JP6424420B2 - Method of cleaning reaction container for producing polymer for electronic material - Google Patents
Method of cleaning reaction container for producing polymer for electronic material Download PDFInfo
- Publication number
- JP6424420B2 JP6424420B2 JP2013220857A JP2013220857A JP6424420B2 JP 6424420 B2 JP6424420 B2 JP 6424420B2 JP 2013220857 A JP2013220857 A JP 2013220857A JP 2013220857 A JP2013220857 A JP 2013220857A JP 6424420 B2 JP6424420 B2 JP 6424420B2
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- JP
- Japan
- Prior art keywords
- reaction vessel
- solvent
- polymer
- washing
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000006243 chemical reaction Methods 0.000 title claims description 165
- 229920000642 polymer Polymers 0.000 title claims description 68
- 238000000034 method Methods 0.000 title claims description 61
- 238000004140 cleaning Methods 0.000 title claims description 26
- 239000012776 electronic material Substances 0.000 title claims description 10
- 239000002904 solvent Substances 0.000 claims description 110
- 238000005406 washing Methods 0.000 claims description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 238000006116 polymerization reaction Methods 0.000 claims description 56
- 239000002184 metal Substances 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 23
- 238000009835 boiling Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 64
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- -1 for example Substances 0.000 description 40
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 25
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Landscapes
- Cleaning In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、電子材料用重合体を製造する反応容器の洗浄方法に関する。 The present invention relates to a method of cleaning a reaction container for producing a polymer for electronic materials.
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。レジストパターンの形成に用いられるレジスト組成物としては、放射線の照射により酸を発生する光酸発生剤と、発生した酸の作用によりアルカリ溶解性が変化する樹脂とを含有する化学増幅型レジストが知られている。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。 In recent years, the resist pattern formed in the manufacturing process of a semiconductor element, a liquid crystal element and the like has been rapidly miniaturized with the progress of lithography technology. As a resist composition used to form a resist pattern, a chemically amplified resist is known which contains a photoacid generator which generates an acid upon irradiation with radiation, and a resin whose alkali solubility changes by the action of the generated acid. It is done. For example, as a polymer for a chemically amplified resist used in ArF excimer laser lithography, an acrylic polymer that is transparent to light with a wavelength of 193 nm has attracted attention.
該重合体、工業的には、重合槽、析出槽、ろ過器、乾燥機等を有する製造設備を用いて製造され、不純物の少ない反応容器を用いて重合体を製造する方法が提案されている。例えば、特許文献１、２には、重合に先立って、容器充填前後の水（水の電気伝導度が０．５μＳ／ｃｍ以下である純水）の電気伝導度の差が、１．８μＳ／ｃｍ以下である容器を用いる重合体の製造方法が提案されている。これらの製造方法によれば、前ロットからの重合体や金属などの不純物含有量が極めて少ない重合体を製造することが可能であるが、容器洗浄に用いる溶剤の種類によっては、または複数の溶剤を用いて洗浄を行う場合に用いる順番によっては、溶剤が容器中に残留することがある。また、重合反応時、水などの洗浄溶剤が反応容器内へ残留していると所望の重合体を得ることができない問題がある。 Industrially, this polymer is manufactured using a manufacturing facility having a polymerization tank, a precipitation tank, a filter, a dryer and the like, and a method of manufacturing a polymer using a reaction container with few impurities is proposed. . For example, in Patent Documents 1 and 2, the difference in electric conductivity of water (pure water whose electric conductivity of water is 0.5 μS / cm or less) before and after container filling is 1.8 μS / s prior to polymerization. A method of producing a polymer using a container having a diameter of less than or equal to cm has been proposed. According to these production methods, it is possible to produce a polymer having a very low content of impurities such as a polymer or metal from the previous lot, but depending on the type of solvent used for container washing, or a plurality of solvents The solvent may remain in the container depending on the order in which it is used for washing with. In addition, when a washing solvent such as water remains in the reaction vessel during the polymerization reaction, there is a problem that a desired polymer can not be obtained.
本発明は前記事情に鑑みてなされたもので、反応容器内の洗浄溶剤残留量を低減するとともに、金属含有量も低減させることが出来る電子材料用重合体の製造する反応容器の洗浄方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a method for cleaning a reaction container for producing a polymer for electronic materials, which can reduce the amount of residual cleaning solvent in the reaction container and can also reduce the metal content. The purpose is to
[１]単量体を含む混合物を重合し電子材料用重合体を製造する反応容器の洗浄方法であって、下記の工程１，２を順次行うことを含む、反応容器の洗浄方法。
１．反応容器内の金属成分を除去する。
２．反応容器内の水、単量体、重合体のいずれかを除去する。
[２]工程１において、水を含む溶液を用いて洗浄する、[１]に記載の洗浄方法。
[３]工程１において、金属含有量が５０ｐｐｂ以下の水を含む溶液を用いて洗浄する、[１]または[２]に記載の洗浄方法。
[４]工程２において、親水性溶剤を含む溶液を用いて洗浄する、[１]〜[３]の何れかに記載の洗浄方法。
[５]工程２において、親水性の溶剤のＳＰ値が１９．０ [ＭＰａ１／２]以上である、[１]〜[４]の何れかに記載の洗浄方法。
[６]工程２において、大気圧下での沸点が１００℃以下である親水性の溶剤を用いる、[１]〜[５]の何れかに記載の洗浄方法。
[７]工程２において、親水性溶剤を還流させて洗浄する、[１]〜[６]の何れかに記載の洗浄方法。
[８]工程２の後に、下記工程３をさらに含む、[１]〜[７]の何れかに記載の洗浄方法。
工程３．反応容器を、重合に用いる溶剤を用いて洗浄する。
[９]反応容器の内容量が３０Ｌ以上である、[１]〜[８]の何れかに記載の洗浄方法。
[１０] [１]〜[９]の何れかにに記載の洗浄方法で得られた反応容器を用いて電子材料用重合体を製造する方法。
[1] A method of cleaning a reaction container for producing a polymer for an electronic material by polymerizing a mixture containing a monomer, the method comprising cleaning the steps 1 and 2 below sequentially.
1. Remove metal components in the reaction vessel.
2. Water, monomer, or polymer in the reaction vessel is removed.
[2] The washing method according to [1], wherein the washing is carried out using a solution containing water in step 1.
[3] The cleaning method according to [1] or [2], wherein the cleaning is performed using a solution containing water having a metal content of 50 ppb or less in Step 1.
[4] The washing method according to any one of [1] to [3], wherein the washing is carried out using a solution containing a hydrophilic solvent in step 2.
[5] The washing method according to any one of [1] to [4], wherein in the step 2, the SP value of the hydrophilic solvent is 19.0 [MPa 1/2 ] or more.
[6] The washing method according to any one of [1] to [5], wherein in step 2, a hydrophilic solvent having a boiling point of 100 ° C. or less at atmospheric pressure is used.
[7] The washing method according to any one of [1] to [6], wherein in step 2, the hydrophilic solvent is refluxed for washing.
[8] The cleaning method according to any one of [1] to [7], further including the following step 3 after step 2.
Step 3. The reaction vessel is washed with the solvent used for the polymerization.
[9] The washing method according to any one of [1] to [8], wherein the internal volume of the reaction vessel is 30 L or more.
[10] A method for producing a polymer for electronic materials using a reaction container obtained by the cleaning method according to any one of [1] to [9].
本発明の洗浄方法によれば、重合に用いる容器内の反応前の洗浄に由来する洗浄溶剤残留量を低減し、金属含有量も低減することで所望の重合体を得るための反応容器を提供することが出来る。 According to the cleaning method of the present invention, a reaction container for obtaining a desired polymer is provided by reducing the residual amount of cleaning solvent derived from the cleaning before the reaction in the container used for polymerization and reducing the metal content. You can do it.
本発明の洗浄方法は、下記の工程１，２を順次行うことを含む、単量体を含む混合物を重合し電子材料用重合体を製造する反応容器の洗浄する、ことを特徴とする。
１．反応容器内の金属成分を除去する。
２．反応容器内の水、単量体、重合体のいずれかを除去する。
これにより、反応容器内の洗浄溶剤残留量を低減するとともに、金属含有量も低減させることができる。
The cleaning method of the present invention is characterized in that the reaction vessel for polymerizing a mixture containing monomers to produce a polymer for electronic materials is cleaned, which comprises sequentially carrying out the following steps 1 and 2.
1. Remove metal components in the reaction vessel.
2. Water, monomer, or polymer in the reaction vessel is removed.
Thereby, the amount of residual cleaning solvent in the reaction vessel can be reduced, and the metal content can also be reduced.
