JP2015038051A - Processing method of alkali metal salt and/or ammonium salt of organic sulfonic acid, and production method of organic sulfonic acid ammonium salt type surfactant - Google Patents
Processing method of alkali metal salt and/or ammonium salt of organic sulfonic acid, and production method of organic sulfonic acid ammonium salt type surfactant Download PDFInfo
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Abstract
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本発明は、有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩の処理方法並びに有機スルホン酸アンモニウム塩型界面活性剤の製造方法に関し、更に詳しくは、電子、半導体及び精密加工分野等で使用可能なレベルにまで金属イオン濃度を低減することができる有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩の処理方法並びにかかる処理方法によって得られた有機スルホン酸を用いることにより同様に金属イオン濃度を低減することができる有機スルホン酸アンモニウム塩型界面活性剤の製造方法に関する。 The present invention relates to a method for treating an alkali metal salt and / or ammonium salt of an organic sulfonic acid and a method for producing an organic sulfonic acid ammonium salt type surfactant, and more specifically, can be used in the fields of electronics, semiconductors, precision processing and the like. The metal ion concentration can be similarly reduced by using the organic sulfonic acid alkali metal salt and / or ammonium salt treatment method capable of reducing the metal ion concentration to the level and using the organic sulfonic acid obtained by such treatment method. The present invention relates to a method for producing an organic sulfonic acid ammonium salt type surfactant.
従来、電子、半導体及び精密加工分野等、様々な分野で不純物としての金属イオンの濃度を低減した界面活性剤が使用されており、かかる精製した界面活性剤を得るための方法が提案されている。例えば、非イオン界面活性剤については、イオン交換樹脂と機能性フィルターとを組み合わせて用いる方法（例えば特許文献１参照）や、非金属塩基水溶液で洗浄し、高温にて界面活性剤層を分離採取する方法（例えば特許文献２参照）、またアニオン界面活性剤については、一般的な濃縮、晶析、抽出による方法の他に逆浸透膜や限外濾過膜を用いる方法（例えば特許文献３参照）、イオン交換膜を用いて電気透析する方法（例えば特許文献４参照）が提案されている。 Conventionally, surfactants with reduced concentrations of metal ions as impurities have been used in various fields such as electronics, semiconductors and precision processing, and methods for obtaining such purified surfactants have been proposed. . For example, for nonionic surfactants, a method using a combination of an ion exchange resin and a functional filter (see, for example, Patent Document 1), or washing with a nonmetallic base aqueous solution, and separating and collecting the surfactant layer at a high temperature For an anionic surfactant, a method using a reverse osmosis membrane or an ultrafiltration membrane in addition to a general method of concentration, crystallization, and extraction (for example, see Patent Literature 3) A method of electrodialysis using an ion exchange membrane (see, for example, Patent Document 4) has been proposed.
しかし、前記のような従来法によると、非イオン界面活性剤の場合は望まれるレベルにまで金属イオン濃度を低減したものを比較的容易に得ることができるが、アニオン界面活性剤の場合は望まれるレベルにまで金属イオン濃度を低減したもの、より具体的には各金属イオン毎でその濃度をｐｐｂ単位にまで低減したものを得ることが難しいという問題があり、なかでも有機スルホン酸型界面活性剤の場合は特に難しいという問題がある。 However, according to the conventional method as described above, in the case of a nonionic surfactant, a metal ion concentration reduced to a desired level can be obtained relatively easily, but in the case of an anionic surfactant, it is desirable. There is a problem that it is difficult to obtain a metal ion concentration reduced to a level that can be reduced, more specifically, each metal ion having a concentration reduced to the ppb unit. In the case of an agent, there is a problem that it is particularly difficult.
本発明が解決しようとする課題は、電子、半導体及び精密加工分野等で使用可能なレベルにまで金属イオン濃度を低減することができる有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩の処理方法、並びにかかる処理方法によって得られる金属イオン濃度を低減した有機スルホン酸を用いることにより同様に金属イオン濃度を低減することができる有機スルホン酸アンモニウム塩型界面活性剤の製造方法を提供するところにある。 The problem to be solved by the present invention is a method for treating an alkali metal salt and / or ammonium salt of an organic sulfonic acid capable of reducing the metal ion concentration to a level that can be used in the fields of electronics, semiconductors and precision processing, etc. The present invention also provides a method for producing an organic sulfonate ammonium salt type surfactant that can similarly reduce the metal ion concentration by using an organic sulfonic acid having a reduced metal ion concentration obtained by such a treatment method.
