cooling, 250 g of ethyl acetate and 100 g of water were added and washed with water. After removing the water layer, washing with water (100 g) was performed five times. After concentrating the obtained resin solution, it was dropped into a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), and the resin precipitated. After filtration and recovery, it was vacuum dried to obtain resin (PA-1) in an 89% yield.

[0421] <Synthesis Example 3: Synthesis of Resin PA-3> Deprotection Condition B

[0422]

[0423] To 8 g of resin (P-3), 10.0 g of cyclohexanone, 15.0 g of methanol, and 4.93 g of triethylamine (48.7 mmol, 2.1 equivalents relative to the number of moles of base-decomposable protecting group unit (unit derived from a-2)) were added, heated at 60 ° C., and reacted for 12 hours. After cooling, 200 g of ethyl acetate, 80 g of water, and 2.38 g of acetic acid (39.4 mmol, 1.7 equivalents relative to the base-decomposable protecting group unit) were added for neutralization. After removing the aqueous layer, washing with water (80 g) was performed five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), and the resin precipitated. After filtration and recovery, it was dried under vacuum to obtain resin (PA-3) in a yield of 92%.

[0424] <Synthesis Example 4: Synthesis of Resin PA-12> Deprotection Condition C

[0425]

[0426] To 8 g of resin (P-12), 50 g of THF and 10 g of acetic acid (AcOH) were added, heated at 50°C, and reacted for 6 hours. After cooling, 200 g of ethyl acetate and 80 g of water were added, and the mixture was washed with water. After removing the aqueous layer, washing with water (80 g) was performed five times. The resulting resin solution was concentrated and then dropped into a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio), causing the resin to precipitate. The resin was filtered, recovered, and then vacuum dried to obtain resin (PA-12) in a yield of 85%.

[0427] (Comparative polymer without terminal treatment) P-4 and P-8 were deprotected according to deprotection condition B to obtain PA-4 and PA-8.

[0428] The protecting groups of resin (P-6) were deprotected according to deprotection conditions A to obtain resin (PA-6).

[0429] The protecting groups of resin (P-7) were deprotected according to deprotection condition C to obtain resin (PA-7).

[0430] Synthesis Example 5: Synthesis of Resin PB-1> End Group Reaction Conditions AA

[0431]

[0432] 10 g of resin (PA-1) and triethylsilane (969 mg, 8.33 mmol) were added to 30 ml of cyclohexanone and heated to 100°C. A 20 ml solution of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) (382 mg, 1.66 mmol) in cyclohexanone was added dropwise over 2 hours, and the mixture was then reacted at 100°C for 3 hours. After cooling, 250 g of ethyl acetate and 100 g of water were added and the mixture was washed with water. After removing the aqueous layer, the mixture was washed with water (100 g) five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio). The resin precipitated, filtered, recovered, and vacuum dried to obtain resin (PB-1) in an 88% yield. The structure of the main chain end is also shown in the above reaction formula.

[0433] <Synthesis Example 6: Synthesis of Resin PB-2> End Group Reaction Conditions BB

[0434]

[0435] 10 g of resin (PA-2) was added to 50 ml of DMF (dimethyl sulfoxide), heated to 90°C, and a 10 ml DMF solution of 4,4'-azobis(4-cyanovaleric acid) (1.50 g, 5.35 mmol) was added dropwise over 1 hour, followed by a reaction at 90°C for 4 hours. After cooling, 250 g of ethyl acetate and 100 g of water were added and washed with water. After removing the aqueous layer, the mixture was further washed with water (100 g) five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio), causing the resin to precipitate. The resin was then filtered, recovered, and vacuum dried to obtain resin (PB-2) in an 85% yield.

[0436] <Synthesis Example 7: Synthesis of Resin PB-3> End Group Reaction Conditions CC

[0437]

[0438] To 7 g of resin (PA-3), 20 mL of PGMEA and piperidine (261 mmg, 3.50 mmol) were added, and the mixture was heated to 60°C and reacted for 5 hours. After cooling, 200 g of ethyl acetate, 80 g of water, and 1.00 g of acetic acid were added to neutralize. After removing the aqueous layer, washing with water (80 g) was performed five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio), causing the resin to precipitate. The resin was filtered, recovered, and then vacuum dried to obtain resin (PB-3) in a yield of 90%.

[0439] <Synthesis Example 8: Synthesis of Resin PB-4> End group reaction conditions DD

[0440]

[0441] To 10 g of resin (P-4), 12.5 mL of cyclohexanoic acid and 1-dodecanethiol (2.89 g, 14.3 mmol) were added, heated at 100 ° C., and reacted for 6 hours. After cooling, 18.75 g of methanol and 6.16 g of triethylamine were added in the same manner as in deprotection condition B (Synthesis Example 3), heated at 60 ° C., and reacted for 12 hours. After cooling, 250 g of ethyl acetate, 100 g of water, and 2.98 g of acetic acid were added for neutralization. After removing the aqueous layer, washing with water (100 g) was performed five times. The resulting resin solution was concentrated and then dropped into a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), and the resin precipitated. After filtration, recovery, and vacuum drying, resin (PB-4) was obtained in a yield of 91%.

