JP5959134B1 - Method for treating nonionic surfactant and method for producing nonionic surfactant with reduced metal ion concentration - Google Patents

Abstract

Disclosed is a nonionic surfactant treatment method capable of reducing the concentration of contained metal ions to a level of several ppb required for use in the fields of electronics, semiconductors and precision processing, and such nonionic types. A surfactant is provided. An aqueous dilute solution obtained by adding water to a nonionic surfactant containing metal ions so as to be 40.0% by mass or more and less than 98.0% by mass is strongly mixed with a strongly acidic cation exchange resin. It used for the ion exchange method using the mixed resin with alkaline anion exchange resin, and processed so that the metal ion concentration with respect to a nonionic surfactant might be 5 ppb or less for every metal ion. [Selection figure] None

Description

  The present invention relates to a method for treating a nonionic surfactant and a method for producing a nonionic surfactant having a reduced metal ion concentration. Nonionic surfactants used in the fields of electronics, semiconductors, precision processing, etc. are required to have a metal ion concentration contained therein as low as possible. The present invention relates to a method for treating a nonionic surfactant that meets such requirements, and a method for producing a nonionic surfactant having a reduced metal ion concentration.

  Conventionally, as a treatment method for reducing the concentration of metal ions contained in a surfactant, a method using a combination of an ion exchange resin and a functional filter for a nonionic surfactant (see, for example, Patent Document 1), an anion For type surfactants, in addition to general methods of concentration, crystallization and extraction, a method using a reverse osmosis membrane or an ultrafiltration membrane (for example, see Patent Document 2) or a method using electrodialysis using an ion exchange membrane (for example, Patent Document 3) has been proposed.

  However, in the conventional method as described above, when trying to reduce the metal ion concentration to the level of several ppb required for the nonionic surfactant, it is not only necessary to assemble a very complicated processing apparatus, There is a problem that the filter is easily clogged during processing, and the filter is likely to be selected or improperly mounted. In fact, it is difficult to reduce the metal ion concentration to a unit of several ppb for each metal ion. .

JP-A-2005-213200 JP-A-5-317654 JP-A-62-63555

  A problem to be solved by the present invention is a method for treating a nonionic surfactant capable of reducing the concentration of contained metal ions to a level of several ppb required for use in the fields of electronics, semiconductors, precision processing, etc. The present invention also provides a method for producing a nonionic surfactant having a metal ion concentration reduced to such a level.

  As a result of researches to solve the above-mentioned problems, the present inventors have identified an aqueous diluted solution in which water is added to a nonionic surfactant containing metal ions at a specific ratio as a specific cation exchange resin. It has been found that the metal ion concentration can be reduced to 5 ppb or less for each metal ion when subjected to an ion exchange method using a mixed resin with an anion exchange resin.

  That is, in the present invention, an aqueous diluted solution obtained by adding water to a nonionic surfactant containing metal ions so as to be 40.0% by mass to less than 98.0% by mass is used as a strongly acidic cation exchange resin. A nonionic type characterized by being subjected to an ion exchange method using a mixed resin with a strongly alkaline anion exchange resin and treating the metal ion concentration with respect to the nonionic surfactant to be 5 ppb or less for each metal ion The present invention relates to a method for treating a surfactant. The present invention also relates to a method for producing a nonionic surfactant with reduced metal ion concentration, characterized in that a nonionic surfactant containing metal ions is treated by such a treatment method.

  First, the nonionic surfactant processing method according to the present invention (hereinafter simply referred to as the processing method of the present invention) will be described. In the treatment method of the present invention, an aqueous diluted solution in which water is added to a nonionic surfactant containing metal ions at a specific ratio is subjected to an ion exchange method.

  The ratio of water to be added is set to be 40.0% by mass to less than 98.0% by mass with respect to the nonionic surfactant containing metal ions. By making the amount of water to be added 40.0 mass% or more and less than 98.0 mass% with respect to the nonionic surfactant containing metal ions, a solid nonionic interface solid at room temperature with strong hydrophilicity Even an active agent can be made into a homogeneous aqueous diluted solution, and the present invention can be applied. In the case where it is desired to use a nonionic surfactant treated by the ion exchange method without containing water, water can be easily distilled off.