本発明者らは、前記の課題を解決するべく研究した結果、市場で入手が容易であり、また設備腐食等の問題が少なく、更に取扱いの容易な有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩を原料として用い、これを特定のカチオン交換樹脂を用いたイオン交換法に供して処理すると、不純物としての金属イオンの濃度を各金属イオン毎でｐｐｂ単位にまで低減した有機スルホン酸を得ることができ、またかかる有機スルホン酸を特定の塩基性化合物で中和すると、同様に金属イオン濃度を低減した有機スルホン酸アンモニウム塩型界面活性剤を得ることができることを見出した。 As a result of researches to solve the above-mentioned problems, the inventors of the present invention are easily available in the market, have few problems such as equipment corrosion, and are easy to handle. When a salt is used as a raw material, and this is subjected to an ion exchange method using a specific cation exchange resin, an organic sulfonic acid is obtained in which the concentration of metal ions as impurities is reduced to ppb units for each metal ion. It was also found that when such an organic sulfonic acid is neutralized with a specific basic compound, an organic sulfonic acid ammonium salt surfactant having a reduced metal ion concentration can be obtained.
すなわち本発明は、下記の化１で示される有機スルホン酸のアルカリ金属塩、下記の化１で示される有機スルホン酸のアンモニウム塩、下記の化２で示される有機スルホン酸のアルカリ金属塩及び／又は下記の化２で示される有機スルホン酸のアンモニウム塩を水で希釈し、強酸性カチオン交換樹脂を用いたイオン交換法に供して、有機スルホン酸に対するＮａ、Ｋ、Ｃａ、Ｆｅ、Ｎｉ、Ｃｒ及びＺｎの各金属イオン濃度を１００ｐｐｂ以下となるように、またＭｇ、Ａｌ、Ｍｎ及びＣｕの各金属イオン濃度を５０ｐｐｂ以下となるように処理することを特徴とする有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩の処理方法に係る。 That is, the present invention relates to an alkali metal salt of an organic sulfonic acid represented by the following chemical formula 1, an ammonium salt of an organic sulfonic acid represented by the following chemical formula 1, an alkali metal salt of an organic sulfonic acid represented by the following chemical formula 2 and / or Or the ammonium salt of the organic sulfonic acid shown by following Chemical formula 2 is diluted with water, and it uses for the ion exchange method using strong acidic cation exchange resin, Na, K, Ca, Fe, Ni, Cr with respect to organic sulfonic acid And an alkali metal salt of organic sulfonic acid, characterized in that each metal ion concentration of Mg and Al, Mn and Cu is treated to be 50 ppb or less It relates to a method for treating ammonium salt.
化１及び化２において、
ｎ：０〜１０の整数
In Chemical Formula 1 and Chemical Formula 2,
n: an integer from 0 to 10
また本発明は、前記の本発明に係る有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩の処理方法によって得られる金属イオン濃度を低減した有機スルホン酸を、下記の化３で示される塩基性化合物、化４で示される塩基性化合物、５員環を有する有機環状塩基性化合物及び６員環を有する有機環状塩基性化合物から選ばれる一つ又は二つ以上の塩基性化合物で中和することを特徴とする有機スルホン酸アンモニウム塩型界面活性剤の製造方法に係る。
The present invention also provides an organic sulfonic acid having a reduced metal ion concentration obtained by the method for treating an alkali metal salt and / or ammonium salt of an organic sulfonic acid according to the present invention, a basic compound represented by the following chemical formula 3 Neutralizing with one or two or more basic compounds selected from the basic compounds represented by Chemical Formula 4, an organic cyclic basic compound having a 5-membered ring and an organic cyclic basic compound having a 6-membered ring: The present invention relates to a method for producing a characteristic organic sulfonate ammonium salt type surfactant.
化３及び化４において、
Ｒ１，Ｒ２，Ｒ３，Ｒ４，Ｒ５，Ｒ６，Ｒ７：水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のヒドロキシアルキル基
In Chemical Formula 3 and Chemical Formula 4,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 : a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms
先ず、本発明に係る有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩の処理方法（以下、本発明の処理方法という）について説明する。本発明の処理方法は、前記の化１で示される有機スルホン酸のアルカリ金属塩、前記の化１で示される有機スルホン酸のアンモニウム塩、前記の化２で示される有機スルホン酸のアルカリ金属塩及び／又は前記の化２で示される有機スルホン酸のアンモニウム塩を水で希釈し、強酸性カチオン交換樹脂を用いたイオン交換法に供して、該有機スルホン酸に対するＮａ、Ｋ、Ｃａ、Ｆｅ、Ｎｉ、Ｃｒ及びＺｎの各金属イオン濃度を１００ｐｐｂ以下となるように、またＭｇ、Ａｌ、Ｍｎ及びＣｕの各金属イオン濃度を５０ｐｐｂ以下となるように処理する方法であり、好ましくはＮａ、Ｋ、Ｃａ、Ｆｅ、Ｎｉ、Ｃｒ及びＺｎの各金属イオン濃度を５０ｐｐｂ以下となるように、またＭｇ、Ａｌ、Ｍｎ及びＣｕの各金属イオン濃度を３０ｐｐｂ以下となるように処理する方法である。 First, a method for treating an alkali metal salt and / or ammonium salt of an organic sulfonic acid according to the present invention (hereinafter, referred to as a treatment method of the present invention) will be described. The treatment method of the present invention includes an alkali metal salt of an organic sulfonic acid represented by the chemical formula 1, an ammonium salt of an organic sulfonic acid represented by the chemical formula 1, and an alkali metal salt of an organic sulfonic acid represented by the chemical formula 2 And / or diluting the organic sulfonic acid ammonium salt represented by Chemical Formula 2 with water and subjecting it to an ion exchange method using a strongly acidic cation exchange resin, Na, K, Ca, Fe, It is a method of processing each metal ion concentration of Ni, Cr and Zn to be 100 ppb or less, and each metal ion concentration of Mg, Al, Mn and Cu to be 50 ppb or less, preferably Na, K, Each metal ion concentration of Ca, Fe, Ni, Cr and Zn is set to 50 ppb or less, and each metal ion concentration of Mg, Al, Mn and Cu is set to 30 ppb or less. A method of processing such that.
