Method for producing organic sulfonic acid compound

Abstract

A method for manufacturing an organic sulfonic acid compound is provided, comprising a reaction process 1, a contact process 2, and a contact process 3, wherein in the reaction process 1, an organic sulfonic acid compound is synthesized using a reaction base containing a chlorine-based compound, in the contact process 2, a solution of the organic sulfonic acid compound obtained in the reaction process 1 is contacted with an anion exchange resin, and in the contact process 3, the solution of the organic sulfonic acid compound that has passed through the contact process 2 is contacted with a cation exchange resin, and wherein the anion exchange resin of the contact process 2 and the cation exchange resin of the contact process 3 are spaced apart from each other.

Description

Technology Field

[0001] The present disclosure relates to a method for producing an organic sulfonic acid compound. Background Technology

[0003] High-performance cleaning agents containing surfactants are used in the technical fields of manufacturing and precision machining for devices such as electronic components or semiconductors. Examples of contaminants or deposits that may arise during the manufacturing process of silicon wafers or semiconductors include debris or dust known as particles, as well as various impurity ions. Particles on semiconductors can cause malfunctions, such as circuit breaks. As a result, the semiconductor becomes unusable, leading to a decrease in product yield. Furthermore, impurity ions, such as chloride ions or metal ions, can penetrate the gaps between the metal wiring of semiconductors. In this case, current leakage caused by these impurity ions can lead to a situation where the semiconductor fails to operate normally. The presence of impurity ions can potentially indicate serious problems with the manufactured device, such as insufficient performance resulting from fluctuations in electrical characteristics. Moreover, chloride ions on the metal wiring of semiconductors tend to accelerate corrosion of the metal wiring. Consequently, the metal wiring is susceptible to damage, causing the resistance of the metal wiring to increase. As such, the presence of particles or impurity ions significantly affects the quality of semiconductors. In recent years, the miniaturization of devices such as smartphones and PCs has been remarkable. The miniaturization of the semiconductors used in these devices is also progressing. The circuit linewidths of these miniaturized semiconductors are extremely fine. Consequently, circuit deformation and other issues can occur due to smaller particles. Therefore, a higher degree of particle and impurity ion removal is required. For this reason, there is a demand for surfactants with a higher degree of purification that have reduced concentrations of chloride and metal ions.

[0004] Regarding purification methods for surfactants, in addition to general methods involving concentration, crystallization, or extraction, methods using, for example, ion exchange using an ion exchange resin are known. For example, in the method disclosed in Japanese Patent Publication No. 2009-143842 (Patent Document 1), an alkali metal salt of an organic sulfonic acid is subjected to an ion exchange method using a strong acidic cation exchange resin. By treating such an organic sulfonate, the concentration of various metal ions is reduced. Furthermore, in the method disclosed in Japanese Patent Publication No. 2015-38051 (Patent Document 2), an alkali metal salt and / or ammonium salt of an organic sulfonic acid is subjected to an ion exchange method using a strong acidic cation exchange resin. By treating such an organic sulfonate, the concentration of various metal ions is reduced. In addition, in the method disclosed in Japanese Patent Publication No. 2001-64249 (Patent Document 3), an aqueous solution of alkanesulonic acid and a basic anion exchange resin are brought into contact with each other in order to reduce the sulfuric acid content in alkanesulonic acid.

[0005] However, when impurities are reduced by purification methods such as general crystallization and extraction, the quality of the surfactant is far from the quality required in the semiconductor field. Furthermore, according to the method disclosed in Patent Document 1 or Patent Document 2, it is possible to reduce the concentration of metal ions contained in the surfactant solution. However, it is unclear whether it is possible to reduce the chloride ion concentration by this method. According to the method disclosed in Patent Document 3, it is possible to reduce the concentration of sulfate ions contained in the surfactant solution. However, it is unclear whether it is possible to reduce the chloride ion concentration or the metal ion concentration by this method. Neither patent document specifies that chloride ions and metal ions, etc., are reduced to the quality required in the field of semiconductor manufacturing.

