JP2008095087A - Polymer, method for producing the same, resist composition, and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer whose metal content is small, and a resist composition made therefrom is high in photographic sensitivity and resolution, and little in defect, and line-edge roughness of the resist is small, and a color filter etc. made from the polymer has an excellent balance of photographic sensitivity, pigment dispersibility, and development properties, and to provide a method for producing a resist composition and a substrate or a color filter whose pattern is formed by using the resist composition. <P>SOLUTION: The polymer for a resist is represented by a polymer comprised of a polymer unit (P<SB>G</SB>) containing a component unit having a glycidyl residue and a polymer unit (P<SB>A</SB>) containing a component unit having at least one sort of residue selected from a carboxyl residue and an acid anhydride residue, and a method for producing the polymer, and methods for producing the resist composition, the substrate, and the color filter are also interpreted. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymer, a resist composition containing the polymer, and a method for producing a substrate or color filter on which a pattern is formed, and more particularly to a resist composition suitable for microfabrication using ultraviolet rays, excimer laser, and electron beam lithography. .

In recent years, in the field of microfabrication in the manufacture of semiconductor elements and liquid crystal elements, miniaturization has rapidly progressed due to advances in lithography technology. As a miniaturization technique, in general, miniaturization is attempted by shortening the wavelength of irradiation light used for creating a pattern. Specifically, the irradiation light has changed from conventional ultraviolet rays typified by g-line (wavelength: 438 nm) and i-line (wavelength: 365 nm) to deeper ultraviolet rays (DUV) having a shorter wavelength.
At present, lithography technology using a KrF excimer laser (wavelength: 248 nm) is introduced into the market, and lithography technology using an ArF excimer laser (wavelength: 193 nm) with a shorter wavelength is also being introduced into the market. Further, a lithography technique using a short wavelength F ₂ excimer laser (wavelength: 157 nm) and an extreme ultraviolet (EUV) excimer laser (wavelength: 13 nm) is also being studied. On the other hand, immersion lithography technology that can achieve high resolution and wide depth of focus is also being actively researched for market introduction. In addition, energetically researching electron beam lithography technology as a different type of lithography technology.

A chemically amplified resist containing a photoacid generator has been proposed as a high resolution resist using irradiation light or an electron beam of the above short wavelength, and improvement and development of this chemically amplified resist are currently underway. .
For example, an acrylic polymer that is transparent to light having a wavelength of 193 nm is widely used as a chemically amplified resist polymer used in lithography using an ArF excimer laser. As such an acrylic polymer, for example, a polymer of (meth) acrylic acid ester having an adamantane skeleton in the ester portion and a polymer of (meth) acrylic acid ester having a lactone skeleton in the ester portion are Patent Document 1 and Patent Document 2. Is disclosed.

However, when these acrylic polymers are used as resist compositions, development defects called defects may occur during development with an alkaline developer for producing a resist pattern and rinsing with pure water. Further, this defect causes resist pattern omission and bridging between resist patterns, which may result in circuit disconnection, defects, short circuits, and the like, leading to a decrease in yield in the semiconductor manufacturing process.
In addition, the unevenness (also referred to as line edge roughness) of the side wall of the resist pattern may be large, and as with defects, circuit disconnection, defects, and the like may occur, leading to a decrease in yield in the semiconductor manufacturing process.

Patent Document 3 describes a graft polymer for photoresist comprising a trunk polymer and a branch polymer.
However, since the graft polymer is synthesized by the ATRP method, which is a kind of living radical polymerization, a large amount of metal impurities may remain, which may lead to a decrease in yield in the semiconductor manufacturing process.

On the other hand, as a manufacturing method of a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, in recent years, a pigment dispersion type resist composition using a pigment as a colorant is used from the viewpoint of heat resistance and light resistance. The conventional photolithography method is generally employed and disclosed in, for example, Patent Document 4 and Patent Document 5.
However, the resist composition used for the color filter may not have sufficient dispersibility of the colorant represented by the pigment and developability of the resist composition itself. As a result, display unevenness of the liquid crystal occurs, which causes a decrease in performance as a liquid crystal display element.
JP 10-319595 A JP-A-10-274852 JP 2003-268057 A JP-A-2-144502 JP-A-3-53201

The present invention has a low metal content, high sensitivity and high resolution when used as a resist composition for lithography or the like using a DUV excimer laser, few defects during development, and low resist line edge roughness. It is an object of the present invention to provide a polymer and a polymer excellent in balance of sensitivity, pigment dispersibility and developability when used as a resist composition such as a color filter.
Furthermore, it aims at providing the manufacturing method of the resist composition containing the said polymer, and the board | substrate or color filter in which the pattern using this resist composition was formed.

（式（２）中、Ｒは水素原子、メチル基、炭素数１〜４のヒドロキシアルキル基又は炭素数１〜４のパーフルオロアルキル基を表す。Ｇは単結合、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−又は−Ｏ−Ｃ（＝Ｏ）−を表す。Ｌは単結合又は炭素数１〜２０の直鎖、分岐若しくは環状の２価の炭化水素基を表し、置換基及びヘテロ原子から選ばれる少なくとも１種を有していてもよい。Ｐｏｌｙはポリマー鎖を表す。） A first invention for solving the above problem is a resist polymer (hereinafter referred to as “polymer (P)”) containing a structural unit represented by the formula (2).

(In Formula (2), R represents a hydrogen atom, a methyl group, a C1-C4 hydroxyalkyl group, or a C1-C4 perfluoroalkyl group. G is a single bond, -C (= O)-. O—, —O— or —O—C (═O) —, L represents a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, (It may have at least one selected from atoms. Poly represents a polymer chain.)

According to a second aspect of the invention the structural unit (hereinafter, referred to as "structural unit (G)") having a glycidyl group containing at least one selected from the polymer (P _G) with a carboxyl group and acid anhydride group containing This is a method for producing the resist polymer (P) including a reaction step (R1) with a polymer (P _A ) containing a structural unit (hereinafter referred to as “structural unit (A)”).
Furthermore, the third invention is a reaction step (R2 _GA ) of a polymer (P _G ) as a trunk polymer and a vinyl monomer (m _A ) having at least one selected from a carboxyl group and an acid anhydride group. And a method for producing the resist polymer (P), which comprises a polymerization step (P2 _GA ) in which a branched polymer is produced by polymerization of the vinyl monomer (v) thereafter.
The fourth invention is a reaction step (R3 _AG ) of a polymer (P _A ) as a trunk polymer and a vinyl monomer (m _G ) having a glycidyl group, and a subsequent vinyl monomer (v) This is a method for producing the resist polymer (P), which includes a polymerization step (P3 _AG ) in which a branched polymer is produced by polymerization of the above-mentioned polymer.
The fifth invention is a resist composition containing the polymer (P).
According to a sixth aspect of the present invention, there is provided a method of manufacturing a substrate on which a pattern including a step of applying the resist composition on a substrate to be processed, a step of exposing with light having a wavelength of 450 nm or less, and a step of developing using a developer. Is the method.
According to a seventh aspect of the present invention, there is provided a color filter on which a pattern including a step of applying the resist composition onto a substrate to be processed, a step of exposing with light having a wavelength of 450 nm or less, and a step of developing with a developer is formed. It is a manufacturing method.

There are few metal impurities in the polymer (P) of the present invention, and the resist composition of the present invention has high sensitivity and high resolution when used in lithography using a DUV excimer laser, and has few defects during development. The resulting resist has low line edge roughness. Therefore, it is suitable as a polymer for resist for microfabrication used in the production of semiconductor elements and liquid crystal elements. The resist composition of the present invention is excellent in the balance of sensitivity, pigment dispersibility and developability when used in a color filter or the like.
Therefore, the polymer (P) and the resist composition of the present invention use lithography using a DUV excimer laser, immersion lithography and electron beam lithography, particularly lithography using an ArF excimer laser, immersion lithography, and a mercury lamp. Suitable for lithography.
Further, according to the present invention, a substrate or a color filter on which a highly accurate fine pattern is formed can be obtained. Furthermore, a substrate on which a highly accurate fine pattern is formed can be manufactured with high yield by the method of the present invention.
The polymer (P) of the present invention is suitably used for resist compositions for various uses such as semiconductor production, metal etching, photofabrication, plate making, hologram, color filter, retardation film and the like. be able to.

Polymer (P)
The polymer (P) of this invention contains the structural unit represented by Formula (2).
G in the formula (2) represents a single bond, —C (═O) —O—, —O— or —O—C (═O) —. G is preferably —C (═O) —O— or —O—C (═O) — in terms of polymerizability, and preferably a single bond or —O— in terms of heat resistance of the polymer (P). .

L in Formula (2) represents a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and may have at least one selected from a substituent and a hetero atom. Good.
L is a single bond, a linear or branched divalent hydrocarbon group having 1 to 4 carbon atoms, and — (CH ₂ CH ₂ O) _g1 — in terms of solubility of the polymer (P) in an organic solvent. or _{- (CH 2 CH (CH 3} ) O) g2 - are preferred. Here, g1 and g2 each independently represent an integer of 1 to 5, and 1 or 2 is preferable in terms of the resolution of the resist composition.
Further, L is preferably a divalent aromatic hydrocarbon group from the viewpoint of pigment dispersibility of the resist composition, and more preferably has a benzene ring, a naphthalene ring or an anthracene ring.
L is preferably at least one selected from the formulas (2-1) to (2-4) from the viewpoint of resist dry etching resistance.

In Formula (2-1) to Formula (2-4), R ²¹¹ , R ²¹² , R ²¹³ , R ²¹⁴ , R ²¹⁵ and R ²¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Z represents an atomic group constituting a cyclic hydrocarbon group with a carbon atom in L.
In formulas (2-1) to (2-4), the upper left bond is bonded to G, and the lower right bond is bonded to the carbon atom bonded to the oxygen atom of L and the carboxyl residue. .
Furthermore, when G is -C (= O) of -O-, L is _-C in terms of resist sensitivity _{(CH 3) 2 -, -} C (CH 3) 2 -CH 2 -, - C (CH 3) At least one selected from (CH ₂ CH ₃ ) —, formula (2-1) and formula (2-2) is more preferable.

Poly in the formula (2) represents a polymer chain. As the polymer chain, for example, (1) a polymer having a unit containing a glycidyl residue (P _G) and (2) structural unit containing at least one selected from carboxylic acid residues and acid anhydride residue containing a polymer _{(P a)} can be mentioned.

The structural unit represented by Formula (2) can be used alone or in combination of two or more.
Further, the content of the structural unit represented by the formula (2) is preferably 1 mol% or more in the structural unit of the polymer (P) in terms of the defect and developability of the resist composition and the line edge roughness of the resist. Mole% or more is more preferable. In addition, the content of the structural unit represented by the formula (2) is preferably 30 mol% or less, more preferably 25 mol% or less, and more preferably 20 mol% or less in terms of adhesion of the resist composition to the substrate surface or the like. Further preferred.

  As a structural unit represented by Formula (2), the structural unit represented by Formula (6-1)-Formula (6-14) is mentioned, for example. In formula (6-1) to formula (6-14), R represents a hydrogen atom or a methyl group.

As a specific structural example of the polymer (P) of the present invention, at least one selected from a polymer (P _G ) unit containing a structural unit having a glycidyl residue, a carboxyl residue, and an acid anhydride residue is used. polymer (P _a) cross-linked polymer units having a unit having, as well as one of the polymer (P _G) units and the polymer (P _a) units and trunk polymer units, and the other Examples thereof include a graft-bonded polymer having a branched polymer unit.
In the present invention, at least one selected from a glycidyl residue, a carboxyl residue and an acid anhydride residue is reacted with at least one selected from a glycidyl group and a carboxyl group and an acid anhydride group, respectively. The state after reaction of each group which exists is shown.
The weight average molecular weight of the polymer (P) is preferably 1,000 or more, more preferably 2,500 or more, and still more preferably 4,000 or more in terms of the dry etching resistance and pattern shape of the resist.
The mass average molecular weight of the polymer (P) is preferably 100,000 or less, more preferably 50,000 or less, and more preferably 30,000 in terms of the solubility of the polymer (P) in the resist solution and the resolution of the resist composition. The following is more preferable.
The polymer _{(P G)} Unit

The polymer constituting the polymer (P _G) units (P _G), for example, polymers containing vinyl monomer (m _G) units.
Vinyl monomer (m _G )

Examples of the vinyl monomer (m _G ) include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, oxocyclohexylmethyl (meth) acrylate, and 3-glycidyloxy. Propyl (meth) acrylate, 3-glycidyloxybutyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, 6-glycidyloxyhexyl (meth) acrylate, 8-glycidyloxyoctyl (meth) acrylate, 9-glycidyloxy Nonyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 2-glycidyloxypropyl (meth) acrylate, 2-glycidyloxybutyl (meth) acrylate
Among these, glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate are preferable in terms of resolution and developability of the resist composition.
In the present invention, (meth) acrylate and (meth) acrylic acid mean methacrylate or acrylate and methacrylic acid or acrylic acid, respectively.

Examples of the polymer (P _G ) include a polymer containing a polymerization initiator (i _gl ) unit having a glycidyl group or a chain transfer agent (c _g1 ) unit having a glycidyl group.
Examples of the polymerization initiator (i _gl ) include diglycidyl-2,2′-azobisisobutyrate.
Examples of the chain transfer agent (c _gl ) include epoxy methyl mercaptan.

Examples of the polymer (P _G ) include a polymer having a polymerization terminator (t _gl ) unit having a glycidyl group at the molecular end.
Examples of the polymerization terminator (t _gl ) include chrycidyl bromoacetate.

Furthermore, examples of the polymer (P _G ) include a polyester resin having a glycidyl group other than the molecular terminal or the molecular terminal.
Polymer (P _A ) unit

The polymer constituting the polymer (P _A) unit (P _A), for example, polymers containing vinyl monomer (m _A) units.
Vinyl monomer _(m A)

Examples of the vinyl monomer (m _A ) include carboxyl group-containing α, β-unsaturated vinyl monomers such as (meth) acrylic acid, crotonic acid, vinyl benzoic acid, fumaric acid, itaconic acid and maleic acid. Β- (meth) acryloxyethyl acid succinate, β- (meth) acryloxyethyl acid maleate, β- (meth) acryloxyethyl acid phthalate, β- (meth) acryloxyethyl hexahydrophthalate, γ- Ring-opening adduct of ε-caprolactone or γ-butyrolactone to (meth) acryloxypropyl-acid succinate, 2-hydroxyethyl (meth) acrylate (for example, Plaxel F monomer, UCC manufactured by Daicel Chemical Industries, Ltd., UCC) The terminal hydroxyl group of Tone M monomer, etc. manufactured by the company is succinic anhydride, phthalic anhydride or hexahydro anhydride Half esterification reaction product of monosuccinate esterified with taric acid and introduced carboxyl group at the end, caprolactone modified hydroxyl group-containing (meth) acrylate such as monophthalate or anhydrous hexahydromonophthalate and acid anhydride compound, etc. Long-chain carboxyl group-containing vinyl monomers; vinyl monomers having an α, β-dicarboxylic anhydride group such as maleic anhydride, itaconic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride; Dicarboxylic acid monoester groups such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monooctyl itaconate, monobutyl fumarate, mono-2-ethylhexyl fumarate, monoethyl citraconate The vinyl monomer which has is mentioned.
Of these, (meth) acrylic acid and maleic anhydride are preferred in terms of resolution and developability of the resist composition.

Further, as the vinyl monomer (m _A ), in addition to those described above, cyclopentadiene, furan, or thiophene and the above-described carboxyl group-containing α, β-unsaturated vinyl monomers such as (meth) acrylic acid Norbornene-based monomers obtained by Diels-Alder addition reaction with azobenzene; cyclopentadiene, furan or thiophene and long-chain carboxyl group-containing vinyl monomers such as β- (meth) acryloxyethyl acid succinate described above Norbornene-based monomers obtained by Diels-Alder addition reaction with azophene; cyclopentadiene, furan or thiophene and vinyl monomers having an α, β-dicarboxylic anhydride group such as maleic anhydride as described above Norbornene monomers obtained by Diels-Alder addition reaction; cyclopentadiene, furan or Norbornene monomers obtained by the Diels-Alder addition reaction between vinyl monomers such as having a dicarboxylic acid monoester group of monomethyl maleate described above with thiophene and the like.
Further, tetracyclododecene obtained by Diels-Alder addition reaction between cyclopentadiene, furan or thiophene and norbornene monomers obtained by the above-mentioned Diels-Alder addition reaction as vinyl monomer (m _A ). System monomers and the like.