＜工程１＞
工程１では、重合に先立って重合に用いる反応（重合）容器内の金属成分を除去する。
金属成分を除去する方法として、工程１では、水を含む溶液を用いて反応容器を洗浄する方法があげられる。洗浄に用いる水としては、金属をより効果的に除去する観点から、超純水（純水をイオン交換処理後、メンブラン膜処理したもの）が好ましい。超純水の金属含有量は５０ｐｐｂ以下、好ましくは１０ｐｐｂ以下、さらに好ましくは１ｐｐｂ以下としたものが好ましい。
工程１では、水のみを用いて洗浄してもよく、前ロットの重合物等の不純物も除去する観点から、水以外の溶剤との混合溶液を用いて洗浄してもよい。
混合溶液を用いる場合、水以外の溶剤は反応容器への供給前にあらかじめ水と混合させておいてもよく、水または水以外の溶剤のいずれかを先に反応容器内に供給させておき、その後に供給していない溶剤を供給し反応容器内で混合してもよい。
水以外の溶剤としては特に限定されず、後述する工程２、必要な場合は工程３で用いる溶剤と同じ溶剤を用いてもよい。水以外の溶剤は１種を単独で用いてもよく、２種以上を併用してもよい。
水以外の溶剤としては、例えば、メチルエチルケトン（以下、「ＭＥＫ」と記す。）、テトラヒドロフラン、メタノール、アセトン、乳酸エチル、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。）、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。）等が挙げられる。前ロットの重合物等の不純物の除去の観点から、ＭＥＫ、乳酸エチル、ＰＧＭＥ、ＰＧＭＥＡ等が好ましい。
水以外の溶剤には電子工業用グレードのものを用いるのが好ましい。水と水以外の溶剤の混合割合としては、特に限定されないが、金属低減の観点から水の割合が高い方が効果的であることから、水の割合は５０％より多いことが好ましく、８０％以上がさらに好ましく、９０％以上がより好ましく、９５％以上が特に好ましい。
<Step 1>
In step 1, metal components in a reaction (polymerization) container used for polymerization are removed prior to polymerization.
As a method of removing the metal component, in step 1, there is a method of washing the reaction vessel using a solution containing water. As water used for cleaning, ultrapure water (pure water subjected to ion exchange treatment and then membrane membrane treatment) is preferable from the viewpoint of removing metal more effectively. The metal content of the ultrapure water is preferably 50 ppb or less, preferably 10 ppb or less, more preferably 1 ppb or less.
In the step 1, washing may be performed using only water, or washing may be performed using a mixed solution with a solvent other than water from the viewpoint of removing impurities such as the polymer of the previous lot.
When a mixed solution is used, a solvent other than water may be mixed with water in advance before being supplied to the reaction vessel, and either water or a solvent other than water may be supplied into the reaction vessel first, Solvents not supplied after that may be supplied and mixed in the reaction vessel.
It does not specifically limit as solvents other than water, You may use the same solvent as the solvent used at the process 2 mentioned later and the process 3 as needed. The solvents other than water may be used alone or in combination of two or more.
As solvents other than water, for example, methyl ethyl ketone (hereinafter referred to as "MEK"), tetrahydrofuran, methanol, acetone, ethyl lactate, propylene glycol monomethyl ether (hereinafter referred to as "PGME"), propylene glycol monomethyl ether acetate (Hereafter, it describes as "PGMEA.") Etc. are mentioned. MEK, ethyl lactate, PGME, PGMEA and the like are preferable from the viewpoint of removal of impurities such as the polymer of the previous lot.
As solvents other than water, it is preferable to use those of electronic grade. The mixing ratio of water and solvents other than water is not particularly limited, but the higher the ratio of water from the viewpoint of metal reduction, the more effective, so the ratio of water is preferably more than 50%, 80% The above is more preferable, 90% or more is more preferable, and 95% or more is particularly preferable.
工程１における洗浄は、複数回繰り返してもよい。その場合、混合割合を変更してもよいが、最終的に水以外の溶剤が極力残留しないように、段階的に水の混合割合を高めていくことがより好ましい。 The washing in step 1 may be repeated multiple times. In that case, although the mixing ratio may be changed, it is more preferable to gradually increase the mixing ratio of water so that the solvent other than water may not remain as much as possible.
工程１における洗浄方法としては、反応容器内へ溶剤を供給し同時に排出しながら洗浄してもよく、溶剤を貯めて一気に排出してもよく、シャワーノズルやホース等を用いて反応容器内面へかけ洗いしてもよい。また、洗浄時に反応容器を加熱してもよく、減圧条件下にし、容器内で溶剤を還流させて洗浄してもよい。
後述する工程２の操作を行う前に、工程１で用いた溶剤を極力系外に排出しておくことが好ましい。
As a cleaning method in the step 1, the solvent may be supplied into the reaction container and the solvent may be simultaneously discharged and cleaned, or the solvent may be stored and drained at once, and it is applied to the inner surface of the reaction container using a shower nozzle or hose. You may wash it. In addition, the reaction vessel may be heated at the time of washing, or under reduced pressure conditions, the solvent may be refluxed for washing in the vessel.
It is preferable to discharge the solvent used in step 1 out of the system as much as possible before performing the operation of step 2 described later.
＜工程２＞
工程２では、反応容器内の水、単量体、重合体のいずれかを除去する。反応容器内の水、単量体、重合体のいずれかを除去する方法として、工程１の後、さらに、親水性溶剤を含む溶液を用いて反応容器を洗浄することがあげられる。このような親水性溶剤を含む溶液で洗浄を行うことにより、工程１で用いた水等の溶剤を反応容器から除去することができる。
本発明において親水性溶剤とは、水と質量割合１対１で混合しても分離せずに相溶する溶剤のことを言う。親水性溶剤としては、水との相溶性が高い溶剤であれば特に限定されないが、水を除去する効率を高める観点から、親水性の溶剤のＳＰ値が１９．０[ＭＰａ１／２]以上が好ましく、２１[ＭＰａ１／２]以上がより好ましく、２３[ＭＰａ１／２]以上がさらに好ましく、２５[ＭＰａ１／２]以上であることが特に好ましい。
また、親水性溶剤としては、水との相溶性が高い溶剤であれば特に限定されないが、容器内で親水性溶剤のみを還流させて洗浄するのに適した大気圧下での沸点が水よりも低い溶剤を用いることが好ましい。還流による洗浄を効率よく行う観点から、親水性溶剤の沸点としては９０℃以下が好ましく、８０℃以下がより好ましく、７０℃以下がさらに好ましい。
親水性溶剤の例としては、特に限定されないが、テトラヒドロフラン（沸点：６６．０ ℃、ＳＰ値：１９．４[ＭＰａ１／２]）、アセトン（沸点：５６．１ ℃、ＳＰ値：２０．１[ＭＰａ１／２]）、メタノール（沸点：６４．５ ℃、ＳＰ値：２９．７[ＭＰａ１／２]）などが挙げられる。金属低減の観点から、電子工業用グレードの溶剤を用いるのが好ましい。
<Step 2>
In step 2, any of water, monomers, and polymers in the reaction vessel is removed. As a method of removing any of water, monomers, and polymers in the reaction container, after step 1, it is possible to mention washing the reaction container using a solution containing a hydrophilic solvent. By washing with a solution containing such a hydrophilic solvent, the solvent such as water used in step 1 can be removed from the reaction vessel.
In the present invention, the hydrophilic solvent means a solvent which is compatible with water without being separated even when mixed in a mass ratio of 1: 1. The hydrophilic solvent is not particularly limited as long as it is a solvent having high compatibility with water, but from the viewpoint of enhancing the efficiency of removing water, the SP value of the hydrophilic solvent is 19.0 [MPa 1/2 ] or more Is preferable, 21 [MPa 1/2 ] or more is more preferable, 23 [MPa 1/2 ] or more is further preferable, and 25 [MPa 1/2 ] or more is particularly preferable.
The hydrophilic solvent is not particularly limited as long as it is a solvent having high compatibility with water, but the boiling point at atmospheric pressure suitable for refluxing only the hydrophilic solvent in the container for washing is higher than that of water It is preferable to use a low solvent. From the viewpoint of efficiently performing washing by reflux, the boiling point of the hydrophilic solvent is preferably 90 ° C. or less, more preferably 80 ° C. or less, and still more preferably 70 ° C. or less.
Examples of the hydrophilic solvent include, but not limited to, tetrahydrofuran (boiling point: 66.0 ° C., SP value: 19.4 [MPa 1/2 ]), acetone (boiling point: 56.1 ° C., SP value: 20. 1 [MPa 1/2 ]), methanol (boiling point: 64.5 ° C., SP value: 29.7 [MPa 1/2 ]), and the like. From the viewpoint of metal reduction, it is preferable to use a solvent for electronic industry grade.
親水性溶剤は、複数の溶剤を任意の割合で混合させてもよい。その場合、水との相溶性の高い溶剤の割合が高い方が好ましい。
必要に応じて行う後述する工程３で用いる重合溶媒が親水性溶剤である場合、工程２においても重合溶媒を用いてもよい。あるいは、工程３を行わない場合は、工程２において、親水性溶剤として重合溶媒を用いることが好ましく、この場合、工程２を複数回繰り返して行うのがより好ましい。
The hydrophilic solvent may be a mixture of a plurality of solvents in any proportion. In that case, it is preferable that the proportion of the solvent having high compatibility with water is high.
When the polymerization solvent used in step 3 to be described later, which is performed as needed, is a hydrophilic solvent, the polymerization solvent may be used in step 2 as well. Alternatively, when step 3 is not performed, it is preferable to use a polymerization solvent as the hydrophilic solvent in step 2, and in this case, it is more preferable to repeat step 2 multiple times.