[0442] <Synthesis Example 9: Synthesis of Resin PB-5> Deprotection Condition EE

[0443]

[0444] To 5 g of resin (PA-5), 30 mL of chloroform, zinc chloride (170 mmg, 1.25 mmol), and 2,4-hexadienyl acetate (175 mmg, 1.25 mmol) were added, and the mixture was heated to 50°C and reacted for 20 hours. After cooling, 100 g of ethyl acetate, 40 g of water, and 1.00 g of acetic acid were added and washed. After removing the aqueous layer, washing with water (40 g) was performed five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio), causing the resin to precipitate. The resin was then filtered, recovered, and vacuum dried to obtain resin (PB-5) in a yield of 78%.

[0445] Synthesis Example 10: Synthesis of Resin PB-6> End Group Reaction Conditions FF

[0446]

[0447] In the above scheme, X and Y are groups derived from the monomers used.

[0448] To 10 g of resin (P-6), 15 mL of cyclohexanone was added and the mixture was allowed to react for 24 hours at boiling point reflux. After cooling, 90 ml of a 1 mol% tetra-n-butylammonium fluoride THF solution was added in the same manner as in deprotection condition A (Synthesis Example 2), and the mixture was heated to 50 ° C. and reacted for 6 hours. After cooling, 250 g of ethyl acetate and 100 g of water were added and washed with water. After removing the water layer, further washing with water (100 g) was performed five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), the resin precipitated, filtered, recovered, and then vacuum dried to obtain resin (PB-6) in an 85% yield.

[0449] <Synthesis Example 11: Synthesis of Resin PB-7> End Group Reaction Conditions GG

[0450]

[0451] 10 g of resin (PA-7) was added to 50 ml of THF and heated to 60 °C under atmospheric pressure (in the presence of oxygen). A 20 ml solution of 4,4'-azobis(isobutylnitrile) (279 mg, 1.70 mmol) in THF was added dropwise over 1 hour, and the mixture was allowed to react at 60 °C for 4 hours. After cooling to 40 °C, triphenylphosphine (1.42 g, 5.40 mmol) was added and the mixture was allowed to react for 1 hour. 250 g of ethyl acetate and 100 g of water were added and the mixture was washed with water. After removing the aqueous layer, the mixture was washed with water (100 g) five times. The resulting resin solution was concentrated and then added dropwise to a water:methanol = 0.5:9.5 (mass ratio) mixed solvent to precipitate the resin. The resin was then filtered, recovered, and vacuum dried to obtain resin (PB-7) in an 85% yield.

[0452] <Synthesis Example 12: Synthesis of Resin PB-8> End group reaction conditions HH

[0453]

[0454] 10 g of resin (P-8) was added to 25 ml of methyl ethyl ketone and heated to 75°C in an atmospheric atmosphere (in the presence of oxygen). A 25 ml solution of 4,4'-azobis(isobutylnitrile) (952 mg, 5.80 mmol) and N-methylmaleimide (644 mg, 5.80 mmol) in methyl ethyl ketone was added dropwise over 1 hour, and the mixture was allowed to react at 75°C for 4 hours. After cooling to 40°C, triphenylphosphine (1.42 g, 5.40 mmol) was added and the mixture was allowed to react for 1 hour. 250 g of ethyl acetate and 100 g of water were added and the mixture was washed with water. After removing the aqueous layer, the mixture was washed with water (100 g) five times. The resulting resin solution was concentrated and then added dropwise to isopropyl alcohol to precipitate the resin. The resin was then filtered, recovered, and vacuum-dried to obtain a resin powder in a 90% yield. The resulting resin powder was reacted according to the above-mentioned deprotection conditions B (Synthesis Example 3), to obtain a resin powder (PB-8) in a yield of 85%.

[0455] Synthesis Example 13: Synthesis of Resin PB-12> End Group Reaction Conditions II

[0456]

[0457] To 7 g of resin (PA-12), 30 ml of 2-butanone was added, heated to 100 ° C., and a 10 ml solution of triethylamine hypophosphite (508.2 mg, 3.00 mmol) and dimethyl 2,2'-azobis(2-methylpropionate) (I-1) (460.52 mg, 2.00 mmol) in cyclohexanone was added dropwise over 2 hours, followed by a reaction at 100 ° C. for 3 hours. After cooling, 250 g of ethyl acetate and 100 g of water were added and washed with water. After removing the aqueous layer, the mixture was further washed with water (100 g) five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio), causing the resin to precipitate. The resin was then filtered, recovered, and vacuum dried to obtain resin (PB-12) in an 88% yield.