[0006] Surfactant solutions using organic sulfonic acid compounds are used in semiconductor manufacturing for purposes such as dispersion, surface modification, or cleaning. Regarding the synthesis of organic sulfonic acid compounds, methods using chlorine-based compounds and methods using sulfuric acid-based compounds are widely known. In manufacturing methods using chlorine-based compounds, the synthesized organic sulfonic acid contains a large amount of chloride ions derived from reactants such as chlorosulfonic acid. In manufacturing methods using sulfuric acid-based compounds, chlorine-based solvents such as chloroform are used as reaction solvents in most cases. Consequently, chloride ions are incorporated into the synthesized sulfonic acid compounds. Thus, in manufacturing methods using chlorine-based compounds, chloride ions derived from reactants such as chlorosulfonic acid are contained in the organic sulfonic acid compounds. Furthermore, in manufacturing methods using sulfuric acid-based compounds, when sodium salts are formed, a large amount of chloride ions derived from salt impurities are contained in the organic sulfonic acid compounds. For this reason, these chloride ions are becoming a problem in the semiconductor manufacturing field. Under these circumstances, the reduction of these chloride ions is desired. Prior art literature

[0008] 1. Japanese Patent Publication No. 2009-143842 2. Japanese Patent Publication No. 2015-38051 3. Japanese Patent Publication No. 2001-64249 The problem to be solved

[0009] Accordingly, the present disclosure provides a method for producing an organic sulfonic acid compound capable of efficiently reducing chloride ion content and metal ion content. means of solving the problem

[0011] To solve the above problem, the present disclosure technology includes the following means.

[0012] (1) A method for producing an organic sulfonic acid compound comprising a reaction process 1, a contact process 2, and a contact process 3', wherein in reaction process 1, an organic sulfonic acid compound is synthesized using a reaction base containing a chlorine-based compound, in contact process 2, a solution of the organic sulfonic acid compound obtained in reaction process 1 is brought into contact with an anion exchange resin, and in contact process 3, a solution of the organic sulfonic acid compound that has passed through contact process 2 is brought into contact with a cation exchange resin, and the anion exchange resin of contact process 2 and the cation exchange resin of contact process 3 are spaced apart from each other.

[0013] (2) The above organic sulfonic acid compound is a surfactant, as described in (1) of the manufacturing method.

[0014] (3) In the above contact process 2, the above solution having an organic sulfonic acid compound concentration of 1 to 50 mass% is in contact with the anion exchange resin. The manufacturing method described in (1).

[0015] (4) In the above contact process 3, the above solution having an organic sulfonic acid compound concentration of 1 to 40 mass% is in contact with the cation exchange resin. The manufacturing method described in (1).

[0016] (5) In the above contact process 2, the solution has a space velocity (SV) of 0.3 to 4.9 h -1 The manufacturing method described in (1) that contacts the anion exchange resin.

[0017] (6) In the above contact process 3, the solution has a space velocity (SV) of 0.3 to 4.9 h -1 The manufacturing method described in (1) that contacts the above cation exchange resin.

[0018] Furthermore, in the description of the present embodiment, the numerical range represented as "A ~ B" includes its upper and lower limits unless otherwise specified. That is, "A ~ B" means "A or greater, B or less." Effects of the invention

[0020] According to the manufacturing method of the present disclosure described above, a method for manufacturing an organic sulfonic acid compound capable of efficiently reducing chloride ion content and metal ion content can be provided. Specific details for implementing the invention

[0022] The method for preparing an organic sulfonic acid compound according to the present embodiment comprises a reaction process 1 for synthesizing an organic sulfonic acid compound, and a contact process 2 and a contact process 3 for performing ion exchange. Here, the ion exchange resin of the contact process 2 and the ion exchange resin of the contact process 3 are spaced apart from each other.

[0023] Reaction Process 1

[0024] In reaction process 1, an organic sulfonic acid compound is synthesized using a reaction base containing a chlorine-based compound. In this embodiment, "reaction base containing a chlorine-based compound" refers to a series of reaction bases included in the starting materials of the reaction, such as a solvent or a catalyst. Examples of reaction bases include aromatic hydrocarbons containing benzene, octylbenzene, dodecylbenzene, and octadecylbenzene, and unsaturated hydrocarbons containing double bonds containing octene, decene, undecene, dodecene, tetradecene, hexadecene, and octadecene. Among these, benzene, dodecylbenzene, octene, dodecene, hexadecene, and octadecene are preferred. One of these reaction bases may be used alone. Alternatively, two or more reaction bases may be used in combination.

[0025] (Chlorine compounds)

[0026] The chlorinated compounds used are not particularly limited. Examples of chlorinated compounds include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ammonium chloride, aluminum chloride, hydrogen chloride, iron chloride, copper chloride, chloromethane, chloroethane, chlorosulfonic acid, chloroform, and chlorobenzene. Any one of these chlorinated compounds may be used alone. Alternatively, two or more chlorinated compounds may be used in combination.