工程２において、前ロットの重合物等の不純物の除去を目的に、親水性溶剤以外に非親水性溶剤を含んでもよい。この場合、水除去の観点から極力親水性溶剤の割合が非親水性溶剤よりも高いことが好ましい。非親水性溶剤は反応容器への供給前にあらかじめ親水性溶剤と混合させておいてもよく、あるいは、親水性溶剤または非親水性溶剤のいずれかを先に反応容器内に供給させておき、その後に供給していない溶剤を供給し反応容器内で混合してもよい。
非親水性溶剤としては、特に限定されないが、例えば、ＭＥＫ、ＰＧＭＥＡ、ジエチルエーテル、メチルイソブチルケトン等が挙げられる。前ロットの重合物等の不純物の除去の観点から、ＭＥＫ、ＰＧＭＥＡ等が好ましい。
非親水性溶剤を用いる場合、１種を単独で用いてもよく、２種以上を併用してもよい。
In the step 2, for the purpose of removing impurities such as the polymer of the previous lot, a non-hydrophilic solvent may be included in addition to the hydrophilic solvent. In this case, the ratio of the hydrophilic solvent is preferably as high as possible from the non-hydrophilic solvent from the viewpoint of water removal. The non-hydrophilic solvent may be previously mixed with the hydrophilic solvent before being supplied to the reaction vessel, or either the hydrophilic solvent or the non-hydrophilic solvent may be supplied into the reaction vessel first, Solvents not supplied after that may be supplied and mixed in the reaction vessel.
The non-hydrophilic solvent is not particularly limited, and examples thereof include MEK, PGMEA, diethyl ether, methyl isobutyl ketone and the like. MEK, PGMEA and the like are preferable from the viewpoint of removal of impurities such as the polymer of the previous lot.
When a non-hydrophilic solvent is used, one type may be used alone, or two or more types may be used in combination.
非親水性溶剤との混合割合としては、工程１で用いた水除去の観点から、親水性溶剤の割合が５０％より多いことが好ましく、８０％以上となることがより好ましく、９０％以上となることがさらに好ましく、９５％以上となることが特により好ましい。 The mixing ratio with the non-hydrophilic solvent is preferably 50% or more, more preferably 80% or more, and more preferably 90% or more, from the viewpoint of water removal used in Step 1. Is more preferably 95% or more.
工程２における洗浄は、複数回繰り返しても良い。その際、混合割合を変更しても良いが、水除去の効率を高めるために、段階的に親水性溶剤の混合割合を高めていくことがより好ましい。 The washing in step 2 may be repeated multiple times. At that time, although the mixing ratio may be changed, it is more preferable to gradually increase the mixing ratio of the hydrophilic solvent in order to enhance the efficiency of water removal.
工程２における洗浄方法としては、反応容器内へ溶剤を供給し同時に排出しながら洗浄してもよく、溶剤を貯めて一気に排出してもよく、あるいはシャワーノズルやホース等を用いて反応容器内面へかけ洗いしてもよい。
反応容器内の上部など不純物等が除去されにくい部分に、工程１で用いた溶剤が残留する場合があり、これをできるだけ除去することを目的として、反応容器内を加熱もしくは減圧条件下またはその両方の状態にして、容器内で親水性溶剤を還流させて洗浄することが好ましい。加熱条件及び減圧条件としては、工程１で用いた溶剤を極力還流させない条件で行うことが好ましい。
As a washing method in the step 2, the solvent may be supplied into the reaction vessel and the solvent may be washed while discharging simultaneously, or the solvent may be stored and discharged at once, or to the inner surface of the reaction vessel using a shower nozzle or hose. You may wash it over.
The solvent used in step 1 may remain in a portion where impurities and the like are difficult to remove, such as the upper part in the reaction vessel, and the inside of the reaction vessel is heated or decompressed or both for the purpose of removing it as much as possible. It is preferable to wash | clean by refluxing a hydrophilic solvent in a container in the state of (1). As heating conditions and pressure reduction conditions, it is preferable to carry out on the conditions which do not reflux the solvent used at the process 1 as much as possible.
後述する工程３を行う場合は、工程２の作業を行う前に工程１および工程２で用いた溶剤を極力系外に排出しておくことが好ましい。 In the case of performing step 3 described later, it is preferable to discharge the solvent used in steps 1 and 2 out of the system as much as possible before performing the operation of step 2.
＜工程３＞
本発明の製造方法は、上記工程２の後に、さらに工程３として重合溶媒を用いて洗浄を行ってもよい。工程３により、上記工程２で用いた溶剤を極力除去することができるため好ましい。重合溶媒としては、金属低減の観点から、電子工業用グレードの溶媒を用いるのが好ましい。
特に限定されないが、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、ＰＧＭＥ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、ＰＧＭＥＡ、γ−ブチロラクトン等。
ケトン類：アセトン、ＭＥＫ、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。
<Step 3>
In the production method of the present invention, after step 2 above, washing may be performed using a polymerization solvent as step 3 further. The step 3 is preferable because the solvent used in the step 2 can be removed as much as possible. As a polymerization solvent, it is preferable to use a solvent of electronic industrial grade from the viewpoint of metal reduction.
Although not particularly limited, examples of the polymerization solvent include the following.
Ethers: linear ethers (diethyl ether, PGME etc.), cyclic ethers (tetrahydrofuran, 1,4-dioxane etc.) etc.
Esters: methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, PGMEA, γ-butyrolactone and the like.
Ketones: acetone, MEK, 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 etc.
Alicyclic hydrocarbon: cyclohexane and the like.
The polymerization solvents may be used alone or in combination of two or more.
工程３は必ずしも必要でなく、工程２で用いた親水性溶剤が重合溶媒である場合や、工程２で溶剤を排出した後に反応容器を加熱するなどして反応容器から溶剤及び水を系外へ極力除去した場合は工程３を行わなくてもよい。 Step 3 is not necessarily required, and when the hydrophilic solvent used in step 2 is a polymerization solvent, or after discharging the solvent in step 2, the reaction vessel is heated to discharge the solvent and water from the reaction vessel to the outside of the system. When removing as much as possible, step 3 may not be performed.
工程３における洗浄方法としては、反応容器内へ溶媒を供給し同時に排出しながら洗浄してもうよく、溶媒を貯めて一気に排出してもよく、あるいはシャワーノズルやホース等を用いて反応容器内面へかけ洗いしてもよい。また、洗浄時に反応容器を加熱してもよく、減圧条件下にし、容器内で溶媒を還流させて洗浄してもよい。 As a washing method in the step 3, the solvent may be supplied into the reaction vessel and the solvent may be washed while being discharged simultaneously, or the solvent may be stored and discharged at once, or to the inner surface of the reaction vessel using a shower nozzle or hose. You may wash it over. In addition, the reaction vessel may be heated at the time of washing, or may be under reduced pressure, and the solvent may be refluxed and washed in the vessel.
工程３の洗浄は、工程１および工程２で用いた溶剤を出来るだけ除去することを目的として、複数回繰り返して行ってもよい。 The washing in step 3 may be repeated several times for the purpose of removing the solvent used in steps 1 and 2 as much as possible.
上記工程１を行う前に、あらかじめ反応容器から前ロットの重合体を出来るだけ除去しておくことが好ましい。前ロットの重合体の除去には、重合体との溶解性が良い溶剤を用いて洗浄を行うことが好ましい。反応容器内への重合体の残留を低減させる観点から、例えば、ＭＥＫ、テトラヒドロフラン、アセトン、乳酸エチル、ＰＧＭＥ，ＰＧＭＥＡなどが挙げられる。 It is preferable to remove the polymer of the previous lot from the reaction vessel as much as possible before the step 1 is carried out. It is preferable to wash | clean using the solvent with good solubility with a polymer for the removal of the polymer of a front lot. From the viewpoint of reducing the residue of the polymer in the reaction vessel, for example, MEK, tetrahydrofuran, acetone, ethyl lactate, PGME, PGMEA and the like can be mentioned.
反応容器のサイズが大きい程、またその構造が複雑である程、反応容器内のデッドスペースなどに水などの洗浄溶剤が残留しやすいことから、本発明は内容量３０Ｌ以上の反応容器において効果的であり、内容量１００Ｌ以上の容器においてより効果的であり、内容量２００Ｌ以上の容器においてさらに効果的である。 The larger the size of the reaction vessel and the more complicated the structure thereof, the more easily the washing solvent such as water remains in the dead space in the reaction vessel, so the present invention is effective in a reaction vessel with an internal volume of 30 L or more. It is more effective in a container with an inner volume of 100 L or more, and more effective in a container with an inner volume of 200 L or more.
＜重合工程＞
前記の洗浄方法によって洗浄された反応容器を重合工程に用いる。重合溶媒の存在下で、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。重合方法は溶液重合法である。溶液重合法において、単量体及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、単量体及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。
<Polymerization process>
The reaction vessel washed by the above washing method is used for the polymerization step. In the presence of a polymerization solvent, a monomer is radically polymerized using a polymerization initiator to obtain a polymerization reaction solution. The polymerization method is a solution polymerization method. In the solution polymerization method, the supply of the monomer and the polymerization initiator to the reaction vessel may be continuous supply or drop supply. In the solution polymerization method, the monomer and the polymerization initiator are dropped into the reaction vessel from the viewpoint that a reproducible polymer is easily obtained with small variation in average molecular weight, molecular weight distribution, etc. due to differences in production lot. The drop 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、単量体及び重合開始剤を、それぞれ独立に、又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。滴下は、連続的に行ってもよく、間欠的に行ってもよい。
In the drop polymerization method, after the inside of the reaction vessel is heated to a predetermined polymerization temperature, monomers and a polymerization initiator are dropped into the reaction vessel independently or in any combination.