本発明の処理方法に供する有機スルホン酸のアルカリ金属塩は、化１で示される有機スルホン酸及び／又は化２で示される有機スルホン酸のナトリウム塩、カリウム塩及びリチウム塩等のアルカリ金属塩である。また本発明の処理方法に供する有機スルホン酸のアンモニウム塩は、化１で示される有機スルホン酸及び／又は化２で示される有機スルホン酸のアンモニウム塩である。化１及び化２において、ｎは０〜１０の整数であり、縮合度を表す。かかる有機スルホン酸としては、ｎの平均である平均縮合度が０．０５〜１．５の範囲にあるものが好ましい。 The alkali metal salt of the organic sulfonic acid used in the treatment method of the present invention is an organic sulfonic acid represented by Chemical Formula 1 and / or an alkali metal salt such as a sodium salt, potassium salt and lithium salt of the organic sulfonic acid represented by Chemical Formula 2. is there. The organic sulfonic acid ammonium salt used in the treatment method of the present invention is an organic sulfonic acid represented by Chemical Formula 1 and / or an organic sulfonic acid ammonium salt represented by Chemical Formula 2. In Chemical Formula 1 and Chemical Formula 2, n is an integer of 0 to 10, and represents the degree of condensation. As such organic sulfonic acid, those having an average degree of condensation in the range of 0.05 to 1.5 are preferable.
本発明の処理方法に供する強酸性カチオン交換樹脂としては、いずれも市販されている商品名で、デュオライト Ｃ２５５ＬＦＨ、アンバーライト ＩＲ−１２４、アンバーライト ＩＲ−１２０Ｂ（いずれも米国ダウ・ケミカル社製）、ダイヤイオン ＳＫ−１１０、ダイヤイオン ＳＫ−１Ｂ（共に三菱化学社製）等のスルホン酸型強酸性カチオン交換樹脂を使用できる。またダイヤイオン ＷＫ１１（三菱化学社製）等の弱酸性カチオン交換樹脂、ダイヤイオン ＣＲ１１（三菱化学社製）等のキレート樹脂、ダイヤイオン ＰＡ３１２（三菱化学社製）等の塩基性アニオン交換樹脂であっても、これらを前記のスルホン酸型強酸性カチオン交換樹脂と組み合わせて使用することもできる。複数のイオン交換樹脂を組み合わせて使用する場合は、複層又は混合のいずれの系でも使用できる。このような予め混合されたイオン交換樹脂としては、デュオライト ＭＢ５１１３、アンバーライト ＭＢ−２（共に米国ダウ・ケミカル社製）が市販されている。 The strongly acidic cation exchange resins used in the treatment method of the present invention are all commercially available under the trade names, Duolite C255LFH, Amberlite IR-124, Amberlite IR-120B (all manufactured by Dow Chemical Co., USA). Sulfonic acid type strongly acidic cation exchange resins such as Diaion SK-110 and Diaion SK-1B (both manufactured by Mitsubishi Chemical Corporation) can be used. Also, weakly acidic cation exchange resins such as Diaion WK11 (Mitsubishi Chemical), chelate resins such as Diaion CR11 (Mitsubishi Chemical), and basic anion exchange resins such as Diaion PA312 (Mitsubishi Chemical). However, these can also be used in combination with the sulfonic acid type strongly acidic cation exchange resin. When a plurality of ion exchange resins are used in combination, any of a multilayer system or a mixed system can be used. As such premixed ion exchange resins, Duolite MB5113 and Amberlite MB-2 (both manufactured by Dow Chemical Co., USA) are commercially available.