  Nonionic surfactants suitable for applying the treatment method of the present invention are those having an HLB value of 7 to 18 by the Griffin method. The HLB value by the Griffin method is a value calculated by the following formula 1, and details thereof are described in, for example, Takehiko Fujimoto “Introduction to Surfactant”, published by Sanyo Chemical Industries, Ltd., pages 141 to 145 (2007). Have been described.

  The number 1 is usually not applicable to a nonionic surfactant having a polyoxyalkylene chain other than a polyoxyethylene chain, but in the present invention, only the polyoxyethylene chain portion is a hydrophilic group. Other polyoxyalkylene chains are calculated as hydrophobic groups. In the case of polyoxyalkylene random chains or polyoxyalkylene block chains containing oxyethylene units, the total of oxyethylene units is calculated as a hydrophilic group. The total of oxyalkylene units other than oxyethylene units is calculated as a hydrophobic group.

  Specific examples of the nonionic surfactant suitable for applying the treatment method of the present invention include polyoxyalkylene alkyl ether, polyoxyalkylene secondary alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkylamino ether. , Polyoxyalkylene alkenyl amino ether, polyoxyalkylene fatty acid amide ether, fatty acid diethanolamide, polyoxyalkylene polystyryl phenyl ether, polyoxyalkylene polystyryl phenyl ether formalin condensate, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene fatty acid Ether ester, polyoxyalkylene castor oil ether, polyoxyalkylene hydrogenated castor oil ether, polyoxyalkylene solvent Sorbitan ether esters, mono-ol type polyether diol polyether, polyol polyether, polyalkylene glycol monoalkyl ethers, polyalkylene glycol dialkyl ethers, polyoxyalkylene acetylene ethers and Pluronic type polyethers.

  In the treatment method of the present invention, water is added as described above, and at least one selected from lower alcohols having 1 to 4 carbon atoms, glycols having 2 to 4 carbon atoms, propylene glycol monomethyl ether and lactic acid esters is appropriately added. It can also be added.

  In the treatment method of the present invention, the aqueous diluted solution as described above is subjected to an ion exchange method using a mixed resin of a strongly acidic cation exchange resin and a strongly alkaline anion exchange resin. Commercially available products can be used as the strongly acidic cation exchange resin, but it is particularly preferable to use a gel-type strongly acidic cation exchange resin. As such gel type strongly acidic cation exchange resin, all are trade names, Amberlite IR-124, Amberlite IR-120B (both manufactured by Dow Chemical Co., USA), Allite DS-1 (manufactured by Organo), Duolite. C20J, Duolite C20LF, Duolite C255LFH (all manufactured by Dow Chemical Co., USA), Diaion SK-110, Diaion SK-1B (both manufactured by Mitsubishi Chemical Co., Ltd.), etc. It is done. As the strong alkaline anion exchange resin, a commercially available product can also be used, and it is preferable to use a gel-type strong alkaline anion exchange resin. As such gel type strong alkaline anion exchange resin, all are trade names, Amberlite IRA-400J, Amberlite IRA-410J, Duolite A113LF, Duolite A116 (all manufactured by Dow Chemical Co., USA), Alright DS- 2 (manufactured by Organo Co., Ltd.), Diaion SA12A, Diaion SA20A (both manufactured by Mitsubishi Chemical Co., Ltd.), and the like, and quaternary ammonium salt type.