The monomer may be dropped as the monomer alone, or may be dropped as a monomer solution in which the monomer is dissolved in the polymerization solvent. The dripping may be performed continuously or intermittently.
＜単量体＞
電子材料用重合体の重合に用いる単量体としては、レジスト用重合体を製造する場合においては、極性基を有する構成単位を有することが好ましい。
［極性基を有する構成単位］
「極性基」とは、極性を持つ官能基又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。
<Monomer>
As a monomer used for the polymerization of the polymer for electronic materials, in the case of manufacturing the polymer for resists, it is preferable to have a structural unit having a polar group.
[Constituent Unit Having Polar Group]
The “polar group” is a functional group having polarity or a group having an atomic group having polarity, and specific examples thereof include a hydroxy group, a cyano group, an alkoxy group, a carboxy group, an amino group, a carbonyl group and a fluorine atom. And groups containing a sulfur atom, a group containing a lactone skeleton, a group containing an acetal structure, and a group containing an ether bond.
Among these, the polymer for a resist to be applied to a pattern forming method of exposing with light having a wavelength of 250 nm or less preferably has a structural unit having a lactone skeleton as a structural unit having a polar group, and further has hydrophilicity described later. It is preferable to have a structural unit having a sexing 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員環程度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又は芳香族の炭素環又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、感度及び解像度の点から、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。
(Constituent unit / monomer having lactone skeleton)
Examples of lactone skeletons include lactone skeletons of about 4 to 20-membered rings. The lactone skeleton may be a single ring of only a lactone ring, or an aliphatic or aromatic carbocyclic or heterocyclic ring may be fused to the lactone ring.
When the polymer contains a structural unit having a lactone skeleton, its content is preferably 20 mol% or more, and 25 mol% or more of all structural units (100 mol%) from the viewpoint of adhesion to a substrate or the like. Is more preferred.
In addition, from the viewpoint of sensitivity and resolution, 60 mol% or less is preferable, 55 mol% or less is more preferable, and 50 mol% or less is 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、置換若しくは無置換のδ−バレロラクトン環を有する（メタ）アクリル酸エステル、又は、置換若しくは無置換の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。
なお、本明細書において、「（メタ）アクリル酸」は、アクリル酸又はメタクリル酸を意味し、「（メタ）アクリロイルオキシ」は、アクリロイルオキシ又はメタクリロイルオキシを意味する。
As a monomer having a lactone skeleton, a (meth) acrylic ester having a substituted or unsubstituted δ-valerolactone ring or a substituted or unsubstituted γ-butyrolactone from the viewpoint of excellent adhesion to a substrate or the like At least one selected from the group consisting of monomers having a ring is preferable, and a monomer having an unsubstituted γ-butyrolactone ring is particularly preferable.
In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and "(meth) acryloyloxy" means acryloyloxy or methacryloyloxy.
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-norbornane carbolactone, 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 . Moreover, methacryloyloxy succinic anhydride etc. are also mentioned as a monomer which has a similar structure.
As the monomer having a lactone skeleton, one type may be used alone, or two or more types may be used in combination.
（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、カルボキシ基及びアミノ基からなる群より選ばれる、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又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 having a hydrophilic group, monomer)
The “hydrophilic group” in the present specification is at least one selected from the group consisting 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 polymer for resists applied to the pattern formation method exposed with the light 250 nm or less in wavelength has a hydroxyl group or a cyano group as a hydrophilic group.
The content of the structural unit having a hydrophilic group in the polymer is preferably 5 to 30 mol%, and more preferably 10 to 25 mol%, of all structural units (100 mol%) from the viewpoint of 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。 As a monomer having a hydrophilic group, for example, (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 (eg, cyclohexyl (meth) acrylate, 1-isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, (meth) acrylate) 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; It 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−若しくは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−若しくは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, 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 and the like Can be mentioned.
From the point of adhesion to a substrate etc., 3-hydroxyadamantyl (meth) acrylate, 3,5-dihydroxyadamantyl (meth) acrylate, 2- or 3-cyano-5-norbornyl (meth) acrylate, 2-cyanomethyl- 2-adamantyl (meth) acrylate etc. are preferable.
The monomers having a hydrophilic group may be used alone or in combination of two or more.
［酸脱離性基を有する構成単位］
本発明によって得られる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又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、感度及び解像度の点から、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。
[Constituent unit having an acid leaving group]
When the polymer obtained by the present invention is used for a resist application, it is preferable to have a structural unit having an acid-eliminating group in addition to the above-described structural unit having a polar group, and in addition, known as necessary. It may further have a structural unit of
The "acid-eliminating group" is a group having a bond which is cleaved by an acid, and the cleavage of the bond causes a part or all of the acid-eliminating group to leave the main chain of the polymer.
In the resist composition, a polymer having a structural unit having an acid-eliminating group reacts with an acid component to be soluble in an alkaline solution, and has an effect of enabling formation of a resist pattern.
The proportion of the structural unit having an acid-eliminating group is preferably 20 mol% or more, more preferably 25 mol% or more, of the total structural units (100 mol%) constituting the polymer from the viewpoint of sensitivity and resolution. . Further, from the viewpoint of adhesion to a substrate or the like, 60 mol% or less is preferable, 55 mol% or less is more preferable, and 50 mol% or less is more preferable.
酸脱離性基を有する単量体は、酸脱離性基及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、又は、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、直接若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 a compound having an acid leaving group and a polymerizable multiple bond, and known monomers can be used. The polymerizable multiple bond is a multiple bond which is cleaved during a polymerization reaction to form a copolymer chain, and is preferably an ethylenic double bond.
Specific examples of the monomer having an acid leaving group include (meth) acrylic esters having an alicyclic hydrocarbon group having 6 to 20 carbon atoms and having an acid leaving group. Be
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 ester has an alicyclic hydrocarbon group having a carbon number of 6 to 20, and a tertiary carbon atom at a binding site to an oxygen atom constituting an ester bond of the (meth) acrylic ester. (Meth) acrylic acid ester having an alicyclic hydrocarbon group having 6 to 20 carbon atoms and at the same time, the alicyclic hydrocarbon group has a —COOR group (R may have a substituent) And (meth) acrylic acid esters in which a tertiary hydrocarbon group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group) is bonded directly or through a linking group.
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 to be applied to a pattern forming method of exposing with light having a wavelength of 250 nm or less, as a preferable example of a monomer having an acid-eliminating 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 meta) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, isopropyladamantyl (meth) acrylate, 1-ethylcyclooctyl (meth) acrylate and the like.
As the monomers having an acid leaving group, one type may be used alone, or two or more types may be used in combination.
重合溶媒としては、前記の工程３で使用した溶媒であれば特に限定されない。金属低減の観点から、電子工業用グレードの溶媒を用いるのが好ましい。 The polymerization solvent is not particularly limited as long as it is the solvent used in the above step 3. From the viewpoint of metal reduction, it is preferable to use a solvent of electronics grade.
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。 As a polymerization initiator, what generate | occur | produces a radical efficiently by heat is preferable. For example, azo compounds (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.
前記の重合工程により得られた重合反応溶液は、必要に応じて、再沈殿工程、リスラリ工程、乾燥工程、再溶解工程、濃縮工程を有しても良い。 The polymerization reaction solution obtained by the above-mentioned polymerization step may have a re-precipitation step, a reslurry step, a drying step, a re-dissolution step, and a concentration step, as required.
本発明によって得られる重合体の用途は特に限定されない。例えば、リソグラフィー工程に用いられるリソグラフィー用重合体が好ましい。リソグラフィー用重合体としては、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）、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、又は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、などが例として挙げられる。
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 application of the polymer obtained by the present invention is not particularly limited. For example, a polymer for lithography used in a lithography process is preferable. As a polymer for lithography, a resist polymer used for forming a resist film, an antireflection film (TARC) formed on the upper layer of the resist film, and an antireflection film (BARC) formed on the lower layer of the resist film Examples thereof include a polymer for an antireflective film used in the above, a gap fill film polymer used for forming a gap fill film, a polymer for top coat film used for forming a top coat film, and the like.
As an example of the polymer for resists, the copolymer containing 1 or more types of the structural unit which has the said acid eliminable group, and 1 or more types of the structural unit which has the said polar group is mentioned.
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。
ここで、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。
Examples of the antireflective film polymer include an amino group, an amido group, a hydroxyl group, an epoxy group, etc. which can be cured by reacting with a curing agent etc. to avoid mixing with the structural unit having a light absorbing group and the resist film. And copolymers containing a structural unit having a reactive functional group of
Here, the light absorbing group is a group having high absorption performance to light in a wavelength region where the photosensitive component in the resist composition has sensitivity, and specific examples thereof include an anthracene ring, a naphthalene ring, and a benzene ring. And groups having a ring structure (which may have an optional substituent) such as quinoline ring, quinoxaline ring and thiazole ring.
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 the top coat film polymer used for liquid immersion lithography include copolymers containing a structural unit having a carboxyl group, and copolymers containing a structural unit having a fluorine-containing group substituted with a hydroxyl group.