[0458] Synthesis Example 14: Synthesis of Resin PB-38> End group reaction conditions DD

[0459]

[0460] Resin (PA-38) was treated under end group reaction conditions DD. 10 g of polymer, 12.5 mL of cyclohexanoate, and 1-dodecanethiol (2.89 g, 14.3 mmol) were added, heated at 100°C, and reacted for 6 hours. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate and n-heptane (1:9 by mass) to precipitate the resin. The resin was filtered, recovered, and then vacuum-dried to obtain resin (PB-38) in an 88% yield.

[0461] Table 2 shows the resin types (resins before deprotection treatment and end group treatment) that serve as precursors for Resins PB-1 to PB-8, PB-12, and PB-38, the deprotection treatment method, the end group treatment method, and the weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resulting resins. Note that post-polymerization treatment 1 and post-polymerization treatment 2 were performed in this order, with A to C representing the above-mentioned deprotection treatments and AA to II representing the above-mentioned end group treatments.

[0462]

[0463] Synthesis Example 15: Synthesis of Resin PN-1

[0464]

[0465] A monomer solution was prepared by mixing the monomers (A-1) and (AA-1) at a molar ratio of 50 / 50 (A-1):(AA-1), and adding acetic anhydride to the solution to obtain a monomer concentration of 75% by mass. This solution was divided into two portions at a mass ratio of 30:70, designated as Monomer Solution A and Monomer Solution B, respectively. To Monomer Solution A, 0.030 molar equivalents (0.03 eq) of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) was added as an initiator, relative to the total amount of monomers, and 0.042 eq of 2,2,6,6-tetramethylpiperidine 1-oxyl (N-1) was added as a nitroxide radical, relative to the total amount of monomers. Monomer Solution A was added dropwise to a reaction vessel at 80°C under a nitrogen atmosphere over one hour, and then heated at 80°C for an additional hour. The liquid was heated to 130°C, the reaction temperature for polymerization, and then Monomer Solution B (room temperature, 22°C) was added dropwise over 3 hours, followed by reaction at 130°C for 1 hour. The resulting resin solution was added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio) to precipitate the resin, which was then filtered, recovered, and vacuum dried to obtain Resin (PN-1) in a yield of 75%. The introduction ratio (molar ratio) of (A-1):(AA-1) was 58 / 42, the Mw was 5,400, and the Mw / Mn was 1.19.

[0466] Resins (PN-2) to (PN-3), (PN-11) to (PN-12), (PN-17) to (PN-18), (PN-21), (PN-36), and (PN-39) were synthesized in the same manner as for Resin (PN-1), except that the monomers used and their ratios, solvent, monomer concentration, initiator, nitroxide radical source and its molar equivalent, and the dropwise addition time and reaction temperature of Monomer Solution B were changed as shown in Table 3. In Table 3, Ac ２ O represents acetic anhydride. The content ratio of the mixed solvent is a mass ratio.

[0467]

[0468] In PN-1 to PN-3, PN-11, PN-12, PN-17, PN-18, PN-21, PN-36, and PN-39 in Table 1 above, the raw material monomers are as follows.

[0469]

[0470]

[0471]

[0472]

[0473]

[0474] The compounds used as the nitroxide radicals in Table 3 above are as follows:

[0475]

[0476] <Synthesis Example 16: Synthesis of Resin (Pa-1)>

[0477]

[0478] Resin (PN-1) was deprotected according to deprotection condition B to obtain resin (Pa-1). To 8 g of resin (PN-1), 10.0 g of cyclohexanone, 15.0 g of methanol, and 10.11 g of triethylamine (99.95 mmol, 2.1 equivalents relative to the total moles of base-decomposable protecting group units (units derived from A-1 and AA-1)) were added, heated to reflux at the boiling point, and reacted for 24 hours. After cooling, 200 g of ethyl acetate, 80 g of water, and 4.8 g of acetic acid (79.96 mmol, 1.7 equivalents relative to the base-decomposable protecting group units) were added for neutralization. After removing the aqueous layer, the mixture was washed with water (80 g) five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), and the resin was precipitated. The precipitate was filtered, recovered, and then vacuum-dried to obtain resin Pa-1 in a yield of 91%.