  The strong acid cation exchange resin and the strong alkaline anion exchange resin used for the ion exchange method have been described above. However, in the treatment method of the present invention, the gel type sulfonic acid type strong acid cation exchange resin or the gel type quaternary ammonium is used. When used in combination with a salt-type strongly alkaline anion exchange resin, they are all trade names, such as weakly acidic cation exchange resins such as Duolite C-433LF (manufactured by Dow Chemical Co., USA) and Amberlite IRA67 (Dow Weak alkaline anion exchange resins such as Duolite A-375LF (manufactured by Dow Chemical Co., USA) and Diaion WA10 (manufactured by Mitsubishi Chemical Corporation) can also be used. Also, all are trade names: Duolite MB5113, Duolite UP6000, Duolite UP7000 (all manufactured by Dow Chemical Co., USA), Amberlite EG-4A-HG, Amberlite MB-1, Amberlite MB-2, Amber Jet ESP-2, Amberjet ESP-1 (all manufactured by Dow Chemical Co., USA), Diaion SMNUP, Diaion SMT100L (both manufactured by Mitsubishi Chemical), Allite DS-3 (manufactured by Organo), etc. Commercially available products in which a cation exchange resin and a strong alkaline anion exchange resin are mixed can also be used.

  In the treatment method of the present invention, as described above, a mixed resin of a strongly acidic cation exchange resin and a strongly alkaline anion exchange resin is used, but the mixing ratio of both is strong acid cation exchange resin / strong alkali anion exchange resin. The volume ratio is preferably 1/4 to 4/1, and more preferably 1/3 to 3/1.

  The space velocity (SV) during the ion exchange treatment is preferably 0.01 to 20.0, and more preferably 0.1 to 10.0. Further, the temperature of the aqueous diluted solution during the ion exchange treatment is preferably 0 to 60 ° C, and more preferably 10 to 50 ° C.

  In the treatment method of the present invention, specific methods for the ion exchange treatment include a batch method and a column method, and among them, the column method is preferable.

  In the treatment method of the present invention, by the ion exchange method described above, the metal ion concentration with respect to the nonionic surfactant is 5 ppb or less for each metal ion, preferably Na, K, Ca, Mg, Mn, Fe, Al, The metal ion concentration of Cu, Zn, Ni, and Cr is set to 3 ppb or less for each of these metal ions, and more preferably 1 ppb or less for each of these metal ions.

  In the treatment method of the present invention, the concentration of each metal ion can be determined by measuring by inductively coupled plasma mass spectrometry.

  Next, the manufacturing method of the nonionic surfactant which reduced the metal ion concentration which concerns on this invention is demonstrated. The method for producing a nonionic surfactant with reduced metal ion concentration according to the present invention is characterized in that a nonionic surfactant containing metal ions is treated by the treatment method of the present invention described above. Thus, as described above, this is a method for producing a nonionic surfactant in which the metal ion concentration is reduced for each metal ion.

  The aqueous diluted solution of a nonionic surfactant treated with the treatment method of the present invention and having a reduced metal ion concentration can be used after being concentrated, diluted, or optionally dried depending on the purpose of use.

  A known method can be applied to distilling off water or the like from the aqueous diluted solution of the nonionic surfactant used in the ion exchange method. Examples thereof include a vacuum distillation method, a thin film distillation method, a molecular distillation method and the like.

  The nonionic surfactant treated with the treatment method of the present invention and reduced in the metal ion concentration is a cleaning solution or a surface treatment solution used in each step of the semiconductor manufacturing process, a processing solution for a photoresist process, a stripping solution, a developing solution, or a cleaning solution. Electrolytic solutions and electrode manufacturing compositions such as coating agents, batteries, capacitors and capacitors, various coating agents, pigments and carbon black dispersants in inks and paints, carbon nanotubes, fullerenes and metal nanoparticle dispersants in nanotechnology It is useful in many fields such as a titanium oxide dispersant in a dye-sensitized solar cell.

  According to the present invention described above, it is possible to obtain a nonionic surfactant having a metal ion concentration reduced to a level of several ppb required for use in the fields of electronics, semiconductors and precision processing.

  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”.

