JP2014202943A - Production method of polymer for lithography, production method of resist composition, and production method of patterned substrate - Google Patents

Production method of polymer for lithography, production method of resist composition, and production method of patterned substrate Download PDF

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JP2014202943A
JP2014202943A JP2013079505A JP2013079505A JP2014202943A JP 2014202943 A JP2014202943 A JP 2014202943A JP 2013079505 A JP2013079505 A JP 2013079505A JP 2013079505 A JP2013079505 A JP 2013079505A JP 2014202943 A JP2014202943 A JP 2014202943A
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一晃 向井
Kazuaki Mukai
一晃 向井
敦 安田
Atsushi Yasuda
敦 安田
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Mitsubishi Rayon Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a production method of a polymer for lithography, a production method of a resist composition, and a production method of a patterned substrate.SOLUTION: The production method of a polymer for lithography is a production method of a polymer obtained by solution polymerization of a monomer having a (meth)acrylate skeleton; and in the method, after a reaction rate is increased in 85% or more of the whole use amount of the monomer supplied, a solution which contains a polymerization initiator by 1.0% to 15.0% of the whole use amount of the polymerization initiator to be supplied and which contains no monomer is further supplied to a reaction chamber. The polymer is used in the production method of a resist composition; and the composition is used in the production method of a substrate.

Description

本発明はリソグラフィー用重合体の製造方法、レジスト組成物の製造方法、およびパターンが形成された基板の製造方法に関する。   The present invention relates to a method for producing a polymer for lithography, a method for producing a resist composition, and a method for producing a substrate on which a pattern is formed.

近年、半導体素子、液晶素子等の製造工程において形成されるレジストパターンは、リソグラフィー技術の進歩により急速に微細化が進んでいる。微細化の手法としては、照射光の短波長化がある。具体的には、従来のｇ線（波長：４３８ｎｍ）、ｉ線（波長：３６５ｎｍ）に代表される紫外線から、より短波長のＤＵＶ（Ｄｅｅｐ Ｕｌｔｒａ Ｖｉｏｌｅｔ）へと照射光が短波長化してきている。   In recent years, a resist pattern formed in a manufacturing process of a semiconductor element, a liquid crystal element, or the like has been rapidly miniaturized due to progress in lithography technology. As a technique for miniaturization, there is a reduction in wavelength of irradiation light. Specifically, the irradiation light has become shorter from conventional ultraviolet rays typified by g-line (wavelength: 438 nm) and i-line (wavelength: 365 nm) to shorter wavelength DUV (Deep Ultra Violet). .

最近では、ＫｒＦエキシマレーザー（波長：２４８ｎｍ）リソグラフィー技術が導入され、さらなる短波長化を図ったＡｒＦエキシマレーザー（波長：１９３ｎｍ）リソグラフィー技術およびＥＵＶ（波長：１３．５ｎｍ）リソグラフィー技術が研究されている。さらに、これらの液浸リソグラフィー技術も研究されている。また、これらとは異なるタイプのリソグラフィー技術として、電子線リソグラフィー技術についても精力的に研究されている。   Recently, KrF excimer laser (wavelength: 248 nm) lithography technology has been introduced, and ArF excimer laser (wavelength: 193 nm) lithography technology and EUV (wavelength: 13.5 nm) lithography technology for further shortening the wavelength have been studied. . Furthermore, these immersion lithography techniques are also being studied. Also, as a different type of lithography technology, electron beam lithography technology has been energetically studied.

該短波長の照射光または電子線を用いたレジストパターンの形成に用いられる高感度のレジスト組成物として、光酸発生剤を含有する「化学増幅型レジスト組成物」が提唱され、該化学増幅型レジスト組成物の改良および該化学増幅型レジスト組成物用の重合体の開発が進められている。
例えば、ＡｒＦエキシマレーザーリソグラフィーにおいて用いられる化学増幅型レジスト用重合体として、波長１９３ｎｍの光に対して透明なアクリル系重合体が注目されている。該アクリル系重合体としては、例えば、エステル部にアダマンタン骨格を有するメタクリル酸エステルとエステル部にラクトン骨格を有するメタクリル酸エステルとの重合体が提案されている。
また、露光時に基板からの反射を防ぐ役割を果たすため、露光光に対する光線透過率が低い反射防止膜の開発が進められており、アクリル系重合体を用いた反射防止膜が提案されている。 A “chemically amplified resist composition” containing a photoacid generator has been proposed as a highly sensitive resist composition used for forming a resist pattern using the irradiation light or electron beam of the short wavelength. Improvement of the resist composition and development of a polymer for the chemically amplified resist composition are underway.
For example, as a chemically amplified resist polymer used in ArF excimer laser lithography, an acrylic polymer that is transparent with respect to light having a wavelength of 193 nm has attracted attention. As the acrylic polymer, for example, a polymer of a methacrylic acid ester having an adamantane skeleton in an ester portion and a methacrylic acid ester having a lactone skeleton in an ester portion has been proposed.
Further, in order to prevent reflection from the substrate at the time of exposure, development of an antireflection film having a low light transmittance with respect to exposure light has been advanced, and an antireflection film using an acrylic polymer has been proposed.

レジストパターンの微細化に伴って、リソグラフィー用重合体の品質への要求も厳しくなっている。
例えば、優れたレジストパターンプロファイルを得るためには、リソグラフィー用重合体中の残存単量体および重量平均分子量（以下、Ｍｗという。）で１０００以下の低分子重合体の含有量を出来るだけ少なくする必要がある。
そこで、これまで、重合開始剤を反応の途中で追加供給する方法や、重合工程にて得られたリソグラフィー用重合体溶液を貧溶媒へ供給し、析出し固液分離することでリソグラフィー用重合体を精製する再沈殿と呼ばれる手法を用いることが提案されている。（特許文献１、２等） With the miniaturization of resist patterns, the demands on the quality of lithography polymers are becoming stricter.
For example, in order to obtain an excellent resist pattern profile, the content of a low molecular polymer having a residual monomer in a lithography polymer and a weight average molecular weight (hereinafter referred to as Mw) of 1000 or less is minimized. There is a need.
Therefore, until now, a method for additionally supplying a polymerization initiator during the reaction or a polymer for lithography obtained by supplying the polymer solution for lithography obtained in the polymerization step to a poor solvent, and precipitating and solid-liquid separation. It has been proposed to use a technique called reprecipitation to purify the slag. (Patent Documents 1, 2, etc.)

特開２００１−１０９１５３号公報JP 2001-109153 A 特開２０１２−８７１８６号公報JP 2012-87186 A

しかし、再沈殿工程のみで残存単量体や低分子量重合体の含有量を十分に低減させようとすると大量の貧溶媒を用いなければならず、生産効率、コストの面で必ずしも満足できる手法ではなかった。
また、重合開始剤を反応の途中で追加供給する方法においては、残存単量体の含有量は低減できるが、低分子量重合体の含有量を低減するのが困難であった。
本発明は前記事情に鑑みてなされたもので、大量の貧溶媒を使用しなくても、重合体に含まれる残存単量体を効率良く低減できるリソグラフィー用重合体の製造方法、該製造方法で得られるリソグラフィー用重合体を含むレジスト組成物、および該レジスト組成物を用いて、パターンが形成された基板を製造する方法を提供することを目的とする。 However, in order to sufficiently reduce the content of residual monomer and low molecular weight polymer only by the reprecipitation process, a large amount of poor solvent must be used, and this is not always a satisfactory method in terms of production efficiency and cost. There wasn't.
Further, in the method of additionally supplying the polymerization initiator during the reaction, the content of the residual monomer can be reduced, but it is difficult to reduce the content of the low molecular weight polymer.
The present invention has been made in view of the above circumstances, and it is possible to efficiently reduce a residual monomer contained in a polymer without using a large amount of a poor solvent, It is an object of the present invention to provide a resist composition containing the resulting lithographic polymer, and a method for producing a substrate on which a pattern is formed using the resist composition.

つまり、本発明は下記の態様を有する。   That is, this invention has the following aspect.

［１］ （メタ）アクリレート骨格を有する単量体を溶液重合して得られる重合体の製造方法であって、
供給される単量体の全使用量のうち８５％以上まで反応率が上昇した後に、
供給される重合開始剤の全使用量のうち１．０％〜１５．０％の重合開始剤を含み、かつ、単量体を含まない溶液を該反応容器内にさらに供給する、
リソグラフィー用重合体の製造方法。
［２］ ［１］に記載の製造方法によりリソグラフィー用重合体を製造する工程と、
得られたリソグラフィー用重合体と、活性光線または放射線の照射により酸を発生する化合物とを混合する工程を有する、
レジスト組成物の製造方法。
［３］ ［２］に記載の製造方法によりレジスト組成物を製造する工程と、
得られたレジスト組成物を基板の被加工面上に塗布してレジスト膜を形成する工程と、
該レジスト膜に対して、露光する工程と、
現像液を用いて、露光されたレジスト膜を現像する工程とを含む、
パターンが形成された基板の製造方法。 [1] A method for producing a polymer obtained by solution polymerization of a monomer having a (meth) acrylate skeleton,
After the reaction rate has increased to 85% or more of the total amount of monomer used,
A solution containing 1.0% to 15.0% of the polymerization initiator out of the total amount of the polymerization initiator to be supplied and further containing no monomer is further supplied into the reaction vessel.
A method for producing a polymer for lithography.
[2] A step of producing a polymer for lithography by the production method according to [1],
A step of mixing the obtained polymer for lithography with a compound that generates an acid upon irradiation with actinic rays or radiation,
A method for producing a resist composition.
[3] A step of producing a resist composition by the production method according to [2];
Applying the obtained resist composition on the work surface of the substrate to form a resist film;
A step of exposing the resist film;
And developing the exposed resist film using a developer.
A method for manufacturing a substrate on which a pattern is formed.

本発明によれば、大量の貧溶媒を使用しなくても、低分子量重合体の生成を抑制し、残存単量体の含有量を低減することができる。
これにより、重合体を精製することなく生産効率良く、残存単量体および低分子量重合体の含有量が少ないリソグラフィー用重合体を製造することができる。
このような残存単量体や低分子量重合体の含有量が少ないリソグラフィー用重合体は、レジスト組成物に用いた時の感度に優れる。
本発明によれば、感度に優れたレジスト組成物が得られ、該組成物を用いて、高精度の微細レジストパターンを安定して形成することができる。 According to the present invention, the formation of a low molecular weight polymer can be suppressed and the content of residual monomer can be reduced without using a large amount of poor solvent.
Thereby, it is possible to produce a lithographic polymer having a low content of the residual monomer and the low molecular weight polymer with high production efficiency without purifying the polymer.
Such a polymer for lithography with a small content of residual monomer or low molecular weight polymer is excellent in sensitivity when used in a resist composition.
According to the present invention, a resist composition having excellent sensitivity can be obtained, and a highly accurate fine resist pattern can be stably formed using the composition.

＜リソグラフィー用重合体＞
本発明のリソグラフィー用重合体（以下、単に重合体ということもある。）は、極性基を有する構成単位を有することが好ましい。
本発明のリソグラフィー用重合体は、残存単量体および重合開始剤の分解物等から構成されるＭｗ３５０以下の化合物の存在割合は、レジスト性能を向上させる観点より、重合体全体の１５．０％以下であることが好ましく、１０.０％以下であることがより好ましい。
また、Ｍｗ３５０〜１０００に相当する低分子量重合体の存在割合は、レジスト性能を向上させる観点より、重合体全体の１５．０％以下であることが好ましく、１０.０％以下であることがより好ましく、５．０％以下であることがさらに好ましく、３．５％以下であることが特に好ましい。 <Polymer for lithography>
The polymer for lithography of the present invention (hereinafter sometimes simply referred to as a polymer) preferably has a structural unit having a polar group.
In the polymer for lithography of the present invention, the proportion of the compound having a Mw of 350 or less composed of a residual monomer and a decomposition product of a polymerization initiator is 15.0% of the whole polymer from the viewpoint of improving resist performance. Or less, more preferably 10.0% or less.
Further, the proportion of the low molecular weight polymer corresponding to Mw 350 to 1000 is preferably 15.0% or less, more preferably 10.0% or less of the whole polymer from the viewpoint of improving resist performance. Preferably, it is more preferably 5.0% or less, and particularly preferably 3.5% or less.

［極性基を有する構成単位］
「極性基」とは、極性を持つ官能基または極性を持つ原子団を有する基であり、具体例としては、ヒドロキシ基、シアノ基、アルコキシ基、カルボキシ基、アミノ基、カルボニル基、フッ素原子を含む基、硫黄原子を含む基、ラクトン骨格を含む基、アセタール構造を含む基、エーテル結合を含む基などが挙げられる。
これらのうちで、波長２５０ｎｍ以下の光で露光するパターン形成方法に適用されるレジスト用重合体は、極性基を有する構成単位として、ラクトン骨格を有する構成単位を有することが好ましく、さらに後述の親水性基を有する構成単位を有することが好ましい。 [Structural unit having a polar group]
The “polar group” is a group having a polar functional group or a polar atomic group. Specific examples include a hydroxy group, a cyano group, an alkoxy group, a carboxy group, an amino group, a carbonyl group, and a fluorine atom. A group containing a sulfur atom, a group containing a lactone skeleton, a group containing an acetal structure, a group containing an ether bond, and the like.
Among these, the resist polymer applied to the pattern forming method that is exposed to light having a wavelength of 250 nm or less preferably has a structural unit having a lactone skeleton as the structural unit having a polar group, It is preferable to have a structural unit having a functional group.