[0479] Synthesis Example 17: Synthesis of Resin (Pb-1)

[0480]

[0481] To 5.00 g of resin (Pa-1), 80 g of tetrahydrofuran (THF) and 8.03 g (79.4 mmol) of triethylamine were added and cooled to 0 ° C. 2.40 g (14.6 mmol) of 1-chloro-1-isopropoxy-2,2-dimethylpropane was added dropwise, and the mixture was allowed to react for 1 hour after warming to room temperature. 200 g of ethyl acetate and 80 g of water were added to the resulting reaction solution, and the mixture was separated. After removing the aqueous layer, the mixture was washed with water (80 g) four more times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), causing the resin to precipitate. The resin was then filtered, recovered, and vacuum dried to obtain resin (Pb-1) in a yield of 95%.

[0482] (Comparative polymer, no terminal treatment) Resin (PN-11) was deprotected according to deprotection condition A to obtain resin (Pa-11). Resins (PN-2), (PN-3), (PN-12), (PN-18), and (PN-36) were deprotected according to deprotection condition B to obtain resins (Pa-2), (Pa-3), (Pa-12), (Pa-18), and (Pa-36).

[0483] Synthesis Example 18: Synthesis of Resin (Pc-1) End Group Reaction Conditions DD

[0484]

[0485] 10 g of resin (Pb-1) was added to 12.5 mL of cyclohexanone and 1-dodecanethiol (2.89 g, 14.3 mmol), and the mixture was heated at 130°C and reacted for 6 hours. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio) to precipitate the resin, which was then filtered, recovered, and vacuum dried to obtain resin (Pc-1) in a yield of 91%.

[0486] Synthesis Example 19: Synthesis of Resin (Pc-2) End Group Reaction Conditions JJ

[0487]

[0488] 10 g of resin (Pa-2) and N-phenylmaleimide (1.15 g, 6.67 mmol) were added to 50 mL of DMF, heated at 130° C., and reacted for 8 hours. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of water:methanol = 0.5:9.5 (mass ratio) to precipitate the resin, which was then filtered, recovered, and vacuum dried to obtain resin (Pc-2) in a yield of 81%.

[0489] Synthesis Example 20: Synthesis of Resin (Pc-3) End Group Reaction Conditions KK

[0490]

[0491] 10 g of resin (Pa-3), ammonium cerium (IV) nitrate (9.14 g, 16.6 mmol), and 10 mL of distilled water were added to 100 ml of THF, and the mixture was allowed to react at the boiling point under reflux for 12 hours and then allowed to cool. 250 g of ethyl acetate and 100 g of water were added and washed with water. After removing the aqueous layer, the mixture was washed with water (100 g) five times. The resulting resin solution was concentrated and then added dropwise to a water:methanol = 0.5:9.5 (mass ratio) mixed solvent to precipitate the resin. The resin was then filtered, recovered, and vacuum dried to obtain resin (Pc-3) in an 83% yield.

[0492] <Synthesis Example 21: Synthesis of Resin (Pc-11)> End Group Reaction Conditions LL

[0493]

[0494] 10 g of resin (Pa-11), 250 mg of triethylamine, and 50 mL of ethyl 2-bromoisobutyrate were added, heated at 80°C, and reacted for 72 hours. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of water:methanol = 0.5:9.5 (mass ratio) to precipitate the resin, which was then filtered, recovered, and vacuum dried to obtain resin (Pc-11) in a yield of 83%.

[0495] <Synthesis Example 22: Synthesis of Resin (Pc-12)> End group reaction conditions MM

[0496]

[0497] 10 g of resin (Pa-12) and 30 mL of acetic acid were added to 70 mL of THF and refluxed at the boiling point. While refluxing at the boiling point, zinc powder (5 g, 76.5 mmol) was gradually added in five portions, and the reaction was allowed to proceed for 5 hours. The reaction mixture was filtered through Celite, and 250 g of ethyl acetate, 100 g of water, and 5 mL of hydrochloric acid were added and washed with water. After removing the aqueous layer, the mixture was further washed with water (100 g) five times. The resulting resin solution was concentrated and then added dropwise to a water:methanol = 0.5:9.5 (mass ratio) mixed solvent to precipitate the resin. The resin was then filtered, recovered, and vacuum dried to obtain resin (Pc-12) in an 85% yield.

[0498] <Synthesis Example 23: Synthesis of Resin (Pc-17)> End group reaction conditions NN (oxidation)

[0499]

[0500] In the above scheme, Y is a group derived from the monomer used.

[0501] 10 g of resin (PN-17) was added to 100 ml of toluene, cooled to 10°C, and m-chloroperbenzoic acid (575 mg, 3.33 mmol) was added and reacted for 10 minutes. 250 g of ethyl acetate and 100 g of water were added and washed with water. After removing the aqueous layer, washing with water (100 g) was performed five times. The resulting resin solution was concentrated and then dropped into isopropyl alcohol solvent to precipitate the resin. The resin was filtered, recovered, and vacuum dried to obtain a resin powder in a 90% yield. The resulting resin powder was reacted according to the above deprotection condition B to obtain resin (Pc-17) in a 85% yield.