[0027] (Organic sulfonic acid compounds)

[0028] The synthesis method of reaction process 1 is not particularly limited. Conventionally known methods may be used. Examples of synthesis methods include a method of sulfochlorination using a chlorine-based compound, a sulfonation reaction using a sulfuric acid-based compound, or a method of neutralization with sodium hydroxide after a sulfonation reaction using sulfur dioxide and oxygen. The organic sulfonic acid compound to be synthesized may be any one of a monosulfonic acid compound, a disulfonic acid compound, or a mixture thereof. In addition, the alkyl groups included in the organic sulfonic acid compound include straight-chain alkyl groups and branched alkyl groups. The number of carbon atoms in the alkyl groups may be distributed.

[0029] Preferably, an organic sulfonic acid compound is a surfactant. Examples of such organic sulfonic acid compounds include sodium octylsulfonate, sodium dodecylbenzenesulfonate, and sodium octadecylsulfonate. However, the surfactants that can be used are not limited to these examples.

[0030] In reaction process 1, along with the production of the organic sulfonic acid compound, a halogen (a compound containing chlorine) is produced as a byproduct. Alternatively, chlorine derived from the chlorine-based compound used as the solvent for the reaction is included in the organic sulfonic acid compound. Therefore, in order to purify the synthesized organic sulfonic acid compound, the following contact processes 2 and 3 are carried out in this order.

[0031] Contact Process 2

[0032] In contact process 2, the solution of the organic sulfonic acid compound obtained in reaction process 1 comes into contact with an anion exchange resin. The purpose of contact process 2 is primarily to adsorb chloride ions from the organic sulfonic acid compound onto the anion exchange resin. In contact process 2 and contact process 3 described later, the method of contacting the solution of the organic sulfonic acid compound with the ion exchange resin is not particularly limited. For example, a column method or a batch method may be used. A column method is preferred from the perspective of work efficiency, etc. Known devices, such as ion exchange columns, may be used to contact the ion exchange resin according to the method of the present disclosure.

[0033] The solution of the organic sulfonic acid compound obtained in reaction process 1 is passed through an anion exchange resin. Then, chloride ions contained in the organic sulfonic acid compound solution are adsorbed onto the anion exchange resin. As a result, the chloride ion concentration in the obtained purified solution can be reduced. In the present disclosure, contact process 2 is performed after reaction process 1. That is, by performing anion exchange in contact process 2 on the organic sulfonic acid compound in the state synthesized in reaction process 1, only chloride ions are selectively captured by the anion exchange resin. As a result, it becomes possible to effectively reduce the chloride ion concentration. Furthermore, the solution of the organic sulfonic acid compound is a solution obtained by dissolving the organic sulfonic acid compound synthesized in reaction process 1 in a solvent suitable for ion exchange methods, such as ion-exchanged water.

[0034] (Anion exchange resin)

[0035] The anion exchange resin used in contact process 2 may be any of a strong basic resin, a weak basic resin, or a mixture thereof. Among these, an anion exchange resin containing a strong basic anion exchange resin is preferred. The anion exchange resin used is not particularly limited. Known anion exchange resins may be used. The shape of the anion exchange resin is not limited to granular form. The shape of the resin may be powder, fibrous, or membrane-like. The structure of the anion exchange resin may be gel-type or macroporous-type. One of these anion exchange resins may be used alone. Alternatively, two or more anion exchange resins may be used in combination.

[0036] The proportion of the content of the strong basic anion exchange resin contained in the anion exchange resin is not particularly limited. The preferred proportion is 50 volume% or more. When the proportion of the strong basic anion exchange resin is within this range, the chloride ion content in the solution of the organic sulfonic acid compound is effectively reduced as chloride ions are adsorbed onto the strong basic anion exchange resin.

[0037] A strong basic anion exchange resin is an anion exchange resin into which a strong basic functional group, such as a quaternary ammonium base (R-N+R1R2R3), has been introduced. Examples of usable strong basic anion exchange resins include Amberlite (registered trademark, hereinafter the same), IRA400J Cl, IRA402BL, and IRA900J (all manufactured by DuPont, USA), Duolite (registered trademark, hereinafter the same) A113LF, A161JCL, and AGP (all manufactured by DuPont, USA), and Diion (registered trademark, hereinafter the same) SA10A and SA11A (all manufactured by Mitsubishi Chemical). In addition, other examples include Type II strong basic anion exchange resins, such as Amberlite IRA410J, IRA910CT, and HPR4010 (all manufactured by DuPont, USA), Duolite A116 and A162LF (all manufactured by DuPont, USA), and Diion SA20A and SA20ALL (both manufactured by Mitsubishi Chemical).

[0038] Weakly basic anion exchange resins are anion exchange resins into which weakly basic functional groups, such as primary to tertiary amines, have been introduced. Examples of weakly basic anion exchange resins include Amberlite IRA67, IRA96SB, and IRA98 (all manufactured by DuPont, USA), Duolite A368MS, A378D, and A375LF (all manufactured by DuPont, USA), and Diion WA10 and WA20 (all manufactured by Mitsubishi Chemical).