The polymer (P _A ) has at least one polymerization initiator (i _ac ) unit having at least one selected from a carboxyl group and an acid anhydride group or at least one selected from a carboxyl group and an acid anhydride group. _Examples include polymers containing chain transfer agent (c _ac ) units.

Examples of the polymerization initiator (i _ac ) include 4,4′-azobis (4-cyanovaleric acid).

Examples of the chain transfer agent (c _ac ) include mercaptoacetic acid, thiosalicylic acid, dithiodiglycolic acid, 3,3′-dithiodipropionic acid, 2,2′-dithiodibenzene acid, and DL-2-mercapto. Methyl-3-guanidinoethylthiopropanoic acid, 2-mercapto-4-methyl-5-thiazoleacetic acid, p-mercaptophenol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, (5-mercapto-1, 3,4-thiadiazol-2-ylthio) acetic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) propionic acid, 3- (5-mercapto-1,3,4-thiadiazole-2) -Ilthio) propionic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) succinic acid It is done.

Examples of the polymer (P _A ) include a polymer having a polymerization terminator (t _ac ) unit having at least one selected from a carboxyl group and an acid anhydride group at the molecular end.
Examples of the polymerization terminator (t _ac ) include bromoacetic acid, 2-bromobenzoic acid, 3-bromobenzoic acid, 4-bromobenzoic acid, 2-bromobutyric acid, 3-bromobutyric acid, 4-bromobutyric acid, chloroacetic acid. 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2-chlorobutyric acid, 3-chlorobutyric acid, 4-chlorobutyric acid, iodoacetic acid, 2-iodobenzoic acid, 3-iodobenzoic acid, 4 -Iodobenzoic acid, 2-iodobutyric acid, 3-iodobutyric acid, 4-iodobutyric acid.

Furthermore, examples of the polymer (P _A ) include a polyester resin having at least one selected from a carboxyl group and an acid anhydride group in addition to the molecular terminal or the molecular terminal.

If necessary, the polymer (P _G ) or the polymer (P _A ) may have a structural unit (A) having a lactone skeleton, an lactone skeleton and a naphthalene skeleton, and an acid leaving group (decomposed by the action of an acid). (Or a leaving group), a lactone skeleton, an acid-eliminable group, a structural unit (C) having a hydrophilic group without a naphthalene skeleton, and a naphthalene skeleton without a lactone skeleton. Other structural units such as the structural unit (D) can be contained.

The polymer (P _G ) or the polymer (P _A ) preferably contains a structural unit (A) having a lactone skeleton from the viewpoint of adhesion of the resist composition to the substrate surface or the like.
The structural unit (A) is not particularly limited as long as it is a structural unit including a structure having a cyclic saturated hydrocarbon containing a carbonyloxy group (—C (═O) —O—) in the ring.
The structural unit (A) can be used alone or in combination of two or more.
The content of the structural unit (A) is preferably 30 mol% or more based on the total structural unit of the polymer (P _G ) or the polymer (P _A ) in terms of adhesion to the substrate surface of the resist composition. 35 mol% or more is more preferable. Further, the content of the structural unit (A) is preferably 60 mol% or less with respect to the total structural units of the polymer (P _G ) or the polymer (P _A ) in terms of sensitivity and resolution of the resist composition, % Or less is more preferable, and 50 mol% or less is still more preferable.

Further, when the structural unit (A) has an acid-eliminable group, the adhesion and sensitivity of the resist composition to the substrate surface and the like tend to be more excellent.
Examples of the acid leaving group include the same units as the structural unit (B) described later.
Moreover, when the structural unit (A) has a hydrophilic group, the sensitivity of the resist composition tends to be better and the resist pattern rectangularity tends to be better.
Examples of the hydrophilic group include those similar to the structural unit (C) described later.
Furthermore, when the structural unit (A) has a naphthalene skeleton, process margins such as substrate adhesion and depth of focus of the resist composition tend to be good.
Examples of the structural unit having a naphthalene skeleton include the same structural units as those described later (D).

In order to make the resist composition containing the polymer (P _G ) or the polymer (P _A ) particularly suitable for lithography including a step of exposing with light having a wavelength of 250 nm or less, the structural unit (A) Is preferably a structural unit derived from (meth) acrylate, α-fluorine-substituted (meth) acrylate or α-methylene.
Here, α-fluorine-substituted (meth) acrylate is α-fluoro methacrylate in which a hydrogen atom of a methyl group bonded to a carbon atom at α-position of methacrylic acid is substituted with a fluorine atom and / or a hydrogen atom at α-position of acrylic acid. Means α-fluoroacrylate substituted with a fluorine atom.
In addition, a structural unit derived from (meth) acrylate, α-fluorine-substituted (meth) acrylate or α-methylene uses (meth) acrylate, α-fluorine-substituted (meth) acrylate or α-methylene as a monomer. Means that.

  The structural unit (A) is preferably at least one selected from the group consisting of formulas (4-1) to (4-6) in terms of sensitivity of the resist composition or dry etching resistance.

In formula (4-1) to formula (4-6), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ each independently represent a hydrogen atom or a methyl group.

R ²¹⁰ and R ²¹¹ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ⁹³ , R ⁹⁴ , R ²⁰⁸ and R ²⁰⁹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group or a carbon The carboxy group esterified with the alcohol of number 1-6 is represented.

R ⁴⁰¹ , R ⁴⁰² , A ¹ , A ² , A ³ , A ⁴ , R ⁹¹ , R ⁹² , A ⁵ and A ⁶ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, hydroxy Represents a group, a carboxy group or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or R ⁴⁰¹ and R ⁴⁰² , A ¹ and A ² , A ³ and A ⁴ , R ⁹¹ and R ⁹² and A ⁵ And A ⁶ together represent —O—, —S—, —NH— or a methylene chain having a chain length of 1 to 6 (— (CH ₂ ) _j — (j represents an integer of 1 to 6)). To express.

X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, or 1 to 1 carbon atoms. 6 represents an alkoxy group, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, a cyano group, or an amino group. The linear or branched alkyl group having 1 to 6 carbon atoms is a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alcohol having 1 to 6 carbon atoms as a substituent. It may have at least one group selected from the group consisting of an esterified carboxy group, cyano group and amino group.
n5, n6, n7, n8 and n9 each independently represents an integer of 0 to 4. When n5, n6, n7, n8 and n9 are 2 or more, X ⁵ , X ⁶ , X ⁷ , X ⁸ and X ⁹ can each have a plurality of different groups.

Y ¹¹ , Y ¹² and Y ¹³ each independently represent —CH ₂ — or —C (═O) —O—, and at least one of them represents —C (═O) —O—.
Y ²¹ and Y ²² each independently represent —CH ₂ — or —C (═O) —, and at least one of them represents —C (═O) —.

  i represents 0 or 1; m and m1 represent 1 or 2.

  N5 in Formula (4-1) is preferably 0 from the viewpoint of dry etching resistance of the resist. m is preferably 1 in terms of sensitivity and resolution of the resist composition.

In addition, A ¹ and A ² preferably represent —CH ₂ — or —CH ₂ CH ₂ — together in terms of resistance to dry etching of the resist, and the solubility of the polymer (P) in an organic solvent It is preferable to represent -O- together in terms of points.
R ²⁰¹ and R ²⁰² are each independently preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group from the viewpoint of solubility of the polymer (P) in an organic solvent.
n6 is preferably 0 in view of dry etching resistance of the resist.

A ³ and A ⁴ in the formula (4-3) preferably represent —CH ₂ — or —CH ₂ CH ₂ — together in terms of dry etching resistance of the resist, and the organic polymer (P) It is preferable to represent -O- together in terms of solubility in a solvent.
R ²⁰³ and R ²⁰⁴ are each independently preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group from the viewpoint of the solubility of the polymer (P) in an organic solvent.
n7 is preferably 0 in view of dry etching resistance of the resist.

R ²⁰⁵ , R ²⁰⁶ and R ^{207 in} formula (4-4) are preferably hydrogen atoms from the viewpoint of solubility of the polymer (P) in an organic solvent.
Y ¹¹ , Y ^12, and Y ¹³ are preferably —C (═O) —O— and the remaining two are —CH ₂ — in terms of adhesion of the resist composition to the substrate surface and the like. .
n8 is preferably 0 in view of dry etching resistance of the resist.

In formula (4-5), R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ are each independently preferably a hydrogen atom or a methyl group from the viewpoint of solubility of the polymer (P) in an organic solvent.
Further, m1 is preferably 1 in terms of sensitivity and resolution of the resist composition.

In formula (4-6), A ⁵ and A ⁶ preferably represent together —CH ₂ — or —CH ₂ CH ₂ — in terms of dry etching resistance of the resist, and the organic polymer (P) It is preferable to represent -O- together in terms of solubility in a solvent.
R ²⁰⁸ and R ²⁰⁹ are each independently preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group from the viewpoint of solubility of the polymer (P) in an organic solvent.
R ²¹⁰ and R ²¹¹ are each independently preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group from the viewpoint of solubility of the polymer (P) in an organic solvent.
Y ²¹ and Y ²² are preferably —C (═O) —, and the remaining one is preferably —CH ₂ —, from the viewpoint of adhesion of the resist composition to the substrate surface or the like.
n9 is preferably 0 from the standpoint of dry etching resistance of the resist.

  The polymer (P) having the structural unit (A) can be produced by polymerizing a monomer containing the monomer (a) that gives the structural unit (A).

  Examples of the monomer (a) include monomers represented by formulas (10-1) to (10-29). In formula (10-1) to formula (10-29), R represents a hydrogen atom or a methyl group.

  Among these, monomers represented by formula (10-1) to formula (10-3) and formula (10-5) and geometric isomers and optical isomers are preferable in terms of sensitivity. In terms of resistance to dry etching of the resist, Formula (10-7), Formula (10-9), Formula (10-10), Formula (10-12), Formula (10-14), Formula (10-24) The monomers represented by formulas (10-26) and (10-29), and geometrical isomers and optical isomers thereof are preferable. Further, in terms of solubility of the polymer (P) in an organic solvent, the formula (10-8), the formula (10-13), the formula (10-16) to the formula (10-23), and the formula (10-28) And the geometric isomers and optical isomers thereof are preferred.

Further, the polymer (P _G ) or the polymer (P _A ) preferably contains a structural unit (B) having an acid-eliminable group in order to improve the sensitivity of the resist composition.
Acid-leaving groups are generally blended in chemically amplified resist compositions, and are bonded in acid-leaving groups by the action of acids generated from photoacid generators that generate acids upon light irradiation (exposure). Is cleaved, and part or all of the acid leaving group is separated or eliminated from the main chain of the polymer.
Therefore, the structural unit (B) makes the polymer (P) insoluble in alkali before part or all of the acid leaving group is eliminated, and part or all of the acid leaving group is eliminated by the acid. Thus, the polymer (P) is a component that makes the polymer (P) alkali-soluble, and has an effect of enabling resist pattern formation in a positive chemically amplified resist.
When the polymer (P _G ) or the polymer (P _A ) contains the structural unit (B), it is suitable for a chemically amplified resist.
The chemically amplified resist includes a positive type in which an exposed portion is soluble in a developer (alkaline aqueous solution) and a negative type in which an exposed portion is insoluble in a developer.

The structural unit (B) can be used alone or in combination of two or more.
The content of the structural unit (B) is preferably 20 mol% or more, preferably 25 mol% or more with respect to the total structural units of the polymer (P _G ) or the polymer (P _A ) in terms of the sensitivity and resolution of the resist composition. Is more preferable. In addition, the content of the structural unit (B) is 70 mol% or less based on the total structural unit of the polymer (P _G ) or the polymer (P _A ) in terms of the adhesion of the resist composition to the substrate surface and the like. Preferably, 65 mol% or less is more preferable, and 60 mol% or less is still more preferable.

Further, when the structural unit (B) has a hydrophilic group, it tends to have a higher sensitivity.
Examples of the hydrophilic group include those similar to the structural unit (C) described later.

In order to make the resist composition containing the polymer (P _G ) or the polymer (P _A ) particularly suitable for lithography including a step of exposing with light having a wavelength of 250 nm or less, the structural unit (B) As the structural unit (A), a structural unit derived from (meth) acrylate or α-fluorine-substituted (meth) acrylate is preferable.

  As the structural unit (B), the formula (3-1-1), the formula (3-2-1), the formula (3-3-1), and the formula (3-4-1) in terms of resistance to dry etching of the resist. And at least one selected from the group consisting of formula (3-5-1), formula (3-6-1), formula (3-7-1) and formula (3-8-1).

In formulas (3-1-1) to (3-8-1), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are each independently a hydrogen atom or methyl Represents a group.
R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 3 carbon atoms.
X ¹ , X ² , X ³ , X ⁴ , X ⁵¹ and X ⁶¹ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.

n1, n2, n3, n4, n51 and n61 each independently represents an integer of 0 to 4. When n1, n2, n3, n4, n51 and n61 are 2 or more, X ¹ , X ² , X ³ , X ⁴ , X ⁵¹ and X ⁶¹ can each have a plurality of different groups.

R ³³¹ , R ³³² , R ³³³ , R ³³⁴ , R ³⁵¹ , R ³⁵² , R ³⁵³ , R ³⁵⁴ , R ³⁶¹ , R ³⁶² , R ³⁶³ and R ³⁶⁴ are each independently a hydrogen atom or a straight chain having 1 to 6 carbon atoms Or represents a branched alkyl group.
V ¹ , V ² , V ³ , V ⁴ , V ⁵ and V ⁶ are each independently —O—, —S—, —NH— or a methylene chain having a chain length of 1 to 6 (— (CH ₂ ) _u1 — ( u1 represents an integer of 1 to 6)).
q, q3, and q4 represent 0 or 1. r represents an integer of 0-2.

R ³⁵⁵ , R ³⁵⁶ and R ³⁵⁷ each independently represent a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, and At least one of R ³⁵⁵ , R ³⁵⁶ and R ^{357 is} an alicyclic hydrocarbon group or a derivative thereof, or any two of R ³⁵⁵ , R ³⁵⁶ and R ³⁵⁷ are bonded to each other, and each is bonded Together with the carbon atom, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, and one of R ³⁵⁵ , R ³⁵⁶ and R ³⁵⁷ that is not involved in bonding is carbon. It represents a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof.

R ³⁶⁷ and R ³⁷³ each independently represent a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms. R ³⁶⁵ , R ³⁶⁶ , R ³⁷¹ and R ³⁷² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, or R ³⁶⁵ and R ³⁶⁷ , R ³⁶⁶ and R ³⁶⁷ , Two of R ³⁷¹ and R ³⁷³ or R ³⁷² and R ³⁷³ are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atom to which each is bonded. , R ³⁶⁵ , R ³⁶⁶ , R ³⁷¹ and R ³⁷² , the remaining one not involved in the bond represents a hydrogen atom.
R ³⁸¹ , R ³⁸² and R ³⁸³ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms.

R ¹ in formula (3-1-1) is preferably a methyl group, an ethyl group, or an isopropyl group in terms of sensitivity and resolution of the resist composition.
N1 is preferably 0 from the standpoint of dry etching resistance of the resist.

R ² and R ^{3 in} formula (3-2-1) are each independently preferably a methyl group, an ethyl group or an isopropyl group from the viewpoint of the sensitivity and resolution of the resist composition.
Further, n2 is preferably 0 in terms of resistance to dry etching of the resist.

R ⁴ in formula (3-3-1) is preferably a methyl group, an ethyl group, or an isopropyl group in terms of the sensitivity and resolution of the resist composition.
V ¹ and V ² are each preferably —CH ₂ — or —CH ₂ CH ₂ — independently from the standpoint of resistance to dry etching of the resist.
R ³³¹ , R ³³² , R ³³³ and R ³³⁴ are each independently preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group from the viewpoint of solubility of the polymer (P) in an organic solvent.
n3 is preferably 0 in view of dry etching resistance of the resist.
Further, q is preferably 1 from the viewpoint of dry etching resistance of the resist, and 0 is preferable from the viewpoint of solubility of the polymer (P) in an organic solvent.

R ⁵ in formula (3-4-1) is preferably a methyl group, an ethyl group, or an isopropyl group in terms of sensitivity and resolution of the resist composition.
N4 is preferably 0 from the viewpoint of dry etching resistance of the resist.
r is preferably 1 from the viewpoint of dry etching resistance of the resist, and preferably 0 from the viewpoint of solubility of the polymer (P) in an organic solvent.