（ラクトン骨格を有する構成単位・単量体)
ラクトン骨格としては、例えば、４〜２０員環のラクトン骨格が挙げられる。ラクトン骨格は、ラクトン環のみの単環であってもよく、ラクトン環に脂肪族、芳香族の炭素環または複素環が縮合していてもよい。
重合体がラクトン骨格を有する構成単位を含む場合、その含有量は、基板等への密着性の点から、全構成単位（１００モル％）のうち、２０モル％以上が好ましく、２５モル％以上がより好ましい。
また、感度および解像度の点から、６０モル％以下が好ましく、５５モル％以下がより好ましく、５０モル％以下がさらに好ましい。 (Constitutional unit / monomer having a lactone skeleton)
Examples of the lactone skeleton include a 4- to 20-membered lactone skeleton. The lactone skeleton may be a monocycle having only a lactone ring, and an aliphatic or aromatic carbon ring or a heterocyclic ring may be condensed to the lactone ring.
In the case where the polymer contains a structural unit having a lactone skeleton, the content thereof is preferably 20 mol% or more, more preferably 25 mol% or more of all structural units (100 mol%) from the viewpoint of adhesion to a substrate or the like. Is more preferable.
Moreover, from the point of a sensitivity and resolution, 60 mol% or less is preferable, 55 mol% or less is more preferable, and 50 mol% or less is further more preferable.

ラクトン骨格を有する単量体としては、基板等への密着性に優れる点から、置換もしくは無置換のδ−バレロラクトン環を有する（メタ）アタクリル酸エステル、置換もしくは無置換のγ−ブチロラクトン環を有する単量体からなる群から選ばれる少なくとも１種が好ましく、無置換のγ−ブチロラクトン環を有する単量体が特に好ましい。   As a monomer having a lactone skeleton, a (meth) acrylate ester having a substituted or unsubstituted δ-valerolactone ring, a substituted or unsubstituted γ-butyrolactone ring is used because of its excellent adhesion to a substrate or the like. Preferably, at least one selected from the group consisting of monomers having it is preferred, and monomers having an unsubstituted γ-butyrolactone ring are particularly preferred.

ラクトン骨格を有する単量体の具体例としては、β−（メタ）アクリロイルオキシ−β−メチル−δ−バレロラクトン、４，４−ジメチル−２−メチレン−γ−ブチロラクトン、β−（メタ）アクリロイルオキシ−γ−ブチロラクトン、β−（メタ）アクリロイルオキシ−β−メチル−γ−ブチロラクトン、α−（メタ）アクリロイルオキシ−γ−ブチロラクトン、２−（１−（メタ）アクリロイルオキシ）エチル−４−ブタノリド、（メタ）アクリル酸パントイルラクトン、５−（メタ）アクリロイルオキシ−２，６−ノルボルナンカルボラクトン、８−メタクリロキシ−４−オキサトリシクロ［５．２．１．０２，６ ］デカン−３−オン、９−メタクリロキシ−４−オキサトリシクロ［５．２．１．０２，６ ］デカン−３−オン等が挙げられる。
また、類似構造を持つ単量体として、メタクリロイルオキシこはく酸無水物等も挙げられる。
ラクトン骨格を有する単量体は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Specific examples of the monomer having a lactone skeleton include β- (meth) acryloyloxy-β-methyl-δ-valerolactone, 4,4-dimethyl-2-methylene-γ-butyrolactone, β- (meth) acryloyl. Oxy-γ-butyrolactone, β- (meth) acryloyloxy-β-methyl-γ-butyrolactone, α- (meth) acryloyloxy-γ-butyrolactone, 2- (1- (meth) acryloyloxy) ethyl-4-butanolide , (Meth) acrylic acid pantoyl lactone, 5- (meth) acryloyloxy-2,6-norbornanecarbolactone, 8-methacryloxy-4-oxatricyclo [5.2.1.0 2,6 ] decane-3 - one, 9-methacryloxy-4-oxatricyclo [5.2.1.0 2, 6] cited decan-3-one and the like .
Examples of the monomer having a similar structure include methacryloyloxysuccinic anhydride.
Monomers having a lactone skeleton may be used alone or in combination of two or more.

（親水性基を有する構成単位・単量体）
本明細書における「親水性基」とは、−Ｃ（ＣＦ３）２−ＯＨ、ヒドロキシ基、シアノ基、メトキシ基、カルボキシ基およびアミノ基の少なくとも１種である。
これらのうちで、波長２５０ｎｍ以下の光で露光するパターン形成方法に適用されるレジスト用重合体は、親水性基としてヒドロキシ基またはシアノ基を有することが好ましい。
重合体における親水性基を有する構成単位の含有量は、レジストパターン矩形性の点から、全構成単位（１００モル％）のうち、５〜３０モル％が好ましく、１０〜２５モル％がより好ましい。 (Structural unit / monomer having a hydrophilic group)
The “hydrophilic group” in the present specification is at least one of —C (CF 3 ) 2 —OH, a hydroxy group, a cyano group, a methoxy group, a carboxy group, and an amino group.
Among these, it is preferable that the resist polymer applied to the pattern forming method exposed to light having a wavelength of 250 nm or less has a hydroxy group or a cyano group as a hydrophilic group.
The content of the structural unit having a hydrophilic group in the polymer is preferably from 5 to 30 mol%, more preferably from 10 to 25 mol%, of the total structural units (100 mol%) from the viewpoint of the resist pattern rectangularity. .

親水性基を有する単量体としては、例えば、末端ヒドロキシ基を有する（メタ）アクリ酸エステル；単量体の親水性基上にアルキル基、ヒドロキシ基、カルボキシ基等の置換基を有する誘導体；環式炭化水素基を有する単量体（例えば（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸１−イソボルニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸トリシクロデカニル、（メタ）アクリル酸ジシクロペンチル、（メタ）アクリル酸２−メチル−２−アダマンチル、（メタ）アクリル酸２−エチル−２−アダマンチル等。）が置換基としてヒドロキシ基、カルボキシ基等の親水性基を有するもの；が挙げられる。   Examples of the monomer having a hydrophilic group include a (meth) acrylic acid ester having a terminal hydroxy group; a derivative having a substituent such as an alkyl group, a hydroxy group, or a carboxy group on the hydrophilic group of the monomer; Monomers having a cyclic hydrocarbon group (for example, cyclohexyl (meth) acrylate, 1-isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, (meth) acrylic acid) Dicyclopentyl, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, etc.) having a hydrophilic group such as a hydroxy group or a carboxy group as a substituent; Can be mentioned.

親水性基を有する単量体の具体例としては、（メタ）アクリル酸、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシ−ｎ−プロピル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸３−ヒドロキシアダマンチル、２−または３−シアノ−５−ノルボルニル（メタ）アクリレート、２−シアノメチル−２−アダマンチル（メタ）アクリレート等が挙げられる。基板等に対する密着性の点から、（メタ）アクリル酸３−ヒドロキシアダマンチル、（メタ）アクリル酸３，５−ジヒドロキシアダマンチル、２−または３−シアノ−５−ノルボルニル（メタ）アクリレート、２−シアノメチル−２−アダマンチル（メタ）アクリレート等が好ましい。
親水性基を有する単量体は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Specific examples of the monomer having a hydrophilic group include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy- (meth) acrylate. -Propyl, 4-hydroxybutyl (meth) acrylate, 3-hydroxyadamantyl (meth) acrylate, 2- or 3-cyano-5-norbornyl (meth) acrylate, 2-cyanomethyl-2-adamantyl (meth) acrylate, etc. Is mentioned. From the point of adhesion to a substrate or the like, 3-hydroxyadamantyl (meth) acrylate, 3,5-dihydroxyadamantyl (meth) acrylate, 2- or 3-cyano-5-norbornyl (meth) acrylate, 2-cyanomethyl- 2-adamantyl (meth) acrylate and the like are preferable.
The monomer which has a hydrophilic group may be used individually by 1 type, and may be used in combination of 2 or more type.

［酸脱離性基を有する構成単位］
本発明のリソグラフィー用重合体がレジスト用途に用いられる場合、上述した極性基を有する構成単位の他に、酸脱離性基を有する構成単位を有することが好ましく、その他に、必要に応じて公知の構成単位をさらに有していてもよい。
「酸脱離性基」とは、酸により開裂する結合を有する基であり、該結合の開裂により酸脱離性基の一部または全部が重合体の主鎖から脱離する基である。
レジスト用組成物において、酸脱離性基を有する構成単位を有する重合体は、酸成分と反応してアルカリ性溶液に可溶となり、レジストパターン形成を可能とする作用を奏する。
酸脱離性基を有する構成単位の割合は、感度および解像度の点から、重合体を構成する全構成単位（１００モル％）のうち、２０モル％以上が好ましく、２５モル％以上がより好ましい。また、基板等への密着性の点から、６０モル％以下が好ましく、５５モル％以下がより好ましく、５０モル％以下がさらに好ましい。 [Constitutional unit having acid leaving group]
When the polymer for lithography of the present invention is used for resist applications, it is preferable to have a structural unit having an acid-eliminable group in addition to the above-mentioned structural unit having a polar group. The structural unit may be further included.
The “acid leaving group” is a group having a bond that is cleaved by an acid, and a part or all of the acid leaving group is removed from the main chain of the polymer by cleavage of the bond.
In the resist composition, a polymer having a structural unit having an acid-eliminable group reacts with an acid component to become soluble in an alkaline solution, and has an effect of enabling resist pattern formation.
The proportion of the structural unit having an acid leaving group is preferably 20 mol% or more, more preferably 25 mol% or more, out of all the structural units (100 mol%) constituting the polymer from the viewpoint of sensitivity and resolution. . Moreover, 60 mol% or less is preferable from the point of the adhesiveness to a board | substrate etc., 55 mol% or less is more preferable, and 50 mol% or less is further more preferable.

酸脱離性基を有する単量体は、酸脱離性基および重合性多重結合を有する化合物であればよく、公知のものを使用できる。重合性多重結合とは重合反応時に開裂して共重合鎖を形成する多重結合であり、エチレン性二重結合が好ましい。
酸脱離性基を有する単量体の具体例として、炭素数６〜２０の脂環式炭化水素基を有し、かつ酸脱離性基を有している（メタ）アクリル酸エステルが挙げられる。該脂環式炭化水素基は、（メタ）アクリル酸エステルのエステル結合を構成する酸素原子と直接結合していてもよく、アルキレン基等の連結基を介して結合していてもよい。
該（メタ）アクリル酸エステルには、炭素数６〜２０の脂環式炭化水素基を有するとともに、（メタ）アクリル酸エステルのエステル結合を構成する酸素原子との結合部位に第３級炭素原子を有する（メタ）アクリル酸エステル、または、炭素数６〜２０の脂環式炭化水素基を有するとともに、該脂環式炭化水素基に−ＣＯＯＲ基（Ｒは置換基を有していてもよい第３級炭化水素基、テトラヒドロフラニル基、テトラヒドロピラニル基、またはオキセパニル基を表す。）が直接もしくは連結基を介して結合している（メタ）アクリル酸エステルが含まれる。 The monomer having an acid leaving group may be any compound having an acid leaving group and a polymerizable multiple bond, and known ones can be used. The polymerizable multiple bond is a multiple bond that is cleaved during the polymerization reaction to form a copolymer chain, and an ethylenic double bond is preferable.
Specific examples of the monomer having an acid leaving group include (meth) acrylic acid esters having an alicyclic hydrocarbon group having 6 to 20 carbon atoms and having an acid leaving group. It is done. The alicyclic hydrocarbon group may be directly bonded to an oxygen atom constituting an ester bond of (meth) acrylic acid ester, or may be bonded via a linking group such as an alkylene group.
The (meth) acrylic acid ester has an alicyclic hydrocarbon group having 6 to 20 carbon atoms, and a tertiary carbon atom at the bonding site with the oxygen atom constituting the ester bond of the (meth) acrylic acid ester. A (meth) acrylic acid ester having an alicyclic group or an alicyclic hydrocarbon group having 6 to 20 carbon atoms and a -COOR group (R may have a substituent) on the alicyclic hydrocarbon group. (Meth) acrylic acid ester in which a tertiary hydrocarbon group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group is bonded directly or via a linking group is included.