[0039] Preferably, the anion exchange resin is regenerated into the OH type using a salt such as an aqueous solution of tetramethylammonium salt. The obtained OH type anion exchange resin is thoroughly washed, for example, with ion-exchanged water or ultrapure water.

[0040] In contact process 2, the concentration of the organic sulfonic acid compound in the solution of the organic sulfonic acid compound in contact with the anion exchange resin is not particularly limited. The preferred concentration is 1 to 50 mass%. If the concentration of the solution is excessively high, the viscosity of the solution increases. Consequently, molecular movement within the solution is restricted. As a result, the number of contacts between the ion exchange resin and chloride ions decreases, making it difficult to efficiently reduce the chloride ion concentration.

[0041] The concentration of the organic sulfonic acid compound in the solution of the organic sulfonic acid compound in contact with the anion exchange resin is more preferably 15 to 35 mass%. If the concentration is too low, the amount of water required for dilution increases. Therefore, the flow rate of the organic sulfonic acid compound solution per unit time during ion exchange must be increased. For this reason, a concentration that is too low is not suitable from the perspective of productivity.

[0042] The space velocity (SV) when ion-exchanging a solution of an organic sulfonic acid compound in contact process 2 is preferably 0.3 to 4.9 h -1 , more preferably 0.3 to 1.0 h -1 It is set to. If the flow rate becomes too fast, it is difficult to sufficiently adsorb chloride ions. In addition, the space velocity (SV) value, that is, the SV value, is a unit that indicates how many times the amount of treated water is passed per hour relative to the amount of ion exchange resin being charged.

[0043] Contact Process 3

[0044] In contact process 3, the solution of the organic sulfonic acid compound that has passed through contact process 2 comes into contact with a cation exchange resin. The purpose of contact process 3 is primarily to adsorb metal ions from the organic sulfonic acid compound onto the cation exchange resin. When the solution of the organic sulfonic acid compound that has passed through contact process 2 passes through the cation exchange resin, the metal ions contained in the organic sulfonic acid compound solution are adsorbed onto the cation exchange resin. As a result, not only chloride ions but also metal ions in the resulting purified solution can be further reduced.

[0045] (Cation exchange resin)

[0046] The cation exchange resin used in contact process 3 may be any of a strong acid resin, a weak acid resin, or a mixture thereof. Among these, a cation exchange resin containing a strong acid cation exchange resin is preferred. The cation exchange resin used is not particularly limited. Known cation exchange resins may be used. The shape of the cation exchange resin is not limited to granular form. The shape of the resin may be powder, fibrous, or membrane-like. The structure of the cation exchange resin may be gel-type or macro-pole-type. One of these cation exchange resins may be used alone. Alternatively, a combination of two or more cation exchange resins may be used.

[0047] The content ratio of the strong acid cation exchange resin contained in the cation exchange resin is not particularly limited. The preferred content ratio is 90 volume% or more. When the content ratio of the strong acid cation exchange resin is within this range, the metal ions are adsorbed onto the strong acid cation exchange resin, thereby effectively reducing the metal ion content in the solution of the organic sulfonic acid compound.

[0048] A strong acid cation exchange resin is a cation exchange resin that has an adsorption capacity for relatively large cation components. Strong acid cation exchange resins have strong acid exchange groups, such as sulfonic acid groups (R-SO3-H+), as functional groups. Examples of usable strong acid cation exchange resins include Amberlite IR120BNa, IR-124Na and 200CTNa (all manufactured by DuPont, USA), Duolite C20, C20LF and C255LFH (all manufactured by DuPont, USA), and Diion SK104H, SK110 and SK1B (all manufactured by Mitsubishi Chemical).

[0049] Weakly acidic cation exchange resins are cation exchange resins that possess adsorption capacity for relatively small cation components. Weakly acidic cation exchange resins have weakly acidic exchange groups, such as carboxylic acid groups (R-COO-H+), as functional groups. Examples of usable weakly acidic cation exchange resins include Amberlite IRC76, FPC3500, and HPR8400 (all manufactured by DuPont, USA), Duolite C476 (manufactured by DuPont, USA), and Diion WK10 and WK11 (both manufactured by Mitsubishi Chemical).

[0050] Preferably, the cation exchange resin is regenerated into the H-type beforehand using an acid such as hydrochloric acid or sulfuric acid. The obtained H-type cation exchange resin is thoroughly washed, for example, with ion-exchanged water or ultrapure water.