V ³ and V ^{4 in} formula (3-5-1) are each preferably —CH ₂ — or —CH ₂ CH ₂ — independently from the viewpoint of dry etching resistance of the resist.
R ³⁵¹ , R ³⁵² , R ³⁵³ , and R ³⁵⁴ are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of solubility of the polymer (P) in an organic solvent.
n51 is preferably 0 from the standpoint of dry etching resistance of the resist.
Further, q3 is preferably 1 from the viewpoint of dry etching resistance of the resist, and 0 is preferable from the viewpoint of solubility of the polymer (P) in an organic solvent.
Further, -C (R ³⁵⁵ ) (R ³⁵⁶ ) (R ³⁵⁷ ) is preferably a structure represented by formula (K-1) to formula (K-6) in terms of the line edge roughness of the resist, and dry etching of the resist. The structure represented by Formula (K-7)-Formula (K-17) is preferable at the point of tolerance.

In formula (3-6-1), V ⁵ and V ⁶ are each preferably —CH ₂ — or —CH ₂ CH ₂ — independently from the viewpoint of dry etching resistance of the resist.
R ³⁶¹ , R ³⁶² , R ³⁶³ and R ³⁶⁴ are each independently preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group from the viewpoint of solubility of the polymer (P) in an organic solvent.
n61 is preferably 0 from the standpoint of dry etching resistance of the resist.
Further, q4 is preferably 1 in terms of dry etching resistance, and is preferably 0 in terms of solubility of the polymer (P) in an organic solvent.
Further, -C (R ³⁶⁵ ) (R ³⁶⁶ ) -O-R ³⁶⁷ is preferably a structure represented by formula (J-1) to formula (J-24) in terms of the line edge roughness of the resist. The structure represented by Formula (J-25)-Formula (J-52) is preferable at the point of etching tolerance.

-C (R ³⁷¹ ) (R ³⁷² ) -O-R ³⁷³ in the formula (3-7-1) is represented by the formula (J-1) to the formula (J-24) in terms of the line edge roughness of the resist. The structure is preferable. Moreover, the structure represented by Formula (J-25)-Formula (J-52) is preferable at the point of the dry etching tolerance of a resist.

The polymer (P) having the structural unit (B) can be produced by polymerizing a monomer containing the monomer (b) that gives the structural unit (B).
Examples of the monomer (b) include monomers represented by formulas (9-1) to (9-224). In formula (9-1) to formula (9-224), R and R ′ each independently represent a hydrogen atom or a methyl group.

  Furthermore, n-butoxyethyl (meth) acrylate, iso-butoxyethyl (meth) acrylate, etc. are mentioned as a monomer (b).

  Among these, the above formula (9-1) to formula (9-3), formula (9-5), formula (9-16), formula (9-19) in terms of the sensitivity and resolution of the resist composition. , Formula (9-20), Formula (9-22), Formula (9-23), Formula (9-25) to Formula (9-28), Formula (9-30), Formula (9-31), Monomers represented by the formula (9-33), the formula (9-34) and the formula (9-102) to the formula (9-129) and their geometrical isomers and optical isomers are preferable, and the formula (9 -1), formula (9-2), formula (9-16), formula (9-20), formula (9-23), formula (9-28), formula (9-31), formula (9- 34), Formula (9-109), Formula (9-111), Formula (9-114) to Formula (9-117), Formula (9-125), Formula (9-128), and Formula (9-129). ) Is more preferable.

  In terms of the line edge roughness of the resist, the equations (9-35) to (9-40), (9-52) to (9-62), and (9-76) to (9-88) are used. ), A monomer represented by formula (9-130) to formula (9-135), formula (9-147) to formula (9-157) and formula (9-171) to formula (9-183). These geometric isomers and optical isomers are preferred.

  In terms of resistance to dry etching of the resist, the equations (9-41) to (9-51), (9-63) to (9-75), and (9-89) to (9-101) ), Monomers represented by formulas (9-136) to (9-146), formulas (9-158) to (9-170), and formulas (9-184) to (9-196). These geometric isomers and optical isomers are preferred.

  Moreover, the monomer represented by Formula (9-197)-Formula (9-224) and these geometric isomers and optical isomers are preferable at the point of the pattern rectangularity of a resist.

Further, as a specific example of the monomer (b), an α-fluoromethyl acrylate in which a hydrogen atom of a methyl group bonded to a carbon atom at the α-position of methacrylic acid is substituted with a fluorine atom or a hydrogen atom at the α-position of acrylic acid is An α-fluorine-substituted (meth) acrylate substituted with a fluorine atom can be mentioned.
Specific examples of the monomer include tert-butyl α-trifluoromethyl acrylate, methoxymethyl α-trifluoromethyl acrylate, ethoxyethyl α-trifluoromethyl acrylate, and n-propoxyethyl α-trifluoromethyl acrylate. , Iso-propoxyethyl α-trifluoromethyl acrylate, n-butoxyethyl α-trifluoromethyl acrylate, iso-butoxyethyl α-trifluoromethyl acrylate, tert-butoxyethyl α-trifluoromethyl acrylate, tert-butyl α- Fluoroacrylate, methoxymethyl α-fluoroacrylate, ethoxyethyl α-fluoroacrylate, n-propoxyethyl α-fluoroacrylate, iso-propoxyethyl α-fu Oro acrylate, n- butoxyethyl α- fluoro acrylate, iso- butoxy α- fluoroacrylate and tert- butoxyethyl α- fluoroacrylate.

  Further, as the monomer (b), in addition to the above, 2-methyl-2,4-butanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 1, 4-butanediol di (1- (meth) acryloyloxy) ethyl ether, 1,4-butanediol di (1- (meth) acryloyloxy) methyl ether, (meth) acryloyloxyethylene glycol dimer (1- (meth) And polyfunctional (meth) acrylates such as (acryloyloxy) ethyl ether and (meth) acryloyloxyethylene glycol dimer (1- (meth) acryloyloxy) methyl ether.

The polymer (P _G ) or the polymer (P _A ) preferably contains a structural unit (C) having a hydrophilic group in terms of reducing defects in the resist composition and resist pattern rectangularity.
Examples of the hydrophilic group include —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a methoxy group, a carboxy group, and an amino group, and the structural unit (C) is one kind or a combination of two or more kinds. Can be used.

The content of the structural unit (C) is preferably from 5 to 35 mol%, preferably from 10 to 30 mol% based on the total structural units of the polymer (P _G ) or the polymer (P _A ) in terms of the resist pattern rectangularity. Is more preferable.

In order to make the resist composition containing the polymer (P _G ) or the polymer (P _A ) particularly suitable for lithography including a step of exposing with a light having a wavelength of 250 nm or less, as the structural unit (C) Is preferably a structural unit derived from (meth) acrylate or α-fluorine-substituted (meth) acrylate.

  The structural unit (C) is preferably at least one selected from the group consisting of formulas (5-1) to (5-7) in terms of dry etching resistance of the resist.

In formulas (5-1) to (5-7), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom or a methyl group.

R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ and R ⁵⁰⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , X ⁵⁵ , X ⁵⁶ and X ⁵⁷ are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, —C (CF ₃ ) ₂ —OH, a hydroxy group, A cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or an amino group. A linear or branched alkyl group _-C as a substituent _(CF 3) 2 -OH, hydroxy groups of the 1 to 6 carbon atoms, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms It may have at least one group selected from the group consisting of a carboxy group esterified with an alcohol and an amino group.
Further, the position substituted with X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , X ⁵⁵ , X ⁵⁶ and X ⁵⁷ may be any position in the cyclic structure.

n51, n52, n53, n54, n55 and n56 each independently represents an integer of 1 to 4. When n51, n52, n53, n54, n55 and n56 are 2 or more, X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , X ⁵⁵ and X ⁵⁶ can each have a plurality of different groups.

R ^{531 to} R ⁵³⁶ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. W ¹ , W ² and W ³ are each independently —O—, —S—, —NH— or a methylene chain having a chain length of 1 to 6 (— (CH ₂ ) _u2 — (u2 represents an integer of 1 to 6). )).

  q1 and q2 represent 0 or 1. Moreover, r1 represents the integer of 0-2.

R ⁵⁷¹ is a carbon atom having a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a bridged cyclic hydrocarbon group having 4 to 16 carbon atoms, or a bridged cyclic hydrocarbon group having 4 to 16 carbon atoms. 1 to 6 linear or branched alkyl groups are represented.
R ⁵⁷² is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, or a bridged ring having 4 to 16 carbon atoms together with the carbon atoms to which R ⁵⁷¹ and R ⁵⁷² are bonded together. A formula hydrocarbon group may be formed.
Here, the alkyl group in ^R571 and ^R572 may have a hydroxy group, a carboxy group, an acyl group having 2 to 6 carbon atoms, or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms. The bridged cyclic hydrocarbon group for R ⁵⁷¹ and R ⁵⁷² may have a linear or branched alkyl group having 1 to 6 carbon atoms, and the alkyl group can be a hydroxy group, a carboxy group, or a carbon number of 2 to 2. It may have a carboxy group esterified with an acyl group of 6 or an alcohol having 1 to 6 carbon atoms.

R ⁵⁰¹ in the formula (5-1) is preferably a methyl group, an ethyl group or an isopropyl group in terms of the sensitivity and resolution of the resist composition, and a hydrogen atom in terms of solubility of the polymer (P) in an organic solvent. preferable.
Further, n51 is preferably 1 in view of dry etching resistance of the resist.
X ⁵¹ is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group in terms of the pattern shape of the resist.

In formula (5-2), n52 is preferably 1 in view of dry etching resistance of the resist.
X ⁵² is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group in terms of the pattern shape of the resist.

R ⁵⁰² in formula (5-3) is preferably a methyl group, an ethyl group or an isopropyl group from the viewpoint of the sensitivity and resolution of the resist composition, and a hydrogen atom from the viewpoint of solubility of the polymer (P) in an organic solvent. preferable.
W ¹ and W ² are each preferably —CH ₂ — or —CH ₂ CH ₂ — independently from the viewpoint of dry etching resistance of the resist.
R ⁵³¹ , R ⁵³² , R ⁵³³ and R ⁵³⁴ are each independently preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group from the viewpoint of solubility of the polymer (P) in an organic solvent.
Further, n53 is preferably 1 in view of dry etching resistance of the resist.
X ⁵³ is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group in terms of the pattern shape of the resist.
Further, q1 is preferably 1 from the viewpoint of dry etching resistance of the resist, and 0 is preferable from the viewpoint of solubility of the polymer (P) in an organic solvent.

R ⁵⁰³ in the formula (5-4) is preferably a methyl group, an ethyl group or an isopropyl group in terms of the sensitivity and resolution of the resist composition, and a hydrogen atom in terms of solubility of the polymer (P) in an organic solvent. preferable.
Further, n54 is preferably 1 in view of dry etching resistance of the resist.
X ⁵⁴ is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group in terms of the pattern shape of the resist.
Further, r1 is preferably 1 from the viewpoint of dry etching resistance of the resist, and 0 is preferable from the viewpoint of solubility of the polymer (P) in an organic solvent.

In formula (5-5), R ⁵⁰⁴ and R ⁵⁰⁵ are each independently preferably a methyl group, an ethyl group or an isopropyl group in terms of the sensitivity and resolution of the resist composition.
Further, n55 is preferably 1 in view of dry etching resistance of the resist.
X ⁵⁵ is _{-C (CF} 3) 2 -OH in terms of resist pattern shape, hydroxy group, a cyano group or a methoxy group.

R ⁵⁰⁶ in formula (5-6) is preferably a methyl group, an ethyl group or an isopropyl group in terms of the sensitivity and resolution of the resist composition, and a hydrogen atom in terms of solubility of the polymer (P) in an organic solvent. preferable.
W ³ is preferably —CH ₂ — or —CH ₂ CH ₂ — in terms of resistance to dry etching of the resist.
R ⁵³⁵ and R ⁵³⁶ are preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group from the viewpoint of the solubility of the polymer (P) in an organic solvent.
Further, n56 is preferably 1 from the viewpoint of resist dry etching resistance.
X ⁵⁶ is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group in terms of the pattern shape of the resist.
Further, q2 is preferably 1 from the viewpoint of dry etching resistance of the resist, and 0 is preferable from the viewpoint of solubility of the polymer (P) in an organic solvent.

R ⁵⁷¹ and R ^{572 in} formula (5-7) are a bridge having 4 to 16 carbon atoms together with the carbon atoms to which R ⁵⁷¹ and R ⁵⁷² are combined in terms of dry etching resistance of the resist. A structure that forms a cyclic hydrocarbon group is preferred. Further, in terms of the heat resistance and stability of the resist, R ⁵⁷¹ and R ⁵⁷² are combined together, and as a ring structure contained in the bridged cyclic hydrocarbon group formed together with the carbon atoms to which they are bonded, It preferably has a ring, an adamantane ring, a norbornane ring, a pinane ring, a bicyclo [2.2.2] octane ring, a tetracyclododecane ring, a tricyclodecane ring, or a decahydronaphthalene ring.
X ⁵⁷ is a resist pattern shape point —C (CF ₃ ) ₂ —OH, —CH ₂ —OH, —CH ₂ —CN, —CH ₂ —O—CH _3, or — (CH ₂ ) ₂ —. O—CH ₃ is preferred.

  The polymer (P) having the structural unit (C) can be produced by polymerizing a monomer including the monomer (c) that gives the structural unit (C) having a hydrophilic group.

  Examples of the monomer (c) include monomers represented by formulas (13-1) to (13-79). In formula (13-1) to formula (13-79), R represents a hydrogen atom or a methyl group.

  Further, as the monomer (c), in addition to the above, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-n-propyl (meth) acrylate and 4-hydroxy-n- (Meth) acrylate monomer having no ring structure such as butyl (meth) acrylate; unsaturated carboxylic acid such as (meth) acrylic acid, maleic acid and itaconic acid; p-hydroxystyrene, p-tert-butoxycarbonyl Aromatic alkenyl compounds such as hydroxystyrene, 3,5-di-tert-butyl-4-hydroxystyrene, 3,5-dimethyl-4-hydroxystyrene, p- (2-hydroxy-iso-propyl) styrene and the like can be mentioned. .

  Among these, in terms of solubility of the polymer (P) in an organic solvent, the formula (13-1) to the formula (13-9), the formula (13-13) to the formula (13-16), and the formula (13) -21) to formula (13-24), formula (13-30) to formula (13-34), formula (13-37) to formula (13-43), formula (13-56) to formula (13- 59), Formula (13-62), Formula (13-63), Formula (13-66) to Formula (13-69), Formula (13-72), Formula (13-76) to Formula (13-79) And the geometric isomers and optical isomers thereof are preferred.

  In terms of resistance to dry etching of the resist, the equations (13-25) to (13-30), the equations (13-44) to (13-55), and the equations (13-60) to (13-61) are used. ), Monomers represented by formula (13-64) to formula (13-65), formula (13-71) and formula (13-73) to formula (13-75), and geometric isomers thereof, and These optical isomers are preferred.

The polymer (P _G ) or the polymer (P _A ) has a process margin such as a depth of focus of the resist composition, a water repellency with respect to an immersion liquid (for example, water) in an immersion lithography process, and a thinned resist. It is preferable to contain the structural unit (D) having a naphthalene skeleton from the viewpoint of antireflection properties of the film.

The content of the structural unit (D) is preferably 3 mol% or more with respect to the total structural units of the polymer (P _G ) or the polymer (P _A ), preferably 5 mol% in terms of the dry etching resistance and refractive index of the resist. The above is more preferable. Further, the content of the structural unit (D) is preferably 50 mol% or less with respect to the total structural units of the polymer (P _G ) or the polymer (P _A ) in terms of sensitivity and resolution of the resist composition, % Or less is more preferable, and 30 mol% or less is still more preferable.

  When the structural unit (D) has an acid leaving group or a hydrophilic group, it tends to have a process margin such as a better depth of focus of the resist composition.

  In the polymer (P) containing the structural unit (D), when the structural unit (D) has an acid-eliminable group (preferably, in formula (1) described later, Y is an acid-eliminable group. In some cases, the acid-eliminable group is eliminated by the action of an acid, so that it becomes soluble in alkali. Therefore, the exposed portion becomes alkali-soluble, and the unexposed portion remains insoluble in alkali. Therefore, when the polymer (P) is used as a positive chemically amplified resist, a resist pattern is formed. .

Further, when the structural unit (D) does not have an acid leaving group (preferably, when Y is —C (═O) —OH or —OH in the formula (1) described later), the structural unit Since (D) itself is acidic, the structural unit (D) has improved affinity for alkali, and process margins such as resist line edge roughness and depth of focus are improved.
Therefore, the polymer (P) containing the structural unit (D) is suitable for resists, and particularly suitable for positive chemically amplified resists.

  As the structural unit (D), for example, a unit represented by the formula (1) is preferable in terms of a process margin such as a depth of focus required for the resist.