有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩を、強酸性カチオン交換樹脂を用いたイオン交換法に供するに際して、該有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩は、水に溶解して希釈した水溶液とする。 When an alkali metal salt and / or ammonium salt of an organic sulfonic acid is subjected to an ion exchange method using a strongly acidic cation exchange resin, the alkali metal salt and / or ammonium salt of the organic sulfonic acid is dissolved in water and diluted. The resulting aqueous solution.
水に溶解して希釈した有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩の溶液の濃度は５〜４０質量％とするのが好ましく、１０〜３０質量％とするのがより好ましい。 The concentration of the organic sulfonic acid alkali metal salt and / or ammonium salt solution dissolved and diluted in water is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass.
また水に溶解した有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩の水溶液を、強酸性カチオン交換樹脂と接触させてイオン交換処理する具体的な方法としては、バッチ法、カラム法が適用できるが、なかでもカラム法が好ましい。 In addition, as a specific method for performing an ion exchange treatment by contacting an aqueous solution of an alkali metal salt and / or ammonium salt of an organic sulfonic acid dissolved in water with a strongly acidic cation exchange resin, a batch method and a column method can be applied. Of these, the column method is preferred.
更に水に溶解した有機スルホン酸のアルカリ金属塩及び／又はアンモニウム塩の水溶液を、強酸性カチオン交換樹脂と接触させてイオン交換処理する際の空間速度（ＳＶ）は、０．１〜４．０とするのが好ましく、０．５〜３．０とするのがより好ましい。 Furthermore, the space velocity (SV) when an aqueous solution of an alkali metal salt and / or ammonium salt of an organic sulfonic acid dissolved in water is brought into contact with a strongly acidic cation exchange resin is 0.1 to 4.0. It is preferable to set it as 0.5 to 3.0.
本発明の処理方法では、以上説明したイオン交換法による精製処理により、有機スルホン酸に対するＮａ、Ｋ、Ｃａ、Ｆｅ、Ｎｉ、Ｃｒ及びＺｎの各金属イオン濃度を１００ｐｐｂ以下となるように、またＭｇ、Ａｌ、Ｍｎ及びＣｕの各金属イオン濃度を５０ｐｐｂ以下となるように処理し、好ましくはＮａ、Ｋ、Ｃａ、Ｆｅ、Ｎｉ、Ｃｒ及びＺｎの各金属イオン濃度を５０ｐｐｂ以下となるように、またＭｇ、Ａｌ、Ｍｎ及びＣｕの各金属イオン濃度を３０ｐｐｂ以下となるように処理する。 In the treatment method of the present invention, the metal ion concentration of Na, K, Ca, Fe, Ni, Cr and Zn with respect to the organic sulfonic acid is reduced to 100 ppb or less by the purification treatment by the ion exchange method described above, and Mg. The metal ion concentration of Al, Mn, and Cu is processed to be 50 ppb or less, preferably the metal ion concentration of Na, K, Ca, Fe, Ni, Cr, and Zn is 50 ppb or less. Each metal ion concentration of Mg, Al, Mn and Cu is processed to be 30 ppb or less.
本発明において、各金属イオンの濃度は原子吸光分光測定法により測定して求めることができる。なお１ｐｐｂは１μｇ／Ｌの濃度を示す。 In the present invention, the concentration of each metal ion can be determined by measurement by atomic absorption spectrometry. 1 ppb indicates a concentration of 1 μg / L.
次に、本発明に係る有機スルホン酸アンモニウム塩型界面活性剤の製造方法（以下、本発明の製造方法という）について説明する。本発明の製造方法は、前記した本発明の処理方法によって得られる金属イオン濃度を低減した有機スルホン酸を、特定の塩基性化合物及び／又は有機環状塩基性化合物で中和する方法である。 Next, a method for producing an organic sulfonic acid ammonium salt surfactant according to the present invention (hereinafter referred to as the production method of the present invention) will be described. The production method of the present invention is a method of neutralizing an organic sulfonic acid having a reduced metal ion concentration obtained by the above-described treatment method of the present invention with a specific basic compound and / or an organic cyclic basic compound.
有機スルホン酸の中和に供する塩基性化合物は、前記の化３で示される塩基性化合物、化４で示される塩基性化合物、５員環を有する有機環状塩基性化合物及び６員環を有する有機環状塩基性化合物から選ばれる一つ又は二つ以上の塩基性化合物である。 The basic compound used for neutralization of the organic sulfonic acid includes the basic compound represented by the chemical formula 3, the basic compound represented by the chemical formula 4, the organic cyclic basic compound having a 5-membered ring, and the organic having a 6-membered ring. One or two or more basic compounds selected from cyclic basic compounds.