[0051] In contact process 3, the concentration of the organic sulfonic acid compound in the solution of the organic sulfonic acid compound in contact with the cation exchange resin is not particularly limited. The preferred concentration is 1 to 40 mass%. If the concentration of the solution is excessively high, the viscosity of the solution increases. Consequently, molecular motion within the solution is restricted. As a result, the number of contacts between the ion exchange resin and the metal ion is reduced, making it difficult to efficiently reduce the concentration of the metal ion.

[0052] The concentration of the organic sulfonic acid compound in the solution of the organic sulfonic acid compound in contact with the cation exchange resin is more preferably 15 to 30 mass%. If the concentration is too low, the amount of water required for dilution increases. Therefore, the flow rate of the organic sulfonic acid compound solution per unit time must be increased when performing ion exchange. For this reason, a concentration that is too low is not suitable from the perspective of productivity.

[0053] The space velocity (SV) when ion-exchanging the solution of the organic sulfonic acid compound in contact process 3 is preferably 0.3 to 4.9 h -1 , more preferably 0.3 to 1.0 h -1 It is set to. If the flow rate becomes too fast, it is difficult to sufficiently adsorb metal ions.

[0054] In this embodiment, reaction process 1, contact process 2, and contact process 3 are carried out in this order. By doing so, an organic sulfonic acid compound is produced. In reaction process 1, an organic sulfonic acid compound is synthesized using a reaction base containing a chlorine-based compound.

[0055] From the organic sulfonic acid compound in this synthesized state, in contact process 2, only chloride ions are selectively captured by anion exchange resin through anion exchange. Then, in contact process 3, metal ions can be removed by cation exchange from the solution of the organic sulfonic acid compound in the state obtained from contact process 2 through cation exchange resin. Thus, as a result of purification, an organic sulfonic acid compound with reduced concentrations of chloride ions and metal ions can be obtained.

[0056] On the other hand, when contact process 2 and contact process 3 are carried out in reverse order, cation exchange in contact process 3 is performed on the organic sulfonic acid compound synthesized using a reaction base containing a chlorine compound in reaction process 1. Consequently, when metal ions are adsorbed onto the cation exchange resin during the cation exchange in contact process 3, the organic sulfonic acid compound changes into an organic alkylsulfonic acid. Subsequently, when anion exchange is performed in contact process 2, chloride ions are adsorbed onto the anion exchange resin. At this time, sulfonic acid is also anion-exsorbed. Therefore, as a result of purification, an organic sulfonic acid compound from which chloride ions and metal ions have been removed cannot be obtained.

[0057] Furthermore, in this embodiment, the anion exchange resin of contact process 2 and the cation exchange resin of contact process 3 are spaced apart from each other. On the other hand, when the anion exchange resin and the cation exchange resin are in contact, carbonate ions and protons are generated at the contact point. That is, the anion exchange resin comes into contact with air and adsorbs carbon dioxide. Then, carbonate ions are released from the anion exchange resin. Then, the released carbonate ions [contain] protons (H₂) generated in the cation exchange resin + It comes into contact with ). As a result, carbon dioxide bubbles up. Because of this, it becomes difficult for the solution of the organic sulfonic acid compound to pass through. Consequently, sufficient ion exchange cannot be performed. In addition, even when contact process 2 and contact process 3 are performed using a mixed resin of anion exchange resin and cation exchange resin, carbon dioxide bubbles are generated in the same way. As a result, sufficient ion exchange cannot be performed.

[0058] By the manufacturing method described above, an organic sulfonic acid compound with reduced concentrations of chloride ions and metal ions can be obtained. Furthermore, the inability to perform ion exchange due to, for example, the generation of foam during the flow can be avoided. As a result, an organic sulfonic acid compound with a high degree of purification can be efficiently manufactured.

[0059] Examples

[0060] Hereinafter, the operation and effects of the present embodiment are explained more specifically through examples and comparative examples. However, the present embodiment is not limited to these examples. In the following examples and comparative examples, % means mass%. Table 1 shows the compounds synthesized in reaction process 1 and the synthesis methods in each example and each comparative example. Furthermore, Table 1 shows the solution concentration, SV value, and test method in each of contact process 2 and contact process 3.

[0061] Reaction Process 1

[0062] In reaction process 1, the following synthesis methods 1 to 3 were carried out. In Examples 1 to 5, 7 to 10, and 14 to 31, and Comparative Examples 1 to 5, synthesis method 1 was carried out. In Example 6, synthesis method 2 was carried out. In Example 32, synthesis method 3 was carried out. In Examples 11 to 13, synthesis method 1 and synthesis method 3 were carried out.