H1 in the formula (1) is 0 or 1. H1 is preferably 0 in terms of resolution of the resist composition, and h1 is preferably 1 in terms of defects and resist sensitivity.
h2 represents an integer of 1 to 4. h2 is preferably 1 from the viewpoint of the resolution of the resist composition, and preferably 2 to 4 from the viewpoint of the defect of the resist composition and the sensitivity of the resist.

g1 is 0 or 1, and g2 is an integer of 0-20.
When h1 = 1, g2 is preferably 1 to 4 in terms of the resolution of the resist composition. G3 is 0 or 1. R ¹⁰ represents a hydrogen atom or a methyl group.
G ¹ represents a single bond, —C (═O) —O—, —O— or —O—C (═O) —. Among these, —C (═O) —O— or —O—C (═O) — is preferable in terms of polymerizability.

L ¹ represents a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and the divalent hydrocarbon group has at least one selected from a substituent and a hetero atom. You may do it.
L ¹ is a linear or branched divalent hydrocarbon group having 1 to 4 carbon atoms in terms of solubility of the polymer (P) in an organic solvent, — (CH ₂ CH ₂ O) _g21 — or — (CH _{2 CH (CH 3) O)} g22 - it is preferred. Here, g21 and g22 each represent an integer of 1 to 5, and g21 and g22 are each preferably 1 or 2 in terms of the resolution of the resist composition.
L ¹ is preferably at least one selected from the formulas (1-11) to (1-14) from the viewpoint of dry etching resistance of the resist.

In formula (1-11) to formula (1-14), R ^{111 to} R ¹¹⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Z represents an atomic group constituting a cyclic hydrocarbon group with a carbon atom in L ¹ .
Incidentally, in the formula (1-11) to (1-14), upper left bond is in ^{G 1,} bond the lower right is respectively coupled to an oxygen atom of the carboxyl residues bound to ^{L 1.}

Further, when G is —C (═O) —O—, L ¹ is —C (CH ₃ ) ₂ —, —C (CH ₃ ) ₂ —CH ₂ —, —C (CH) in terms of resist sensitivity. ₃ ) At least one selected from (CH ₂ CH ₃ ) —, formula (1-11) and formula (1-12) is preferred.
When h1 = 1, L ¹ is —C (CH ₃ ) ₂ —, —CH ₂ —C (CH ₃ ) ₂ —, —C (CH ₃ ) (CH ₂ CH ₃ ) in terms of resist sensitivity. -, At least 1 sort (s) chosen from Formula (1-13) and Formula (1-14) is more preferable.

R ¹¹ and R ¹² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or R ¹¹ and R 12. ¹² together represent -O-, -S-, -NH- or a methylene chain having a chain length of 1-6.
In the case of h1 = 1, R ¹¹ and R ¹² are each independently a hydrogen atom or a linear or branched alkyl having 1 to 4 carbon atoms in terms of transparency to the excimer laser light of the polymer (P) and the resolution of the resist composition. Groups are preferred.

Y represents —C (═O) —OH, —OH or an acid leaving group.
Y is preferably -C (= O) -OH or -OH in terms of the defect and sensitivity of the resist composition and the line edge roughness of the resist, and in terms of storage stability of the resist composition, the formula (1-2) to the formula The acid leaving group represented by (1-5) is preferred.

In Formula (1-2) and Formula (1-4), R ¹²¹ , R ¹²² and R ¹²³ and R ¹⁴¹ , R ¹⁴² and R ¹⁴³ are each independently (i) a monovalent fat having 4 to 20 carbon atoms. Represents a cyclic hydrocarbon group or a derivative thereof or a linear or branched alkyl group having 1 to 4 carbon atoms, and at least one of R ¹²¹ , R ¹²² and R ¹²³ , R ¹⁴¹ , R ¹⁴² and R ¹⁴³ is the above An alicyclic hydrocarbon group or a derivative thereof, or (ii) any two of R ¹²¹ , R ¹²² and R ¹²³ and R ¹⁴¹ , R ¹⁴² and R ¹⁴³ are bonded to each other, and together are carbon atoms, form a divalent alicyclic hydrocarbon group or a derivative thereof having 4 to 20 carbon ^atoms, R ^{121, R 122} and ^{R 123} and ^{R 141, R 142} and R The remaining one not involved in binding of ⁴³ represents a monovalent alicyclic hydrocarbon group or a derivative thereof having 4 to 20 alkyl group carbon atoms or a straight-chain or branched having 1 to 4 carbon atoms.

In Formula (1-3) and Formula (1-5), R ¹³³ and R ¹⁵³ are each independently (i) a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or carbon number 1 Represents a linear or branched alkyl group of ˜4, and R ¹³¹ , R ¹³² , R ¹⁵¹ and R ¹⁵² each independently represent a hydrogen atom or a linear or branched alkyl group of 1 to 4 carbon atoms, or ( ii) Two of R ¹³¹ and R ¹³³ or R ¹³² and R ¹³³ or R ¹⁵¹ and R ¹⁵³ or R ¹⁵² and R ¹⁵³ are bonded to each other, together with the carbon atom to which each is bonded, together with 2 to 4 carbon atoms The remaining one of R ¹³¹ , R ¹³² , R ^151, and R ¹⁵² that did not participate in the bond forming a valent alicyclic hydrocarbon group or a derivative thereof represents a hydrogen atom.

G4 in the formula (1) is 0 or 1, and when Y is any one of the formulas (1-2) to (1-4), the polymer (P) has transparency to the excimer laser beam. 1 is preferable from the viewpoint of the sensitivity of the resist composition, and when Y is the formula (1-5), 0 is preferable from the viewpoint of the transparency of the polymer (P) to the excimer laser beam and the sensitivity of the resist composition.
L ² represents a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and the divalent hydrocarbon group has at least one selected from a substituent and a hetero atom. It may be. Here, _-C examples of the substituent _(CF 3) 2 -OH, hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms and An amino group etc. are mentioned. Examples of the hetero atom include a sulfur atom, a nitrogen atom, and a phosphorus atom.
In addition, when g4 = 1, L ² is a linear or branched divalent hydrocarbon group having 1 to 4 carbon atoms in terms of solubility of the polymer (P) in an organic solvent, — (OCH ₂ CH _{2) g31} - or _{- (OCH 2 CH (CH 3} )) g32 - are preferred. Here, g31 and g32 each independently represent an integer of 1 to 5, and 1 or 2 is preferable in terms of resolution of the resist composition.

X ¹⁰ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms having a hydroxy group or a cyano group as a hydroxy group or a substituted group in terms of reducing defects and resist pattern rectangularity of the resist composition.
h11 is preferably 0 in terms of the resolution of the resist composition.
The structural unit (D) having a naphthalene skeleton represented by the formula (1) is transparent to light having a wavelength of 250 nm or less such as excimer laser light (ArF excimer laser light, KrF excimer laser light, etc.) of the polymer (P). What is represented by Formula (7-1) is preferable at the point of property.

In formula (7-1), R ¹⁰ , R ¹¹ , R ¹² , G ¹ , L ¹ , L ² , X ¹⁰ , Y, h 1, h 11, g 1, g 2, g 3 and g 4 are the same as in formula (1). It is.

The structural unit (D) can be used alone or in combination of two or more.
The polymer (P) containing the structural unit (D) can be produced by polymerizing a monomer including the monomer (d) that gives the structural unit (D).

  Examples of the monomer (d) include monomers represented by the formulas (8-1) to (8-75). In formula (8-1) to formula (8-75), R represents a hydrogen atom or a methyl group.

Among these, in terms of the defect of the resist composition and the line edge roughness of the resist, the equations (8-1) to (8-30), the equations (8-38) to the equations (8-52) and (8) The monomers represented by -60) to formula (8-70) and geometrical isomers and optical isomers thereof are preferable.
Further, in terms of the sensitivity of the resist composition, the formula (8-11), the formula (8-12), the formula (8-15) to the formula (8-20), the formula (8-23) to the formula (8-28). ), Formula (8-46), Formula (8-47), Formula (8-49) to Formula (8-52) and Formula (8-69), and their geometric isomers and Optical isomers are preferred.
Further, from the viewpoint of the storage stability of the resist composition, the formula (8-31) to the formula (8-37), the formula (8-53) to the formula (8-59), and the formula (8-71) to the formula (8) -75) and the geometric isomers and optical isomers thereof are preferred.

The polymer (P _G ) or the polymer (P _A ) may contain other structural units (E) as necessary in addition to the structural units (A) to (D).

Examples of the structural unit (E) include the structural unit (E1) having an alicyclic skeleton (nonpolar alicyclic skeleton) without having an acid-eliminable group and a hydrophilic group.
Here, the alicyclic skeleton is a skeleton having one or more cyclic saturated hydrocarbon groups.

The structural unit (E1) tends to exhibit the effect of developing the dry etching resistance of the resist.
The structural unit (E1) can be used alone or in combination of two or more.
As the structural unit (E1), structural units represented by the formulas (11-1) to (11-4) are preferable from the viewpoint of dry etching resistance of the resist.

In formula (11-1) to formula (11-4), R ³⁰¹ , R ³⁰² , R ³⁰³ and R ³⁰⁴ each independently represent a hydrogen atom or a methyl group.
X ³⁰¹ , X ³⁰² , X ³⁰³ and X ³⁰⁴ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, and the position at which they are bonded may be anywhere on the ring.
n301, n302, n303 and n304 each independently represents an integer of 0 to 4. Incidentally, n301, n302, if n303 and n304 is 2 or ^{more, X 301, X 302, X} 303 and ^{X 304} may have a plurality of different groups.

  p and p1 each independently represents an integer of 0 to 2.

  Further, n301, n302, n303 and n304 are preferably 0 from the viewpoint of resist dry etching resistance.

  p and p1 are preferably 0 in view of solubility of the polymer (P) in an organic solvent, and 1 is preferred in view of dry etching resistance of the resist.

  The polymer (P) containing the structural unit (E1) can be produced by polymerizing a monomer containing the monomer (e1) having a nonpolar alicyclic skeleton.

  Examples of the monomer (e1) include cyclohexyl, (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentadienyl. Examples include (meth) acrylates and derivatives having a linear or branched alkyl group having 1 to 6 carbon atoms on the alicyclic skeleton of these compounds.

Examples of the monomer (e1) include monomers represented by formulas (14-1) to (14-5). In formula (14-1) to formula (14-5), R represents a hydrogen atom or a methyl group.
In addition to the above monomers, those having a cycloolefin structure such as norbornene as the alicyclic skeleton can be mentioned.

The polymer (P _G ) or the polymer (P _A ) may further contain a structural unit (E2) other than the structural unit (E1) as the structural unit (E).
The polymer (P) containing the structural unit (E2) can be produced by polymerizing a monomer containing the monomer (e2).

  Examples of the monomer (e2) include methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro-n-propyl (meth) acrylate 2,2,3,3,3-pentafluoro-n-propyl (meth) acrylate, methyl α- (tri) fluoromethyl acrylate, ethyl α- (tri) fluoromethyl acrylate, 2-ethylhexyl α- (tri) Fluoromethyl acrylate, n-propyl α- (tri) fluor (Meth) acrylate having a linear or branched structure such as methacrylate, iso-propyl α- (tri) fluoromethyl acrylate, n-butyl α- (tri) fluoromethyl acrylate, iso-butyl α- (tri) fluoromethyl acrylate Or α-fluorine-substituted (meth) acrylate; aromatic alkenyl compounds such as styrene, α-methylstyrene, vinyltoluene, p-tert-perfluorobutylstyrene; carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; Examples include ethylene, propylene, tetrafluoroethylene, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, vinyl chloride, vinyl fluoride, vinylidene fluoride, and vinylpyrrolidone.

The content of the structural unit (E) is preferably 20 mol% or less relative to the polymer _{(P G)} or polymer all the structural units of _{(P A).}

In order to make the polymer (P _G ) or the polymer (P _A ) suitable for resists, particularly for positive chemically amplified resists among the structural units (A) to (E) listed above. Preferably contains the structural unit (A) and the structural unit (B).
Preferred combinations of the structural unit (A) and the structural unit (B) in the polymer (P _G ) or the polymer (P _A ) include those listed in Tables 1 to 4.

  The structural unit (A) is one or more selected from the group consisting of formula (10-1) and formula (10-3), formula (10-7) and formula (10-) in terms of the defect of the resist composition. 8), Formula (10-10), Formula (10-12), Formula (10-17), and 1 or more types chosen from the group which consists of Formula (10-19) can be used together.

Furthermore, in terms of pattern rectangularity, the polymer (P _G ) or the polymer (P _A ) is not limited to the combination of the structural unit (A) and the structural unit (B) listed in Tables 1 to 4, but the structural unit ( C) is selected from the group consisting of Formula (13-1), Formula (13-26), Formula (13-27), Formula (13-30), Formula (13-31), and Formula (13-68). A combination (hereinafter referred to as “combination (1)”) having three types of structural units including a structural unit obtained from one monomer is preferable.

  Moreover, it is 1 type chosen from the group which consists of Formula (14-1) and Formula (14-3) as a structural unit (E1) to the combination or combination (1) enumerated in Table 1-Table 4 at the point of dry etching tolerance. A combination of the above monomers is preferred.

The weight average molecular weight of the polymer (P _G ) or the polymer (P _A ) is preferably 1,000 or more, more preferably 2,000 or more, and more preferably 3,000 or more in terms of the dry etching resistance and pattern shape of the resist. preferable.
Further, the polymer _{(P G)} or polymer weight average molecular weight of _{(P A)} is a polymer for resist solutions _{(P G)} or polymer _{(P A)} 100 in terms of the resolution of solubility and resist composition, 000 or less is preferable, 50,000 or less is more preferable, 30,000 or less is further preferable, and 20,000 or less is particularly preferable.

The molecular weight distribution of the polymer _{(P G)} or polymer _{(P A) (Mw / Mn} ) in terms of resolution of solubility and resist compositions of the polymer to resist solutions _{(P G)} or polymer _{(P A)} 2.5 or less is preferable, 2.3 or less is more preferable, and 2.0 or less is particularly preferable.

Examples of the method for producing the polymer (P) of the present invention include the following three methods.
The method (1): a polymer containing structural units (G) _{(P G)} and containing the structural units (A) the polymer _{(P A)} and a polymer by undergoing the reaction step a (R1) a (P) How to manufacture.
Method (2): a reaction step (R2 _GA ) of a polymer (P _G ) as a backbone polymer containing the structural unit (G) and a vinyl monomer (m _A ), and a subsequent vinyl monomer ( A method for producing a polymer (P) by passing through a polymerization step (P2 _GA ) in which a branched polymer is produced by polymerization of v).
Method (3): a reaction step (R3 _AG ) of a polymer (P _A ) as a backbone polymer containing the structural unit (A) and a vinyl monomer (m _G ), and a subsequent vinyl monomer ( A method for producing a polymer (P) by passing through a polymerization step (P3 _AG ) in which a branched polymer is produced by polymerization of v).

The production method of the polymer (P _G ) or the polymer (P _A ) will be described below.
As a method for producing the polymer (P _G ) or the polymer (P _A ), known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. Among these, solution polymerization is preferable because a polymer having a relatively low molecular weight is easily obtained.

  The solution polymerization may be batch polymerization or dropping polymerization, but dropping polymerization in which a monomer is dropped into a polymerization vessel is preferable. The monomer to be dropped may be either a monomer alone or a solution obtained by dissolving the monomer in an organic solvent.

As the dropping polymerization method, for example, an organic solvent is charged in a polymerization vessel in advance (hereinafter, this organic solvent is referred to as “charged solvent”), heated to a predetermined polymerization temperature, and then a monomer or a polymerization initiator is used alone or A method in which a solution dissolved in an organic solvent in any combination (hereinafter, this organic solvent is referred to as “dropping solvent”) is charged and dropped into the solvent.
The dropping method is not limited to this. The monomer can also be dropped without dissolving in the dropping solvent, and in that case, the polymerization initiator can be dissolved in the monomer or in the dropping solvent. Moreover, a monomer and a polymerization initiator can be dripped in the polymerization container in which the preparation solvent does not exist.
The monomer and the polymerization initiator may be dropped directly into a charged solvent heated from a separate storage tank to a predetermined polymerization temperature, or mixed immediately before dropping the monomer and the polymerization initiator, It may be dropped into the inside.
Further, a part of the monomer may be charged in advance into the polymerization vessel together with the charged solvent.

Furthermore, as a method of charging the monomer and the polymerization initiator and dropping them into the solvent, a method of dropping the monomer first and then dropping the polymerization initiator, a monomer after dropping the polymerization initiator first, Either the dropping method or the dropping method of the monomer and the polymerization initiator at the same timing may be used.
Moreover, these dropping speeds are any of a method of making a constant speed until the end of dropping, a method of changing the speed in multiple steps according to the consumption rate of the monomer and the polymerization initiator, or a method of intermittently dropping. Good.
The polymerization temperature in the drop polymerization method is preferably 50 to 150 ° C.