特に、波長２５０ｎｍ以下の光で露光するパターン形成方法に適用されるレジスト組成物を製造する場合には、酸脱離性基を有する単量体の好ましい例として、例えば、２−メチル−２−アダマンチル（メタ）アクリレート、２−エチル−２−アダマンチル（メタ）アクリレート、１−（１’−アダマンチル）−１−メチルエチル（メタ）アクリレート、１−メチルシクロヘキシル（メタ）アクリレート、１−エチルシクロヘキシル（メタ）アクリレート、１−メチルシクロペンチル（メタ）アクリレート、１−エチルシクロペンチル（メタ）アクリレート、イソプロピルアダマンチル（メタ）アクリレート、１−エチルシクロオクチル（メタ）アクリレート等が挙げられる。
酸脱離性基を有する単量体は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In particular, in the case of producing a resist composition that is applied to a pattern forming method that is exposed to light having a wavelength of 250 nm or less, as a preferred example of a monomer having an acid leaving group, for example, 2-methyl-2- Adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 1- (1′-adamantyl) -1-methylethyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl ( Examples include meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, isopropyl adamantyl (meth) acrylate, 1-ethylcyclooctyl (meth) acrylate, and the like.
As the monomer having an acid leaving group, one type may be used alone, or two or more types may be used in combination.

［その他の構成単位］
その他の構成単位に対応する単量体は、上記極性基を有する単量体および上記酸脱離性基を有する単量体と共重合可能な公知の単量体を使用することができる。
例えば、以下のものが挙げられる。
酸脱離性基および極性基を有しない、脂環式骨格（非極性脂環式骨格）を有する単量体；（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ノルボルニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸トリシクロデカニル、（メタ）アクリル酸ジシクロペンタジエニル、これらの化合物の脂環式骨格上に炭素数１〜６の直鎖もしくは分岐のアルキル基を有する誘導体等。
直鎖もしくは分岐構造を有する（メタ）アクリル酸エステル；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸メトキシメチル、（メタ）アクリル酸ｎ−プロポキシエチル、（メタ）アクリル酸イソプロポキシエチル、（メタ）アクリル酸ｎ−ブトキシエチル、（メタ）アクリル酸イソブトキシエチル、（メタ）アクリル酸ｔｅｒｔ−ブトキシエチル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシ−ｎ−プロピル、（メタ）アクリル酸４−ヒドロキシ−ｎ−ブチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸１−エトキシエチル、（メタ）アクリル酸２，２，２−トリフルオロエチル、（メタ）アクリル酸２，２，３，３−テトラフルオロ−ｎ−プロピル、（メタ）アクリル酸２，２，３，３，３−ペンタフルオロ−ｎ−プロピル、α−（トリ）フルオロメチルアクリル酸メチル、α−（トリ）フルオロメチルアクリル酸エチル、α−（トリ）フルオロメチルアクリル酸２−エチルヘキシル、α−（トリ）フルオロメチルアクリル酸ｎ−プロピル、α−（トリ）フルオロメチルアクリル酸イソプロピル、α−（トリ）フルオロメチルアクリル酸ｎ−ブチル、α−（トリ）フルオロメチルアクリル酸イソブチル、α−（トリ）フルオロメチルアクリル酸ｔｅｒｔ−ブチル、α−（トリ）フルオロメチルアクリル酸メトキシメチル、α−（トリ）フルオロメチルアクリル酸エトキシエチル、α−（トリ）フルオロメチルアクリル酸ｎ−プロポキシエチル、α−（トリ）フルオロメチルアクリル酸イソプロポキシエチル、α−（トリ）フルオロメチルアクリル酸ｎ−ブトキシエチル、α−（トリ）フルオロメチルアクリル酸イソブトキシエチル、α−（トリ）フルオロメチルアクリル酸ｔｅｒｔ−ブトキシエチル等。 [Other structural units]
As the monomer corresponding to the other structural unit, a known monomer copolymerizable with the monomer having the polar group and the monomer having the acid leaving group can be used.
For example, the following are mentioned.
Monomers having an alicyclic skeleton (non-polar alicyclic skeleton) having no acid leaving group or polar group; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate Adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, linear or branched having 1 to 6 carbon atoms on the alicyclic skeleton of these compounds Derivatives having an alkyl group.
(Meth) acrylic acid ester having a straight chain or branched structure; methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic Isopropyl acid, butyl (meth) acrylate, isobutyl (meth) acrylate, methoxymethyl (meth) acrylate, n-propoxyethyl (meth) acrylate, isopropoxyethyl (meth) acrylate, (meth) acrylate n -Butoxyethyl, isobutoxyethyl (meth) acrylate, tert-butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxy-n-propyl, (meth) acrylic acid 4-hydroxy-n Butyl, 2-ethoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- (meth) acrylate Tetrafluoro-n-propyl, 2,2,3,3,3-pentafluoro-n-propyl (meth) acrylate, methyl α- (tri) fluoromethyl acrylate, ethyl α- (tri) fluoromethyl acrylate , Α- (tri) fluoromethyl acrylate 2-ethylhexyl, α- (tri) fluoromethyl acrylate n-propyl, α- (tri) fluoromethyl acrylate, α- (tri) fluoromethyl acrylate n-butyl , Α- (tri) fluoromethyl acrylate, tert-butyl α- (tri) fluoromethyl acrylate, α- (tri Methoxymethyl fluoromethyl acrylate, ethoxyethyl α- (tri) fluoromethyl acrylate, n-propoxyethyl α- (tri) fluoromethyl acrylate, isopropoxyethyl α- (tri) fluoromethyl acrylate, α- (tri ) N-butoxyethyl fluoromethyl acrylate, isobutoxyethyl α- (tri) fluoromethyl acrylate, tert-butoxyethyl α- (tri) fluoromethyl acrylate, and the like.

本発明におけるリソグラフィー用重合体は、リソグラフィー工程に用いられる重合体であれば、特に限定されずに適用することができる。
例えば、レジスト膜の形成に用いられるレジスト用重合体、レジスト膜の上層に形成される反射防止膜（ＴＡＲＣ）またはレジスト膜の下層に形成される反射防止膜（ＢＡＲＣ）の形成に用いられる反射防止膜用重合体、ギャップフィル膜の形成に用いられるギャップフィル膜重合体、トップコート膜の形成に用いられるトップコート膜用重合体等が挙げられる。
レジスト用重合体の例としては、前記酸脱離性基を有する構成単位の１種以上と、前記極性基を有する構成単位の１種以上とを含む共重合体が挙げられる。 The polymer for lithography in the present invention is not particularly limited as long as it is a polymer used in the lithography process.
For example, a resist polymer used for forming a resist film, an antireflection film (TARC) formed on the upper layer of the resist film, or an antireflection film (BARC) formed on the lower layer of the resist film. Examples thereof include a film polymer, a gap fill film polymer used for forming a gap fill film, and a top coat film polymer used for forming a top coat film.
Examples of the resist polymer include a copolymer containing one or more of the structural units having the acid-eliminable group and one or more of the structural units having the polar group.

反射防止膜用重合体の例としては、吸光性基を有する構成単位と、レジスト膜と混合を避けるため、硬化剤などと反応して硬化可能なアミノ基、アミド基、ヒドロキシル基、エポキシ基等の反応性官能基を有する構成単位とを含む共重合体が挙げられる。
吸光性基とは、レジスト組成物中の感光成分が感度を有する波長領域の光に対して、高い吸収性能を有する基であり、具体例としては、アントラセン環、ナフタレン環、ベンゼン環、キノリン環、キノキサリン環、チアゾール環等の環構造（任意の置換基を有していてもよい。）を有する基が挙げられる。
特に、照射光として、ＫｒＦレーザ光が用いられる場合には、アントラセン環または任意の置換基を有するアントラセン環が好ましく、ＡｒＦレーザ光が用いられる場合には、ベンゼン環または任意の置換基を有するベンゼン環が好ましい。
上記任意の置換基としては、フェノール性水酸基、アルコール性水酸基、カルボキシ基、カルボニル基、エステル基、アミノ基、またはアミド基等が挙げられる。これらのうち、吸光性基として、保護されたまたは保護されていないフェノール性水酸基を有するものが、良好な現像性・高解像性の観点から好ましい。上記吸光性基を有する構成単位・単量体として、例えば、ベンジル（メタ）アクリレート、ｐ−ヒドロキシフェニル（メタ）アクリレート等が挙げられる。 Examples of the polymer for antireflection film include a structural unit having a light-absorbing group and an amino group, an amide group, a hydroxyl group, an epoxy group, etc. that can be cured by reacting with a curing agent to avoid mixing with the resist film. And a copolymer containing a structural unit having a reactive functional group.
The light-absorbing group is a group having high absorption performance with respect to light in a wavelength region where the photosensitive component in the resist composition is sensitive. Specific examples include an anthracene ring, naphthalene ring, benzene ring, quinoline ring. , A group having a ring structure (optionally substituted) such as a quinoxaline ring and a thiazole ring.
In particular, when KrF laser light is used as irradiation light, an anthracene ring or an anthracene ring having an arbitrary substituent is preferable, and when ArF laser light is used, a benzene ring or a benzene having an arbitrary substituent is used. A ring is preferred.
Examples of the optional substituent include a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxy group, a carbonyl group, an ester group, an amino group, and an amide group. Of these, those having a protected or unprotected phenolic hydroxyl group as the light-absorbing group are preferable from the viewpoint of good developability and high resolution. Examples of the structural unit / monomer having the light-absorbing group include benzyl (meth) acrylate and p-hydroxyphenyl (meth) acrylate.

ギャップフィル膜用重合体の例としては、狭いギャップに流れ込むための適度な粘度を有し、レジスト膜や反射防止膜との混合を避けるため、硬化剤などと反応して硬化可能な反応性官能基を有する構成単位を含む共重合体、具体的にはアルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、エポキシアルキル（メタ）アクリレート等の単量体との共重合体が挙げられる。
液浸リソグラフィーに用いられるトップコート膜用重合体の例としては、カルボキシル基を有する構成単位を含む共重合体、水酸基が置換したフッ素含有基を有する構成単位を含む共重合体等が挙げられる。 Examples of polymers for gap fill films are reactive functionalities that have a suitable viscosity for flowing into narrow gaps and can be cured by reacting with curing agents to avoid mixing with resist films and antireflection films. A copolymer containing a structural unit having a group, specifically, a copolymer with a monomer such as an alkyl (meth) acrylate, a hydroxyalkyl (meth) acrylate, or an epoxyalkyl (meth) acrylate may be mentioned.
Examples of the polymer for the topcoat film used in immersion lithography include a copolymer containing a structural unit having a carboxyl group, a copolymer containing a structural unit having a fluorine-containing group substituted with a hydroxyl group, and the like.

また、本発明に用いられる単量体は、反応性、残存単量体および低分子量重合体の低減、レジスト性能の観点から、メタクリレート骨格を有する単量体であることが好ましい。   The monomer used in the present invention is preferably a monomer having a methacrylate skeleton from the viewpoints of reactivity, reduction of residual monomers and low molecular weight polymers, and resist performance.

＜リソグラフィー用重合体溶液の製造方法＞
本発明のリソグラフィー用重合体の製造方法は、下記工程を有する。
［重合工程］
重合方法としては溶液重合法を用いる。すなわち、重合溶媒の存在下に重合開始剤を使用して単量体をラジカル重合させて重合反応溶液を得る。
溶液重合法において、単量体および重合開始剤の反応容器への供給は、連続供給であってもよく、滴下供給であってもよい。溶液重合法としては、製造ロットの違いによる平均分子量、分子量分布等のばらつきが小さく、再現性のある重合体が簡便に得られる点から、単量体および重合開始剤を反応容器内に滴下する滴下重合法が好ましい。 <Method for producing polymer solution for lithography>
The manufacturing method of the polymer for lithography of this invention has the following process.
[Polymerization process]
A solution polymerization method is used as the polymerization method. That is, the polymerization reaction solution is obtained by radical polymerization of the monomer using a polymerization initiator in the presence of a polymerization solvent.
In the solution polymerization method, the monomer and the polymerization initiator may be supplied to the reaction vessel either continuously or dropwise. As a solution polymerization method, a monomer and a polymerization initiator are dropped into a reaction vessel from the viewpoint that variations in average molecular weight and molecular weight distribution due to differences in production lots are small and a reproducible polymer can be easily obtained. The dropping polymerization method is preferred.