[0063] Example 1

[0064] (Synthesization Method 1)

[0065] 116.5 g (1.0 mol, 1.0 eq.) of chlorosulfonic acid was added dropwise over 10 minutes to 246.4 g (1.0 mol) of dodecylbenzene weighed into a 500 mL four-necked flask. After adding, the mixture was heated to 150 °C. The reaction was then carried out for 10 hours. The above reaction mixture was added to 500 g of water weighed into a 2 L beaker. The reaction mixture was stirred at 70 °C for 2 hours and then cooled. Subsequently, a 30 wt% aqueous sodium hydroxide solution was added to the neutral region. In this way, the reaction product was recovered as an aqueous sodium dodecylbenzenesulfonate solution. Subsequently, water and unreacted dodecylbenzene were removed by vacuum distillation of the obtained aqueous solution. From the obtained solid, chloroform was removed by vacuum distillation from the organic layer obtained by extraction with chloroform. In this way, sodium dodecylbenzenesulfonate with impurities removed was obtained.

[0066] Examples 2–5, 7–10, 14–31, Comparative Examples 1–5

[0067] The sulfonic acid compounds listed in Table 1 could be obtained by the same method as Synthesis Method 1, except that the reaction base of Synthesis Method 1 was changed from dodecylbenzene to an unsaturated hydrocarbon (C8-C18) containing a double bond.

[0068] Example 6

[0069] (Synthesization Method 2)

[0070] 113.4 g (1.2 mol, 1.0 eq.) of 20% fuming sulfuric acid was added dropwise over 10 minutes to 295.7 g (1.2 mol) of dodecylbenzene weighed into a 500 mL four-necked flask. After adding the dropwise mixture, the mixture was heated to 160 °C. The reaction was then carried out for 4 hours. The above reaction mixture was added to 700 g of water weighed into a 2 L beaker. The reaction mixture was stirred at 70 °C for 2 hours and then cooled. Subsequently, a 30 wt% aqueous sodium hydroxide solution was added until the pH reached neutral. In this way, the reaction product was recovered as an aqueous sodium dodecylbenzenesulfonate solution. Subsequently, water and unreacted dodecylbenzene were removed by vacuum distillation of the obtained aqueous solution. From the obtained solid, chloroform was removed from the organic layer obtained by extraction with chloroform by vacuum distillation. In this way, sodium dodecylbenzenesulfonate with impurities removed was obtained.

[0071] Example 11

[0072] Sodium dodecylbenzenesulfonate was obtained by synthesis method 1. Sodium dodecylbenzenedisulfonate was obtained by synthesis method 3 below. The sulfonic acid compound of Example 11 was prepared at a ratio of sodium dodecylbenzenesulfonate / sodium dodecylbenzenedisulfonate = 9:1.

[0073] (Synthesization Method 3)

[0074] 226.7 g (2.4 mol, 2.0 eq.) of 20% fuming sulfuric acid was added dropwise over 10 minutes to 295.7 g (1.2 mol) of measured dodecylbenzene in a 500 mL four-necked flask. After adding, the mixture was heated to 160 °C. The reaction was then carried out for 4 hours. The above reaction mixture was added to 700 g of water measured in a 2 L beaker. This reaction mixture was stirred at 70 °C for 2 hours and then cooled. Subsequently, a 30 wt% aqueous sodium hydroxide solution was added to the neutral region. In this way, the reaction product was recovered as an aqueous sodium dodecylbenzene disulfonate solution. Subsequently, water and unreacted dodecylbenzene were removed by vacuum distillation of the obtained aqueous solution. From the obtained solid, chloroform was removed from the organic layer obtained by extraction with chloroform by vacuum distillation. In this way, sodium dodecylbenzene disulfonate with impurities removed was obtained.

[0075] Examples 12, 13

[0076] Sodium alkyl (C10-C18) sulfonate of Example 12 and sodium tetradecylsulfonate of Example 13 could be obtained by the same method as Synthesis Method 1, except that the reaction base of Synthesis Method 1 was changed from dodecylbenzene to an unsaturated hydrocarbon (C10-C18) containing a double bond. Sodium alkyl (C10-C18) disulfonate of Example 12 and tetradecyldisulfonic acid of Example 13 could be obtained by the same method as Synthesis Method 3, except that the reaction base of Synthesis Method 3 was changed from dodecylbenzene to an unsaturated hydrocarbon (C10-C18) containing a double bond.

[0077] The sulfonic acid compound of Example 12 was prepared in a ratio of alkyl (C10-C18) sulfonate sodium:alkyl (C10-C18) disulfonate sodium = 1:9. The sulfonic acid compound of Example 13 was prepared in a ratio of tetradecyl sulfonate sodium:tetradecyl disulfonate sodium = 1:1.