化３で示される塩基性化合物において、Ｒ１、Ｒ２及びＲ３としては、１）水素原子、２）メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基等の炭素数１〜４のアルキル基、３）ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシイソプロピル基、ヒドロキシブチル基、ヒドロキシイソブチル基等の炭素数１〜４のヒドロキシアルキル基が挙げられる。なかでも、Ｒ１、Ｒ２及びＲ３としては、１）全てが水素原子、２）任意の二つが水素原子であり且つ残りの一つがエチル基、３）任意の一つが水素原子であり且つ残りの二つがエチル基、４）全てがエチル基、５）任意の二つが水素原子であり且つ残りの一つがヒドロキシエチル基、６）任意の一つが水素原子であり且つ残りの二つがヒドロキシエチル基、又は７）全てがヒドロキシエチル基である場合が好ましい。具体的に化３で示される塩基性化合物としては、アンモニア、エチルアミン、ジエチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン又はこれらの任意の混合物が好ましい。 In the basic compound represented by Chemical Formula 3, R 1 , R 2 and R 3 are as follows: 1) hydrogen atom, 2) methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group 3) C1-C4 alkyl groups such as hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxyisopropyl group, hydroxybutyl group, hydroxyisobutyl group, etc. . Among them, as R 1 , R 2 and R 3 , 1) all are hydrogen atoms, 2) any two are hydrogen atoms and the remaining one is an ethyl group, 3) any one is a hydrogen atom, and The remaining two are ethyl groups, 4) all are ethyl groups, 5) any two are hydrogen atoms and the other is a hydroxyethyl group, 6) any one is a hydrogen atom and the remaining two are hydroxyethyl Group or 7) all are preferably hydroxyethyl groups. Specifically, the basic compound represented by Chemical Formula 3 is preferably ammonia, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine or any mixture thereof.
化４で示される塩基性化合物において、Ｒ４、Ｒ５、Ｒ６及びＲ７としては、１）水素原子、２）メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基等の炭素数１〜４のアルキル基、３）ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシイソプロピル基、ヒドロキシブチル基、ヒドロキシイソブチル基等の炭素数１〜４のヒドロキシアルキル基が挙げられる。なかでも、Ｒ４、Ｒ５、Ｒ６及びＲ７としては、すべてが同時に水素原子、メチル基、エチル基、プロピル基又はブチル基である場合が好ましい。具体的に化４で示される塩基性化合物としては、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド又はこれらの任意の混合物がより好ましい。 In the basic compound represented by Chemical Formula 4 , R 4 , R 5 , R 6 and R 7 are: 1) hydrogen atom, 2) methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t -C1-C4 alkyl group such as butyl group, 3) C1-C4 hydroxyalkyl group such as hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxyisopropyl group, hydroxybutyl group, hydroxyisobutyl group, etc. Is mentioned. Among them, it is preferable that R 4 , R 5 , R 6 and R 7 are all simultaneously a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group. Specifically, the basic compound represented by Chemical Formula 4 is more preferably tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, or any mixture thereof.
有機スルホン酸の中和に供する有機環状塩基性化合物としては、１）ピロール、ピロリン、ピロリジン、ピロリドン、イミダゾール、ピラゾール、オキサゾール、イソオキサゾール、チアゾール、イソチアゾール、チアゾリン、チアゾリジン等の５員環を有する複素環式の有機環状塩基性化合物、２）ピリジン、ピリジル、ピリジレン、ピペリジン、ピペリジル、ピリダジン、ピラジン、ピペラジン、ピリミジン、シトシン、チミン、モルホリン、チオモルホリン等の６員環を有する複素環式の有機環状塩基性化合物が挙げられる。なかでも、有機環状塩基性化合物としては、ピロール、ピリジン又はこれらの混合物が好ましい。 The organic cyclic basic compound used for neutralization of organic sulfonic acid has 1) a 5-membered ring such as pyrrole, pyrroline, pyrrolidine, pyrrolidone, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, thiazoline, thiazolidine, etc. Heterocyclic organic cyclic basic compounds 2) Heterocyclic organic compounds having 6-membered rings such as pyridine, pyridyl, pyridylene, piperidine, piperidyl, pyridazine, pyrazine, piperazine, pyrimidine, cytosine, thymine, morpholine, thiomorpholine A cyclic basic compound is mentioned. Especially, as an organic cyclic basic compound, pyrrole, pyridine, or a mixture thereof is preferable.
以上説明したような塩基性化合物や有機環状塩基性化合物としては、特級又は一級の試薬や電子材料用グレードとして市販されているものを使用できる。また中和方法それ自体については特に限定するものではなく、通常の中和方法が適用できる。 As the basic compound and organic cyclic basic compound as described above, those commercially available as special grade or first grade reagents and grades for electronic materials can be used. Further, the neutralization method itself is not particularly limited, and a normal neutralization method can be applied.