Example 1
1800 g of water was added to and mixed with 200 g of a commercially available nonionic surfactant (A-1) containing metal ions, and this was used as a sample as an aqueous diluted solution. 75 mL of Amberlite IR-120B (trade name, manufactured by Dow Chemical Co., USA) that has been regenerated to H type using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin and 1N tetramethylammonium salt as a strongly alkaline anion exchange resin Amberlite IRA-400J (trade name, manufactured by Dow Chemical Co., Ltd.), which has been regenerated to OH type using an aqueous solution, is uniformly mixed, and the mixed resin is packed vertically into a 300 mL column with a set content. After thoroughly washing with 4000 g of ion exchange water, the mixture was allowed to stand for 24 hours. The sample and the liquid temperature in the column were kept constant at 10 ° C., and the sample was passed through the column at a space velocity (SV) of 1.4 to perform ion exchange treatment.

Example 2
1900 g of water was added to and mixed with 100 g of a commercially available nonionic surfactant (A-2) containing metal ions, and this was used as a sample as an aqueous diluted solution. 50 mL of Amberlite IR-120B (trade name, manufactured by Dow Chemical Co., Ltd.), which has been regenerated to H type using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin, and 1N tetramethylammonium salt as a strongly alkaline anion exchange resin 100 mL of Amberlite IRA-400J (trade name, manufactured by Dow Chemical Co., Ltd.), which has been regenerated to OH type using an aqueous solution, is uniformly mixed, and packed in a 300 mL column with a mixed resin set vertically. After thoroughly washing with 4000 g of ion exchange water, the mixture was allowed to stand for 24 hours. The sample and the liquid temperature in the column were kept constant at 25 ° C., and the sample was passed through the column at a space velocity (SV) of 0.4 to perform ion exchange treatment.

Example 3
1200 g of water was added to and mixed with 800 g of a commercially available nonionic surfactant (A-3) containing metal ions, and this was used as a sample as an aqueous diluted solution. 120 mL of Amberlite IR-120B (trade name, manufactured by Dow Chemical Co., USA) that has been regenerated to H type using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin, and 1N tetramethylammonium salt as a strongly alkaline anion exchange resin. 40 mL of Amberlite IRA-400J (trade name, manufactured by Dow Chemical Co., Ltd.), which has been regenerated to OH type using an aqueous solution, is uniformly mixed, and packed into a 300 mL column with a mixed resin set vertically. After thoroughly washing with 4000 g of ion exchange water, the mixture was allowed to stand for 24 hours. The sample and the liquid temperature in the column were kept constant at 40 ° C., and the sample was passed through the column at a space velocity (SV) of 2.5 to perform ion exchange treatment.

Example 4
1600 g of water was added to 400 g of the nonionic surfactant (A-4) containing metal ions and mixed to prepare a sample as an aqueous diluted solution. Hereinafter, the sample was passed through the column and subjected to ion exchange treatment in the same manner as in Example 1 except that the liquid temperature in the sample and the column and the space velocity (SV) were changed as described in Table 1.

Example 5
1200 g of water and 50 g of 2-propanol were added to and mixed with 750 g of nonionic surfactant (A-5) containing metal ions, and this was used as a sample as an aqueous diluted solution. 120 mL of Amberlite IR-120B (trade name, manufactured by Dow Chemical Co., USA) that has been regenerated to H type using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin, and 1N tetramethylammonium salt as a strongly alkaline anion exchange resin. 40 mL of Amberlite IRA-400J (trade name, manufactured by Dow Chemical Co., Ltd.), which has been regenerated to OH type using an aqueous solution, is uniformly mixed, and packed into a 300 mL column with a mixed resin set vertically. After thoroughly washing with 4000 g of ion exchange water, the mixture was allowed to stand for 24 hours. The sample and the liquid temperature in the column were kept constant at 25 ° C., and the sample was passed through the column at a space velocity (SV) of 1.5 to perform ion exchange treatment.