滴下重合法においては、反応容器内を所定の重合温度まで加熱した後、単量体および重合開始剤を、それぞれ独立に、または任意の組み合わせで、反応容器内に滴下する。
単量体は、単量体のみで滴下してもよく、単量体を重合溶媒に溶解させた単量体溶液として滴下してもよい。
重合溶媒および／または単量体をあらかじめ反応容器に仕込んでもよい。
重合開始剤は、単量体に直接に溶解させてもよく、単量体溶液に溶解させてもよく、重合溶媒のみに溶解させてもよい。
単量体および重合開始剤は、同じ貯槽内で混合した後、反応容器中に滴下してもよく；それぞれ独立した貯槽から反応容器中に滴下してもよく；それぞれ独立した貯槽から反応容器に供給する直前で混合し、反応容器中に滴下してもよい。
単量体および重合開始剤は、一方を先に滴下した後、遅れて他方を滴下してもよく、両方を同じタイミングで滴下してもよい。
滴下速度は、滴下終了まで一定であってもよく、単量体または重合開始剤の消費速度に応じて、多段階に変化させてもよい。
滴下は、連続的に行ってもよく、間欠的に行ってもよい。
重合温度は、５０〜１５０℃が好ましい。 In the dropping polymerization method, the inside of the reaction vessel is heated to a predetermined polymerization temperature, and then the monomer and the polymerization initiator are dropped into the reaction vessel independently or in any combination.
A monomer may be dripped only with a monomer, and may be dripped as a monomer solution which melt | dissolved the monomer in the polymerization solvent.
A polymerization solvent and / or a monomer may be charged into the reaction vessel in advance.
The polymerization initiator may be dissolved directly in the monomer, may be dissolved in the monomer solution, or may be dissolved only in the polymerization solvent.
The monomer and the polymerization initiator may be dropped into the reaction vessel after mixing in the same storage tank; they may be dropped into the reaction container from each independent storage tank; They may be mixed immediately before feeding and dropped into the reaction vessel.
One of the monomer and the polymerization initiator may be dropped first, and then the other may be dropped with a delay, or both may be dropped at the same timing.
The dropping rate may be constant until the end of dropping, or may be changed in multiple stages according to the consumption rate of the monomer or the polymerization initiator.
The dripping may be performed continuously or intermittently.
The polymerization temperature is preferably 50 to 150 ° C.

［追加供給工程］
単量体および重合開始剤の反応容器への供給が終了した後に、重合溶媒で重合開始剤を溶解させた溶液を反応容器に滴下し供給する。（この供給を以後、追加供給と言う。）
本発明において、追加供給工程は、反応容器中に供給される単量体の全使用量のうち８５％以上まで反応率が上昇した後に、供給される重合開始剤の全使用量のうち１．０％〜１５．０％の重合開始剤を含み単量体を含まない溶液を該反応容器内にさらに供給する工程である。 [Additional supply process]
After the supply of the monomer and the polymerization initiator to the reaction vessel is completed, a solution in which the polymerization initiator is dissolved with the polymerization solvent is dropped into the reaction vessel and supplied. (This supply is hereinafter referred to as additional supply.)
In the present invention, the additional supply step is performed after the reaction rate has increased to 85% or more of the total amount of monomers supplied into the reaction vessel, and then 1. In this step, a solution containing 0% to 15.0% of a polymerization initiator and no monomer is further supplied into the reaction vessel.

ここで、単量体を含まない溶液とは、実質的に単量体を含まないことを意味する。即ち、単量体の添加を目的とする意図的な手段を取らないことを意味し、例えば不純物として原材料に含有されるものなどによる微量分まで除外する趣旨ではない。
追加供給を行うタイミングは、反応溶液の反応率が８５％以上であれば、単量体の反応容器への供給終了の直後であってもよく、さらなる低分子量重合体低減を目的として、所定の重合温度を所定時間保持し反応率を高めた後に供給しても良い。
低分子量重合体低減の観点から、追加供給を行うタイミングは、反応溶液の反応率が８６％以上であることがより好ましく、８８％以上であることがさらに好ましく、９０％以上であることが特に好ましい。
重合開始剤の全使用量に対する追加供給の重合開始剤の使用割合としては、重合体溶液中の重合開始剤由来の不純物含有量を低減させる観点から、１５％以下が好ましく、１０％以下がより好ましく、７．０％以下がさらに好ましく、５．０％以下が特に好ましい。
また、追加供給による効果を満足させる観点から、１．０％以上が好ましく、１．５％以上がより好ましく、２．０％以上がさらに好ましく、２．５％以上が特に好ましい。 Here, the solution containing no monomer means substantially not containing any monomer. In other words, it means that intentional means for the addition of the monomer are not taken, and it is not intended to exclude a minute amount due to, for example, those contained in the raw material as impurities.
As long as the reaction rate of the reaction solution is 85% or more, the additional supply may be performed immediately after the completion of the supply of the monomer to the reaction vessel. For the purpose of further reducing the low molecular weight polymer, The polymerization temperature may be maintained for a predetermined time and supplied after increasing the reaction rate.
From the viewpoint of reducing the low molecular weight polymer, the timing of the additional supply is more preferably a reaction rate of the reaction solution of 86% or more, further preferably 88% or more, and particularly preferably 90% or more. preferable.
The proportion of the additionally supplied polymerization initiator relative to the total amount of polymerization initiator used is preferably 15% or less, more preferably 10% or less, from the viewpoint of reducing the content of impurities derived from the polymerization initiator in the polymer solution. Preferably, 7.0% or less is more preferable, and 5.0% or less is particularly preferable.
Further, from the viewpoint of satisfying the effect of additional supply, 1.0% or more is preferable, 1.5% or more is more preferable, 2.0% or more is further preferable, and 2.5% or more is particularly preferable.

重合終了時の反応溶液中における未反応の重合開始剤の残存量を低減させるために、重合開始剤溶液の供給後から所定温度で所定時間保持し、残存する重合開始剤を分解させてもよい。この場合、工程時間短縮の観点から重合温度を所定の重合温度から変動させてもよい。
所定温度で所定時間、重合反応させた後、重合反応を停止させ、重合反応溶液を得る。重合反応を停止させる手法は反応液を冷却させる工程が一般的に用いられるが、ラジカル捕捉剤を投入することによって停止させることもできる。 In order to reduce the remaining amount of the unreacted polymerization initiator in the reaction solution at the end of the polymerization, the remaining polymerization initiator may be decomposed by holding at a predetermined temperature for a predetermined time after the supply of the polymerization initiator solution. . In this case, the polymerization temperature may be varied from a predetermined polymerization temperature from the viewpoint of shortening the process time.
After a polymerization reaction at a predetermined temperature for a predetermined time, the polymerization reaction is stopped to obtain a polymerization reaction solution. As a method for stopping the polymerization reaction, a process of cooling the reaction solution is generally used, but it can also be stopped by adding a radical scavenger.

重合反応溶液の固形分濃度としては、反応率を効率的に高める観点から、２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることがさらに好ましい。   The solid content concentration of the polymerization reaction solution is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more from the viewpoint of efficiently increasing the reaction rate. preferable.

（重合溶媒）
重合溶媒としては、例えば、下記のものが挙げられる。
エーテル類：鎖状エーテル（ジエチルエーテル、プロピレングリコールモノメチルエーテル（以下、「ＰＧＭＥ」と記す。）、トリプロピレングリコールモノメチルエーテル（以下、「ＴＧＭＥ」と記す。）等。）、環状エーテル（テトラヒドロフラン、１，４−ジオキサン等。）等。
エステル類：酢酸メチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、プロピレングリコールモノメチルエーテルアセテート（以下、「ＰＧＭＥＡ」と記す。）、γ−ブチロラクトン等。
ケトン類：アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等。
アミド類：Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド等。
スルホキシド類：ジメチルスルホキシド等。
芳香族炭化水素：ベンゼン、トルエン、キシレン等。
脂肪族炭化水素：ヘキサン等。
脂環式炭化水素：シクロヘキサン等。
重合溶媒は、１種を単独で用いてもよく、２種以上を併用してもよい。 (Polymerization solvent)
Examples of the polymerization solvent include the following.
Ethers: chain ether (diethyl ether, propylene glycol monomethyl ether (hereinafter referred to as “PGME”), tripropylene glycol monomethyl ether (hereinafter referred to as “TGME”), etc.), cyclic ether (tetrahydrofuran, 1 , 4-dioxane, etc.).
Esters: methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”), γ-butyrolactone, and the like.
Ketones: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like.
Amides: N, N-dimethylacetamide, N, N-dimethylformamide and the like.
Sulfoxides: dimethyl sulfoxide and the like.
Aromatic hydrocarbons: benzene, toluene, xylene and the like.
Aliphatic hydrocarbon: hexane and the like.
Alicyclic hydrocarbons: cyclohexane and the like.
A polymerization solvent may be used individually by 1 type, and may use 2 or more types together.

（重合開始剤）
重合開始剤としては、熱により効率的にラジカルを発生するものが好ましい。例えば、アゾ化合物（２,２’−アゾビスイソブチロニトリル、ジメチル−２,２’−アゾビスイソブチレート、２,２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］等。）、有機過酸化物（２,５−ジメチル−２,５−ビス（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、ジ（４−ｔｅｒｔ−ブチルシクロヘキシル）パーオキシジカーボネート等。）等が挙げられる。 (Polymerization initiator)
As the polymerization initiator, those that generate radicals efficiently by heat are preferable. For example, an azo compound (2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Etc.), organic peroxides (2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, di (4-tert-butylcyclohexyl) peroxydicarbonate, etc.) and the like.

重合工程によって得られた重合反応溶液は、必要に応じて重合反応溶液を希釈溶媒で適当な溶液粘度に希釈してもよい。希釈溶媒としては、１，４−ジオキサン、アセトン、ＴＨＦ、ＭＥＫ、ＭＩＢＫ、γ−ブチロラクトン、ＰＧＭＥＡ、ＰＧＭＥ、乳酸エチル等が挙げられる。これらは１種を用いてもよく、２種以上を併用してもよい。   The polymerization reaction solution obtained by the polymerization step may be diluted to an appropriate solution viscosity with a diluting solvent as necessary. Examples of the dilution solvent include 1,4-dioxane, acetone, THF, MEK, MIBK, γ-butyrolactone, PGMEA, PGME, and ethyl lactate. These may use 1 type and may use 2 or more types together.

本発明において、重合体を高い生産性を維持したまま取得できる点では、再沈殿工程やリスラリ工程を含む精製工程を行わず、重合工程のみで未反応の単量体等の不純物の残存および低分子量体の生成を低減することが好ましい。
本発明において、低分子量重合体とは重量平均分子量３５０〜１０００の重合体のことを示し、低分子量重合体の存在割合は、ゲル・パーミエーション・クロマトグラフィー（以下「ＧＰＣ」と記す。）によって求めた重合体ピークのうち、Ｍｗ３５０〜１０００に相当する重合体部分のピーク面積値を重合体ピーク全体の面積値の合計で割った値（面積割合）により求めることができる。
また、残存単量体および重合開始剤の分解物等から構成されるＭｗ３５０以下の化合物の存在割合も、ＧＰＣ測定によって求めた重合体ピークのうち、Ｍｗ３５０以下に相当する重合体部分のピーク面積値を重合体ピーク全体の面積値の合計で割った値（面積割合）により求めることができる。 In the present invention, a polymer can be obtained while maintaining high productivity, and a refining process and a refining process including a recycle process are not performed, and the residual and low impurities such as unreacted monomers are reduced only in the polymerization process. It is preferable to reduce the production of molecular weight bodies.
In the present invention, the low molecular weight polymer means a polymer having a weight average molecular weight of 350 to 1,000, and the existence ratio of the low molecular weight polymer is determined by gel permeation chromatography (hereinafter referred to as “GPC”). Among the obtained polymer peaks, it can be obtained by a value (area ratio) obtained by dividing the peak area value of the polymer portion corresponding to Mw 350 to 1000 by the total area value of the entire polymer peak.
In addition, the proportion of the compound having an Mw of 350 or less composed of the residual monomer and the decomposition product of the polymerization initiator is also the peak area value of the polymer portion corresponding to the Mw of 350 or less among the polymer peaks determined by GPC measurement. Can be determined by a value (area ratio) divided by the total area value of the entire polymer peak.

また、本発明における反応率とは、反応容器中に仕込んだ単量体のうち、重合体へと転化した割合を示し、未反応の残存単量体を定量することで求める。
残存単量体は高速液体クロマトグラフィー（以下「ＨＰＬＣ」と記す。）により定量される。
重合体中の不純物としての単量体含有量は２．０質量％以下がより好ましく、１．０質量％以下がさらに好ましく、０．５質量％以下が特に好ましい。
本発明におけるリソグラフィー用重合体の製造方法では、（メタ）アクリレート骨格を持った単量体１種のみを重合してもよく、２種以上を共重合しても良い。 Moreover, the reaction rate in this invention shows the ratio converted into the polymer among the monomers prepared in reaction container, and calculates | requires it by quantifying the unreacted residual monomer.
The residual monomer is quantified by high performance liquid chromatography (hereinafter referred to as “HPLC”).
The monomer content as an impurity in the polymer is more preferably 2.0% by mass or less, further preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less.
In the method for producing a lithography polymer in the present invention, only one monomer having a (meth) acrylate skeleton may be polymerized, or two or more monomers may be copolymerized.

本発明の効果は、炭化水素環を含む単量体を用いて共重合する系において効果が得られやすく、その炭化水素環が嵩高い程、より効果が得られやすいことから、この炭化水素環としては、多環であることが好ましい。
ここで、炭化水素環は置換基を有してもよい。 The effect of the present invention is that an effect is easily obtained in a system in which a monomer containing a hydrocarbon ring is used for copolymerization, and the higher the volume of the hydrocarbon ring, the easier the effect is obtained. Is preferably polycyclic.
Here, the hydrocarbon ring may have a substituent.