[0502] Synthesis Example 24: Synthesis of Resin (Pc-18) End Group Reaction Conditions FF

[0503]

[0504] In the above scheme, Y is a group derived from the monomer used.

[0505] Resin (Pa-18) was treated under the above-mentioned terminal group reaction conditions FF. 30 mL of cyclohexanone was added to 10 g of resin (Pa-18), and the mixture was allowed to react at the boiling point under reflux for 24 hours. The resulting resin solution was added dropwise to a mixed solvent of ethyl acetate and n-heptane (1:9 by mass), causing the resin to precipitate. The resin was then filtered, recovered, and vacuum-dried to obtain resin (Pc-18) in an 85% yield.

[0506] Synthesis Example 25: Synthesis of Resin (Pc-21) End Group Reaction Conditions DD

[0507]

[0508] 10 g of resin (PN-21) was added with 12.5 mL of cyclohexanone and 1-dodecanethiol (2.89 g, 14.3 mmol), heated at 130 ° C, and reacted for 6 hours. After cooling, 18.75 g of methanol and 6.16 g of triethylamine were added, and heated at 60 ° C, and reacted for 12 hours, as in the above deprotection condition B. After cooling, 250 g of ethyl acetate, 100 g of water, and 2.98 g of acetic acid were added for neutralization. After removing the aqueous layer, the mixture was washed with water (100 g) five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), and the resin precipitated. After filtration, recovery, and vacuum drying, resin (Pc-21) was obtained in a yield of 90%.

[0509] Synthesis Example 26: Synthesis of Resin (Pc-36) End Group Reaction Conditions B'B'

[0510]

[0511] 10 g of resin (Pa-36) was added to 50 ml of DMF and heated to 120°C. A 10 ml solution of 1,1'-azobis(4-cyclohexane-1-carbonitrile) (1.31 g, 5.35 mmol) in DMF was added dropwise over 1 hour, and the mixture was allowed to react at 120°C for 4 hours. After cooling, 250 g of ethyl acetate and 100 g of water were added and washed with water. After removing the aqueous layer, the mixture was further washed with water (100 g) five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio). The resin precipitated, filtered, recovered, and then vacuum dried to obtain resin (Pc-36) in an 82% yield.

[0512] Synthesis Example 27: Synthesis of Resin (Pc-39) End Group Reaction Conditions DD

[0513]

[0514] Resin (Pa-39) was treated under end group reaction conditions DD. 10 g of polymer, 12.5 mL of cyclohexanoate, and 1-dodecanethiol (2.89 g, 14.3 mmol) were added, heated at 100°C, and reacted for 6 hours. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate and n-heptane (1:9 by mass) to precipitate the resin. The resin was filtered, recovered, and then vacuum-dried to obtain resin (Pc-39) in a 90% yield.

[0515] Table 4 shows the resin types (resins before deprotection treatment and end group treatment), deprotection treatment methods, end group treatment methods, weight average molecular weights (Mw) and dispersities (Mw / Mn) of the resins that serve as precursors to resins Pc-1 to Pc-3, Pc-11, Pc-12, P-17, P-18, P-21, P-36, and P-39. Post-polymerization treatments 1 to 3 were performed in this order, with B and C representing the deprotection treatments described above and B'B' to NN representing the end group treatments described above.

[0516]

[0517] Synthesis Example 28: Synthesis of Resin (PBX-1)

[0518]

[0519]

[0520] Monomers (a-5), (b-1), (c-1), and (d-5) were used, and the monomers were mixed in a molar ratio of (a-1) / (b-1) / (c-1) / (d-5) = 64 / 28 / 5 / 3. PGMEA (propylene glycol monomethyl ether acetate) was added to the solution to obtain a monomer concentration of 65% by mass. A monomer solution was prepared. To the monomer solution, 0.030 molar equivalents (0.03 eq) of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) was added as an initiator relative to the total amount of monomers, and 0.03 eq of RA-1 was added as a RAFT source (dithiocarbonyl compound) relative to the total amount of monomers. Under a nitrogen atmosphere, monomer solution A was added dropwise to a reaction vessel at 85 ° C. over 1 hour, and then the reaction was continued for another 4 hours at 85 ° C. The resulting resin solution was dropped into a mixed solvent of ethyl acetate and n-heptane at a mass ratio of 1:9 to precipitate the resin, which was then filtered, recovered, and vacuum dried to obtain Resin (PX-1) in a yield of 75%. The introduction ratio (molar ratio) of (a-5) / (b-1) / (c-1) / (d-5) was 63 / 29 / 5 / 3, and the Mw was 7560 and the Mw / Mn was 1.24.