Example 6
1000 g of water was added to and mixed with 1000 g of nonionic surfactant (A-5) containing metal ions, and this was used as a sample as an aqueous diluted solution. 120 mL of Amberlite IR-120B (trade name, manufactured by Dow Chemical Co., USA) that has been regenerated to H type using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin, and 1N tetramethylammonium salt as a strongly alkaline anion exchange resin. 40 mL of Amberlite IRA-400J (trade name, manufactured by Dow Chemical Co., Ltd.), which has been regenerated to OH type using an aqueous solution, is uniformly mixed, and packed into a 300 mL column with a mixed resin set vertically. After thoroughly washing with 4000 g of ion exchange water, the mixture was allowed to stand for 24 hours. The sample and the liquid temperature in the column were kept constant at 20 ° C., and the sample was passed through the column at a space velocity (SV) of 2.2 to perform ion exchange treatment.

Comparative Example 1
2000 g of nonionic surfactant (A-1) containing metal ions was dissolved in 800 g of methanol and used as a sample. 75 mL of Amberlite IR-120B (trade name, manufactured by Dow Chemical Co., USA) that has been regenerated to H type using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin and 1N tetramethylammonium salt as a strongly alkaline anion exchange resin Amberlite IRA-400J (trade name, manufactured by Dow Chemical Co., Ltd.), which has been regenerated to OH type using an aqueous solution, is uniformly mixed, and the mixed resin is packed vertically into a 300 mL column with a set content. After thoroughly washing with 4000 g of methanol, it was allowed to stand for 24 hours. The sample and the liquid temperature in the column were kept at 25 ° C., and the sample was passed through the column at a space velocity (SV) of 1.0 to perform ion exchange treatment.

Comparative Example 2
A commercially available nonionic surfactant (A-2) containing metal ions was used as a sample. 75 mL of Amberlite IR-120B (trade name, manufactured by Dow Chemical Co., USA) that has been regenerated to H type using 1N dilute hydrochloric acid as a strongly acidic cation exchange resin and 1N tetramethylammonium salt as a strongly alkaline anion exchange resin Amberlite IRA-400J (trade name, manufactured by Dow Chemical Co., Ltd.) that has been regenerated to OH type using an aqueous solution is uniformly mixed, and the mixed resin is furnace-separated with a glass filter. After vacuum-drying, the sample was blended in a 500 g sample and allowed to stand for 24 hours. Fill the 300 ml column with the fixed mixed resin set vertically, keep the sample and the liquid temperature in the column constant at 30 ° C, and add 2000 g of sample with water at a space velocity (SV) of 0.1. Instead, it was passed through a column and subjected to ion exchange treatment.

Comparative Example 3
1900 g of water was added to and mixed with 100 g of a commercially available nonionic surfactant (A-2) containing metal ions, and this was used as a sample as an aqueous diluted solution. As a strongly acidic cation exchange resin, 75 mL of Amberlite IR-120B (trade name, manufactured by Dow Chemical Co., USA) that has been regenerated to H type using 1N dilute hydrochloric acid in advance is packed into a 300 mL column with a vertical setting, After thoroughly washing with 4000 g of ion-exchanged water, the mixture was allowed to stand for 24 hours. The sample and the liquid temperature in the column were kept constant at 25 ° C., and the sample was passed through the column at a space velocity (SV) of 1.1 for ion exchange treatment.

Comparative Example 4
1800 g of water was added to and mixed with 200 g of a commercially available nonionic surfactant (A-1) containing metal ions, and this was used as a sample as an aqueous diluted solution. 75 mL of Amberlite IR-120B (trade name, manufactured by Dow Chemical Co., Ltd.), which has been regenerated to H type using 1N dilute hydrochloric acid in advance, is used as the strong acid cation exchange resin, and 1N tetra 75 mL of Amberlite IRA-400J (trade name, manufactured by Dow Chemical Co., USA) that had been regenerated to OH type using an aqueous methylammonium salt solution was used. ), The latter was set in the latter part of the column (lower part), and the others were performed in the same manner as in Example 1, and the sample was subjected to ion exchange treatment.