本発明の製造方法によって得られる有機スルホン酸アンモニウム塩型界面活性剤は、半導体製造プロセスの各工程で用いる洗浄液や表面処理液、フォトレジストプロセスの処理液、剥離液、現像液、洗浄液、及びコート剤、電池、コンデンサ及びキャパシター等の電解液や電極製造組成物、種々のコート剤、インクや塗料における顔料やカーボンブラックの分散剤、ナノテクノロジーにおけるカーボンナノチューブ、フラーレン及び金属ナノ粒子の分散剤、色素増感型太陽電池における酸化チタンの分散剤等、多くの分野において有用である。 The organic sulfonate ammonium salt-type surfactant obtained by the production method of the present invention includes a cleaning solution and a surface treatment solution used in each step of the semiconductor production process, a photoresist process treatment solution, a stripping solution, a developing solution, a washing solution, and a coating. Electrolytic solutions and electrode manufacturing compositions for agents, batteries, capacitors and capacitors, various coating agents, pigments and carbon black dispersants in inks and paints, carbon nanotubes, fullerenes and metal nanoparticle dispersants and dyes in nanotechnology It is useful in many fields such as a titanium oxide dispersant in a sensitized solar cell.
以上説明した本発明によると、電子、半導体及び精密加工分野等で使用可能なレベルにまで金属イオン濃度を低減した有機スルホン酸を得ることができ、またこれを用いて同様に金属イオン濃度を低減した有機スルホン酸アンモニウム塩型界面活性剤を得ることができる。 According to the present invention described above, it is possible to obtain an organic sulfonic acid having a metal ion concentration reduced to a level that can be used in the fields of electronics, semiconductors, precision processing, and the like. The obtained organic sulfonate ammonium salt type surfactant can be obtained.
以下、本発明の構成及び効果をより具体的にするために実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, examples and the like will be described in order to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
試験区分１（有機スルホン酸のアルカリ金属塩等の処理）
実施例１
ナフタレンスルホン酸のナトリウム塩・ホルムアルデヒド縮合物５０ｇを純水１５０ｇに溶解して２５％水溶液を調製し、これを試料とした。強酸性カチオン交換樹脂として予め１Ｎ希塩酸を用いてＨ型に再生しておいたアンバーライト ＩＲ−１２４Ｎａ（米国ダウ・ケミカル社製の商品名）を用い、その２００ｍＬを垂直にセットした内容量３００ｍＬカラムに充填し、４０００ｇの純水で十分に洗浄した後、２４時間静置した。試料及びカラム内の水の温度を１５〜２５℃の範囲内で一定に保温し、空間速度（ＳＶ）３．０で試料をカラムに通して、金属イオン濃度を低減したナフタレンスルホン酸・ホルムアルデヒド縮合物を得た。
Test category 1 (treatment of alkali metal salts of organic sulfonic acids, etc.)
Example 1
Naphthalenesulfonic acid sodium salt / formaldehyde condensate 50 g was dissolved in pure water 150 g to prepare a 25% aqueous solution, which was used as a sample. Amberlite IR-124Na (trade name, manufactured by Dow Chemical Co., USA) that had been regenerated into H-type using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin, and 200 mL of the column was set vertically. And thoroughly washed with 4000 g of pure water, and allowed to stand for 24 hours. Naphthalenesulfonic acid / formaldehyde condensation with reduced metal ion concentration by keeping the temperature of the sample and water in the column constant within a range of 15 to 25 ° C., and passing the sample through the column at a space velocity (SV) of 3.0 I got a thing.
実施例２〜８及び比較例１〜４
実施例１と同様にして実施例２〜８及び比較例１〜４を行なった。実施例を含め、各例の内容と結果を表１及び表２にまとめて示した。
Examples 2-8 and Comparative Examples 1-4
In the same manner as in Example 1, Examples 2 to 8 and Comparative Examples 1 to 4 were performed. Tables 1 and 2 collectively show the contents and results of each example including the examples.