[0521] The reaction conditions for deprotection of the protecting groups in resin (PX-1) were the same as those for P-1, and resin (PAX-1) was obtained by reaction under deprotection conditions A. The reaction conditions for the terminal groups of resin (PAX-1) were the same as those for P-1, and resin (PBX-1) was obtained by reaction under terminal group reaction conditions AA. The weight average molecular weight (Mw) of resin (PBX-1) was 6730, and the polydispersity (Mw / Mn) was 1.23.

[0522] Comparative Example: Synthesis of Resin PXX-1

[0523]

[0524] Monomers (a-5), (b-1), (c-1), and (d-5) were used, and the monomers were mixed in a molar ratio of (a-1) / (b-1) / (c-1) / (d-5) = 62 / 30 / 5 / 3. Cyclohexanone was added so that the monomer concentration became a 30% by mass solution. 8 mol% of dimethyl 2,2'-azobis(2-methylpropionate) was added as an initiator. 0.1 mass of cyclohexanone was heated to 85 ° C. under a nitrogen atmosphere, and the monomer solution was added dropwise over 4 hours, and then the reaction was continued for another 2 hours at 85 ° C. The resulting resin solution was added dropwise to a 1:9 mixed solvent of ethyl acetate and n-heptane, and the resin was precipitated. After filtration and recovery, it was dried under vacuum to obtain a resin with a yield of 75%. The resulting resin was reacted according to deprotection conditions A to obtain PXX-1. The introduction ratio of (A-1) / (B-1) / (C-1) / (D-5) = 62 / 30 / 5 / 3, Mw was 7210, and Mw / Mn was 1.58.

[0525] [Resist Composition] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0526] <Resin (A)> The resin shown above was used as the resin (A).

[0527] <Photoacid Generator (B)> As the photoacid generator (B), B-1 and B-2 were used.

[0528]

[0529] <Acid Diffusion Controller (C)> As the acid diffusion controller (C), C-1 to C-14 were used.

[0530]

[0531] <Surfactant> The following surfactants W-1 to W-4 were used: W-1: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.; fluorine and silicone-based) W-2: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based) W-3: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine-based) W-4: PF6320 (manufactured by OMNOVA; fluorine-based)

[0532] <Solvents> The solvents used are as follows: S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Diacetone alcohol (DAA) S-3: Propylene glycol monomethyl ether (PGME) S-4: Ethyl lactate (EL) S-5: Ethyl 3-ethoxypropionate (EEP) S-6: 2-heptanone (MAK) S-7: Methyl 3-methoxypropionate (MMP) S-8: 3-methoxybutyl acetate S-9: γ-butyrolactone

[0533] <Preparation of Resist Compositions> Each component other than the solvent shown in Tables 5 and 6 was used in the amount (mass %) shown in Tables 5 and 6 and mixed with the solvent shown in Tables 5 and 6 to obtain a solution. The content of each component is the mass ratio relative to the total solids content of the resist composition. The resulting solution was filtered through a polyethylene filter with a pore size of 0.02 μm to obtain resist compositions R-1 to R-21 and RX-1 to RX-22. The solids concentration of the resist compositions was adjusted to the concentrations shown in Tables 5 and 6. The solids content refers to all components other than the solvent. The resulting resist compositions were used in the examples and comparative examples. Tables 5 and 6 list the types of solvents used and their mass ratios.

[0534]

[0535]

[0536] <Coating of Resist Composition> The prepared resist composition was applied to a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and then dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm. Note that similar results were obtained even if the Si wafer was replaced with a chromium substrate.

[0537] (Examples 1a to 21a, Comparative Examples 1a to 22a) <Pattern Forming Method (1): EB Exposure, Alkali Development (Positive)> A wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 keV). The lithography was performed so as to form a 1:1 line and space pattern. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and then dried. The wafer was then rotated at 4000 rpm for 30 seconds, baked at 95°C for 60 seconds, and dried.

[0538] [Evaluation] The obtained patterns were evaluated for resolution, LWR performance, and sensitivity with and without resin terminal treatment by the following methods. The results are shown in Table 7 below.

[0539] The irradiation energy required to resolve a 1:1 line and space pattern with a line width of 50 nm was taken as the sensitivity (Eop).

[0540] <L / S Resolution> The limiting resolving power (the minimum line width at which a line and a space (line:space=1:1) are separately resolved) at the exposure dose exhibiting the above sensitivity (Eop) was taken as the resolving power (nm).

[0541] <Line Width Roughness (LWR) Performance> Line width roughness was measured at the above Eop by measuring the line width at 50 arbitrary points within 0.5 μm in the longitudinal direction of a line and space pattern (line:space=1:1) with a line width of 50 nm, determining the standard deviation, and calculating 3σ (nm). A smaller value indicates better performance.