＜レジスト組成物の製造方法＞
本発明によって得られる重合体を用いてレジスト組成物の製造する場合は、得られた重合体と、活性光線又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。ここで、必要に応じて、さらにレジスト溶媒を加えて混合することもできる。レジスト溶媒としては、前記に重合溶媒として挙げた溶媒を用いることができる。こうして得られるレジスト組成物は化学増幅型レジスト組成物である。
レジスト組成物の製造に用いる重合体溶液は、前記溶解工程で得られた溶液でもよく、その後に濾過した濾液でもよく、前記濃縮工程で得られた濃縮液でもよく、その後に濾過した濾液でもよい。
<Method of Producing Resist Composition>
When manufacturing a resist composition using the polymer obtained by this invention, it has the process of mixing the obtained polymer and the compound which generate | occur | produces an acid by irradiation of an actinic ray or a radiation. Here, if necessary, a resist solvent can be further added and mixed. As the resist solvent, the solvents listed above as the polymerization solvent can be used. The resist composition thus obtained is a chemically amplified resist composition.
The polymer solution used in the preparation of the resist composition may be the solution obtained in the dissolution step, may be a filtrate obtained after filtration, may be a concentrate obtained in the concentration step, or may be a filtrate obtained after filtration .
［活性光線又は放射線の照射により酸を発生する化合物］
活性光線又は放射線の照射により酸を発生する化合物は、化学増幅型レジスト組成物の光酸発生剤として使用可能なものの中から任意に選択できる。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。
光酸発生剤の使用量は、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。
[Compounds that generate an acid upon irradiation with actinic rays or radiation]
The compound capable of generating an acid upon irradiation with an actinic ray or radiation can be optionally selected from those usable as the photoacid generator of the chemically amplified resist composition. A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
As a photo-acid generator, an onium salt compound, a sulfone imide compound, a sulfone compound, a sulfonate ester compound, a quinone diazide compound, a diazomethane compound etc. are mentioned, for example.
0.1-20 mass parts is preferable with respect to 100 mass parts of polymers, and, as for the usage-amount of a photo-acid generator, 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 of placement, and the like are further improved. That is, the cross-sectional shape of the resist pattern becomes closer to a rectangle, and after the resist film is irradiated with light and then baked (PEB), it is allowed to stand for several hours before the next development processing; Although it is a line, the occurrence of deterioration of the cross-sectional shape of the resist pattern is further suppressed when it is left as such (over time).
The nitrogen-containing compound is preferably an amine, and more preferably a secondary lower aliphatic amine or a tertiary lower aliphatic amine.
The amount of the nitrogen-containing compound is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the polymer.
［有機カルボン酸、リンのオキソ酸又はその誘導体］
化学増幅型レジスト組成物は、有機カルボン酸、リンのオキソ酸又はその誘導体（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, these are collectively referred to as an acid compound).
By containing the acid compound, it is possible to suppress the sensitivity deterioration due to the compounding of the nitrogen-containing compound, and further improve the resist pattern shape, the stability over time of placing, and the like.
Examples of organic carboxylic acids 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］
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 may, if necessary, contain various additives such as surfactants, other quenchers, sensitizers, antihalation agents, storage stabilizers, antifoaming agents and the like. Any of the additives known in the art can be used.
Further, the amounts of these additives are not particularly limited, and may be determined appropriately.
＜微細パターンが形成された基板の製造方法＞
本発明によって得られる重合体を用いて製造されるレジスト組成物を用いて微細パターンが形成された基板の製造方法の一例について説明する。
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に、本発明の製造方法で得られる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。
<Method of Manufacturing Substrate Having Fine Pattern Formed>
An example of a method for producing a substrate on which a fine pattern is formed using a resist composition produced using a polymer obtained by the present invention will be described.
First, the resist composition obtained by the manufacturing method of the present invention is applied by spin coating or the like on the surface of a substrate to be processed such as a silicon wafer on which a desired fine pattern is to be formed. Then, the substrate to be processed on which the resist composition has been applied is dried by a baking treatment (pre-baking) or the like to form a resist film on the substrate.
ついで、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。
Subsequently, light having a wavelength of 250 nm or less is irradiated to the resist film 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, or an EUV excimer laser is preferable, and an ArF excimer laser is particularly preferable. Alternatively, an electron beam may be irradiated.
In addition, it is an immersion that irradiates light in a state where a high refractive index liquid such as pure water, perfluoro-2-butyltetrahydrofuran, perfluorotrialkylamine is 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、公知のものが挙げられる。
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 exposure, heat treatment (post-exposure bake, PEB) is appropriately performed to bring the resist film into contact with an alkaline developer, and the exposed portion is dissolved in the developer and removed (development). Examples of the alkali developer include known ones.
After development, the substrate is appropriately rinsed with pure water or the like. Thus, a resist pattern is formed on the processing substrate.
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、微細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 etching, the resist is removed by a release agent to obtain a substrate on which a fine pattern is formed.
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。
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
Moreover, "part" in each example and comparative example indicates "part by mass" unless otherwise noted. The measuring method and the evaluation method used the following methods.
＜水分含有量の評価＞
重合体溶液中の水分は、下記の条件でカールフィッシャー法（電量法）により求めた。
[測定条件]
装置：三菱化学ＣＡ―２００
滴定継続時間：１ｍｉｎ
滴定強制終了時間：１０ｍｉｎ
終点検出レベル：０．１ μｇ／ｓｅｃ
電解液陽極液：三菱化学アクアミクロンＡＫＸ １００ｍＬ
陰極液：三菱化学アクアミクロンＣＸＵ ５ｍＬ
試料：ポリマー溶液１．０ｇ〜１．２ｇ をカールフィッシャー測定セルに投入して測定した。
<Evaluation of water content>
The water content in the polymer solution was determined by the Karl Fischer method (coulometric method) under the following conditions.
[Measurement condition]
Equipment: Mitsubishi Chemical CA-200
Duration of titration: 1 min
Forced termination of titration: 10 min
End point detection level: 0.1 μg / sec
Electrolyte Anolyte: Mitsubishi Chemical Aquamicron AKX 100mL
Catholyte: Mitsubishi Chemical Aquamicron CXU 5mL
Sample: 1.0 g to 1.2 g of a polymer solution was charged into a Karl Fischer measuring cell and measured.
＜残存溶剤含有量の評価＞
重合体中の残存溶剤は、下記の条件（ＧＣ条件）でガス・クロマトグラフィーにより、内部標準法で求めた。
［ＧＣ条件］
装置：アジレント・テクノロジー社製、Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ ６８９０（商品名）
キャリアガス：Ｈｅ
全流量：２４ｍＬ／ｍｉｎ
分離カラム：アジレント・テクノロジー社製、ＨＰ−ＩＮＮＷＡＸ（商品名） 長さ３０ｍ×内径０．３２ｍｍ×膜厚０．２５μｍ
カラム流量：１．５ｍＬ／ｍｉｎ（４０℃）
カラム昇温条件：５０℃（１０分間保持）→（１０℃／ｍｉｎで昇温）→１１０℃（９分間保持）
注入口温度：２３０℃
検出口温度：２３０℃
検出器：水素炎イオン化検出器（ＦＩＤ）
注入量：１μＬ
試料：重合体０．１ｇに５ｍＬのアセトニトリルを加え、１２時間・２５℃で静置した後、上澄み液を０．９８ｍＬ分取し、内部標準であるｎ−ブチルアルコール１％溶液を２０μＬ添加した溶液を測定に用いた。
<Evaluation of residual solvent content>
The residual solvent in the polymer was determined by gas chromatography under the following conditions (GC conditions) by the internal standard method.
[GC condition]
Equipment: Agilent Technologies 6890 (trade name) manufactured by Agilent Technologies
Carrier gas: He
Total flow rate: 24mL / min
Separation column: manufactured by Agilent Technologies, HP-INNWAX (trade name) Length 30 m × inner diameter 0.32 mm × film thickness 0.25 μm
Column flow rate: 1.5 mL / min (40 ° C)
Column temperature rising condition: 50 ° C (hold for 10 minutes) → (rise at 10 ° C / min) → 110 ° C (hold for 9 minutes)
Inlet temperature: 230 ° C
Detection port temperature: 230 ° C
Detector: Hydrogen flame ionization detector (FID)
Injection volume: 1 μL
Sample: 5 mL of acetonitrile was added to 0.1 g of the polymer, and after standing at 25 ° C. for 12 hours, 0.98 mL of the supernatant was taken and 20 μL of 1% solution of n-butyl alcohol as an internal standard was added The solution was used for the measurement.
＜金属含有量の評価＞
金属含有量の測定は、洗浄後の反応容器内に１時間浸漬させた重合溶媒中及び製造後の重合体溶液中の下記金属の含有量を測定した。
測定金属：Ｎａ（ナトリウム）、Ｆｅ（鉄）
測定装置としては、ネブライザーとしてＧｌａｓｓ Ｅｘｐａｎｓｉｏｎ社製、Ｍｉｃｒｏｍｉｓｔ ＡＲ８０−１−ＦＭ０４（商品名）を装備したＡｇｉｌｅｎｔ社製７５００ＣＳ型ＩＣＰ−ＭＳ（商品名）を用いた。
測定用サンプルとしては、非沸騰蒸留した電子工業用グレードのＮ−メチルピロドン（以下、「ＮＭＰ」という）に重合体溶液を添加し、２％の溶液としたものを使用した。
上記の非沸騰蒸留ＮＭＰは、粗体である電子工業グレードのＮＭＰを非沸騰バッチ式透明石英製酸蒸留装置（（株）藤原製作所製、ＳＨＦ−ｓｐｅｃｉａｌ型（商品名））へ導入し、蒸留速度が約１滴／１０秒になるようにヒーター出力を調整して得た。
尚、非沸騰蒸留した金属レベルの低い溶剤（ブランク）と金属濃度１ｐｐｂのチューニング液との金属イオンのカウント数の差が数十倍以上で、ブランクにおいては積分時間０．１秒で全ての金属が１桁カウント以下になるようにチューニングした後に、サンプルの金属含有量を標準添加法で測定した。
<Evaluation of metal content>
The metal content was measured by measuring the contents of the following metals in the polymerization solvent immersed in the washed reaction vessel for 1 hour and in the polymer solution after production.