As an organic solvent (hereinafter referred to as “polymerization solvent”) used in the dropping polymerization method, a known solvent can be used, for example, chain ether such as diethyl ether and propylene glycol monomethyl ether, tetrahydrofuran, 1,4-dioxane and the like. Ethers such as cyclic ethers of; esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; N Amides such as N, N-dimethylacetamide and N, N-dimethylformamide; Sulfoxides such as dimethyl sulfoxide; Aromatic hydrocarbons such as benzene, toluene and xylene; Aliphatic hydrocarbons such as hexane; Cyclohexane and the like Hydrocarbons and mixtures of these solvents, such as cyclic hydrocarbons.
Among these, a hydroxyl group-containing ester such as ethyl lactate is preferable when obtaining a low molecular weight polymer.
These solvents can be used alone or in combination of two or more.

The amount of the polymerization solvent used is usually 30 to 700 parts by mass with respect to 100 parts by mass of the total amount of monomers used for the polymerization.
In the dropping polymerization method, when two or more kinds of polymerization solvents are used, the mixing ratio of the polymerization solvent in the dropping solvent and the charged solvent can be set at an arbitrary ratio.
The monomer concentration of the monomer solution dropped into the polymerization solvent is preferably 5 to 50% by mass.
The amount of the charged solvent is usually 30 to 700 parts by mass with respect to 100 parts by mass of the total amount of monomers used for the polymerization.

As the polymerization initiator, those that generate radicals efficiently by heat are preferable. As such a polymerization initiator (hereinafter referred to as “polymerization initiator A”), for example, 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2,2 Azo compounds such as' -azobis [2- (2-imidazolin-2-yl) propane]; 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, di (4-tert-butylcyclohexyl) ) Organic peroxides such as peroxydicarbonate.
Of these, DAIB is preferred from the viewpoint of the sensitivity of the resist composition when used for lithography using an ArF excimer laser (wavelength: 193 nm).

When the polymer (P _G ) or the polymer (P _A ) is used for lithography using an ArF excimer laser (wavelength: 193 nm), the light transmittance (transmittance for light with a wavelength of 193 nm) is not reduced as much as possible. In addition, it is preferable to use a polymerization initiator A having no aromatic ring in the molecular structure.
Furthermore, in consideration of safety during polymerization, the polymerization initiator A preferably has a 10-hour half-life temperature of 60 ° C. or higher.

The amount of the polymerization initiator A used is 0.3 mol part with respect to 100 mol parts of the total amount of monomers used for the polymerization in order to increase the yield of the polymer (P _G ) or the polymer (P _A ). The above is preferable, and 1 mol part or more is more preferable. The amount of the polymerization initiator A used is 30 mol parts with respect to 100 mol parts of the total amount of monomers used for the polymerization in order to narrow the molecular weight distribution of the polymer (P _G ) or the polymer (P _A ). The following is preferred.

When a polymer (P _G ) or polymer (P _A ) is used for lithography, a chain transfer agent (hereinafter referred to as “chain transfer agent A”) is used as long as it does not interfere with the storage stability of the resist composition. May be.
Examples of such chain transfer agent A include 1-butanethiol, 2-butanethiol, 1-octanethiol, 1-decanethiol, 1-tetradecanethiol, cyclohexanethiol, 2-methyl-1-propanethiol and 2 -Hydroxyethyl mercaptan.
When used for lithography applications using ArF excimer laser (wavelength: 193 nm), the chain transfer agent A does not have an aromatic ring so as not to reduce the light transmittance (transmittance for light with a wavelength of 193 nm) as much as possible. Is preferred.

The polymer solution produced by solution polymerization is diluted with a solvent for polymerization to an appropriate solution viscosity, if necessary, and then dropped into a large amount of poor solvent such as methanol, water, hexane, heptane, etc. A coalescence (P _G ) or a polymer (P _A ) can be precipitated.
The precipitation of the polymer (P _G ) or the polymer (P _A ) is very effective for removing unreacted substances such as monomers and polymerization initiators remaining in the polymer solution. If these unreacted substances remain as they are, the resist performance may be adversely affected. Therefore, when the polymer (P _G ) or the polymer (P _A ) is used for lithography, the unreacted substance is as much as possible. Is preferably removed.
The polymer (P _G ) or polymer (P _A ) precipitate can be filtered and dried as necessary to obtain a polymer (P _G ) or polymer (P _A ) powder. .
Further, after the precipitation, the solution is separated by filtration, followed by re-dissolution in a solvent and concentration of the re-dissolved solution in order to obtain a polymer (P _G ) or polymer (P _A ) solution. .
The polymer (P _G ) or polymer (P _A ) wet powder, dry powder or solution produced through part or all of the above steps is used as it is or diluted with a suitable solvent, and is used in the reaction step described below. Can be used as a raw material. At that time, additives such as a storage stabilizer may be appropriately added.

Next, method (1), which is one of the methods for producing the polymer (P) described above, will be described.
Method (1) is a method for producing a polymer (P) through a reaction step (R1) of a polymer (P _G ) and a polymer (P _A ).
Reaction step (R1)

As the state of the polymer (P _G ) or the polymer (P _A ) used in the reaction step (R1), at least one of them is preferably a polymer solution in terms of reaction efficiency. More preferably.
The reaction step (R1) can be carried out in the same manner as in a known acid-epoxy reaction method in which a glycidyl group is reacted with a carboxyl group or a carboxylic anhydride group.
The above reaction is preferably carried out in an organic solvent that can dissolve both the polymer (P _G ) and the polymer (P _A ), for example, the aforementioned polymerization solvent.
The reaction temperature is preferably 30 to 120 ° C, more preferably 40 to 100 ° C. The reaction time is more suitable for the content of at least one selected from the glycidyl group, carboxyl group and acid anhydride group contained in the polymer (P _G ) or polymer (P _A ), the type of catalyst, the reaction temperature, etc. Although the range is different, for example, it can be 0.1 to 24 hours.

In order to accelerate the thermosetting reaction between the polymer (P _G ) and the polymer (P _A ), for example, acid groups of benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, tetraethylphosphonium bromide and benzyltriphenylphosphonium chloride And a known catalyst used for the esterification reaction of an epoxy group can be added. After completion of the reaction, it is preferable to add a low molecular weight compound having a carboxylic acid or carboxylic acid anhydride to completely eliminate the unreacted epoxy group remaining in the reaction solution. In addition, in order to remove the low molecular weight compound or catalyst having excess carboxylic acid or carboxylic anhydride used for disappearance of the epoxy group, if necessary, it is diluted with a polymerization solvent to obtain an appropriate solution viscosity. Thereafter, the polymer (P) can be precipitated by dropping into a large amount of poor solvent such as methanol, water, hexane, heptane or the like.
The polymer (P) precipitate can be obtained as a polymer (P) powder by filtering and drying, if necessary.
Further, after the precipitation, the solution can be separated by filtration, and subsequently redissolved in a solvent, and the redissolved solution is sequentially concentrated to obtain a polymer (P) solution.
The wet powder, dry powder or solution of the polymer (P) produced through part or all of the above steps can be used as it is or diluted with a suitable solvent as a raw material for the reaction step described later. At that time, additives such as a storage stabilizer may be appropriately added.

Through the reaction step (R1), at least one selected from a glycidyl group contained in the polymer (P _G ) and a carboxyl group and an acid anhydride group contained in the polymer (P _A ) is an acid-epoxy. Crosslinking is carried out by reaction to produce a polymer (P) containing the structural unit of the formula (1).

  In terms of the defect of the resist composition for semiconductors using the polymer (P) thus produced, the line edge roughness of the resist, or the pigment dispersibility and developability of the resist composition for color filters, the following ( In the case where at least one selected from (a) and (b) is reacted with at least one selected from the following (c) to (c), the mass average molecular weights of (c) to (c) are (a) and It is preferable that it is smaller than the mass average molecular weight of (b).

(A) A polymer (P _G ) produced by polymerizing a monomer containing a vinyl monomer (m _G ) that gives a structural unit having a glycidyl group (hereinafter referred to as “polymer (P _G -m)”) Called)
(Ii) polymer is a polyester resin having a glycidyl group other than molecular end _(P G) (hereinafter referred to as "polymer _(P G -Eb)")
(C) _A polymer (P _A ) produced by polymerizing a monomer containing a polymerization initiator (i _ac ) having at least one selected from a carboxyl group and an acid anhydride group (hereinafter referred to as “polymer ( P _A -i) "hereinafter)
(D) a polymer (P _A ) produced by polymerizing a monomer containing a chain transfer agent (c _ac ) having at least one selected from a carboxyl group and an acid anhydride group (hereinafter referred to as “polymer ( P _A -c) ")
(E) _A polymer (P _A ) produced by adding a polymerization terminator (t _ac ) having at least one selected from a carboxyl group and an acid anhydride group during polymerization of the monomer (hereinafter referred to as “ Polymer (P _A -t) ”)
(F) _A polymer (P _A ) which is a polyester resin having at least one selected from a carboxyl group and an acid anhydride group at the molecular terminal (hereinafter referred to as a polymer “(P _A -Ee)”)
(G) _A polymer (P _A ) produced by polymerizing a monomer containing a vinyl monomer (m _A ) that gives a structural unit having at least one selected from a carboxyl group and an acid anhydride group (hereinafter referred to as “P _A” ) referred to as "polymer _(P A -m)")
(H) _A polymer (P _A ) which is a polyester resin having at least one selected from a carboxyl group and an acid anhydride group in addition to the molecular end (hereinafter referred to as polymer “(P _A -Eb)”)

Further, in the case of reacting at least one selected from at least one and following selected from the above polymer _(P A -m) and the polymer _(P A -Eb) (Re) - (e) are (Li) - weight average molecular weight of polymer (e) _(P a -m) and is preferably smaller than the weight average molecular weight of the polymer _(P a -Eb).

(I) a polymerization initiator having a glycidyl group _{(i ac)} prepared by polymerizing a monomer containing the polymer _(P G) (hereinafter referred to as "polymer _(P G -i)")
(Nu) Polymer (P _G ) produced by polymerizing a monomer containing a chain transfer agent (c _ac ) having a glycidyl group (hereinafter referred to as “polymer (P _G -c)”)
(L) A polymer (P _G ) produced by adding a polymerization terminator (t _ac ) having a glycidyl group during the polymerization of the monomer (hereinafter referred to as “polymer (P _G -t)”)
(E) polymer is a polyester resin having a glycidyl group at the molecular end _(P G) (hereinafter referred to as "polymer _(P G -ee)")
In addition, in terms of defects in the resist composition for semiconductors using the polymer (P) thus produced and the line edge roughness of the resist, the polymer (P _G -m) and the polymer (P _G- at least one and a polymer selected from the eb) _(P a -i), the polymer _(P a -c), the polymer _(P a -t), the polymer _(P a -Ee), the polymer _{(P a (in} case of reacting at least one selected from P a -Eb), the latter (polymer _(P a -i) -m) and the polymer, the polymer _(P a -c), the polymer (P _a -t), the polymer _(P a -Ee), the polymer _(P a -m) and the polymer _(P a -Eb)) of the polymer with the structural unit having an acid-eliminable groups contained (B ) And at least one copolymer composition ratio selected from the structural unit (C) having a hydrophilic group is the former (heavy Combined _(P G -m) and polymer _(P G -Eb) structural units) (B) and greater than at least one copolymer composition ratio selected from the structural unit (C) it is preferable.

Further, the polymer _(P A -m) and the polymer _(P A -Eb) of at least one and polymer selected _(P G -i), the polymer _(P G -c), the polymer _{(P G} - _(in case of reacting at least one selected from P G -ee), the latter (polymer _(P G -i) t) and the polymer, the polymer _(P G -c), the polymer _{(P G} -t), the polymer _(P G -ee) at least one selected from the structural units (B) and the structural unit (C)) is the former (polymer _(P a -m) and the polymer _(P a -Eb )) Is preferably larger than at least one copolymer composition ratio selected from the structural unit (B) and the structural unit (C).

Moreover, in this way in terms of pigment dispersibility and developability of the resist composition for a color filter using the produced polymer (P), the polymer (P G _-m) and polymer (P _G - at least one and a polymer selected from the eb) _(P a -i), the polymer _(P a -c), the polymer _(P a -t), the polymer _(P a -Ee), the polymer _{(P a} -m) and polymer _(P a -Eb) is allowed are preferably reacting at least one selected from.
Among them, at least one selected from the polymer _(P G -m) and the polymer of at least one and a polymer selected from _{(P G -Eb) (P A} -m) and the polymer _(P A -Eb) It is more preferable to react.

Next, method (2), which is one of the methods for producing the polymer (P) described above, will be described.
The method of polymerization by the branch polymer (2) the polymer as a trunk polymer (P _G) and the vinyl monomer (m _A) and reaction steps (R2 _GA) and subsequent vinyl monomer (v) This is a method for producing a polymer (P) through a polymerization step (P2 _GA ) to be generated.
Reaction process (R2 _GA )

The state of the polymer (P _G ) used for the reaction is preferably a polymer solution in terms of reaction efficiency.
The reaction in the reaction step (R2 _GA ) between the polymer (P _G ) and the vinyl monomer (m _A ) is the case of the reaction step (R 1) between the polymer (P _G ) and the polymer (P _A ). Can be handled in the same way.
By performing the above reaction, by an acid-epoxy reaction between at least one selected from a glycidyl group contained in the polymer (P _G ) and a carboxyl group and an acid anhydride group contained in the vinyl monomer (m _A ). _A reactive polymer (RP2 _GA ) containing a structural unit of the formula (2) and having an ethylenic double bond derived from a vinyl monomer (m _A ) is produced.

The solution of the reactive polymer (RP2 _GA ) produced through the reaction step (R2 _GA ) is diluted with a polymerization solvent to obtain an appropriate solution viscosity, and then a large amount of poor polymer such as methanol, water, hexane, heptane, etc. The reactive polymer (RP2 _GA ) can be precipitated by dropping into a solvent.
The polymer precipitate can be filtered and dried as necessary to obtain a powder of a reactive polymer (RP2 _GA ).
Further, after the precipitation, the solution is separated by filtration, followed by re-dissolution in a solvent and concentration of the re-dissolved solution in order to obtain a solution of the reactive polymer (RP2 _GA ).
The reactive polymer (RP2 _GA ) wet powder, dry powder or solution produced through part or all of the above steps can be used as it is or diluted with an appropriate solvent as a raw material for the reaction step described later. At that time, additives such as a storage stabilizer may be appropriately added.
Polymerization process (P2 _GA )
Vinyl monomer (v)

  Examples of the vinyl monomer (v) include the aforementioned monomer (a), monomer (b), monomer (c), monomer (d), monomer (e1) and monomer. And a monomer (e2).

As a polymerization method of the reactive polymer (RP2 _GA ) produced through the reaction step (R2 _GA ) and the vinyl monomer (v), known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization are used. A polymerization method is mentioned.
Among these, solution polymerization is preferable in that the molecular weight of the branched polymer produced from the ethylenic double bond contained in the reactive polymer (RP2 _GA ) can be reduced. The solution polymerization may be batch polymerization or dropping polymerization.
Among these, drop polymerization in which at least the vinyl monomer (v) is dropped into the polymerization vessel is preferable. The monomer to be dropped may be either a monomer alone or a solution obtained by dissolving the monomer in an organic solvent.
Further, the reactive polymer (RP2 _GA ) may be dropped into the polymerization vessel in the same manner as the vinyl monomer (v), or may be charged into the polymerization vessel in advance.

In the dropping polymerization, the same dropping method, polymerization temperature, kind and amount of organic solvent, kind and amount of polymerization initiator as those used for producing the polymer (P _G ) or polymer (P _A ), and the chain transfer agent Can be implemented by type and amount used.
Moreover, the precipitation method of the obtained polymer (P), various treatment methods including filtration and drying of the precipitate, the handling method of the wet powder, dry powder or solution of the polymer (P), and various additives at that time The addition of can be handled in the same manner as in the case of the polymer (P _G ) or the polymer (P _A ).