[0542] <Sensitivity Comparison with and without Resin Terminal Treatment> Sensitivity was compared under the same conditions except for the terminal treatment of the resin. Specifically, Examples 1a to 21a were compared with Comparative Examples 1a to 21a. The sensitivity of the resist composition using the resin of the Comparative Example without terminal treatment was defined as Eop(PA), and the sensitivity of the resist composition using the resin of the Example with terminal treatment was defined as Eop(PB), and the sensitivity was compared based on the ratio of Eop(PB) / Eop(PA). An Eop(PB) / Eop(PA) ratio of less than 0.90 was defined as A, 0.90 or more but less than 0.95 as B, and 0.95 or more but less than 1.0 as C. The smaller the value, the higher the sensitivity and the better the performance.

[0543] The resist compositions used and the results are shown in Table 7 below.

[0544]

[0545] (Examples 1b to 21b, Comparative Examples 1b to 22b) <Pattern Forming Method (2): EUV Exposure, Alkali Development (Positive)> The same steps as in the above-mentioned pattern forming method (1) were carried out, except that an EUV exposure apparatus (Micro Exposure Tool, manufactured by Exitech, NA (Numerical Aperture) 0.3, Quadruple, Outer Sigma 0.68, Inner Sigma 0.36) was used instead of the electron beam lithography apparatus. Using the same methods as described above, the resolution, LWR performance, and sensitivity comparison with and without resin terminal treatment were evaluated. Table 8 below shows the resist compositions used and the results.

[0546]

[0547] The results in Tables 7 and 8 show that the composition of the present invention is excellent in resolution, LWR performance, and sensitivity.

[0548] The present invention provides a method for producing a resin that can be suitably used for an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and sensitivity. The present invention also provides an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and sensitivity, an actinic ray-sensitive or radiation-sensitive film that uses the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for producing an electronic device.

[0549] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2024-058307) filed on March 29, 2024, the contents of which are incorporated herein by reference.

Claims

1. A method for producing a resin, comprising: (i) polymerizing raw material monomers including at least one monomer selected from the group consisting of a monomer represented by the following general formula (a) and a monomer represented by the following general formula (aI), and a monomer represented by the following general formula (b), in the presence of a nitroxide radical represented by the following general formula (N) or a dithioester compound represented by the following general formula (Ra); and (ii) substituting the main chain terminal groups of the polymer obtained in (i) with hydrogen atoms or other substituents. In general formula (a), L １ represents a divalent linking group. Ａ１ ~R Ａ３ R each independently represents a hydrogen atom or a monovalent substituent. Ａ４ represents a group that is decomposed and eliminated by the action of an acid. １ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ Rx each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. １ ~Rx ３ may be bonded to form a ring. In general formula (b), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ Is L ３ may be bonded to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group. ３ represents an (n+m+1)-valent aromatic ring group or an alicyclic group. Ｂ３ When R is bonded to form a ring, it represents an (n+m+2)-valent aromatic ring group or alicyclic group. ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group. Ｂ５ represents a halogen atom, m represents an integer of 1 or more, and n represents an integer of 0 or more. In general formula (N), R Ｎ１ Each of R independently represents an organic group. Ｎ１ may be bonded to form a ring. In the general formula (Ra), Ra １ and Ra ２ each independently represents an organic group.

2. A method for producing a resin as described in claim 1, wherein in step (i), a reaction solution containing a solvent, an initiator in an amount of 80% by mass or more based on the total amount of the initiator, and a nitroxide radical or dithioester compound in an amount of 90% by mass or more based on the total amount of the nitroxide radical or dithioester compound is placed in a reaction vessel, and then at least a portion of the raw material monomer is dropped into the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator.

3. A method for producing a resin as described in claim 2, wherein in step (i), a reaction solution containing a solvent, 80% by mass or more of an initiator relative to the total amount of the initiator, 90% by mass or more of a nitroxide radical or dithioester compound relative to the total amount of the nitroxide radical or dithioester compound, and a portion of the raw material monomer is placed in a reaction vessel, and then the remaining raw material monomer is added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator.

4. The method for producing a resin according to claim 3, wherein in step (i), the raw material monomers in the reaction solution are present in an amount of 1 to 50 mol % based on the total amount of the raw material monomers.

5. The method for producing a resin according to claim 2, wherein in step (i), the raw material monomer is added dropwise for 1 to 24 hours.

6. The method for producing a resin according to claim 2, wherein in step (i), the reaction system is heated for less than 2 hours after the dropwise addition of the raw material monomer.

7. The method for producing a resin according to claim 1, wherein the dithioester compound is represented by the following general formula (Ra-2): In general formula (Ra-2), Ra １ and Ra ３ each independently represents an organic group.