（精製）
本発明のリソグラフィー用重合体の製造方法で得られる重合体溶液は、必要に応じて精製を行うこともできる。
例えば、１，４−ジオキサン、アセトン、ＴＨＦ、ＭＥＫ、ＭＩＢＫ、γ−ブチロラクトン、ＰＧＭＥＡ、ＰＧＭＥ、乳酸エチル等の希釈溶媒で適当な溶液粘度に希釈した後、メタノール、エタノール、イソプロピルアルコール、水、ヘキサン、ヘプタン、ジイソプロピルエーテル、またはそれらの混合溶媒等の貧溶媒中に滴下し、重合体を析出させる。この工程は再沈殿工程と呼ばれ、重合体溶液中に残存する未反応の単量体、重合開始剤等を取り除くために非常に有効である。未反応単量体は、そのまま残存しているとレジスト組成物として用いた場合に感度が低下するため、できるだけ取り除くことが好ましい。 (Purification)
The polymer solution obtained by the method for producing a polymer for lithography of the present invention can be purified as necessary.
For example, after diluting to an appropriate solution viscosity with a diluting solvent such as 1,4-dioxane, acetone, THF, MEK, MIBK, γ-butyrolactone, PGMEA, PGME, ethyl lactate, methanol, ethanol, isopropyl alcohol, water, hexane In a poor solvent such as heptane, diisopropyl ether, or a mixed solvent thereof, the polymer is precipitated. This process is called a reprecipitation process, and is very effective for removing unreacted monomers, polymerization initiators and the like remaining in the polymer solution. If the unreacted monomer remains as it is, the sensitivity decreases when used as a resist composition, so it is preferable to remove it as much as possible.

貧溶媒としては、製造する重合体が溶解せずに析出する溶媒であればよく、公知のものを使用できるが、半導体リソグラフィー用重合体に用いられる未反応の単量体、重合開始剤等を効率的に取り除くことができる点で、メタノール、イソプロピルアルコール、ジイソプロピルエーテル、ヘプタン、水、またはそれらの混合溶媒が好ましい。
使用する貧溶媒の量は残存する未反応単量体をより低減できるため、重合体溶液と同質量以上用いることができ、３倍以上が好ましく、４倍以上がより好ましく、５倍以上がさらに好ましく、６倍以上が特に好ましい。 As the poor solvent, any solvent may be used as long as the polymer to be produced is not dissolved, and any known solvent can be used, but unreacted monomers, polymerization initiators and the like used in the polymer for semiconductor lithography can be used. Methanol, isopropyl alcohol, diisopropyl ether, heptane, water, or a mixed solvent thereof is preferable because it can be efficiently removed.
Since the amount of the poor solvent used can further reduce the remaining unreacted monomer, it can be used in the same mass or more as the polymer solution, preferably 3 times or more, more preferably 4 times or more, and further more preferably 5 times or more. Preferably, 6 times or more is particularly preferable.

その後、析出物をろ別し、湿粉を得る。
また、湿粉を再び貧溶媒に分散させて重合体分散液を得た後、重合体をろ別する操作を繰り返すこともできる。この工程は、リスラリ工程と呼ばれ、重合体湿粉中に残存する未反応の単量体、重合開始剤等をより低減させるために非常に有効である。
重合体を高い生産性を維持したまま取得できる点ではリスラリ工程を行わず、再沈殿工程のみで重合体を精製することが好ましい。 Thereafter, the precipitate is filtered off to obtain a wet powder.
Further, after the wet powder is dispersed again in a poor solvent to obtain a polymer dispersion, an operation of filtering the polymer can be repeated. This step is called a restructuring step and is very effective for further reducing unreacted monomers, polymerization initiators and the like remaining in the polymer wet powder.
It is preferable to purify the polymer only by the reprecipitation step without performing the restructuring step in that the polymer can be obtained while maintaining high productivity.

得られた湿粉は、十分に乾燥して、乾燥粉末状の重合体を得ることができる。
また、ろ別した後、乾燥せずに湿粉のまま適当な溶媒に溶解させてリソグラフィー用組成物として用いてもよく、濃縮して低沸点化合物を除去してからリソグラフィー用組成物として用いてもよい。その際、保存安定剤等の添加剤を適宜添加してもよい。
また、乾燥させた後に適当な溶媒に溶解させ、さらに濃縮して低沸点化合物を除去してからリソグラフィー用組成物として用いてもよい。その際、保存安定剤等の添加剤を適宜添加してもよい。 The obtained wet powder can be sufficiently dried to obtain a dry powder polymer.
In addition, after filtering off, it may be used as a lithographic composition by dissolving it in a suitable solvent without drying and using it as a lithographic composition. Also good. At that time, additives such as a storage stabilizer may be appropriately added.
Further, after drying, it may be dissolved in a suitable solvent and further concentrated to remove the low boiling point compound, and then used as a composition for lithography. At that time, additives such as a storage stabilizer may be appropriately added.

製品としてのリソグラフィー用重合体溶液における重合体の固形分濃度は、５〜６０質量％が好ましく、１０〜５０質量％がより好ましい。該固形分濃度が上記範囲の下限値以上であると生産効率を低下させることなく製造ができ、上限値以下であると溶液の粘度上昇が抑えられ取扱性に優れる。
好ましい固形分濃度とするために、重合工程の後に該リソグラフィー用重合体溶液に必要に応じて、例えば１，４−ジオキサン、アセトン、ＴＨＦ、ＭＥＫ、ＭＩＢＫ、γ−ブチロラクトン、ＰＧＭＥＡ、ＰＧＭＥ、乳酸エチル等の希釈溶媒で希釈してもよい。
なお、本発明において、溶液状の重合体（重合体を含有する溶液）における、重合体の固形分濃度の値は、重合反応に用いた単量体の合計質量を重合体の質量とみなして算出される値である。 5-60 mass% is preferable and, as for the solid content concentration of the polymer solution in the polymer solution for lithography as a product, 10-50 mass% is more preferable. When the solid content concentration is not less than the lower limit of the above range, the production can be carried out without decreasing the production efficiency, and when it is not more than the upper limit, the increase in the viscosity of the solution is suppressed and the handleability is excellent.
In order to obtain a preferable solid content concentration, the lithographic polymer solution is optionally added to the lithographic polymer solution after the polymerization step, for example, 1,4-dioxane, acetone, THF, MEK, MIBK, γ-butyrolactone, PGMEA, PGME, ethyl lactate. You may dilute with dilution solvents, such as.
In the present invention, the value of the solid content concentration of the polymer in the solution polymer (solution containing the polymer) is regarded as the total mass of the monomers used in the polymerization reaction as the mass of the polymer. This is a calculated value.

＜レジスト組成物の製造方法＞
本発明のレジスト組成物の製造方法は、本発明の製造方法でレジスト用重合体を製造し、得られたレジスト用重合体と、活性光線または放射線の照射により酸を発生する化合物（以下、「光酸発生剤」ということもある。）を混合する工程を有するレジスト組成物の製造方法である。好ましくは該重合体と、光酸発生剤とをレジスト溶媒に溶解させてレジスト組成物を製造する。
得られるレジスト組成物は、本発明の製造方法で得られるレジスト用重合体と、活性光線または放射線の照射により酸を発生する化合物とを含有する、化学増幅型レジスト組成物である。 <Method for producing resist composition>
The method for producing a resist composition of the present invention comprises producing a resist polymer by the production method of the present invention, and the resulting resist polymer and a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter referred to as “ This is a method for producing a resist composition having a step of mixing a photoacid generator ”. Preferably, the polymer and the photoacid generator are dissolved in a resist solvent to produce a resist composition.
The resulting resist composition is a chemically amplified resist composition containing a resist polymer obtained by the production method of the present invention and a compound that generates an acid upon irradiation with actinic rays or radiation.

［レジスト溶媒］
レジスト溶媒としては、前記重合溶媒と同様の溶媒が挙げられる。 [Resist solvent]
Examples of the resist solvent include the same solvents as the polymerization solvent.

［活性光線または放射線の照射により酸を発生する化合物（光酸発生剤）］
光酸発生剤は、化学増幅型レジスト組成物の光酸発生剤として公知のものを適宜選択して用いることができる。光酸発生剤は、１種を単独で用いてもよく、２種以上を併用してもよい。
光酸発生剤としては、例えば、オニウム塩化合物、スルホンイミド化合物、スルホン化合物、スルホン酸エステル化合物、キノンジアジド化合物、ジアゾメタン化合物等が挙げられる。
レジスト組成物における光酸発生剤の含有量は、重合体１００質量部に対して、０．１〜２０質量部が好ましく、０．５〜１０質量部がより好ましい。 [Compound that generates acid upon irradiation with actinic ray or radiation (photoacid generator)]
As the photoacid generator, known photoacid generators for the chemically amplified resist composition can be appropriately selected and used. A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, quinone diazide compounds, diazomethane compounds, and the like.
0.1-20 mass parts is preferable with respect to 100 mass parts of polymers, and, as for content of the photo-acid generator in a resist composition, 0.5-10 mass parts is more preferable.

［含窒素化合物］
化学増幅型レジスト組成物は、含窒素化合物を含んでいてもよい。含窒素化合物を含むことにより、レジストパターン形状、引き置き経時安定性等がさらに向上する。つまり、レジストパターンの断面形状が矩形により近くなり、また、レジスト膜に光を照射し、ついでベーク（ＰＥＢ）した後、次の現像処理までの間に数時間放置されることが半導体素子の量産ラインではあるが、そのような放置（経時）したときにレジストパターンの断面形状の劣化の発生がより抑制される。
含窒素化合物としては、アミンが好ましく、第２級低級脂肪族アミン、第３級低級脂肪族アミンがより好ましい。
含窒素化合物の量は、重合体１００質量部に対して、０．０１〜２質量部が好ましい。 [Nitrogen-containing compounds]
The chemically amplified resist composition may contain a nitrogen-containing compound. By including the nitrogen-containing compound, the resist pattern shape, the stability over time, and the like are further improved. That is, the cross-sectional shape of the resist pattern becomes closer to a rectangle, and the resist film is irradiated with light, then baked (PEB), and then left for several hours before the next development process. Although it is a line, the occurrence of the deterioration of the cross-sectional shape of the resist pattern is further suppressed when left as such (timed).
The nitrogen-containing compound is preferably an amine, more preferably a secondary lower aliphatic amine or a tertiary lower aliphatic amine.
As for the quantity of a nitrogen-containing compound, 0.01-2 mass parts is preferable with respect to 100 mass parts of polymers.

［有機カルボン酸、リンのオキソ酸またはその誘導体］
化学増幅型レジスト組成物は、有機カルボン酸、リンのオキソ酸またはその誘導体（以下、これらをまとめて酸化合物と記す。）を含んでいてもよい。酸化合物を含むことにより、含窒素化合物の配合による感度劣化を抑えることができ、また、レジストパターン形状、引き置き経時安定性等がさらに向上する。
有機カルボン酸としては、マロン酸、クエン酸、リンゴ酸、コハク酸、安息香酸、サリチル酸等が挙げられる。
リンのオキソ酸またはその誘導体としては、リン酸またはその誘導体、ホスホン酸またはその誘導体、ホスフィン酸またはその誘導体等が挙げられる。
酸化合物の量は、重合体１００質量部に対して、０．０１〜５質量部が好ましい。 [Organic carboxylic acid, phosphorus oxo acid or derivative thereof]
The chemically amplified resist composition may contain an organic carboxylic acid, an oxo acid of phosphorus, or a derivative thereof (hereinafter collectively referred to as an acid compound). By including an acid compound, it is possible to suppress deterioration in sensitivity due to the blending of the nitrogen-containing compound, and further improve the resist pattern shape, stability with time of leaving, and the like.
Examples of the organic carboxylic acid include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid.
Examples of phosphorus oxo acids or derivatives thereof include phosphoric acid or derivatives thereof, phosphonic acid or derivatives thereof, phosphinic acid or derivatives thereof, and the like.
The amount of the acid compound is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymer.

［添加剤］
本発明のレジスト組成物は、必要に応じて、界面活性剤、その他のクエンチャー、増感剤、ハレーション防止剤、保存安定剤、消泡剤等の各種添加剤を含んでいてもよい。該添加剤は、当該分野で公知のものであればいずれも使用可能である。また、これら添加剤の量は、特に限定されず、適宜決めればよい。 [Additive]
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. Any additive can be used as long as it is known in the art. Further, the amount of these additives is not particularly limited, and may be determined as appropriate.