Measurement metal: Na (sodium), Fe (iron)
As a measuring apparatus, 7500CS type ICP-MS (trade name) manufactured by Agilent Technologies equipped with Micromist AR80-1-FM04 (trade name) manufactured by Glass Expansion, Inc. as a nebulizer was used.
As a sample for measurement, a polymer solution was added to non-boiling distilled electronic industrial grade N-methyl pyrodone (hereinafter referred to as "NMP") to prepare a 2% solution.
The above non-boiling distilled NMP is introduced into a non-boiling batch type transparent quartz acid distiller (SHF-special type (trade name) manufactured by Fujiwara Seisakusho Co., Ltd.), which is a crude product of electronic industrial grade It was obtained by adjusting the heater output so that the velocity was about 1 drop / 10 seconds.
The difference in metal ion count between the non-boiling distilled low metal level solvent (blank) and the tuning solution with a metal concentration of 1 ppb is several tens of times or more. In the blank, the integration time is 0.1 seconds for all metals. The metal content of the sample was measured by the standard addition method after tuning so as to be less than one digit count.
標準金属としてはＳＰＥＸ社製ＸＳＴＣ−６２２（商品名）を使用し、各金属１００ｐｐｂになるようにＸＳＴＣ−６２２を非沸騰蒸留ＮＭＰで希釈して使用した。検量線はブランク、２００ｐｐｔ、５００ｐｐｔ、及び１，０００ｐｐｔの４点でブランク値を通る線形回帰直線にて作成した。
非沸騰蒸留ＮＭＰ中の金属含有量の測定では、各金属１０ｐｐｂになるようにＸＳＴＣ−６２２を既に金属含有量測定済みの別の非沸騰蒸留ＮＭＰで希釈して使用した。検量線はブランク、２０ｐｐｔ、５０ｐｐｔ、及び１００ｐｐｔの４点でブランク値を通る線形回帰直線にて作成した。
尚、非沸騰蒸留、サンプル調製及び金属含有量の測定の操作は全てクラス１，０００のクリーンルーム内で実施した。
上記の非沸騰蒸留ＮＭＰの金属含有量は全ての元素について金属及び半金属レベルが１０ｐｐｔ以下であった。
As a standard metal, XSTC-622 (trade name) manufactured by SPEX Corp. 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 as a linear regression line passing 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 used after diluting it with another non-boiling distilled NMP whose metal content was already measured so that each metal became 10 ppb. The calibration curve was prepared as a linear regression line passing the blank value at four points of blank, 20 ppt, 50 ppt and 100 ppt.
The operations of non-boiling distillation, sample preparation and measurement of metal content were all carried out in a class 1,000 clean room.
The metal content of the above non-boiling distilled NMP was less than 10 ppt metal and metalloid levels for all elements.
［実施例１］
重合反応用の反応容器として、窒素導入口、攪拌機、コンデンサー、滴下ポンプ及び温
度計を備えた容量５００ＬのＳＵＳ製の反応容器を用いた。重合反応前に反応容器を洗浄
した。
工程１：イオン交換処理及びメンブラン膜処理して得られた超純水（Ｎａ含有量１ｐｐ
ｂ以下、Ｆｅ含有量１ｐｐｂ以下）５００．０ｋｇを反応容器へ供給し、１時間撹拌し反
応容器内を洗浄し、反応容器から洗浄液を排出した。
工程２：電子工業用グレードのメタノール（Ｎａ含有量１ｐｐｂ以下、Ｆｅ含有量１ｐ
ｐｂ以下）８０．０ｋｇを反応容器へ供給し、撹拌しながら加熱し、１時間メタノールを
還流させて反応容器内を洗浄し、反応容器から洗浄液を排出した。
工程３：電子工業用グレードのＰＧＭＥＡ（Ｎａ含有量１ｐｐｂ以下、Ｆｅ含有量１ｐ
ｐｂ以下）８０．０ｋｇを反応容器へ供給し、撹拌しながら８０℃で１時間加熱洗浄した
後、反応容器から洗浄液を排出した。
上記の洗浄方法によって洗浄した反応容器に、乳酸エチル１２１．０ｋｇを入れた。反
応容器内を窒素で置換し、窒素雰囲気を保ったまま反応容器を加熱し、反応容器内を攪拌
しながら反応容器内の乳酸エチルの温度を８０℃に上げた。
その後、下記混合物１を滴下ポンプより、４時間かけて反応容器内に滴下し、さらに８
０℃の温度で、３時間保持した。
その後、２５℃まで反応容器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。重合反応溶液の一部をサンプリングし、水分含有量および残存溶剤含有量を測定
した。その結果を表１に示す。
［混合物１］
下記式（ｍ１）の単量体を５１．００ｋｇ
下記式（ｍ２）の単量体を５８．８０ｋｇ
下記式（ｍ３）の単量体を３５．４０ｋｇ
乳酸エチル２１７．８ｋｇ
ジメチル−２，２’−アゾビスイソブチレート（和光純薬工業社製、Ｖ６０１（商品名
））４．１４０ｋｇ
また、各単量体の仕込み割合（モル％）は、下記の通りである。
（ｍ−１）／（ｍ−２）／（ｍ−３）＝４０／４０／２０
Example 1
As a reaction container for the polymerization reaction, a 500 L SUS reaction container equipped with a nitrogen inlet, a stirrer, a condenser, a dropping pump and a thermometer was used. The reaction vessel was washed before the polymerization reaction.
Step 1: Ultrapure water (Na content: 1 pp) obtained by ion exchange treatment and membrane treatment
b) 500.0 kg of an Fe content of 1 ppb or less was supplied to the reaction vessel, and stirred for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 2: Electronic industrial grade methanol (Na content: 1 ppb or less, Fe content: 1 p
80.0 kg of pb or less was supplied to the reaction vessel, heated with stirring, refluxing methanol for 1 hour to wash the inside of the reaction vessel, and draining the washing liquid from the reaction vessel.
Step 3: Electronic industrial grade PGMEA (Na content: 1 ppb or less, Fe content: 1 p
After feeding 80.0 kg of the b) or less to the reaction vessel and heating and washing at 80 ° C. for 1 hour while stirring, the washing liquid was discharged from the reaction vessel.
121.0 kg of ethyl lactate was placed in the reaction vessel washed by the above washing method. The inside of the reaction vessel was replaced with nitrogen, the reaction vessel was heated while maintaining the nitrogen atmosphere, and the temperature of ethyl lactate in the reaction vessel was raised to 80 ° C. while stirring the inside of the reaction vessel.
Thereafter, the following mixture 1 is dropped from the dropping pump into the reaction vessel over 4 hours, and further 8
Hold at a temperature of 0 ° C. for 3 hours.
Thereafter, the reaction solution in the reaction vessel was cooled to 25 ° C. to terminate the polymerization reaction, to obtain a polymerization reaction solution. A part of the polymerization reaction solution was sampled to determine the water content and the residual solvent content. The results are shown in Table 1.
[Mix 1]
51.00 kg of a monomer of the following formula (m1)
58.80 kg of a monomer of the following formula (m2)
35.40 kg of a monomer of the following formula (m3)
Ethyl lactate 217.8 kg
Dimethyl-2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., V601 (trade name)) 4.140 kg
Moreover, the preparation ratio (mol%) of each monomer is as follows.
(M-1) / (m-2) / (m-3) = 40/40/20
得られた重合反応溶液を、７．０倍量の貧溶媒中に、該貧溶媒を攪拌しながら滴下し、重合体（白色の析出物）を沈殿させた。貧溶媒としては、メタノールと水の混合溶媒（メタノール／水＝８０／２０容量比）を用いた。
攪拌しながら４０℃に加熱し、３０分間保持した後、２５℃まで冷却して沈殿を加圧ろ過器で濾別し、重合体湿粉を得た。
The obtained polymerization reaction solution was dropped into a 7.0-fold amount of a poor solvent while stirring the poor solvent to precipitate a polymer (white precipitate). As a poor solvent, a mixed solvent of methanol and water (methanol / water = 80/20 volume ratio) was used.
The mixture was heated to 40 ° C. with stirring and maintained for 30 minutes, then cooled to 25 ° C., and the precipitate was separated by filtration using a pressure filter to obtain a wet polymer powder.
得られた湿粉を、重合反応溶液の７．０倍量の貧溶媒と再び混合し、リスラリ操作を行った。貧溶媒としてはメタノールと水の混合溶媒（メタノール／水＝８５／１５容量比）を用いた。
次に、２５℃の雰囲気中で、得られた湿粉の１００ｋｇを、ＰＧＭＥＡ（２５℃）の１０００ｋｇに溶解させた。
The obtained wet powder was again mixed with 7.0 times the amount of poor solvent of the polymerization reaction solution, and a reslurry operation was performed. As a poor solvent, a mixed solvent of methanol and water (methanol / water = 85/15 volume ratio) was used.