表１及び表２において、
スルホン酸型：アンバーライト ＩＲ−１２４Ｎａ（米国ダウ・ケミカル社製の商品名）
カルボン酸型：ダイヤイオン ＷＫ−１１（三菱化学社製の商品名）
ジカルボン酸型：ダイヤイオン ＣＲ−１１（三菱化学社製の商品名）
In Table 1 and Table 2,
Sulfonic acid type: Amberlite IR-124Na (trade name manufactured by Dow Chemical Co., USA)
Carboxylic acid type: Diaion WK-11 (trade name, manufactured by Mitsubishi Chemical Corporation)
Dicarboxylic acid type: Diaion CR-11 (trade name, manufactured by Mitsubishi Chemical Corporation)
試験区分２（有機スルホン酸の金属イオン濃度の測定）
実施例１〜８及び比較例１〜４で得た有機スルホン酸の金属イオン濃度を、ファーネス原子吸光光度計：ＡＡ−２８０Ｚ（Ｖａｒｉａｎ社製の商品名）を使用し、グラファイトファーネス式フレームレス原子化法による原子吸光分析法によって測定した。測定結果を表３及び表４にまとめて示した。
Test category 2 (Measurement of metal ion concentration of organic sulfonic acid)
Using the furnace atomic absorption photometer: AA-280Z (trade name, manufactured by Varian), the metal ion concentration of the organic sulfonic acid obtained in Examples 1 to 8 and Comparative Examples 1 to 4 was used. Measured by atomic absorption spectrophotometry. The measurement results are summarized in Table 3 and Table 4.
試験区分３（有機スルホン酸アンモニウム塩型界面活性剤の製造）
実施例９
実施例１で得た金属イオン濃度を低減したナフタレンスルホン酸・ホルムアルデヒド縮合物２２０ｇに、塩基性化合物として２９％アンモニア水（関東化学製のＥＬグレード）９．９ｇを攪拌しながら滴下し、ｐＨが６．０〜８．０となるよう中和して、濃度１５％のナフタレンスルホン酸・ホルムアルデヒド縮合物アンモニウム塩型界面活性剤を得た。
Test Category 3 (Manufacture of organic sulfonic acid ammonium salt type surfactant)
Example 9
To 220 g of naphthalenesulfonic acid / formaldehyde condensate with reduced metal ion concentration obtained in Example 1, 9.9 g of 29% ammonia water (EL grade manufactured by Kanto Chemical Co., Ltd.) as a basic compound was added dropwise with stirring, and the pH was lowered. By neutralizing to 6.0 to 8.0, a 15% concentration naphthalenesulfonic acid / formaldehyde condensate ammonium salt type surfactant was obtained.
実施例１０〜５０及び比較例５〜８
表５〜表８に記載の塩基性化合物を用い、実施例９と同様にして、表９及び表１０に記載した実施例１０〜５０及び比較例５〜８の有機スルホン酸アンモニウム塩型界面活性剤を得た。実施例９も含め、各例で用いた塩基性化合物の内容を表５〜表８にまとめて示した。
Examples 10-50 and Comparative Examples 5-8
Using the basic compounds described in Table 5 to Table 8, in the same manner as in Example 9, the organic sulfonate ammonium salt type surface activity of Examples 10 to 50 and Comparative Examples 5 to 8 described in Table 9 and Table 10 An agent was obtained. The contents of the basic compounds used in each example including Example 9 are summarized in Tables 5 to 8.
表５及び表６において、
Ｒ１〜Ｒ７：化３及び化４中のＲ１〜Ｒ７
In Table 5 and Table 6,
R 1 to R 7: of R 1 to R 7 of 3 and of 4
試験区分４（有機スルホン酸アンモニウム塩型界面活性剤の評価）
・金属イオン濃度の測定
実施例９〜５０及び比較例５〜８で得た有機スルホン酸アンモニウム塩型界面活性剤の金属イオン濃度を、前記の有機スルホン酸の金属イオン濃度の測定方法と同様にして測定した。結果を表９及び表１０にまとめて示した。
Test category 4 (evaluation of organic sulfonate ammonium salt type surfactant)
Measurement of metal ion concentration The metal ion concentration of the organic sulfonic acid ammonium salt type surfactants obtained in Examples 9 to 50 and Comparative Examples 5 to 8 was the same as the method for measuring the metal ion concentration of the organic sulfonic acid. Measured. The results are summarized in Table 9 and Table 10.
・分散性の評価
実施例９〜５０及び比較例５〜８で得た有機スルホン酸アンモニウム塩型界面活性剤を使用して５％水溶液を調製し、その３００ｍＬを５００ｍＬビーカーにとり、直径５ｃｍの４枚羽根のインペラーを使用して１００ｒｐｍで撹拌した。この水溶液中にカーボンブラック（平均粒径２８ｎｍ、嵩比重０．３３ｇ／ｍＬ）を１０ｇ添加して５分間攪拌を継続した。撹拌を止め、１００ｍＬの沈降管へ分散液を移し、１０分後の分散性を目視で確認した。分散性は下記数１で求めた沈降体積％を基に、以下の基準で評価した。結果を表９及び表１０にまとめて示した。
◎：１０分後での沈降体積％が１％未満である。
○：１０分後での沈降体積％が１％以上３％未満である。
×：１０分後での沈降体積％が３％以上である。
Evaluation of dispersibility A 5% aqueous solution was prepared using the organic sulfonate ammonium salt type surfactants obtained in Examples 9 to 50 and Comparative Examples 5 to 8, and 300 mL of the solution was taken in a 500 mL beaker, and 4 of 5 cm in diameter. Stirring was performed at 100 rpm using a single blade impeller. 10 g of carbon black (average particle size 28 nm, bulk specific gravity 0.33 g / mL) was added to the aqueous solution, and stirring was continued for 5 minutes. Stirring was stopped, the dispersion was transferred to a 100 mL settling tube, and the dispersibility after 10 minutes was visually confirmed. The dispersibility was evaluated according to the following criteria based on the sedimentation volume% obtained by the following formula 1. The results are summarized in Table 9 and Table 10.