  The processing conditions and the like of the ion exchange treatment of each example are shown together in Table 1, and the metal ion concentrations of those subjected to the ion exchange treatment in each example are shown together in Table 2. However, Comparative Example 5 is an untreated example that is not subjected to ion exchange treatment. The metal ion concentration is the concentration with respect to the nonionic surfactant obtained by distilling water and methanol by subjecting the ion exchange treated in each example to reduced pressure, and such metal ion concentration is Agilent as an inductively coupled plasma mass spectrometer. It was measured by inductively coupled plasma mass spectrometry using 7700 s (trade name, manufactured by Agilent Technologies). Although the data is omitted, each of the untreated nonionic surfactants (A-2) to (A-5) is similar to the untreated nonionic surfactant (A-1). In a high concentration.

In Table 1,
A-1: Polyoxyethylene stearyl ether (molecular weight: 1150, HLB (Griffin method): 15.3
A-2: Polyoxyalkylene octyl ether (molecular weight: 2318, HLB (Griffin method): 9.9
A-3: Trimethylolpropane tris (polyoxyalkylene) ether (molecular weight: 4248, HLB (Griffin method): 13.7
A-4: Olphine E1010 (trade name, manufactured by Nissin Chemical Industry Co., Ltd., molecular weight: 666, HLB (Griffin method): 13.3
A-5: Olfine E1020 (trade name, manufactured by Nissin Chemical Industry Co., Ltd., molecular weight: 1106, HLB (Griffin method): 15.9
Amount of water added: Ratio of water added to nonionic surfactant containing metal ions

  Also from the results in Table 2 corresponding to Table 1, according to the treatment method of the present invention, the metal ion concentration is reduced to 5 ppb or less for each metal ion, and in the case of each example, to 1 ppb or less. Can do.

Claims (7)

  A strongly acidic cation exchange resin and a strongly alkaline anion exchange resin are prepared by adding an aqueous diluted solution in which water is added in an amount of 40.0% by mass to less than 98.0% by mass to a nonionic surfactant containing a metal ion. A non-ionic surfactant, characterized by being subjected to an ion exchange method using a mixed resin and a metal ion concentration with respect to the non-ionic surfactant so as to be 5 ppb or less for each metal ion Method.   While adding water so that it may become 40.0 mass% or more and less than 98.0 mass% with respect to the nonionic surfactant containing a metal ion, C1-C4 lower alcohol, C2-C4 The aqueous diluted solution to which at least one selected from glycol, propylene glycol monomethyl ether and lactic acid ester is added is subjected to an ion exchange method using a mixed resin of a strongly acidic cation exchange resin and a strongly alkaline anion exchange resin, and the temperature is 0. Nonionic type, characterized in that the liquid is passed through at a temperature of ˜60 ° C. and a space velocity of 0.1 to 10.0 so that the metal ion concentration with respect to the nonionic surfactant is 5 ppb or less for each metal ion. Surfactant treatment method.   The method for treating a nonionic surfactant according to claim 1 or 2, wherein both the strongly acidic cation exchange resin and the strongly alkaline anion exchange resin are of a gel type.   Any one of Claims 1-3 processed so that each metal ion density | concentration of Na, K, Ca, Mg, Al, Mn, Fe, Cu, Ni, Cr, and Zn with respect to a nonionic surfactant may be 3 ppb or less. A method for treating a nonionic surfactant according to one item.   Any one of Claims 1-3 processed so that each metal ion density | concentration of Na, K, Ca, Mg, Al, Mn, Fe, Cu, Ni, Cr, and Zn with respect to a nonionic surfactant may be 1 ppb or less. A method for treating a nonionic surfactant according to one item.   The method for treating a nonionic surfactant according to any one of claims 1 to 5, wherein the nonionic surfactant has an HLB value of 7 to 18 according to the Griffin method. Preparation of nonionic surfactants having a reduced metal ion concentration, which comprises treating the non-ionic surface active agent containing a metal ion in the processing method of any one of the preceding description of the 請 Motomeko 1-6 Method.