Further, the weight average molecular weight of the branched polymer bonded to the reactive polymer (RP2 _GA ) is determined by the resist composition defect for semiconductor, the line edge roughness of the resist, and the pigment dispersibility of the resist composition for color filter. And in terms of developability, it is preferably smaller than the mass average molecular weight of the reactive polymer (RP2 _GA ).
When the polymer (P) of the present invention is used as a polymer for a resist for a semiconductor, the structural unit (B) and the structural unit contained in the branched polymer bonded to the reactive polymer (RP2 _GA ) At least one copolymer composition ratio selected from the unit (C) is the structural unit (B) and the structural unit contained in the reactive polymer (RP2 _GA ) in terms of the defect of the resist composition and the line edge roughness of the resist. It is preferably larger than at least one copolymer composition ratio selected from (C).
Further, when the polymer (P) of the present invention is used as a polymer for a color filter resist, the structural unit (C) contained in the branch polymer bonded to the reactive polymer (RP2 _GA ). The copolymer composition ratio is preferably larger than the copolymer composition ratio of the structural unit (C) contained in the reactive polymer (RP2 _GA ) in terms of pigment dispersibility and developability of the resist composition.

Next, the method (3), which is one of the methods for producing the polymer (P) described above, will be described.
In the method (3), a branched polymer is obtained by a reaction step (R3 _AG ) of a polymer (P _A ) as a backbone polymer with a vinyl monomer (m _G ) and subsequent polymerization of the vinyl monomer (v). This is a method for producing a polymer (P) through a polymerization step (P3 _AG ) to be generated.
Reaction process (R3 _AG )

The state of the polymer (P _A ) used for the reaction is preferably a polymer solution in terms of reaction efficiency.
The reaction in the reaction step (R3 _AG ) between the polymer (P _A ) and the vinyl monomer (m _G ) is the reaction step (R2 _GA ) between the polymer (P _G ) and the vinyl monomer (m _A ). ).
By performing the above reaction, by an acid-epoxy reaction between at least one selected from a carboxyl group and an acid anhydride group contained in the polymer (P _A ) and a glycidyl group contained in the vinyl monomer (m _G ). A reactive polymer (RP3 _AG ) containing a structural unit of the formula (2) and having an ethylenic double bond derived from a vinyl monomer (m _G ) is produced.

A solution of the reactive polymer (RP3 _AG ) produced through the reaction step (R3 _AG ) is diluted with a polymerization solvent to obtain an appropriate solution viscosity, and then a large amount of poor solvent such as methanol, water, hexane, heptane, etc. The reactive polymer (RP3 _AG ) can be precipitated by dropping into the inside.
The polymer precipitate can be obtained as a reactive polymer (RP3 _AG ) powder by filtering and drying as necessary.
Further, after the precipitation, the solution is separated by filtration, and subsequently, the solution of the reactive polymer (RP3 _AG ) can be obtained by sequentially redissolving in a solvent and concentrating the redissolved solution.
The reactive polymer (RP3 _AG ) wet powder, dry powder or solution produced through part or all of the above steps can be used as it is or diluted with a suitable solvent as a raw material for the reaction step described later. At that time, additives such as a storage stabilizer may be appropriately added.
Polymerization process (P3 _AG )

The polymerization in the polymerization step (P3 _AG ) can be handled in the same manner as in the polymerization step (P2 _GA ).
Moreover, the precipitation method of the obtained polymer (P), various treatment methods including filtration and drying of the precipitate, the handling method of the wet powder, dry powder or solution of the polymer (P), and various additives at that time Can be handled in the same manner as in the case of the polymer (P _G ) or the polymer (P _A ).

Further, the weight average molecular weight of the branched polymer bonded to the reactive polymer (RP3 _AG ) is determined by the resist composition defect, the resist line edge roughness, and the pigment dispersibility and developability of the color filter resist composition. In this respect, it is preferable that the mass average molecular weight of the reactive polymer (RP3 _AG ) is smaller.
When the polymer (P) of the present invention is used as a polymer for a semiconductor resist, the structural unit (B) and the structural unit (B) contained in the branched polymer bonded to the reactive polymer (RP3 _AG ) ( At least one copolymer composition ratio selected from (C) is the structural unit (B) and the structural unit (C) contained in the reactive polymer (RP3 _AG ) in terms of the defect of the resist composition and the line edge roughness of the resist. It is preferable that it is larger than at least one copolymer composition ratio selected from.
Further, when the polymer (P) of the present invention is used as a polymer for a color filter resist, the structural unit (C) contained in the branch polymer bonded to the reactive polymer (RP3 _AG ). The copolymer composition ratio is preferably larger than the copolymer composition ratio of the structural unit (C) contained in the reactive polymer (RP3 _AG ) in terms of pigment dispersibility and developability of the resist composition.
Resist composition

The resist composition of the present invention contains a polymer (P).
The resist composition of the present invention can be prepared by dissolving the polymer (P) in a solvent. Moreover, this polymer solution can also be used for preparation of a resist composition as it is, without isolate | separating a polymer from the polymer solution obtained by solution polymerization etc. Further, the polymer solution can be diluted with an appropriate solvent or concentrated to be used for preparing a resist composition.
In addition, after dropping the polymer (P) solution into a poor solvent and precipitating the polymer (P) to separate the polymer, the resist composition is prepared as a wet powder without drying. Can also be used. Furthermore, after the polymer powder is dissolved in a suitable solvent, the concentrated polymer solution can be used for the preparation of a resist composition.

Examples of the solvent include linear or branched ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone and 2-hexanone; cyclic ketones such as cyclopentanone and cyclohexanone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl Propylene glycol monoalkyl ether acetates such as ether acetate; Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl such as propylene glycol monomethyl ether and propylene glycol monoethyl ether Ethers; ethylene glycol monomethyl ether, ethylene glycol Ethylene glycol monoalkyl ethers such as ethyl ether; diethylene glycol alkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol monomethyl ether; esters such as ethyl acetate and ethyl lactate; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol, Alcohols such as 1-octanol; pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dibutylbutane, 2,3-dibutylbutane, n-heptane, n-octane, isooctane, 2,2 , 3-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n-decane, n-dodecane, etc., aliphatic hydrocarbon solvents having 5 to 11 carbon atoms; 1,4-dioxane, ethyl carbonate Emissions and γ- butyrolactone.
These solvents can be used alone or in combination of two or more.
Among these, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone and γ-butyrolactone are preferable from the viewpoint of safety.

The content of the polymer (P) in the resist composition is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less in terms of the viscosity of the resist composition. In addition, the content of the polymer (P) is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more in terms of the resist film thickness.
Chemically amplified resist composition

When the resist composition of the present invention is a chemically amplified resist composition, the resist composition further contains a photoacid generator.

Photoacid generator

The photoacid generator can be arbitrarily selected from those that can be used as an acid generator of a chemically amplified resist composition.

Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonate ester compounds, quinonediazide compounds, and diazomethane compounds.
Of these, onium salt compounds such as sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts and the like are preferable.
Specific examples include triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate. , Diphenyliodonium hexafluoroantimonate, p-methylphenyldiphenylsulfonium nonafluorobutanesulfonate, and tri (tert-butylphenyl) sulfonium trifluoromethanesulfonate.

The photoacid generator can be used alone or in combination of two or more.
Although content of a photo-acid generator is suitably determined by the kind of photo-acid generator, 0.1 mass part or more is preferable with respect to 100 mass parts of polymers (P), and 0.5 mass part or more is more preferable. By setting the content of the photoacid generator within this range, a chemical reaction due to the catalytic action of the acid generated by exposure can be sufficiently caused.
Moreover, 20 mass parts or less are preferable with respect to 100 mass parts of polymers (P), and, as for content of a photo-acid generator, 10 mass parts or less are more preferable. By making the content of the photoacid generator within this range, the stability of the resist composition is improved, and the occurrence of uneven coating during application of the resist composition and scum during development of the resist composition is reduced. .

  The resist composition of the present invention may further contain a nitrogen-containing compound. By containing the nitrogen-containing compound, the resist pattern shape, the stability over time, and the like are improved. That is, the cross-sectional shape of the resist pattern becomes closer to a rectangle, and when the resist film is exposed, post-exposure baked (PEB), and left for the next development process, the cross-sectional shape of the pattern is deteriorated. Is more suppressed.

Known compounds can be used as the nitrogen-containing compound, but amines are preferable, and secondary lower aliphatic amines and tertiary lower aliphatic amines are more preferable.
Here, the “lower aliphatic amine” refers to an alkyl or alkyl alcohol amine having 5 or less carbon atoms.
Examples of the secondary lower aliphatic amine and tertiary lower aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine and triethanolamine. Can be mentioned. Of these, tertiary alkanolamines such as triethanolamine are more preferred.

The nitrogen-containing compounds can be used alone or in combination of two or more.
Although content of a nitrogen-containing compound is suitably determined by the kind etc. of nitrogen-containing compound, 0.01 mass part or more is preferable with respect to 100 mass parts of polymers (P). By setting the content of the nitrogen-containing compound within this range, the resist pattern can be made more rectangular.
Further, the content of the nitrogen-containing compound is preferably 2 parts by mass or less with respect to 100 parts by mass of the polymer (P). By setting the content of the nitrogen-containing compound within this range, it is possible to reduce the sensitivity deterioration of the resist composition.

The resist composition of the present invention can further contain an organic carboxylic acid, a phosphorus oxo acid or a derivative thereof. By containing these compounds, the sensitivity deterioration of the resist composition due to the blending of the nitrogen-containing compound can be prevented, and the resist pattern shape and the stability over time are further improved.
As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid and salicylic acid are preferable.
Examples of phosphorus oxo acids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and the like; and phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- Examples thereof include phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester, and ester derivatives thereof; phosphinic acids such as phosphinic acid and phenylphosphinic acid, and ester derivatives thereof. Of these, phosphonic acid is preferred.
The organic carboxylic acid or phosphorus oxo acid or derivative thereof can be used alone or in combination of two or more.

The content of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is appropriately determined depending on the type of the compound, but is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polymer (P). By setting the content of the organic carboxylic acid or phosphorus oxo acid or derivative thereof within this range, the resist pattern can be made more rectangular.
The content of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer (P). By reducing the content of the organic carboxylic acid or phosphorus oxo acid or derivative thereof within this range, the film loss of the resist pattern can be reduced.

  The chemically amplified resist composition of the present invention may contain both a nitrogen-containing compound and an organic carboxylic acid or phosphorus oxo acid or derivative thereof.

Furthermore, the resist composition of the present invention may contain various additives such as surfactants, other quenchers, sensitizers, antihalation agents, storage stabilizers, and antifoaming agents as necessary. it can. Any of these additives can be used as long as it is known in the art. Moreover, what is necessary is just to determine the compounding quantity of these additives suitably.

Resist composition for color filter

The resist composition for a color filter of the present invention contains a photopolymerizable monomer (x) and a photopolymerization initiator (I) in the resist composition.

Photopolymerizable monomer (x)

  The photopolymerizable monomer (x) of the present invention is a component for radically polymerizing by exposure to ultraviolet rays and reducing the solubility of the exposed portion in the developer.

Examples of the photopolymerizable monomer (x) include mono- or poly (meth) acrylates of mono- or polyhydric alcohols.
Specifically, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cresol ethoxy (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, isobornyl Mono (meth) acrylates of monohydric alcohols such as (meth) acrylate; 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 2 2-bis [4- (meth) acryloyloxyethoxyethylphenyl] propane, 2,2-bis [4- (meth) acryloyloxypropyloxypropylphenyl] propane, hydroxypivalate neopentyl glycol di (meth) acrylate, glycerin Di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri Methylolpropane tris [ethoxy (meth) acrylate], trimethylolpropane tris [diethoxy (meth) acrylate], trimethylolpropane tris [triethoxy (meth) acrylate N, N '-[di (meth) acryloyloxyethyl] -N "-hydroxyethyl isocyanurate, N, N', N"-[tri (meth) acryloyloxyethyl] -isocyanurate, pentaerythritol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. And poly (meth) acrylate of a monohydric alcohol.

  Further, as the photopolymerizable monomer (x) other than the above (meth) acrylate, for example, polybasic acids such as phthalic acid and adipic acid, and polybasic acids such as ethylene glycol, hexanediol, polyethylene glycol and polytetramethylene glycol Polyester poly (meth) acrylates obtained by reaction of a monohydric alcohol with (meth) acrylic acid or a derivative thereof; (meth) acrylic acid or a derivative thereof with a glycidyl ether compound such as bisphenol A diglycidyl ether or ethylene glycol diglycidyl ether Poly (meth) acrylates reacted with: hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane dii Urethane poly (meth) obtained by reacting isocyanate compounds such as cyanate with (meth) acrylates having hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Acrylates: (Meth) acrylamides such as N-methoxymethyl (meth) acrylamide, N-ethoxymethylacrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and methylenebis (meth) acrylamide It is done.

These photopolymerizable monomers (x) can be used alone or in combination of two or more.
Of these, compounds having three or more (meth) acryloyl groups in the molecule such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like are preferable in terms of the sensitivity of the resist composition.

The compounding amount of the photopolymerizable monomer (x) is 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymer (P), the photopolymerizable monomer (x) and the photopolymerization initiator (I). Is preferred. If the photopolymerizable monomer (x) is 10 parts by mass or more, sufficient sensitivity of the resist composition tends to be obtained, and if it is 50 parts by mass or less, the developability of the resist composition does not tend to decrease.

Photopolymerization initiator (I)

  Known photopolymerization initiators (I) are used. Specific examples include thioxanthones such as benzophenone, 4,4-bis (diethylamino) benzophenone, t-butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one Acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin iso Benzoin ethers such as tilether; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; Methylbenzoylformate 1,7-bisacridinyl heptane and 9-phenylacridine. The photopolymerization initiator (I) can be used alone or in combination of two or more.

  The blending amount of the photopolymerization initiator (I) is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymer (P), the photopolymerizable monomer (x) and the photopolymerization initiator (I). . The photosensitivity of the photosensitive resin obtained when the photopolymerization initiator (I) is 1 part by mass or more tends to be satisfied, and the developability of the photosensitive resin tends not to decrease when it is 20 parts by mass or less.

  The resist composition for a color filter of the present invention contains a known photosensitizer such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, etc. Can be added.

  The following pigments can be further added as colorants to the resist composition for color filters of the present invention. Examples include azo, anthraquinone, xanthene, quinacridone, indigo, dioxazine, indanthrone, and isoindolinone pigments. Specifically, phthalocyanine blue (CI pigment blue 15: 6 or CI pigment blue 15: 3), phthalocyanine green (CI pigment green 7, 36 or 37), perylene pigment (C Pigment Red 155), anthraquinone pigments (CI Pigment Red 177), and the like. In addition, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 154, C.I. I. And CI Pigment Violet 23.

  As for content of a pigment, 10-100 mass parts is preferable with respect to 100 mass parts of total amounts of a polymer (P), a photopolymerizable monomer (x), and a photoinitiator (I). When the amount of the pigment added is 10 parts by mass or more, the color density of the image when using a color filter tends not to decrease, and when it is 100 parts by mass or less, the photosensitivity of the resist composition does not tend to decrease.

In order to disperse the pigment in the resist composition solution for the color filter, a dispersant can be used as necessary.
Examples of the dispersant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, oxyethylene-oxypropylene block copolymer, sorbitan fatty acid ester, glycerin fatty acid ester and the like. Nonionic surfactants; phthalocyanine derivatives, organosiloxane polymers, and poly (meth) acrylic acid copolymers.

The viscosity of the resist composition for a color filter of the present invention can be adjusted with an organic solvent so that it can be easily applied to a substrate such as glass.
Examples of the organic solvent include dioxane, butyl acetate, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, carbitol, cyclohexanone, carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate and β-methoxyisobutyric acid methyl ester.
Among these, those having an appropriate drying rate at the time of application of the resist composition and evaporating to form a uniform and smooth coating film are preferable, and those having a boiling point of 100 to 200 ° C. are preferable.
The organic solvent can be used alone or in combination of two or more. Moreover, the addition amount of the organic solvent is preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the polymer (P), the photopolymerizable monomer (x) and the photopolymerization initiator (I).

Various additives such as a thermal polymerization inhibitor, a flame retardant, a leveling agent, a silane coupling agent, a plasticizer, and a filler can be further added to the resist composition for the color filter as necessary.

substrate

In the present invention, a substrate on which a pattern is formed includes a step of forming a resist film on a substrate to be processed using the resist composition of the present invention, a step of exposing the resist film with light having a wavelength of 450 nm or less, a resist And a step of developing the film using a developer.
Hereinafter, an example of a method for manufacturing a substrate on which a pattern is formed will be described.
First, a resist composition is applied by spin coating or the like to the surface of a substrate to be processed such as a silicon wafer on which a pattern is to be formed. Next, the substrate to be processed coated with the resist composition is dried by baking (pre-baking) or the like to obtain a resist film on the substrate.
Thereafter, the resist film is exposed (irradiated with radiation) through a photomask. As radiation used for exposure, light having a wavelength of 450 nm or less is used, and ultraviolet rays such as i-line and g-line, KrF excimer laser, ArF excimer laser, or F ₂ excimer laser are preferable. In the case of a resist composition for semiconductor production, an ArF excimer laser is preferred.
In addition, a high refractive index liquid such as pure water, perfluoro-2-butyltetrahydrofuran or perfluorotrialkylamine was interposed between the resist composition coating film and the final lens of the exposure apparatus during exposure. Immersion exposure that exposes in a state can be performed. Moreover, you may expose with an electron beam.