A: The sedimentation volume% after 10 minutes is less than 1%.
○: The sedimentation volume% after 10 minutes is 1% or more and less than 3%.
X: The sedimentation volume% after 10 minutes is 3% or more.
・耐変色性の評価
実施例９〜５０及び比較例５〜８で得た有機スルホン酸アンモニウム塩型界面活性剤を温度５０℃の恒温槽中で３０日間密閉して保存した。保存前後の試料をイオン交換水で希釈し、ＪＩＳ Ｋ００７１−１に準じ、ハーゼン標準比色液と比較して、ハーゼン単位色数を測定した。ただし、ハーゼン標準比色液の中間にあるものは、中間の値を採用した。保存前後のハーゼン単位色数の差の絶対値を求め、耐変色性を以下の基準で評価した。結果を表９及び表１０にまとめて示した。
◎：色数の差の絶対値が５以下
○：色数の差の絶対値が１０〜１５以下
×：色数の差の絶対値が２０〜３５以下
-Evaluation of discoloration resistance The organic sulfonate ammonium salt type surfactants obtained in Examples 9 to 50 and Comparative Examples 5 to 8 were sealed and stored in a thermostatic bath at a temperature of 50 ° C for 30 days. Samples before and after storage were diluted with ion-exchanged water, and the number of Hazen unit colors was measured according to JIS K0071-1 and compared with the Hazen standard colorimetric solution. However, intermediate values were adopted for those in the middle of the Hazen standard colorimetric solution. The absolute value of the difference in Hazen unit colors before and after storage was determined, and the resistance to discoloration was evaluated according to the following criteria. The results are summarized in Table 9 and Table 10.
A: Absolute value of the difference in the number of colors is 5 or less ○: Absolute value of the difference in the number of colors is 10 to 15 or less ×: The absolute value of the difference in the number of colors is 20 to 35 or less
Claims (7)
ｎ：０〜１０の整数） An alkali metal salt of an organic sulfonic acid represented by the following chemical formula 1, an ammonium salt of an organic sulfonic acid represented by the following chemical formula 1, an alkali metal salt of an organic sulfonic acid represented by the following chemical formula 2, and / or the following chemical formula 2 Each of the metals of Na, K, Ca, Fe, Ni, Cr and Zn with respect to the organic sulfonic acid is prepared by diluting the ammonium salt of the organic sulfonic acid represented by the formula (1) with water and subjecting it to an ion exchange method using a strongly acidic cation exchange resin An alkali metal salt and / or an ammonium salt of an organic sulfonic acid characterized in that the ion concentration is 100 ppb or less and each metal ion concentration of Mg, Al, Mn and Cu is 50 ppb or less. Processing method.
n: integer from 0 to 10)
Ｒ１，Ｒ２，Ｒ３，Ｒ４，Ｒ５，Ｒ６，Ｒ７：水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のヒドロキシアルキル基） An organic sulfonic acid having a reduced metal ion concentration obtained by the method for treating an alkali metal salt and / or ammonium salt of an organic sulfonic acid according to any one of claims 1 to 4, a base represented by the following chemical formula 3: Neutralizing with one or more basic compounds selected from the group consisting of a basic compound, a basic compound represented by Chemical Formula 4, an organic cyclic basic compound having a 5-membered ring, and an organic cyclic basic compound having a 6-membered ring A method for producing an organic sulfonic acid ammonium salt type surfactant.
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 : hydrogen atom, alkyl group having 1 to 4 carbon atoms or hydroxyalkyl group having 1 to 4 carbon atoms)
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| JP2020147554A (en) * | 2019-03-15 | 2020-09-17 | 竹本油脂株式会社 | Method for treating solution of alkali metal salt or ammonium salt of organic sulfonic acid, and method for producing organic sulfonic acid solution |
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| JP2016022473A (en) * | 2014-07-25 | 2016-02-08 | 竹本油脂株式会社 | Purification processing method of betaine type surfactant, and purified betaine type surfactant |
| JP2020147554A (en) * | 2019-03-15 | 2020-09-17 | 竹本油脂株式会社 | Method for treating solution of alkali metal salt or ammonium salt of organic sulfonic acid, and method for producing organic sulfonic acid solution |
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