[0078] Example 32

[0079] Sodium benzene disulfonate could be obtained by the same method as synthesis method 3, except that the reaction base of synthesis method 3 of Example 11 was changed from dodecylbenzene to benzene.

[0080]

[0081] The sulfonic acid compound synthesized in reaction process 1 was diluted with water to produce an aqueous solution of an organic sulfonic acid compound. Table 1 shows the concentration of the organic sulfonic acid compound in the obtained aqueous solution. Subsequently, contact process 2 and contact process 3 were carried out in this order.

[0082] Contact Process 2

[0083] In contact process 2, the following test methods 2-1 to 2-6 were performed. Test method 2-1 was performed in Examples 1 to 13, 15, 17 to 28, and 31 to 32, and Comparative Example 3. Test method 2-2 was performed in Examples 14 and 16. Test method 2-3 was performed in Example 29. Test method 2-4 was performed in Example 30. Test method 2-5 was performed in Comparative Example 4. Test method 2-6 was performed in Comparative Example 5. Test method 3-1, described below, was performed in Comparative Example 2.

[0084] (Test Method 2-1)

[0085] A vertically set column with a volume of 300 ml was packed with 200 ml of gel-type strong basic anion exchange resin (product name "Amberlite IRA400J Cl"). Here, the strong basic anion exchange resin was regenerated to the OH form beforehand using a 1 N aqueous solution of tetramethylammonium hydroxide. The anion exchange resin was thoroughly washed with 4000 g of pure water and then left to stand for 24 hours. Subsequently, the pure water injected into the column was maintained at a constant temperature within the range of 15 to 25 ℃. Afterward, an aqueous solution of an organic sulfonic acid compound, adjusted to the same temperature as the pure water in the column, was flowed at the space velocity (SV) listed in Table 1.

[0086] (Test Method 2-2)

[0087] Except for the gel-type strong basic anion exchange resin (product name "Amberlite IRA400J Cl") of Test Method 2-1 being changed to an MR-type strong basic anion exchange resin (product name "Amberlite IRA900J"), an aqueous solution of an organic sulfonic acid compound was flowed at the space velocity (SV) listed in Table 1 by the same operation as in Test Method 2-1.

[0088] (Test Method 2-3)

[0089] Except for the gel-type strong basic anion exchange resin (product name "Amberlite IRA400J Cl") of Test Method 2-1 being changed to a gel-type weak basic anion exchange resin (product name "Amberlite IRA67"), an aqueous solution of an organic sulfonic acid compound was flowed at the space velocity (SV) listed in Table 1 by the same operation as in Test Method 2-1.

[0090] (Test Method 2-4)

[0091] 100 ml of the gel-type strong basic anion exchange resin of Test Method 2-1 (product name "Amberlite IRA400J Cl") and 100 ml of the gel-type weak basic anion exchange resin of Test Method 2-3 (product name "Amberlite IRA67") were uniformly mixed. A column with a volume of 300 ml, set vertically in the above-mentioned resin mixture, was filled. Subsequently, pure water injected into the column was maintained at a constant temperature within the range of 15 to 25 ℃. Then, an aqueous solution of an organic sulfonic acid compound, adjusted to the same temperature as the pure water in the column, was flowed at the space velocity (SV) listed in Table 1.

[0092] (Test Method 2-5)

[0093] 100 ml of MR-type strong acid cation exchange resin (product name "Amberlite 200CT") was regenerated into the H-type using 1 N dilute hydrochloric acid. Additionally, 100 ml of MR-type strong basic anion exchange resin (product name "Amberlite IRA900J") was regenerated into the OH-type using a 1 N aqueous tetramethylammonium hydroxide solution. Subsequently, the regenerated cation exchange resin and anion exchange resin were uniformly mixed. A column with a volume of 300 ml, set vertically in the above-mentioned resin mixture, was filled. Then, pure water injected into the column was maintained at a constant temperature within the range of 15 to 25 ℃. Afterward, an aqueous solution of an organic sulfonic acid compound, adjusted to the same temperature as the pure water in the column, was flowed at the space velocity (SV) listed in Table 1.

[0094] (Test Method 2-6)

[0095] A vertically set column with a volume of 300 ml was filled with 100 ml of MR-type strong basic anion exchange resin (product name "Amberlite IRA900J"). Subsequently, the column was filled with 100 ml of MR-type strong acid cation exchange resin (product name "Amberlite 200CT") that had been regenerated to the H-type using 1 N dilute hydrochloric acid. At this time, the anion exchange resin and the cation exchange resin located above it were in contact with each other within the column. Subsequently, pure water injected into the column was maintained at a constant temperature within the range of 15 to 25 ℃. Afterward, an aqueous solution of an organic sulfonic acid compound, adjusted to the same temperature as the pure water in the column, was flowed at the space velocity (SV) listed in Table 1.