＜微細パターンが形成された基板の製造方法＞
本発明の、微細パターンが形成された基板の製造方法は、本発明の製造方法でレジスト組成物を製造する工程と、得られたレジスト組成物を、基板の被加工面上に塗布してレジスト膜を形成する工程と、該レジスト膜に対して露光する工程と、露光されたレジスト膜を現像液を用いて現像する工程を有する。
以下、該基板の製造方法の一例について説明する。 <Manufacturing method of substrate on which fine pattern is formed>
The method for producing a substrate on which a fine pattern is formed according to the present invention comprises a step of producing a resist composition by the production method of the present invention, and applying the obtained resist composition onto a work surface of the substrate to form a resist. A step of forming a film, a step of exposing the resist film, and a step of developing the exposed resist film using a developer.
Hereinafter, an example of the manufacturing method of the substrate will be described.

まず、所望の微細パターンを形成しようとするシリコンウエハー等の被加工基板の表面（被加工面）に、レジスト組成物をスピンコート等により塗布する。
そして、該レジスト組成物が塗布された被加工基板を、ベーキング処理（プリベーク）等で乾燥することにより、基板上にレジスト膜を形成する。
次いで、レジスト膜に、フォトマスクを介して、２５０ｎｍ以下の波長の光を照射して潜像を形成する（露光）。
照射光としては、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー、Ｆ２エキシマレーザー、ＥＵＶエキシマレーザーが好ましく、ＡｒＦエキシマレーザーが特に好ましい。また、電子線を照射してもよい。
また、該レジスト膜と露光装置の最終レンズとの間に、純水、パーフルオロ−２−ブチルテトラヒドロフラン、パーフルオロトリアルキルアミン等の高屈折率液体を介在させた状態で光を照射する液浸露光を行ってもよい。 First, a resist composition is applied by spin coating or the like to the surface (processed surface) of a substrate to be processed such as a silicon wafer on which a desired fine pattern is to be formed.
And the resist film is formed on a board | substrate by drying the to-be-processed board | substrate with which this resist composition was apply | coated by baking process (prebaking) etc.
Next, the resist film is irradiated with light having a wavelength of 250 nm or less through a photomask to form a latent image (exposure).
As irradiation light, a KrF excimer laser, an ArF excimer laser, an F 2 excimer laser, and an EUV excimer laser are preferable, and an ArF excimer laser is particularly preferable. Moreover, you may irradiate an electron beam.
In addition, immersion in which light is irradiated with a high refractive index liquid such as pure water, perfluoro-2-butyltetrahydrofuran, or perfluorotrialkylamine interposed between the resist film and the final lens of the exposure apparatus. Exposure may be performed.

露光後、適宜熱処理（露光後ベーク、ＰＥＢ）し、レジスト膜にアルカリ現像液を接触させ、露光部分を現像液に溶解させ、除去する（現像）。アルカリ現像液としては、公知のものを用いることができる。
現像後、基板を純水等で適宜リンス処理する。このようにして被加工基板上にレジストパターンが形成される。 After the exposure, heat treatment is appropriately performed (post-exposure baking, PEB), an alkali developer is brought into contact with the resist film, and the exposed portion is dissolved in the developer and removed (development). A well-known thing can be used as an alkali developing solution.
After development, the substrate is appropriately rinsed with pure water or the like. In this way, a resist pattern is formed on the substrate to be processed.

レジストパターンが形成された基板は、適宜熱処理（ポストベーク）してレジストを強化し、レジストのない部分を選択的にエッチングする。
エッチング後、レジストを剥離剤によって除去することによって、パターンが形成された基板が得られる。 The substrate on which the resist pattern is formed is appropriately heat-treated (post-baked) to strengthen the resist and selectively etch the portion without the resist.
After the etching, the resist is removed with a release agent to obtain a substrate on which a pattern is formed.

本発明により得られるレジスト組成物は、該レジスト組成物に含まれる半導体リソグラフィー用重合体の分子量バラツキが小さいため、感度および現像コントラスト等のレジスト性能の安定性に優れる。
したがって、本発明によれば、残存単量体や低分子量重合体の含有量が少ないリソグラフィー用重合体を製造することができる。
該レジスト組成物を用いることによって、高精度の微細なレジストパターンを安定して形成できる。
また、高感度のレジスト組成物の使用が要求される、波長２５０ｎｍ以下の露光光を用いるフォトリソグラフィーまたは電子線リソグラフィー、例えばＡｒＦエキシマレーザー（１９３ｎｍ）を使用するリソグラフィーによる、パターン形成にも好適に用いることができる。 The resist composition obtained by the present invention is excellent in stability of resist performance such as sensitivity and development contrast because the molecular weight variation of the polymer for semiconductor lithography contained in the resist composition is small.
Therefore, according to the present invention, it is possible to produce a polymer for lithography with a small content of residual monomer and low molecular weight polymer.
By using the resist composition, a fine resist pattern with high accuracy can be stably formed.
In addition, it is also suitable for pattern formation by photolithography using exposure light having a wavelength of 250 nm or less or lithography using electron beam lithography such as ArF excimer laser (193 nm), which requires use of a highly sensitive resist composition. be able to.

以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。
また、各実施例、比較例中「部」とあるのは、特に断りのない限り「質量部」を示す。
測定方法および評価方法は以下の方法を用いた。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
In addition, “part” in each example and comparative example means “part by mass” unless otherwise specified.
The measurement method and evaluation method used the following methods.

＜重量平均分子量（Ｍｗ）の測定＞
重合体の重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）は、下記の条件（ＧＰＣ条件）でゲル・パーミエーション・クロマトグラフィーにより、ポリスチレン換算で求めた。
［ＧＰＣ条件］
装置：東ソー社製、東ソー高速ＧＰＣ装置 ＨＬＣ−８２２０ＧＰＣ（商品名）、
分離カラム：昭和電工社製、Ｓｈｏｄｅｘ ＧＰＣ Ｋ−８０５Ｌ（商品名）を３本直列に連結したもの、
測定温度：４０℃、
溶離液：テトラヒドロフラン（ＴＨＦ）、
試料：重合体の約２０ｍｇを５ｍＬのＴＨＦに溶解し、０．５μｍメンブレンフィルターで濾過した溶液、
流量：１ｍＬ／分、
注入量：０．１ｍＬ、
検出器：示差屈折計。 <Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined in terms of polystyrene by gel permeation chromatography under the following conditions (GPC conditions).
[GPC conditions]
Equipment: Tosoh Corporation, Tosoh High Speed GPC Equipment HLC-8220GPC (trade name),
Separation column: manufactured by Showa Denko, Shodex GPC K-805L (trade name) connected in series,
Measurement temperature: 40 ° C.
Eluent: Tetrahydrofuran (THF)
Sample: A solution in which about 20 mg of a polymer is dissolved in 5 mL of THF and filtered through a 0.5 μm membrane filter.
Flow rate: 1 mL / min,
Injection volume: 0.1 mL,
Detector: differential refractometer.

検量線Ｉ：標準ポリスチレンの約２０ｍｇを５ｍＬのＴＨＦに溶解し、０．５μｍメンブレンフィルターで濾過した溶液を用いて、上記の条件で分離カラムに注入し、溶出時間と分子量の関係を求めた。ここで、標準ポリスチレンは、下記の東ソー社製の標準ポリスチレン（いずれも商品名）を用いた。
Ｆ−８０（Ｍｗ＝７０６，０００）、
Ｆ−２０（Ｍｗ＝１９０，０００）、
Ｆ−４（Ｍｗ＝３７，９００）、
Ｆ−１（Ｍｗ＝１０，２００）、
Ａ−２５００（Ｍｗ＝２，６３０）、
Ａ−５００（Ｍｗ＝６８２、５７８、４７４、３７０、２６０の混合物）。 Calibration curve I: About 20 mg of standard polystyrene was dissolved in 5 mL of THF, and the solution was filtered through a 0.5 μm membrane filter and injected into a separation column under the above conditions, and the relationship between elution time and molecular weight was determined. Here, the following standard polystyrenes manufactured by Tosoh Corporation (both are trade names) were used as standard polystyrenes.
F-80 (Mw = 706,000),
F-20 (Mw = 190,000),
F-4 (Mw = 37,900),
F-1 (Mw = 10,200),
A-2500 (Mw = 2,630),
A-500 (mixture of Mw = 682, 578, 474, 370, 260).

残存単量体および重合開始剤の分解物等から構成されるＭｗ３５０以下の化合物の存在割合は、ＧＰＣ測定によって求めた重合体ピークのうち、Ｍｗ３５０以下に相当する重合体部分のピーク面積値を重合体ピーク全体の面積値の合計で割った値（面積割合）により求めた。
低分子量重合体の存在割合は、ＧＰＣ測定によって求めた重合体ピークのうち、Ｍｗ３５０〜１０００に相当する重合体部分のピーク面積値を重合体ピーク全体の面積値の合計で割った値（面積割合）により求めた。 The presence ratio of the compound having a Mw of 350 or less composed of the residual monomer, the decomposition product of the polymerization initiator, and the like overlaps the peak area value of the polymer portion corresponding to the Mw of 350 or less among the polymer peaks obtained by GPC measurement. It calculated | required by the value (area ratio) which divided by the sum total of the area value of the whole union peak.
The presence ratio of the low molecular weight polymer is a value obtained by dividing the peak area value of the polymer portion corresponding to Mw 350 to 1000 among the polymer peaks determined by GPC measurement by the total area value of the entire polymer peak (area ratio). ).

＜残存単量体および反応率の測定＞
重合体の残存単量体の含有量および反応率は、下記のＨＰＬＣ条件で求めた。
［ＨＰＬＣ測定条件］
反応容器内の反応液を０．５ｇ採取し、これをアセトニトリルで希釈し、メスフラスコを用いて全量を５０ｍＬとした。この希釈液を０．２μｍのメンブレンフィルターで濾過し、東ソー社製、高速液体クロマトグラフＨＰＬＣ−８０２０（製品名）を用いて、該希釈液中の未反応の単量体含有量を、単量体ごとに求めた。これらの合計単量体量の反応液中における質量割合（質量％）を反応液中に残存する単量体の含有量とした。検出下限以下は残存単量体量を０質量％とした。
また、残存する単量体の含有量から反応率を定量した。 <Measurement of residual monomer and reaction rate>
The residual monomer content and reaction rate of the polymer were determined under the following HPLC conditions.
[HPLC measurement conditions]
0.5 g of the reaction solution in the reaction vessel was collected, diluted with acetonitrile, and the total volume was adjusted to 50 mL using a volumetric flask. The diluted solution was filtered through a 0.2 μm membrane filter, and the unreacted monomer content in the diluted solution was determined by using a high performance liquid chromatograph HPLC-8020 (product name) manufactured by Tosoh Corporation. Asked for each body. The mass ratio (mass%) of these total monomer amounts in the reaction solution was taken as the content of the monomer remaining in the reaction solution. Below the lower limit of detection, the residual monomer amount was 0% by mass.
Further, the reaction rate was quantified from the content of the remaining monomer.

前記高速液体クロマトグラフによる測定において、分離カラムはジーエルサイエンス社製、Ｉｎｅｒｔｓｉｌ ＯＤＳ−２（商品名）を１本使用し、移動相は水／アセトニトリルのグラジエント系、流量０．８ｍＬ／ｍｉｎ、検出器は東ソー社製、紫外・可視吸光光度計ＵＶ−８０２０（商品名）、検出波長２２０ｎｍ、測定温度４０℃、注入量４μＬで測定する。なお、分離カラムであるＩｎｅｒｔｓｉｌ ＯＤＳ−２（商品名）は、シリカゲル粒径５μｍ、カラム内径４．６ｍｍ×カラム長さ４５０ｍｍのものを使用した。また、移動相のグラジエント条件は、Ａ液を水、Ｂ液をアセトニトリルとし、下記の通りとした。また、単量体の含有量を定量するために、濃度の異なる３種類の各単量体溶液を標準液として用いた。
測定時間０〜３分：Ａ液／Ｂ液＝９０体積％／１０体積％。
測定時間３〜２４分：Ａ液／Ｂ液＝９０体積％／１０体積％から、５０体積％／５０体積％まで。
測定時間２４〜３６．５分：Ａ液／Ｂ液＝５０体積％／５０体積％から、０体積％／１００体積％まで。
測定時間３６．５〜４４分：Ａ液／Ｂ液＝０体積％／１００体積％。 In the measurement by the high performance liquid chromatograph, the separation column uses one Inertsil ODS-2 (trade name) manufactured by GL Sciences, the mobile phase is a water / acetonitrile gradient system, the flow rate is 0.8 mL / min, the detector. Is measured with a UV / visible absorptiometer UV-8020 (trade name) manufactured by Tosoh Corporation, a detection wavelength of 220 nm, a measurement temperature of 40 ° C. and an injection volume of 4 μL. The separation column Inertsil ODS-2 (trade name) used was a silica gel particle diameter of 5 μm, a column inner diameter of 4.6 mm × column length of 450 mm. The gradient conditions of the mobile phase were as follows, with the liquid A being water and the liquid B being acetonitrile. In order to quantify the monomer content, three types of monomer solutions having different concentrations were used as standard solutions.
Measurement time 0 to 3 minutes: A liquid / B liquid = 90 vol% / 10 vol%.
Measurement time: 3 to 24 minutes: A liquid / B liquid = 90 volume% / 10 volume% to 50 volume% / 50 volume%.
Measurement time: 24 to 36.5 minutes: A liquid / B liquid = 50 volume% / 50 volume% to 0 volume% / 100 volume%.
Measurement time: 36.5 to 44 minutes: Liquid A / liquid B = 0 volume% / 100 volume%.