After exposure, heat treatment (post-exposure baking (PEB)) is performed, the substrate is immersed in an alkaline developer, and the exposed portion is dissolved and removed with the developer (development). Known alkali developers can be used.
After development, the substrate is rinsed with pure water or the like to obtain a resist pattern on the substrate to be processed.
The substrate to be processed on which the resist pattern is formed is reinforced by heat treatment (post-bake). Thereafter, the resist-free portion on the substrate is selectively etched. After the etching, the resist is removed with a release agent to obtain a substrate on which a pattern is formed.

Color filter

In the present invention, the color filter on which the pattern is formed includes a step of forming a resist film on a substrate to be processed using the resist composition of the present invention, a step of exposing the resist film with light having a wavelength of 450 nm or less, And a step of developing the resist film using a developer.
For example, in order to form a color filter having a pattern formed using a resist composition for a color filter, first, a resist composition is applied to a substrate to be processed, and then a solvent is evaporated and dried to obtain a resist film. Thereafter, exposure is performed through a photomask to form a pattern, and then an unexposed portion is developed and removed with an alkaline aqueous solution.

  A transparent substrate such as glass or quartz is used as a substrate to be used for manufacturing a color filter.

  Examples of the method for coating the color filter resist composition on the transparent substrate include known methods such as spray coating, roll coating, blade coating, screen printing, curtain coating, and spin coating. In that case, it is preferable to apply | coat so that the dry film thickness of a coating film may be set to 0.5-10micrometer, A circulation type oven, an infrared heater, a hot plate, etc. are used for drying of a coating film.

  The conditions for volatilizing and drying the solvent in the coating film differ depending on the solvent contained in the resist composition, but are 50 to 120 in terms of preventing the thermal polymerization by heating during drying and efficiently evaporating the solvent. It is preferable to heat at 30 ° C. for 30 seconds to 30 minutes.

  Examples of the exposure method for forming the pattern include an ultraviolet exposure method using a photomask and a scanning exposure method using laser light.

A desired pattern can be obtained by dissolving and removing the unexposed portion, and examples of the developer used at that time include an alkaline aqueous solution. For example, an inorganic alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium metasilicate, potassium metasilicate, sodium orthosilicate, potassium orthosilicate, Organic alkali aqueous solution, such as ammonia and tetramethylammonium hydroxide, is mentioned.
In these, it is preferable to use the inorganic alkaline aqueous solution whose density | concentration is 0.001-2 mass%. When the density is 0.001% by mass or more, the development time does not become too long, or the development tends to be sufficiently performed. Further, when a developing solution having a concentration of 2% by mass or less is used, alkali metal ions hardly remain in the cured pattern, and there is little fear of shortening the life of a liquid crystal display device using the same.
Various surfactants, dispersants, antifoaming agents, organic solvents, and the like can be added to the alkaline developer in order to impart dispersibility and defoaming properties of the development object in the developer.
Further, as a developing method for a resist formed using a resist composition for a color filter, a spray method is the most common, but a part of it can be replaced by a dipping method depending on circumstances.

  In order to impart heat resistance to the resist pattern for color filter obtained by development, it is preferable to carry out post-cure (post-curing) by thermal polymerization, and post-cure at about 130 to 250 ° C. for about 10 to 60 minutes. It is preferable to implement.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Further, “parts” and “%” in each Example and Comparative Example represent “parts by mass” and “% by mass”, respectively, unless otherwise specified.
Moreover, the polymer and the resist composition were evaluated by the following methods.

1. Evaluation of polymer <content of each constituent unit of polymer>
When the content of each structural unit of the polymer can be determined by ¹ H-NMR measurement, it was determined by ¹ H-NMR measurement. Moreover, when it cannot obtain | require by ¹ H-NMR measurement by the overlap of a proton peak etc., it calculated | required by ¹³ C-NMR measurement.
GSX-400 type FT-NMR (trade name) manufactured by JEOL Ltd. was used for ¹ H-NMR measurement. About 5% of the polymer sample solution (deuterated chloroform solution or deuterated dimethyl sulfoxide solution) was put in a test tube having a diameter of 5 mmφ, and the measurement was carried out with an observation frequency of 400 MHz and a single pulse mode with 64 integrations. . The measurement temperature was 40 ° C. when deuterated chloroform was used as the solvent, and 60 ° C. when deuterated dimethyl sulfoxide was used as the solvent.
^{For 13} C-NMR measurement, UNITY-INOVA FT-NMR (trade name) manufactured by Varian Technologies, Inc. was used. About 20% by mass of a polymer sample in a deuterated dimethyl sulfoxide solution was put into a test tube having a diameter of 5 mmφ, and the proton complete decoupling method in which the measurement temperature was 60 ° C., the observation frequency was 125 MHz, and the nuclear overhauser effect (NOE) was removed. The measurement was carried out at a total of 50,000 times.

<Mass average molecular weight and molecular weight distribution>
About 20 mg of the polymer was dissolved in 5 ml of tetrahydrofuran (hereinafter referred to as “THF”) and filtered through a 0.5 μm membrane filter to prepare a sample solution. The mass average molecular weight and molecular weight distribution of this sample solution were measured by using gel permeation chromatography (GPC) manufactured by Tosoh Corporation.
In addition, the separation column used the Showa Denko Co., Ltd. product and three Shodex GPC K-805L (brand name) in series. In the measurement, THF was used as a solvent, and a differential refractometer was used as a detector. The measurement was performed at a flow rate of 1.0 ml / min, a measurement temperature of 40 ° C., and an injection amount of 0.1 ml, and polystyrene was used as a standard polymer.

<Metal content>
Content of the following metal in a polymer was measured.
Measurement metals: Na (sodium), Mg (magnesium), Al (aluminum), K (potassium), Ca (calcium), Cr (chromium), Mn (manganese), Fe (iron), Ni (nickel), Cu ( Copper), Zn (zinc), Sn (tin), Pb (lead), Co (cobalt), Li (lithium)
As a measuring device, Agilent 7500CS type ICP-MS (trade name) manufactured by Glass Expansion Co., Ltd. and Micromist AR80-1-FM04 (trade name) equipped as a nebulizer was used.
As a measurement sample, a 5% polymer solution was prepared by dissolving a polymer in non-boiling distilled electronic industry grade N-methylpyrodon (hereinafter referred to as “NMP”).
The above non-boiling distillation NMP is obtained by introducing a crude electronic industry grade NMP into a non-boiling batch type transparent quartz acid distillation apparatus (manufactured by Fujiwara Seisakusho, SHF-special type (trade name)). It was obtained by adjusting the heater output so that the speed was about 1 drop / 10 seconds.
It should be noted that the difference in the metal ion count between the non-boiling distilled solvent with a low metal level (blank) and the tuning solution with a metal concentration of 1 ppb is more than several tens of times. Was tuned to be less than one digit count, and the metal content of the sample was measured by the standard addition method.

As the standard metal, XSTC-622 (trade name) manufactured by SPEX was used, and XSTC-622 was diluted with non-boiling distilled NMP so as to be 100 ppb of each metal. The calibration curve was prepared by a linear regression line passing through the blank value at four points of blank, 200 ppt, 500 ppt, and 1,000 ppt.
In the measurement of the metal content in non-boiling distilled NMP, XSTC-622 was diluted with another non-boiling distilled NMP whose metal content had already been measured so that each metal had 10 ppb. A calibration curve was prepared by a linear regression line passing through the blank value at four points of blank, 20 ppt, 50 ppt, and 100 ppt.
The operations of non-boiling distillation, sample preparation, and metal content measurement were all carried out in a class 1,000 clean room.
The metal content of the above non-boiling distilled NMP was such that the metal and metalloid levels for all elements were less than 10 ppt.

2. Evaluation of Resist Composition for Semiconductor <Preparation of Resist Composition for Semiconductor>
100 parts of the polymer in terms of solid content and 2 parts of triphenylsulfonium triflate as a photoacid generator are mixed with propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) so that the polymer concentration becomes 12.5%. ) To obtain a uniform solution. Thereafter, this solution was filtered through a membrane filter having a pore diameter of 0.1 μm to prepare a resist composition solution.

<Creation of resist pattern>
The prepared resist composition solution was spin-coated on a silicon wafer and prebaked at 120 ° C. for 60 seconds using a hot plate to produce a resist film having a thickness of 0.3 μm. Next, after exposure using an ArF excimer laser exposure machine (wavelength: 193 nm), post-exposure baking was performed at 120 ° C. for 60 seconds using a hot plate. Next, development was performed at room temperature using a 2.38% tetramethylammonium hydroxide aqueous solution, washed with pure water, and dried to form a resist pattern.

<Sensitivity>
The exposure amount (mJ / cm ² ) at which a 0.16 μm line-and-space pattern mask was transferred to a line width of 0.16 μm was measured as sensitivity.

<Resolution>
The minimum dimension (μm) of the resist pattern resolved when exposed with the above exposure amount was defined as the resolution.

<Defect amount>
With respect to the resist pattern obtained above, the number of development defects was measured using a surface defect observation apparatus KLA2132 manufactured by KLA Tencor Co., Ltd., and used as a defect amount.

<Line edge roughness>
JSM-6340F type field emission type manufactured by JEOL Ltd. with respect to the range of 5 μm on the side edge in the longitudinal direction of the 0.16 μm resist pattern obtained by the minimum exposure that reproduces the 0.16 μm resist pattern on the mask Using a scanning electron microscope (trade name), measure the distance from the reference line where the pattern side edge should be to the actual pattern side edge at 50 points, calculate the standard deviation, calculate 3σ, and calculate the resist line edge roughness It was used as an index. A smaller value indicates better performance.

3. Evaluation of resist composition for color filter <Preparation of resist composition for color filter>
(Red resist composition)
46 parts of polymer in terms of solid content, 31 parts of trimethylolpropane triacrylate as photopolymerizable monomer (x), 8 parts of pentaerythritol triacrylate, 2-benzyl-2 as photopolymerization initiator (I) -12 parts of dimethylamino-1- (4-morpholinophenyl) -butanone-1-one, 3 parts of isopropylthioxanthone and 50 parts of Pigment Red 177 as a pigment component were mixed. Next, PGMEA was added so that the solid content concentration would be 13%, and the dispersion was stabilized using a ball mill to obtain a red resist composition.

(Green resist composition)
A green resist composition was obtained in the same manner as the red resist composition except that 43 parts of Pigment Green 36 and 7 parts of Pigment Yellow 83 were mixed as pigment components.
(Blue resist composition)
A blue resist composition was obtained in the same manner as the red resist composition except that 47 parts of Pigment Blue 15: 3 and 3 parts of Pigment Violet 23 were mixed as pigment components.

<Pigment dispersibility>
The average particle size of the resist composition was measured using FPAR-1000 (product name) manufactured by Otsuka Electronics Co., Ltd. and used as an index of pigment dispersibility. The measurement temperature was 25 ° C., the measurement time was 120 seconds, the analysis method was the Marquad method, and the average value of three measurements was the average particle diameter. The smaller the average particle size, the better the pigment dispersibility.

<Creation of resist pattern>
The above-described resist composition for each color of RGB was spin-coated on a transparent glass substrate so as to have a dry film thickness of 1.5 μm, and then dried on a hot plate at 70 ° C. for 5 minutes. Ultraviolet light of 11 mW / cm ² was irradiated with an ultrahigh pressure mercury lamp (manufactured by Kyowa Riken, mask aligner K-307PS95 (trade name)) through a photomask having a line / space of 5 μm / 5 μm, 27 ° C., 0. Using a 04% aqueous potassium hydroxide solution, spray development was performed for 60 seconds, followed by washing with pure water, followed by post-cure for 30 minutes in a circulation oven at 220 ° C. to obtain a patterned resist.

<Developability>
In the production of the resist pattern, when developing with an aqueous potassium hydroxide solution, the time required until the unexposed area was completely dissolved was measured and used as an index of developability. The shorter this time, the better the performance.

<Sensitivity>
The film thickness of the resist pattern after post-cure is measured using a surface roughness meter, and the remaining film ratio, which is the ratio of the post-cure film thickness to the dry film thickness after spin coating, is 90% or more, and 5 μm. The exposure amount that can form a pattern of / 5 μm was defined as sensitivity.

[Production Example 1]
Under a nitrogen atmosphere, 666.6 parts of ethyl lactate was added to a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the internal temperature was raised to 80 ° C. while stirring.
Subsequently, 271.4 parts of α-methacryloyloxy-γ-butyrolactone (hereinafter referred to as “GBLMA”) represented by the formula (51), 2-methacryloyloxy-2-methyladamantane (hereinafter referred to as “GBLMA”) 187.2 parts of 1-methacryloyloxy-3-hydroxyadamantane (hereinafter referred to as “HAdMA”) represented by formula (53), glycidyl represented by formula (54) 22.8 parts of methacrylate (hereinafter referred to as “GMA”), 1,200.0 parts of ethyl lactate and 29.4 parts of dimethyl-2,2′-azobisisobutyrate (hereinafter referred to as “DAIB”) were mixed. A monomer solution was prepared. This monomer solution was put into a dropping device and dropped into the flask at a constant rate over 4 hours. After completion of dropping, the mixture was held for 3 hours at an inner temperature of 80 ° C., then cooled to room temperature, to obtain a polymer _(P G -1) polymer ethyl lactate solution containing _(P G -1) 1,890.2 parts It was.

Thereafter, was added dropwise approximately 10 volumes of hexane / ethyl acetate stirring conditions = 90/10 polymer ethyl lactate solution in a mixed solvent (volume% ratio) (P G _-1), to give a white precipitate It was. After this precipitate was filtered off, it was again poured into the same amount of the mixed solvent as the mixed solvent, and the precipitate was washed while stirring.
Subsequently, the precipitate was separated by filtration to obtain 1740 parts of a wet powder of polymer (P _G -1). After drying about 40 hours at this Shimekona 10 parts (dry powder 3.2 g) under reduced pressure at 40 ° C. The evaluation was carried out of the polymer _(P G -1), the results are shown in Table 5.
The remaining wet powder was put into 6,500 parts of PGMEA and completely dissolved, and the resulting solution was filtered with a nylon filter having a pore size of 0.04 μm (Nippon Pole Co., Ltd., Urpotia N66 (trade name)). ) And filtered.
Subsequently, the obtained filtrate was heated under reduced pressure hexanes, ethyl acetate was distilled off and some PGMEA, to obtain a concentration of 30% polymer PGMEA solution _(P G -1). The maximum ultimate vacuum was 0.7 kPa, the maximum solution temperature was 65 ° C., and the distillation time was 8 hours.

[Production Example 2]
The initial charged ethyl lactate in the flask was 409.2 parts, the monomer solution in the dropping apparatus was 114.2 parts GBLMA, 258.4 parts MAdMA, 102.0 parts HAdMA, methacrylic acid represented by the formula (55) (hereinafter referred to as the formula (55)). , “MAA”), and a monomer solution in which 16.6 parts of ethyl lactate, 736.6 parts of ethyl lactate, and 66.2 parts of DAIB were mixed. Other conditions to obtain a polymer in the same manner as in Preparation Example 1 (P A _-1) polymer ethyl lactate solution containing (P A _-1).

Then, for evaluation of the polymer, dropwise polymer ethyl lactate solution (P A _-1) 10 parts of a mixed solvent of about 10 times the amount of agitation states methanol / water = 90/10 (volume% ratio) As a result, a white precipitate was obtained. After the precipitate was filtered off, it was again put into the same amount of the mixed solvent as the mixed solvent, and the precipitate was washed while stirring. Thereafter, the precipitate was separated by filtration and dried under reduced pressure at 60 ° C. for about 40 hours, and then the polymer (P _A -1) was evaluated. The results are shown in Table 5.

[Production Example 3]
414 parts of PGMEA was added to the same flask as in Production Example 1 under a nitrogen atmosphere, and the internal temperature was raised to 100 ° C. while stirring.
Next, 470 parts of styrene represented by formula (56) (hereinafter referred to as “St”), 270 parts of benzyl methacrylate (hereinafter referred to as “BzMA”) represented by formula (57), and represented by formula (58) From a dropping device containing a monomer solution in which 50 parts of α-methylstyrene (hereinafter referred to as “αMS”), 37 parts of GMA, 1,654 parts of PGMEA and 175 parts of DAIB were mixed, It was dropped into the flask over time. After completion of the dropwise addition, 1.3 parts of DAIB was added in three portions every 30 minutes, and then the internal temperature was raised to 120 ° C. After 2 hours at 120 ° C., cooled to room temperature to obtain a polymer PGMEA solution containing a polymer _{(P G -2) (P G} -2).