Next, in an atmosphere of 25 ° C., 100 kg of the obtained wet powder was dissolved in 1000 kg of PGMEA (25 ° C.).
次いで、得られた溶液をナイロン製の孔径０．０４μｍのカートリッジフィルターで濾過した。得られた濾液を圧力２０ｋＰａ、温度５０℃の条件で濃縮し、留出液が出なくなった時点で圧力３ｋＰａ、温度６５℃の条件に変更して、重合体の固形分濃度が２５質量％になるまで濃縮を行った。
得られたＰＧＭＥＡ溶液について、金属含有量を測定した。結果を表１に示す。
The resulting solution was then filtered through a nylon cartridge filter with a pore size of 0.04 μm. The obtained filtrate was concentrated under the conditions of pressure 20 kPa and temperature 50 ° C., and when the distillate did not come out, it was changed to pressure 3 kPa and temperature 65 ° C., and the solid content concentration of the polymer was 25 mass%. It concentrated until it became.
The metal content of the obtained PGMEA solution was measured. The results are shown in Table 1.
［実施例２］
実施例１と同様の反応容器を用いた。
工程１：超純水４７５．０ｋｇを反応容器へ供給し、次いで、電子工業用グレードのＭ
ＥＫ（Ｎａ含有量１ｐｐｂ以下、Ｆｅ含有量１ｐｐｂ以下）２５．０ｋｇを反応容器へ供
給し、１時間撹拌し反応容器内を洗浄し、反応容器から洗浄液を排出した。
工程２：メタノール８０．０ｋｇを反応容器へ供給し、撹拌しながら加熱し、１時間メ
タノールを還流させて反応容器内を洗浄し、反応容器から洗浄液を排出した。
工程３：として、前記ＰＧＭＥＡ８０．０ｋｇを反応容器へ供給し、撹拌しながら８０℃
で１時間加熱洗浄した後、反応容器から洗浄液を排出した。
上記洗浄方法以外は、実施例１と同様にして重合反応溶液およびＰＧＭＥＡ溶液を得た
。得られた重合反応溶液について、水分含有量および残存溶剤含有量を測定し、ＰＧＭＥ
Ａ溶液について、金属含有量を測定した。結果を表１に示す。
Example 2
The same reaction vessel as in Example 1 was used.
Step 1: Supply 475.0 kg of ultrapure water to the reaction vessel, then M grade for electronic industry
25.0 kg of EK (Na content: 1 ppb or less, Fe content: 1 ppb or less) was supplied to the reaction vessel, stirred for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 2: 80.0 kg of methanol was supplied to the reaction vessel, heated with stirring, and refluxed for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Process 3: As an 80.0 kg of PGMEA is supplied to a reaction vessel and 80 ° C. with stirring.
After heating and washing for 1 hour, the washing solution was drained from the reaction vessel.
A polymerization reaction solution and a PGMEA solution were obtained in the same manner as in Example 1 except for the above washing method. The water content and residual solvent content of the obtained polymerization reaction solution are measured
The metal content of the solution A was measured. The results are shown in Table 1.
［実施例３］
実施例１と同様の反応容器を用いた。
工程１：超純水４７５．０ｋｇを反応容器へ供給し、次いで、ＭＥＫ２５．０ｋｇを反
応容器へ供給し、１時間撹拌し反応容器内を洗浄した。反応容器から洗浄液を排出し、次
いで、超純水５００．０ｋｇを反応容器へ供給し、１時間撹拌し反応容器内を洗浄し、反
応容器から洗浄液を排出した。
工程２：メタノール８０．０ｋｇを反応容器へ供給し、撹拌しながら加熱し、１時間メ
タノールを還流させて反応容器内を洗浄し、反応容器から洗浄液を排出した。
工程３：ＰＧＭＥＡ８０．０ｋｇを反応容器へ供給し、撹拌しながら８０℃で１時間加
熱洗浄した後、反応容器から洗浄液を排出した。
上記洗浄方法以外は、実施例１と同様にして重合反応溶液およびＰＧＭＥＡ溶液を得た
。得られた重合反応溶液について、水分含有量および残存溶剤含有量を測定し、ＰＧＭＥ
Ａ溶液について、金属含有量を測定した。結果を表１に示す。
[Example 3]
The same reaction vessel as in Example 1 was used.
Step 1: 475.0 kg of ultrapure water was supplied to the reaction vessel, and then 25.0 kg of MEK was supplied to the reaction vessel, and the inside of the reaction vessel was washed by stirring for 1 hour. The washing solution was discharged from the reaction vessel, and then 500.0 kg of ultrapure water was supplied to the reaction vessel, and the inside of the reaction vessel was washed by stirring for 1 hour, and the washing solution was discharged from the reaction vessel.
Step 2: 80.0 kg of methanol was supplied to the reaction vessel, heated with stirring, and refluxed for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 3 : 80.0 kg of PGMEA was supplied to the reaction vessel, and after heating and washing at 80 ° C. for 1 hour while stirring, the washing liquid was drained from the reaction vessel.
A polymerization reaction solution and a PGMEA solution were obtained in the same manner as in Example 1 except for the above washing method. The water content and residual solvent content of the obtained polymerization reaction solution are measured
The metal content of the solution A was measured. The results are shown in Table 1.
［実施例４］
実施例１と同様の反応容器を用いた。
工程１：超純水５００ｋｇを反応容器へ供給し、１時間撹拌し反応容器内を洗浄し、反
応容器から洗浄液を排出した。
工程２：メタノール７６．０ｋｇを反応容器へ供給し、次いで、ＭＥＫ４．０ｋｇを反
応容器へ供給し、撹拌しながら加熱し、１時間メタノールおよびＭＥＫを還流させて反応
容器内を洗浄し、反応容器から洗浄液を排出した。
工程３：ＰＧＭＥＡ８０．０ｋｇを反応容器へ供給し、撹拌しながら８０℃で１時間加
熱洗浄した後、反応容器から洗浄液を排出した。
上記洗浄方法以外は、実施例１と同様にして重合反応溶液およびＰＧＭＥＡ溶液を得た
。得られた重合反応溶液について、水分含有量および残存溶剤含有量を測定し、ＰＧＭＥ
Ａ溶液について、金属含有量を測定した。結果を表１に示す。
Example 4
The same reaction vessel as in Example 1 was used.
Step 1: 500 kg of ultrapure water was supplied to the reaction vessel, and stirred for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 2: Supply 76.0 kg of methanol to the reaction vessel, then supply 4.0 kg of MEK to the reaction vessel, heat with stirring, reflux the methanol and MEK for 1 hour, and wash the inside of the reaction vessel; The washing solution was drained from the
Step 3: 80.0 kg of PGMEA was supplied to the reaction vessel, and after heating and washing at 80 ° C. for 1 hour while being stirred, the washing liquid was drained from the reaction vessel.
A polymerization reaction solution and a PGMEA solution were obtained in the same manner as in Example 1 except for the above washing method. The water content and residual solvent content of the obtained polymerization reaction solution are measured
The metal content of the solution A was measured. The results are shown in Table 1.
［実施例５］
実施例１と同様の反応容器を用いた。
工程１：超純水５００ｋｇを反応容器へ供給し、１時間撹拌し反応容器内を洗浄し、反
応容器から洗浄液を排出した。
工程２：メタノール７６．０ｋｇを反応容器へ供給し、次いで、ＭＥＫ４．０ｋｇを反
応容器へ供給し、撹拌しながら加熱し、１時間メタノールおよびＭＥＫを還流させて反応
容器内を洗浄し、反応容器から洗浄液を排出した。次いで、メタノール８０．０ｋｇを反
応容器へ供給し、撹拌しながら加熱し、１時間メタノールを還流させて反応容器内を洗浄
し、反応容器から洗浄液を排出した。
工程３：ＰＧＭＥＡ８０．０ｋｇを反応容器へ供給し、撹拌しながら８０℃で１時間加
熱洗浄した後、反応容器から洗浄液を排出した。
上記洗浄方法以外は、実施例１と同様にして重合反応溶液およびＰＧＭＥＡ溶液を得た
。得られた重合反応溶液について、水分含有量および残存溶剤含有量を測定し、ＰＧＭＥ
Ａ溶液について、金属含有量を測定した。結果を表１に示す。
[Example 5]
The same reaction vessel as in Example 1 was used.
Step 1: 500 kg of ultrapure water was supplied to the reaction vessel, and stirred for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 2: Supply 76.0 kg of methanol to the reaction vessel, then supply 4.0 kg of MEK to the reaction vessel, heat with stirring, reflux the methanol and MEK for 1 hour, and wash the inside of the reaction vessel; The washing solution was drained from the Next, 80.0 kg of methanol was supplied to the reaction vessel, heated with stirring, and refluxed for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 3: 80.0 kg of PGMEA was supplied to the reaction vessel, and after heating and washing at 80 ° C. for 1 hour while being stirred, the washing liquid was drained from the reaction vessel.
A polymerization reaction solution and a PGMEA solution were obtained in the same manner as in Example 1 except for the above washing method. The water content and residual solvent content of the obtained polymerization reaction solution are measured
The metal content of the solution A was measured. The results are shown in Table 1.