＜感度測定＞
レジスト組成物を、６インチシリコンウエハー上に回転塗布し、ホットプレート上で１２０℃、６０秒間プリベーク（ＰＡＢ）して、厚さ３００ｎｍの薄膜を形成した。ＡｒＦエキシマレーザー露光装置（リソテックジャパン製 ＶＵＶＥＳ−４５００）を用い、露光量を変えて１０ｍｍ×１０ｍｍ２の１８ショットを露光した。次いで１１０℃、６０秒間ポストベーク（ＰＥＢ）した後、レジスト現像アナライザー（リソテックジャパン製ＲＤＡ−８００）を用い、２３℃にて２．３８質量％テトラメチルアンモニウムヒドロキシド水溶液で６５秒間現像し、各露光量における現像中のレジスト膜厚の経時変化を測定した。 <Sensitivity measurement>
The resist composition was spin-coated on a 6-inch silicon wafer and prebaked (PAB) at 120 ° C. for 60 seconds on a hot plate to form a thin film having a thickness of 300 nm. Using an ArF excimer laser exposure apparatus (VUVES-4500, manufactured by RISOTEC Japan), 18 shots of 10 mm × 10 mm 2 were exposed while changing the exposure amount. Next, after post-baking (PEB) at 110 ° C. for 60 seconds, using a resist development analyzer (RDA-800 manufactured by RISOTEC Japan), development is performed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 65 seconds. The change with time of the resist film thickness during development at each exposure amount was measured.

［解析］
得られたデータを基に、露光量（ｍＪ／ｃｍ２）の対数と、初期膜厚に対する６０秒間現像した時点での残存膜厚率（以下、残膜率という）（％）をプロットした曲線（以下、露光量−残膜率曲線という）を作成し、Ｅｔｈ感度（残膜率０％とするための必要露光量であり、感度を表す。）を以下の通り求めた。
Ｅｔｈ感度：露光量−残膜率曲線が残膜率０％と交わる露光量（ｍＪ／ｃｍ２） [analysis]
A curve plotting the logarithm of the exposure amount (mJ / cm 2 ) and the residual film thickness ratio (hereinafter referred to as the residual film ratio) (%) when developed for 60 seconds with respect to the initial film thickness, based on the obtained data (Hereinafter, exposure amount-residual film rate curve) was prepared, and Eth sensitivity (required exposure amount for setting the residual film rate to 0%, which represents sensitivity) was determined as follows.
Eth sensitivity: exposure amount (mJ / cm 2 ) at which the exposure amount-residual film rate curve intersects with a residual film rate of 0%

＜実施例１＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、乳酸エチル１６１．３ｇを入れた。フラスコ内を窒素で置換し、窒素雰囲気を保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８０℃に上げた。
その後、下記混合物１を滴下漏斗より、４時間かけてフラスコ内に滴下した。混合物１の滴下終了から３０分間温度を保持した。その後、下記混合物２を滴下漏斗より、５分間かけてフラスコ内に滴下し、上記混合物２の滴下終了からさらに８０℃の温度を２時間３０分保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物１滴下終了直後および、混合物２滴下直前および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表１に示す。 <Example 1>
161.3 g of ethyl lactate was placed in a 1 L SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, and a thermometer. The inside of the flask was replaced with nitrogen, the flask was placed in a hot water bath while maintaining the nitrogen atmosphere, and the temperature of the hot water bath was raised to 80 ° C. while stirring the inside of the flask.
Then, the following mixture 1 was dripped in the flask over 4 hours from the dropping funnel. The temperature was maintained for 30 minutes after completion of the dropwise addition of the mixture 1. Thereafter, the following mixture 2 was dropped into the flask over 5 minutes from the dropping funnel, and the temperature of 80 ° C. was further maintained for 2 hours and 30 minutes after the dropping of the mixture 2 was completed.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after completion of dropping of the mixture 1 during the polymerization reaction, immediately before dropping of the mixture 2 and immediately before cooling, 1 g of a reaction solution was sampled from the flask, and the reaction rate and weight average molecular weight of the sampled polymerization reaction solution were collected by the above method. (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 1.

［混合物１］
下記式（ｍ１）の単量体を６８．０ｇ、
下記式（ｍ２）の単量体を７８．４ｇ、
下記式（ｍ３）の単量体を４７．２ｇ、
乳酸エチルを２２８．５ｇ、
ジメチル−２，２’−アゾビスイソブチレート（和光純薬工業株式会社製；以下、Ｖ−６０１）を５．７５ｇ。
［混合物２］
乳酸エチルを１．０ｇ、
Ｖ６０１（商品名）を０．４３ｇ。 [Mixture 1]
68.0 g of a monomer of the following formula (m1),
78.4 g of a monomer of the following formula (m2),
47.2 g of a monomer of the following formula (m3),
228.5 g of ethyl lactate,
5.75 g of dimethyl-2,2′-azobisisobutyrate (Wako Pure Chemical Industries, Ltd .; hereinafter referred to as V-601).
[Mixture 2]
1.0 g of ethyl lactate,
V601 (trade name) is 0.43 g.

＜実施例２＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、乳酸エチル１６１．３ｇを入れた。実施例１と同様にフラスコ内を窒素で置換し、窒素雰囲気下で保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８０℃に上げた。
その後、実施例１と同様の混合物１を滴下漏斗より、４時間かけてフラスコ内に滴下した。混合物１の滴下終了から３０分間温度を保持した。その後、下記混合物３を滴下漏斗より、５分間かけてフラスコ内に滴下し、混合物３の滴下終了からさらに８０℃の温度を２時間３０分保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物１滴下終了直後および、混合物３滴下直前および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、実施例１と同様に上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表１に示す。
［混合物３］
乳酸エチルを２．４ｇ、
Ｖ−６０１を１．０１ｇ。 <Example 2>
161.3 g of ethyl lactate was placed in a 1 L SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, and a thermometer. The inside of the flask was replaced with nitrogen in the same manner as in Example 1, and the flask was placed in a hot water bath while maintaining the nitrogen atmosphere. The temperature of the hot water bath was raised to 80 ° C. while stirring the flask.
Then, the mixture 1 similar to Example 1 was dripped in the flask over 4 hours from the dropping funnel. The temperature was maintained for 30 minutes after completion of the dropwise addition of the mixture 1. Then, the following mixture 3 was dropped into the flask over 5 minutes from the dropping funnel, and the temperature of 80 ° C. was further maintained for 2 hours and 30 minutes after the completion of dropping of the mixture 3.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after the end of dropping of the mixture 1 during the polymerization reaction, immediately before dropping of the mixture 3 and immediately before cooling, 1 g of the reaction solution was sampled from the flask. The reaction rate, weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 1.
[Mixture 3]
2.4 g of ethyl lactate,
1.01 g of V-601.

＜比較例１＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、、乳酸エチル１６１．３ｇを入れた。実施例１と同様にフラスコ内を窒素で置換し、窒素雰囲気下で保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８０℃に上げた。
その後、実施例１と同様の上記混合物１を滴下漏斗より、４時間かけてフラスコ内に滴下した。混合物１の滴下終了直後に、上記混合物２を滴下漏斗より、５分間かけてフラスコ内に滴下し、混合物３の滴下終了からさらに８０℃の温度を３時間保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物１滴下終了直後および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、実施例１と同様に上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表１に示す。 <Comparative Example 1>
161.3 g of ethyl lactate was placed in a 1 L SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, one dropping funnel, and a thermometer. The inside of the flask was replaced with nitrogen in the same manner as in Example 1, and the flask was placed in a hot water bath while maintaining the nitrogen atmosphere. The temperature of the hot water bath was raised to 80 ° C. while stirring the flask.
Then, the said mixture 1 similar to Example 1 was dripped in the flask over 4 hours from the dropping funnel. Immediately after the end of dropping of the mixture 1, the above mixture 2 was dropped into the flask over 5 minutes from the dropping funnel, and the temperature of 80 ° C. was further maintained for 3 hours after the end of dropping of the mixture 3.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after completion of dropping of the mixture 1 during the polymerization reaction and immediately before cooling, 1 g of a reaction solution was sampled from the flask, and the collected polymerization reaction solution was subjected to the reaction rate and weight average molecular weight in the same manner as in Example 1 in the same manner as described above. (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 1.

＜比較例２＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、乳酸エチル１６１．３ｇを入れた。実施例１と同様にフラスコ内を窒素で置換し、窒素雰囲気下で保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８０℃に上げた。
その後、上記混合物１を滴下漏斗より、４時間かけてフラスコ内に滴下し、混合物１の滴下終了からさらに８０℃の温度を３時間５分保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物１滴下終了直後および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、実施例１と同様に上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表１に示す。 <Comparative example 2>
161.3 g of ethyl lactate was placed in a 1 L SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, and a thermometer. The inside of the flask was replaced with nitrogen in the same manner as in Example 1, and the flask was placed in a hot water bath while maintaining the nitrogen atmosphere. The temperature of the hot water bath was raised to 80 ° C. while stirring the flask.
Thereafter, the mixture 1 was dropped into the flask over 4 hours from the dropping funnel, and the temperature of 80 ° C. was further maintained for 3 hours and 5 minutes after completion of the dropping of the mixture 1.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after completion of dropping of the mixture 1 during the polymerization reaction and immediately before cooling, 1 g of a reaction solution was sampled from the flask, and the collected polymerization reaction solution was subjected to the reaction rate and weight average molecular weight in the same manner as in Example 1 in the same manner as described above. (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 1.

＜比較例３＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、乳酸エチル１６１．３ｇを入れた。実施例１と同様にフラスコ内を窒素で置換し、窒素雰囲気下で保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８０℃に上げた。
その後、実施例１と同様の上記混合物１を滴下漏斗より、４時間かけてフラスコ内に滴下した。混合物１の滴下終了から３０分間温度を保持した。その後、下記混合物４を滴下漏斗より、５分間かけてフラスコ内に滴下し、混合物４の滴下終了からさらに８０℃の温度を２時間３０分保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物１滴下終了直後および、混合物４滴下直前および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、実施例１と同様に上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表１に示す。
［混合物４］
乳酸エチルを６．７ｇ、
Ｖ−６０１を２．８３ｇ。 <Comparative Example 3>
161.3 g of ethyl lactate was placed in a 1 L SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, and a thermometer. The inside of the flask was replaced with nitrogen in the same manner as in Example 1, and the flask was placed in a hot water bath while maintaining the nitrogen atmosphere. The temperature of the hot water bath was raised to 80 ° C. while stirring the flask.
Then, the said mixture 1 similar to Example 1 was dripped in the flask over 4 hours from the dropping funnel. The temperature was maintained for 30 minutes after completion of the dropwise addition of the mixture 1. Thereafter, the following mixture 4 was dropped from the dropping funnel into the flask over 5 minutes, and the temperature of 80 ° C. was further maintained for 2 hours 30 minutes from the end of dropping of the mixture 4.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after completion of dropping of the mixture 1 in the middle of the polymerization reaction, immediately before dropping of the mixture 4 and immediately before cooling, 1 g of a reaction solution was sampled from the flask. The reaction rate, weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 1.
[Mixture 4]
6.7 g of ethyl lactate,
2.83 g of V-601.

＜実施例３＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、ＰＧＭＥＡ１６２．５ｇを入れた。フラスコ内を窒素で置換し、窒素雰囲気下で保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８５℃に上げた。
その後、下記混合物５を滴下漏斗より、４時間かけてフラスコ内に滴下した。混合物５の滴下終了から３０分間温度を保持した。その後、下記混合物６を滴下漏斗より、５分間かけてフラスコ内に滴下し、混合物６の滴下終了からさらに８５℃の温度を２時間３０分保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物５滴下終了直後および、混合物６滴下直前および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、実施例１と同様に上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表２に示す。
［混合物５］
下記式（ｍ４）の単量体を７９．２ｇ、
下記式（ｍ５）の単量体を６３．９ｇ、
下記式（ｍ６）の単量体を８．６ｇ、
ＰＧＭＥＡを３９．４ｇ、
Ｖ６０１（商品名）を８．９７ｇ。
［混合物６］
ＰＧＭＥＡを１．６ｇ、
Ｖ−６０１を０．６８ｇ。 <Example 3>
162.5 g of PGMEA was placed in a 1 L capacity SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, one dropping funnel, and a thermometer. The inside of the flask was replaced with nitrogen, and the flask was placed in a hot water bath while maintaining the nitrogen atmosphere, and the temperature of the hot water bath was raised to 85 ° C. while stirring the inside of the flask.
Then, the following mixture 5 was dripped in the flask over 4 hours from the dropping funnel. The temperature was maintained for 30 minutes after completion of the dropwise addition of the mixture 5. Thereafter, the following mixture 6 was dropped from the dropping funnel into the flask over 5 minutes, and a temperature of 85 ° C. was further maintained for 2 hours 30 minutes after the dropping of the mixture 6 was completed.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after completion of dropping of the mixture 5 during the polymerization reaction, immediately before dropping of the mixture 6 and immediately before cooling, 1 g of the reaction solution was sampled from the flask, and the sampled polymerization reaction solution was collected by the above method in the same manner as in Example 1. The reaction rate, weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 2.
[Mixture 5]
79.2 g of a monomer of the following formula (m4),
63.9 g of a monomer of the following formula (m5),
8.6 g of a monomer of the following formula (m6),
39.4 g of PGMEA,
V601 (trade name) is 8.97 g.
[Mixture 6]
1.6 g of PGMEA,
0.68 g of V-601.