8. The method for producing a resin according to claim 1, wherein the monomer represented by general formula (b) is represented by the following general formula (b-1): In general formula (b-1), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ may be bonded to Ar to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R Ｂ３ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. ｂ６ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5.

9. R in the general formula (b-1) ｂ６ The method for producing a resin according to claim 8, wherein is a group represented by any one of the following general formulas (3) to (7): In general formulas (3) to (7), R ３１ represents a hydrogen atom or an organic group. ４１ , R ５１ , R ６１ R each independently represents an organic group. ７１ , R ７２ R each independently represents a hydrogen atom or an organic group. ７３ represents an organic group. ７１ ~R ７３ may be linked to each other to form a ring. * indicates the bonding position to Ar.

10. The method for producing a resin according to claim 8, wherein in general formula (b-1), Ar is a benzene ring group.

11. The method for producing a resin according to claim 1, wherein in general formula (aI), T is an arylene group.

12. The method according to claim 1, wherein in step (ii), the polymer obtained in step (i) is reacted with a compound having hydrogen atom donating properties.

13. The method according to claim 1, wherein in step (ii), the polymer obtained in step (i) is reacted with a compound having hydrogen atom donating ability and a free radical or a compound capable of generating a free radical.

14. The method according to claim 1, wherein in step (ii), the polymer obtained in step (i) is reacted with a free radical or a compound capable of generating a free radical.

15. The method according to claim 1, wherein in step (ii), the polymer obtained in step (i) is reacted with a reducing agent.

16. The method according to claim 1, wherein in step (ii), the polymer obtained in step (i) is reacted with an oxidizing agent.

17. The method according to claim 1, wherein in step (ii), the polymer obtained in step (i) is heated in an inert solvent without adding any other reagents for at least one hour.

18. A method for producing a resin according to claim 1, wherein in step (ii), the polymer obtained in step (i) is reacted with a compound represented by the following general formula (M) or the following general formula (D). In general formula (M), R Ｍ１ R each independently represents a hydrogen atom or a monovalent substituent. Ｍ２ each independently represents a monovalent substituent, and may be bonded to each other to form a ring. Ｄ１ R each independently represents a hydrogen atom or a monovalent substituent. Ｄ２ each independently represents a hydrogen atom or a monovalent substituent.

19. An actinic ray-sensitive or radiation-sensitive resin composition comprising: a resin (A) which contains at least one repeating unit selected from repeating units represented by general formula (A) below and repeating units represented by general formula (AI) below, and a repeating unit represented by general formula (B) below, wherein the terminal structure of the main chain has a hydrogen atom or a group selected from -SH, -OH, a halogen atom, a heterocyclic group, a heterocyclic-S- group, and a hydrocarbon group, and wherein the polydispersity (Mw / Mn) is less than 1.40; a compound (B) which generates an acid upon exposure to actinic rays or radiation; and a solvent (S). In general formula (A), L １ represents a divalent linking group. Ａ１ ~R Ａ３ R each independently represents a hydrogen atom or a monovalent substituent. Ａ４ represents a group that is decomposed and eliminated by the action of an acid. １ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ Rx each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. １ ~Rx ３ may be bonded to form a ring. In general formula (B), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ Is L ３ may be bonded to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group. ３ represents an (n+m+1)-valent aromatic ring group or an alicyclic group. Ｂ３ When R is bonded to form a ring, it represents an (n+m+2)-valent aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. Ｂ４ represents a hydroxyl group, a group that generates an —OH group upon decomposition with an acid or a base, or a fluorinated alcohol group. Ｂ５ represents a halogen atom, m represents an integer of 1 or more, and n represents an integer of 0 or more.

20. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 19, wherein the repeating unit represented by general formula (B) is represented by the following general formula (B-1): In general formula (B-1), R Ｂ１ ~R Ｂ３ each independently represents a hydrogen atom, an organic group, or a halogen atom. Ｂ３ may be bonded to Ar to form a ring, in which case R Ｂ３ represents a single bond or an alkylene group. ２ represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R Ｂ３ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. Ｂ６ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5.

21. R in the general formula (B-1) Ｂ６ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 20, wherein: is a group represented by any one of the following general formulas (3) to (7): In general formulas (3) to (7), R ３１ represents a hydrogen atom or an organic group. ４１ , R ５１ , R ６１ R each independently represents an organic group. ７１ , R ７２ R each independently represents a hydrogen atom or an organic group. ７３ represents an organic group. ７１ ~R ７３ may be linked to each other to form a ring. * indicates the bonding position to Ar.

22. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 20, wherein in general formula (B-1), Ar is a benzene ring group.

23. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 19, wherein in general formula (AI), T is an arylene group.

24. An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 19 to 23.

25. A pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 19 to 23; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

26. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 25.

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