［実施例６］
実施例１と同様の反応容器を用いた。
工程１：超純水５００．０ｋｇを反応容器へ供給し、１時間撹拌し反応容器内を洗浄し
、反応容器から洗浄液を排出した。次いで、再び超純水５００．０ｋｇを反応容器へ供給
し、１時間撹拌し反応容器内を洗浄し、反応容器から洗浄液を排出した。
工程２：メタノール８０．０ｋｇを反応容器へ供給し、撹拌しながら加熱し、１時間メ
タノールを還流させて反応容器内を洗浄し、反応容器から洗浄液を排出した。
工程３：ＰＧＭＥＡ８０．０ｋｇを反応容器へ供給し、撹拌しながら８０℃で１時間加
熱洗浄した後、反応容器から洗浄液を排出した。
上記洗浄方法以外は、実施例１と同様にして重合反応溶液およびＰＧＭＥＡ溶液を得た
。得られた重合反応溶液について、水分含有量および残存溶剤含有量を測定し、ＰＧＭＥ
Ａ溶液について、金属含有量を測定した。結果を表１に示す。
[Example 6]
The same reaction vessel as in Example 1 was used.
Step 1: 500.0 kg of ultrapure water was supplied to the reaction vessel, and stirred for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel. Next, 500.0 kg of ultrapure water was again supplied to the reaction vessel, and the reaction vessel was stirred for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 2: 80.0 kg of methanol was supplied to the reaction vessel, heated with stirring, and refluxed for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 3: 80.0 kg of PGMEA was supplied to the reaction vessel, and after heating and washing at 80 ° C. for 1 hour while being stirred, the washing liquid was drained from the reaction vessel.
A polymerization reaction solution and a PGMEA solution were obtained in the same manner as in Example 1 except for the above washing method. The water content and residual solvent content of the obtained polymerization reaction solution are measured
The metal content of the solution A was measured. The results are shown in Table 1.
［実施例７］
実施例１と同様の反応容器を用いた。
工程１：超純水５００．０ｋｇを反応容器へ供給し、１時間撹拌し反応容器内を洗浄し
、反応容器から洗浄液を排出した。
工程２：メタノール８０．０ｋｇを反応容器へ供給し、撹拌しながら加熱し、１時間メ
タノールを還流させて反応容器内を洗浄し、反応容器から洗浄液を排出した。次いで、再
びメタノール８０．０ｋｇを反応容器へ供給し、撹拌しながら加熱し、１時間メタノール
を還流させて反応容器内を洗浄し、反応容器から洗浄液を排出した。
工程３：ＰＧＭＥＡ８０．０ｋｇを反応容器へ供給し、撹拌しながら８０℃で１時間加
熱洗浄した後、反応容器から洗浄液を排出した。
上記洗浄方法以外は、実施例１と同様にして重合反応溶液およびＰＧＭＥＡ溶液を得た
。得られた重合反応溶液について、水分含有量および残存溶剤含有量を測定し、ＰＧＭＥ
Ａ溶液について、金属含有量を測定した。結果を表１に示す。
[Example 7]
The same reaction vessel as in Example 1 was used.
Step 1: 500.0 kg of ultrapure water was supplied to the reaction vessel, and stirred for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 2: 80.0 kg of methanol was supplied to the reaction vessel, heated with stirring, and refluxed for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel. Next, 80.0 kg of methanol was again supplied to the reaction vessel, heated with stirring, and refluxed for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 3: 80.0 kg of PGMEA was supplied to the reaction vessel, and after heating and washing at 80 ° C. for 1 hour while being stirred, the washing liquid was drained from the reaction vessel.
A polymerization reaction solution and a PGMEA solution were obtained in the same manner as in Example 1 except for the above washing method. The water content and residual solvent content of the obtained polymerization reaction solution are measured
The metal content of the solution A was measured. The results are shown in Table 1.
［実施例８］
実施例１と同様の反応容器を用いた。
工程１：超純水５００．０ｋｇを反応容器へ供給し、１時間撹拌し反応容器内を洗浄し
、反応容器から洗浄液を排出した。
工程２：メタノール８０．０ｋｇを反応容器へ供給し、撹拌しながら加熱し、１時間メ
タノールを還流させて反応容器内を洗浄し、反応容器から洗浄液を排出した。
工程３：ＰＧＭＥＡ８０．０ｋｇを反応容器へ供給し、撹拌しながら８０℃で１時間加
熱洗浄した後、反応容器から洗浄液を排出した。次いで、再び前記乳酸エチル８０．０ｋ
ｇを反応容器へ供給し、撹拌しながら８０℃で１時間加熱洗浄した後、反応容器から洗浄
液を排出した。
工程３：上記洗浄方法以外は、実施例１と同様にして重合反応溶液およびＰＧＭＥＡ溶
液を得た。得られた重合反応溶液について、水分含有量および残存溶剤含有量を測定し、
ＰＧＭＥＡ溶液について、金属含有量を測定した。結果を表１に示す。
[Example 8]
The same reaction vessel as in Example 1 was used.
Step 1: 500.0 kg of ultrapure water was supplied to the reaction vessel, and stirred for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 2: 80.0 kg of methanol was supplied to the reaction vessel, heated with stirring, and refluxed for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel.
Step 3: 80.0 kg of PGMEA was supplied to the reaction vessel, and after heating and washing at 80 ° C. for 1 hour while being stirred, the washing liquid was drained from the reaction vessel. Then, again, the ethyl lactate 80.0 k
g was supplied to the reaction vessel, and after heating and washing at 80 ° C. for 1 hour while stirring, the washing liquid was drained from the reaction vessel.
Step 3: A polymerization reaction solution and a PGMEA solution were obtained in the same manner as in Example 1 except for the above-mentioned washing method. Measure the water content and residual solvent content of the obtained polymerization reaction solution,
The metal content of the PGMEA solution was measured. The results are shown in Table 1.
［比較例１］
実施例１と同様の反応容器を用いた。
工程１：超純水５００．０ｋｇを反応容器へ供給し、１時間撹拌し反応容器内を洗浄し
、反応容器から洗浄液を排出した。工程２は行わなかった。
工程３：ＰＧＭＥＡ８０．０ｋｇを反応容器へ供給し、撹拌しながら８０℃で１時間加
熱洗浄した後、反応容器から洗浄液を排出した。
上記洗浄方法以外は、実施例１と同様にして重合反応溶液およびＰＧＭＥＡ溶液を得た
。得られた重合反応溶液について、水分含有量および残存溶剤含有量を測定し、ＰＧＭＥ
Ａ溶液について、金属含有量を測定した。結果を表１に示す。
Comparative Example 1
The same reaction vessel as in Example 1 was used.
Step 1: 500.0 kg of ultrapure water was supplied to the reaction vessel, and stirred for 1 hour to wash the inside of the reaction vessel, and the washing liquid was discharged from the reaction vessel. Step 2 was not performed.
Step 3: 80.0 kg of PGMEA was supplied to the reaction vessel, and after heating and washing at 80 ° C. for 1 hour while being stirred, the washing liquid was drained from the reaction vessel.
A polymerization reaction solution and a PGMEA solution were obtained in the same manner as in Example 1 except for the above washing method. The water content and residual solvent content of the obtained polymerization reaction solution are measured
The metal content of the solution A was measured. The results are shown in Table 1.
上記結果から明らかなように、本発明の洗浄方法によれば、得られる重合体反応溶液中の金属含有量や容器洗浄に用いた溶剤の含有量等を低減できることが確認された。 As is clear from the above results, according to the cleaning method of the present invention, it was confirmed that the metal content in the obtained polymer reaction solution and the content of the solvent used for container cleaning can be reduced.
Claims (7)
、下記の工程１，２を順次行うことを含む、反応容器の洗浄方法。
１．水を含む溶液を用いて洗浄して、反応容器内の金属成分を除去する。
２．親水性溶剤を含む溶液を還流させて、反応容器内の水、単量体、重合体のいずれかを
除去する。 A method of cleaning a reaction container for producing a polymer for an electronic material by polymerizing a mixture containing a monomer, comprising: performing the following steps 1 and 2 sequentially.
1. The metal component in the reaction vessel is removed by washing with a solution containing water .
2. The solution containing the hydrophilic solvent is refluxed to remove water, monomer or polymer in the reaction vessel.
請求項１に記載の洗浄方法。 In step 1, washing is performed using a solution containing water having a metal content of 50 ppb or less.
The cleaning method according to claim 1.
求項１または２の何れか一項に記載の洗浄方法。 In the step 2, SP value of the hydrophilic solvent is 19.0 [MPa1 / 2] above, the method of cleaning according to any one of claims 1 or 2.
請求項１〜３の何れか一項に記載の洗浄方法。 In step 2, a hydrophilic solvent having a boiling point of 100 ° C. or less at atmospheric pressure is used.
The cleaning method according to any one of claims 1 to 3 .
方法。
工程３．反応容器を、電子材料用重合体の重合に用いる溶剤を用いて洗浄する。 The cleaning method according to any one of claims 1 to 4 , further comprising the following step 3 after the step 2.
Step 3. The reaction vessel is washed with the solvent used for the polymerization of the polymer for electronic materials.
浄方法。 The cleaning method according to any one of claims 1 to 5 , wherein an inner volume of the reaction vessel is 30 L or more.
合体を製造する方法。 The method of manufacturing the polymer for electronic materials using the reaction container obtained by the washing | cleaning method as described in any one of Claims 1-6 .
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