＜実施例４＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、ＰＧＭＥＡ１６２．５ｇを入れた。実施例３と同様にフラスコ内を窒素で置換し、窒素雰囲気下で保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８５℃に上げた。
その後、実施例３と同様の混合物５を滴下漏斗より、４時間かけてフラスコ内に滴下した。混合物５の滴下終了から３０分間温度を保持した。その後、下記混合物７を滴下漏斗より、５分間かけてフラスコ内に滴下し、混合物７の滴下終了からさらに８５℃の温度を２時間３０分保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物５滴下終了直後および、混合物７滴下直前および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、実施例１と同様に上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表２に示す。
［混合物７］
ＰＧＭＥＡを３．７ｇ、
Ｖ−６０１を１．５８ｇ。 <Example 4>
162.5 g of PGMEA was placed in a 1 L capacity SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, one dropping funnel, and a thermometer. In the same manner as in Example 3, the inside of the flask was replaced with nitrogen, and the flask was placed in a hot water bath while maintaining the nitrogen atmosphere. The temperature of the hot water bath was raised to 85 ° C. while stirring the flask.
Then, the same mixture 5 as Example 3 was dripped in the flask over 4 hours from the dropping funnel. The temperature was maintained for 30 minutes after completion of the dropwise addition of the mixture 5. Then, the following mixture 7 was dropped into the flask over 5 minutes from the dropping funnel, and the temperature of 85 ° C. was further maintained for 2 hours 30 minutes after the dropping of the mixture 7 was completed.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after completion of dropping of the mixture 5 in the middle of the polymerization reaction, immediately before dropping of the mixture 7 and immediately before cooling, 1 g of the reaction solution was sampled from the flask, and the sampled polymerization reaction solution was collected by the above method in the same manner as in Example 1. The reaction rate, weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 2.
[Mixture 7]
3.7 g of PGMEA,
1.58 g of V-601.

＜比較例４＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、ＰＧＭＥＡ１６２．５ｇを入れた。実施例３と同様にフラスコ内を窒素で置換し、窒素雰囲気下で保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８５℃に上げた。
その後、実施例３と同様の混合物５を滴下漏斗より、４時間かけてフラスコ内に滴下した。混合物５の滴下終了直後に、上記混合物６を滴下漏斗より、５分間かけてフラスコ内に滴下し、混合物３の滴下終了からさらに８５℃の温度を３時間保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物５滴下終了直後および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、実施例１と同様に上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表２に示す。 <Comparative example 4>
162.5 g of PGMEA was placed in a 1 L capacity SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, one dropping funnel, and a thermometer. In the same manner as in Example 3, the inside of the flask was replaced with nitrogen, and the flask was placed in a hot water bath while maintaining the nitrogen atmosphere. The temperature of the hot water bath was raised to 85 ° C. while stirring the flask.
Then, the same mixture 5 as Example 3 was dripped in the flask over 4 hours from the dropping funnel. Immediately after the completion of dropping of the mixture 5, the mixture 6 was dropped into the flask over 5 minutes from the dropping funnel, and the temperature of 85 ° C. was further maintained for 3 hours after the dropping of the mixture 3 was completed.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after completion of the dropping of the mixture 5 during the polymerization reaction and immediately before cooling, 1 g of the reaction solution was sampled from the flask, and the collected polymerization reaction solution was subjected to the reaction rate and weight average molecular weight in the same manner as in Example 1 in the same manner as described above. (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 2.

＜比較例５＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、ＰＧＭＥＡ１６２．５ｇを入れた。実施例３と同様にフラスコ内を窒素で置換し、窒素雰囲気下で保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８５℃に上げた。
その後、上記混合物５を滴下漏斗より、４時間かけてフラスコ内に滴下し、混合物５の滴下終了からさらに８５℃の温度を３時間５分保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物５滴下終了直後および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、実施例１と同様に上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表２に示す。 <Comparative Example 5>
162.5 g of PGMEA was placed in a 1 L capacity SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, one dropping funnel, and a thermometer. In the same manner as in Example 3, the inside of the flask was replaced with nitrogen, and the flask was placed in a hot water bath while maintaining the nitrogen atmosphere. The temperature of the hot water bath was raised to 85 ° C. while stirring the flask.
Thereafter, the mixture 5 was dropped into the flask over 4 hours from the dropping funnel, and the temperature of 85 ° C. was further maintained for 3 hours and 5 minutes after the completion of dropping of the mixture 5.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after completion of dropping of the mixture 5 in the middle of the polymerization reaction and immediately before cooling, 1 g of the reaction solution was sampled from the flask. (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 2.

＜比較例６＞
窒素導入口、攪拌機、コンデンサー、滴下漏斗１個、および温度計を備えた容量１ＬのＳＵＳ製のフラスコに、ＰＧＭＥＡ１６２．５ｇを入れた。実施例３と同様にフラスコ内を窒素で置換し、窒素雰囲気下で保ったままフラスコを湯浴に入れ、フラスコ内を攪拌しながら湯浴の温度を８０℃に上げた。
その後、実施例３と同様の混合物５を滴下漏斗より、４時間かけてフラスコ内に滴下した。混合物５の滴下終了から３０分間温度を保持した。その後、下記混合物８を滴下漏斗より、５分間かけてフラスコ内に滴下し、混合物８の滴下終了からさらに８５℃の温度を２時間３０分保持した。
その後、２５℃までフラスコ内の反応液を冷却して重合反応を停止させ、重合反応溶液を得た。
重合反応途中の混合物５滴下終了直後および、混合物８滴下直前および、冷却直前にて、フラスコ内から反応溶液を１ｇ採取し、この採取した重合反応溶液について、実施例１と同様に上記の方法で反応率および重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表２に示す。
［混合物８］
ＰＧＭＥＡを１０．５ｇ、
Ｖ−６０１を４．４２ｇ。 <Comparative Example 6>
162.5 g of PGMEA was placed in a 1 L capacity SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, one dropping funnel, and a thermometer. In the same manner as in Example 3, the inside of the flask was replaced with nitrogen, and the flask was placed in a hot water bath while maintaining the nitrogen atmosphere, and the temperature of the hot water bath was raised to 80 ° C. while stirring the inside of the flask.
Then, the same mixture 5 as Example 3 was dripped in the flask over 4 hours from the dropping funnel. The temperature was maintained for 30 minutes after completion of the dropwise addition of the mixture 5. Thereafter, the following mixture 8 was dropped from the dropping funnel into the flask over 5 minutes, and the temperature of 85 ° C. was further maintained for 2 hours and 30 minutes after the completion of dropping of the mixture 8.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
Immediately after completion of dropping of the mixture 5 during the polymerization reaction, immediately before dropping of the mixture 8 and immediately before cooling, 1 g of a reaction solution was sampled from the flask, and the sampled polymerization reaction solution was collected by the above method in the same manner as in Example 1. The reaction rate, weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. The results are shown in Table 2.
[Mixture 8]
10.5g of PGMEA,
4.42-g of V-601.

表１および表２の結果より、各実施例は、高い反応率を実現しながら残存単量体および重合開始剤の分解物等から構成されるＭｗ３５０以下の化合物の含有量だけでなく、低分子量重合体の含有量が低減されたことがわかる。
一方、比較例１および比較例４のように、反応率が上がる前に重合開始剤を追加供給しても低分子量重合体の含有量は低減されなかった。
また、比較例２および比較例５のように、追加供給なしではＭｗ３５０以下の化合物の含有量は低減されなかった。
また、比較例３および比較例６のように、重合開始剤の全使用量に対して追加供給の重合開始剤の使用割合が多いと、Ｍｗ３５０以下の化合物の含有量が多くなった。
これにより、本発明による重合体の製造方法によれば、重合体を精製することなく生産効率良く、残存単量体および低分子量重合体の含有量が少ないリソグラフィー用重合体を製造することができることが示された。 From the results of Tables 1 and 2, each Example shows that not only the content of a compound having a Mw of 350 or less composed of a residual monomer and a decomposition product of a polymerization initiator while realizing a high reaction rate, but also a low molecular weight It can be seen that the polymer content has been reduced.
On the other hand, as in Comparative Example 1 and Comparative Example 4, even when the polymerization initiator was additionally supplied before the reaction rate increased, the content of the low molecular weight polymer was not reduced.
Further, as in Comparative Example 2 and Comparative Example 5, the content of the compound having Mw of 350 or less was not reduced without additional supply.
Further, as in Comparative Example 3 and Comparative Example 6, when the proportion of the additionally supplied polymerization initiator was large with respect to the total amount of polymerization initiator used, the content of the compound having Mw of 350 or less was increased.
Thereby, according to the method for producing a polymer according to the present invention, it is possible to produce a lithographic polymer with a low content of the residual monomer and the low molecular weight polymer with high production efficiency without purifying the polymer. It has been shown.

［レジスト組成物の評価］
実施例１で得られた重合体溶液２００部と、光酸発生剤であるトリフェニルスルホニウムトリフレート１部と、溶媒であるＰＧＭＥＡとを、重合体の固形分濃度が１２．５質量％になるように混合して均一溶液とした後、孔径０．１μｍのメンブレンフィルターで濾過し、レジスト組成物を得た。また、実施例２および比較例１〜３においても、同様にレジスト組成物を得た。得られた各レジスト組成物についてＥｔｈ感度を測定した。結果を表３に示す。 [Evaluation of resist composition]
200 parts of the polymer solution obtained in Example 1, 1 part of triphenylsulfonium triflate as a photoacid generator, and PGMEA as a solvent have a solid content concentration of 12.5% by mass. After mixing to obtain a uniform solution, the solution was filtered through a membrane filter having a pore size of 0.1 μm to obtain a resist composition. Moreover, the resist composition was similarly obtained also in Example 2 and Comparative Examples 1-3. Eth sensitivity was measured for each of the obtained resist compositions. The results are shown in Table 3.

表３の結果より、Ｅｔｈ感度の値を得ることができた。実施例１および実施例２は、各比較例に対しＥｔｈ感度が優れていることから、実施例１および実施例２のリソグラフィー用重合体が、レジスト組成物として好適に使用できることが示された。   From the results shown in Table 3, the value of Eth sensitivity could be obtained. Since Example 1 and Example 2 were excellent in Eth sensitivity with respect to each comparative example, it was shown that the lithographic polymers of Example 1 and Example 2 can be suitably used as a resist composition.

Claims (3)

（メタ）アクリレート骨格を有する単量体を溶液重合して得られる重合体の製造方法であって、
供給される単量体の全使用量のうち８５％以上まで反応率が上昇した後に、
供給される重合開始剤の全使用量のうち１．０％〜１５．０％の重合開始剤を含み、かつ、単量体を含まない溶液を該反応容器内にさらに供給する、
リソグラフィー用重合体の製造方法。 A method for producing a polymer obtained by solution polymerization of a monomer having a (meth) acrylate skeleton,
After the reaction rate has increased to 85% or more of the total amount of monomer used,
A solution containing 1.0% to 15.0% of the polymerization initiator out of the total amount of the polymerization initiator to be supplied and further containing no monomer is further supplied into the reaction vessel.
A method for producing a polymer for lithography. 請求項１に記載の製造方法によりリソグラフィー用重合体を製造する工程と、
得られたリソグラフィー用重合体と、活性光線または放射線の照射により酸を発生する化合物とを混合する工程を有する、
レジスト組成物の製造方法。 A step of producing a lithography polymer by the production method according to claim 1;
A step of mixing the obtained polymer for lithography with a compound that generates an acid upon irradiation with actinic rays or radiation,
A method for producing a resist composition. 請求項２に記載の製造方法によりレジスト組成物を製造する工程と、
得られたレジスト組成物を基板の被加工面上に塗布してレジスト膜を形成する工程と、
該レジスト膜に対して、露光する工程と、
現像液を用いて、露光されたレジスト膜を現像する工程とを含む、
パターンが形成された基板の製造方法。 A step of producing a resist composition by the production method according to claim 2;
Applying the obtained resist composition on the work surface of the substrate to form a resist film;
A step of exposing the resist film;
And developing the exposed resist film using a developer.
A method for manufacturing a substrate on which a pattern is formed.
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