Next, for evaluation of the polymer, 10 parts of the polymer PGMEA solution (P _G -2) was dropped into a mixed solvent of hexane / ethyl acetate = 95/5 (volume% ratio) about 10 times as much as the stirring state. As a result, a white precipitate was obtained. After this precipitate was filtered off, it was again poured into the same amount of the mixed solvent as the mixed solvent, and the precipitate was washed while stirring.
Then filtered off the precipitate after washing and drying in the same manner as in Preparation Example 2, and evaluated for the polymer (P G _-2), the results are shown in Table 6.

[Production Example 4]
105 parts of PGMEA was added to the same flask as in Production Example 1 under a nitrogen atmosphere, and the internal temperature was raised to 100 ° C. while stirring.
Next, from a dropping device containing a monomer solution in which 10 parts of N-phenylmaleimide (hereinafter referred to as “PMID”) represented by the formula (59), 200 parts of MAA, 420 parts of PGMEA and 540 parts of DAIB are mixed, The body solution was dropped into the flask at a constant rate over 4 hours. After 30 minutes from the end of dropping, 1.3 parts of DAIB was added, and the internal temperature was raised to 120 ° C. After 3 hours at 120 ° C., cooled to room temperature to obtain a polymer PGMEA solution containing a polymer _{(P A -2) (P A} -2).
Next, for polymer evaluation, a polymer precipitate was obtained in the same manner as in Production Example 3 using 10 parts of the polymer PGMEA solution (PA-2), washed, filtered, dried, The coalescence (P _A -2) was evaluated, and the results are shown in Table 6.

[Production Example 5]
It was replaced by MAA23 parts GMA37 parts in the same manner as in Preparation Example 3 polymer _(P A -3) polymer PGMEA solution containing _(P A -3) and polymer drying of _(P A -3) Obtained. The polymer (P _A -3) was evaluated and the results are shown in Table 6.

[Example 1]
Added polymer PGMEA solutions (P G _-1) 720 parts obtained in the same flask as in Production Example 1 under a nitrogen atmosphere in Production Example 1 to raise the inner temperature to 100 ° C. with stirring.
Next, 1,690 parts of the ethyl lactate solution (P _A -1) from the dropping apparatus containing the polymer ethyl lactate solution (P _A -1) obtained in Production Example 2 was placed in the flask at a constant rate for 1 hour. It was dripped. After completion of the dropwise addition, the inner temperature was maintained at 100 ° C. for 3 hours to react the polymer (P _G -1) and the polymer (P _A -1). Subsequently, it cooled to room temperature and obtained the polymer PGMEA / ethyl lactate solution (P-1) containing a polymer (P-1).

  The polymer PGMEA / ethyl lactate solution (P-1) was subjected to polymer precipitation, washing and drying in the same manner as in Production Example 2, and evaluation of the resist composition for semiconductors using the polymer (P-1). The results are shown in Table 5.

[Example 2]
The same flask as in Production Example 1, under a nitrogen atmosphere, was added polymer PGMEA solution obtained in Production Example 1 (P G _-1) solution 720 parts, raising the internal temperature to 100 ° C. with stirring It was.
Next, this monomer solution was dropped into the flask at a constant rate over 1 hour from a dropping device containing a monomer solution in which 14.0 parts of MAA and 14.0 parts of PGMEA were mixed. After completion of dropping, the mixture was held for 3 hours at an inner temperature of 100 ° C., vinyl monomers having a carboxyl group (m _A) are reacted in the polymer (P G _-1). Then cooled to room temperature to obtain a reactive polymer PGMEA solution containing reactive polymer _{(RP2 GA -1) (RP2 GA} -1).
Under a nitrogen atmosphere, 107.6 parts of ethyl lactate was added to another flask similar to the above, and the internal temperature was raised to 80 ° C. while stirring.
Dropping apparatus containing a solution prepared by mixing 30.6 parts of GBLMA, 70.2 parts of MAdMA, 28.3 parts of HAdMA, 193.7 parts of ethyl lactate, 16.6 parts of DAIB and 740 parts of a reactive polymer PGMEA solution (RP2 _GA- 1) The solution was added dropwise to the flask at a constant rate over 4 hours. After completion of dropping, the mixture was held for 3 hours at an inner temperature of 80 ° C., to produce a branch polymer in the polymer is a trunk polymer (P G _-1). Subsequently, it cooled to room temperature and obtained the polymer PGMEA / ethyl lactate solution (P-2) containing a polymer (P-2).

  The polymer PGMEA / ethyl lactate solution (P-2) was subjected to polymer precipitation, washing and drying in the same manner as in Production Example 2, and evaluation of the resist composition for semiconductors using the polymer (P-2). The results are shown in Table 5.

[Example 3]
As the initial charged polymer solution in the flask, 720 parts of the polymer ethyl lactate solution (P _A -1) obtained in Production Example 2 was used, and the monomer solution in the dropping apparatus was 12.0 parts of GMA and ethyl lactate. The monomer solution was mixed with 12.0 parts. Other conditions were the same manner as in Example 2 with the polymer (P A _-1) to the polymer containing a vinyl monomer (m _G) reactive polymer obtained by reacting (RP3 AG _-1) having a glycidyl group An ethyl lactate solution (RP3 _AG- 1) was obtained.
Then, in the same way as in the polymer solution of Preparation 1 _(P G -1) to obtain a Shimekona reactive polymer _(RP3 AG -1), the amount of PGMEA dissolving the Shimekona 3,200 A reactive polymer PGMEA solution (RP3 _AG- 1) having a concentration of 30% was obtained in the same manner as in Production Example 1 except that the content was changed to the part.
In another flask similar to the above, 107.6 parts of ethyl lactate was stirred under a nitrogen atmosphere, and the internal temperature was raised to 80 ° C. with stirring.
From a dropping apparatus containing a solution in which 30.6 parts of GBLMA, 70.2 parts of MAdMA, 28.3 parts of HAdMA, 193.7 parts of ethyl lactate, 16.6 parts of DAIB and 740 parts of a reactive polymer solution (RP2 _GA- 1) were mixed. This solution was dropped into the flask at a constant rate over 4 hours. After completion of the dropwise addition, the inner temperature was maintained at 80 ° C. for 3 hours to produce a branched polymer in the polymer (P _A -1) which is a trunk polymer. Subsequently, it cooled to room temperature and obtained the polymer PGMEA / ethyl lactate solution (P-3) containing a polymer (P-3).

  The polymer PGMEA / ethyl lactate solution (P-3) was subjected to polymer precipitation, washing and drying in the same manner as in Production Example 2, and evaluation of the resist composition for semiconductors using the polymer (P-3). The results are shown in Table 5.

[Comparative Example 1]
The initial charged ethyl lactate in the flask was 346.9 parts, and the monomer solution in the dropping apparatus was 139.4 parts GBLMA, 182.5 parts MAdMA, 94.4 parts HAdMA, 624.5 parts ethyl lactate and 12.4 parts DAIB. A mixed monomer solution was obtained. Other conditions were the same as in Production Example 2, and a polymer ethyl lactate solution (C-1) containing the polymer (C-1) was obtained.
Further, the polymer was precipitated, washed and dried in the same manner as in Production Example 2, and the semiconductor resist composition using the polymer (C-1) was evaluated. The results are shown in Table 5.

[Comparative Example 2]
(1) Production of trunk polymer In a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, 8.02 parts of cyclohexyl methacrylate, 1.98 parts of 2-bromopropanoyloxyethyl methacrylate, 40 parts of THF, and 0.6 part of mercaptoethanol. 8 parts and 0.3 part of azobisisobutyronitrile were charged and stirred until completely dissolved. Subsequently, after argon gas was blown in and fully deoxygenated, it heated up at 80 degreeC and superposed | polymerized for 6 hours. The solution after completion of the polymerization was poured into 10 times the amount of methanol and stirred vigorously for 1 hour. The mixture was cooled at −40 ° C. for several hours, and then the precipitate was filtered and dried at 40 ° C. under reduced pressure to obtain a trunk polymer.
(2) Production of graft polymer In a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, 2.0 parts of the above trunk polymer, 2.0 parts of 2-methyl-2-adamantyl methacrylate and 2.0 parts of THF And stirred until completely dissolved. Subsequently, after argon gas was blown in and sufficient deoxygenation was performed, 0.0966 part of a nickel complex (dibromo-bis (tributylphosphine) nickel (II)) was added, and the mixture was vigorously stirred until it showed a reddish brown color. Thereafter, the temperature was raised and polymerization was performed for 1 day under reflux. The solution after polymerization was poured into 10 times the amount of methanol, and the precipitate was filtered and dried at 40 ° C. under reduced pressure. The obtained polymer was a crude graft polymer containing a residual metal catalyst, and purified by silica gel column fractionation to obtain a polymer (C-2). Evaluation of the resist composition for semiconductors using the polymer (C-2) was carried out, and the results are shown in Table 5.

[Example 4]
2,400 parts of the polymer PGMEA solution (P _G -2) obtained in Production Example 3 was initially charged into the flask, and 720 parts of the polymer PGMEA solution (P _A -2) obtained in Production Example 4 was dropped. Put in the device. The other conditions in the same manner as in Example 1 the polymer _(P G -2) and the polymer _(P A -2) polymer obtained by reacting the (P-4) polymer PGMEA solution containing (P-4) Got.

  The polymer PGMEA solution (P-4) was subjected to polymer precipitation, washing and drying in the same manner as in Production Example 3 to evaluate the resist composition for semiconductors using the polymer (P-4). The results are shown in Table 6.

[Example 5]
The polymer PGMEA solution _(P G -2) 2,400 parts obtained in Production Example 3 in the flask was initially charged, MAA46 parts, placed in a dropping apparatus monomer solution obtained by mixing PGMEA46 parts. The other conditions were the same as in Example 2 except that the polymer (P _G -2) was reacted with a vinyl monomer (m _A ) having a carboxyl group and a reactive polymer (RP2 _GA -2) was included. A polymer PGMEA solution (RP2 _GA- 2) was obtained.
Next, 105 parts of PGMEA was added to another flask similar to the above, and the internal temperature was raised to 80 ° C. while stirring.
From a dropping apparatus containing a solution obtained by mixing 200 parts of MAA, 10 parts of PMID, 420 parts of PGMEA, 540 parts of DAIB and 2,400 parts of a reactive polymer solution (RP2 _GA- 2), this solution was placed in a flask at a constant rate for 4 hours. It was dripped. After 30 minutes from the end of dropping, 1.3 parts of DAIB was added, and the internal temperature was raised to 120 ° C. And held for 3 hours at 120 ° C., to produce a branch polymer in the polymer is a trunk polymer (P G _-2). Then, it cooled to room temperature and obtained the polymer PGMEA solution (P-5) containing a polymer (P-5).

  For the polymer PGMEA solution (P-5), the polymer was precipitated, washed and dried in the same manner as in Production Example 3, and the resist composition for semiconductor using the polymer (P-5) was evaluated. The results are shown in Table 6.

[Example 6]
Put polymer PGMEA solution obtained in Production Example 5 In a flask _(P A -3), under a nitrogen atmosphere to raise the inner temperature to 100 ° C. with stirring.
This monomer solution was dropped into the flask at a constant rate for 1 hour from a dropping device containing a monomer solution in which 30 parts of GMA and 30 parts of PGMEA were mixed. After completion of the dropwise addition, the internal temperature was maintained for 3 hours at 100 ° C., vinyl monomers having a glycidyl group and (m _G) are reacted in the polymer (P A _-3). Then cooled to room temperature to obtain the reactive polymer PGMEA solution containing the reactive polymer _(RP3 AG -2) and _(RP3 AG -2).
Next, a polymer (P) which is a trunk polymer in the same manner as in Example 5 except that the reactive polymer PGMEA solution (RP3 _AG- 2) is used instead of the reactive polymer PGMEA solution (RP2 _GA- 2). _A polymer PGMEA solution (P-6) containing a polymer (P-6) in which a branched polymer was formed in _A- 3) was obtained.

  For the polymer PGMEA solution (P-6), the polymer was precipitated, washed and dried in the same manner as in Production Example 3, and the resist composition for semiconductor using the polymer (P-6) was evaluated. The results are shown in Table 6.

[Comparative Example 3]
The monomer solution in the dropping apparatus was mixed with St470 parts, BzMA270 parts, αMS50 parts, MAA200 parts, PMID10 parts, PGMEA2,000 parts and DAIB175 parts with 500 parts of the initial charge PGMEA in the flask. It was. Other conditions were the same as in Production Example 3, and a polymer PGMEA solution (C-3) containing the polymer (C-3) was obtained.
For the polymer PGMEA solution (C-3), the polymer was precipitated, washed and dried in the same manner as in Production Example 3, and the semiconductor resist composition using the polymer (C-3) was evaluated. The results are shown in Table 6.

  As apparent from Table 5, the polymers of Examples 1 to 3 having the structural unit of the formula (2) had a low metal content. Moreover, the resist composition for semiconductors using the above polymer had sufficient sensitivity and resolution, a small amount of defects, and a low line edge roughness of the resist.

On the other hand, the resist composition for semiconductors using the polymer of Comparative Example 1 having no structural unit of the formula (2) has a large defect amount and a large line edge roughness of the resist.
Further, the polymer of Comparative Example 2 having no structural unit of the formula (2) has a high metal content, the resist composition for semiconductors using the above polymer has a large defect amount, and the line edge roughness of the resist is also large. It was.

  In addition, the color filter resist composition using the polymers of Examples 4 to 6 having the structural unit of the formula (2) has excellent pigment dispersibility, sufficient sensitivity, and good developability. there were.

  On the other hand, the resist composition for a color filter using the polymer of Comparative Example 3 having no structural unit of the formula (2) has poor pigment dispersibility and developability.

Claims (10)

A resist polymer containing a structural unit represented by formula (2).

(In Formula (2), R represents a hydrogen atom, a methyl group, a C1-C4 hydroxyalkyl group, or a C1-C4 perfluoroalkyl group. G is a single bond, -C (= O)-. O—, —O— or —O—C (═O) —, L represents a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, (It may have at least one selected from atoms. Poly represents a polymer chain.) Claims having a polymer (P _G ) unit containing a structural unit having a glycidyl residue and a polymer (P _A ) unit containing a structural unit having at least one selected from a carboxyl residue and an acid anhydride residue Item 11. The resist polymer according to Item 1. _A reaction step (R1) with a polymer (P _G ) containing a structural unit having a glycidyl group and a polymer (P _A ) containing a structural unit having at least one selected from a carboxyl group and an acid anhydride group The manufacturing method of the polymer of Claim 2 containing. Vinyl monomer having at least one selected from the polymer (P _G) with a carboxyl group and acid anhydride group as a trunk polymer having a unit having a glycidyl group (m _A) and reaction steps (R2 3. The method for producing a polymer according to claim 2, further comprising a polymerization step (P2 _GA ) in which a branched polymer is formed by polymerization of _GA ) and the subsequent vinyl monomer (v). Reaction process (R3) of a polymer (P _A ) as a trunk polymer containing a structural unit having at least one selected from a carboxyl group and an acid anhydride group and a vinyl monomer (m _G ) having a glycidyl group _The method for producing a polymer according to claim 2, further comprising a polymerization step (P3 _AG ) in which a branched polymer is formed by polymerization of _AG ) and subsequent polymerization of the vinyl monomer (v).   A resist composition containing the polymer according to claim 1 or 2 or the polymer obtained by the method according to any one of claims 3 to 5.   A chemically amplified resist composition comprising the polymer according to claim 1 or 2 or the polymer obtained by the method according to any one of claims 3 to 5 and a photoacid generator.   A color comprising the polymer according to claim 1 or 2 or the polymer obtained by the method according to any one of claims 3 to 5, a photopolymerizable monomer (x) and a photopolymerization initiator (I). A resist composition for a filter.   A substrate on which a pattern is formed, comprising a step of applying the resist composition according to claim 6 or 7 onto a substrate to be processed, a step of exposing to light having a wavelength of 450 nm or less, and a step of developing using a developer. Production method.   A color filter on which a pattern is formed, comprising a step of applying the resist composition according to claim 6 or 8 onto a substrate to be processed, a step of exposing with light having a wavelength of 450 nm or less, and a step of developing using a developer. Manufacturing method.