[0096] Contact Process 3

[0097] In contact process 3, the following test methods 3-1 to 3-3 were performed. Test method 3-1 was performed in Examples 1 to 14, 17 to 30, and 32, and Comparative Example 1. Test method 3-2 was performed in Examples 15 and 16. Test method 3-3 was performed in Example 31. In Comparative Example 2, test method 2-1 of the above contact process 2 was performed.

[0098] (Test Method 3-1)

[0099] A vertically set column with a volume of 300 ml was packed with 200 ml of gel-type strong acid cation exchange resin (trade name "Amberlite IR-124Na") that had been regenerated to the H-type using 1 N dilute hydrochloric acid. The cation exchange resin was thoroughly washed with 4000 g of pure water and then left to stand for 24 hours. Subsequently, the pure water injected into the column was maintained at a constant temperature within the range of 15 to 25 ℃. Afterward, an aqueous solution of an organic sulfonic acid compound, adjusted to the same temperature as the pure water in the column, was flowed at the space velocity (SV) listed in Table 1.

[0100] (Test Method 3-2)

[0101] Except for the gel-type strong acid cation exchange resin (product name "Amberlite IR-124Na") of Test Method 3-1 being changed to an MR-type strong acid cation exchange resin (product name "Amberlite 200CT"), an aqueous solution of an organic sulfonic acid compound was flowed at the space velocity (SV) listed in Table 1 with the same operation as in Test Method 3-1.

[0102] (Test Method 3-3)

[0103] 180 ml of the gel-type strong acid cation exchange resin (product name "Amberlite IR-124Na") of Test Method 3-1 and 20 ml of the MR-type weak acid cation exchange resin (product name "Amberlite FPC3500") were uniformly mixed. A column with a volume of 300 ml, set vertically in the above-mentioned resin mixture, was filled. Subsequently, pure water injected into the column was maintained at a constant temperature within the range of 15 to 25 ℃. Then, an aqueous solution of an organic sulfonic acid compound, adjusted to the same temperature as the pure water in the column, was flowed at the space velocity (SV) listed in Table 1.

[0104] The chlorine content, each metal content, and purification amount per unit time of the aqueous solutions of organic sulfonic acid compounds obtained in Examples 1 to 32 and Comparative Examples 1 to 5 were measured and evaluated by the following test methods. Table 2 shows the results.

[0105] Chlorine content

[0106] The chloride ion content in the aqueous solution of the organic sulfonic acid compound after purification was quantified by adding 0.01 mol / l of silver nitrate aqueous solution using a potentiometric titration device (AT-610, manufactured by Kyoto Denshigo Kyo Co., Ltd.). The chloride ion content in the aqueous solution of the organic sulfonic acid compound after purification was evaluated according to the evaluation criteria below.

[0107] (Evaluation criteria for chloride ions (aqueous solution equivalent))

[0108] A: Chloride ion content less than 20 ppm (Excellent)

[0109] B: Chloride ion content 20 ppm or more and less than 50 ppm (Good)

[0110] C: Chloride ion content 50 ppm or more and less than 100 ppm (possible)

[0111] D: Chloride ion content 100 ppm or more (not allowed)

[0112] Metal content

[0113] The metal ion content in the aqueous solution of the organic sulfonic acid compound after purification was measured using an inductively coupled plasma mass spectrometer (ICP-MS7700, manufactured by Agilent Technologies). The content of each metal ion in the aqueous solution of the organic sulfonic acid compound after purification was evaluated according to the evaluation criteria below.

[0114] (Evaluation criteria for Na ions (aqueous solution equivalent))

[0115] A: Na ion content less than 30 ppb (Excellent)

[0116] B: Na ion content 30 ppb or more and less than 50 ppb (Good)

[0117] C: Na ion content 50 ppb or more and less than 80 ppb (possible)

[0118] D: Na ion content 80 ppb or higher (not allowed)

[0119] (Evaluation criteria for K ions (aqueous solution equivalent))

[0120] A: K ion content less than 5 ppb (Excellent)

[0121] B: K ion content 5 ppb or more and less than 20 ppb (good)

[0122] C: K ion content 20 ppb or more and less than 50 ppb (possible)

[0123] D: K ion content 50 ppb or higher (not allowed)

[0124] (Evaluation criteria for Ca ions (aqueous solution equivalent))

[0125] A: Ca ion content less than 10 ppb (Excellent)

[0126] B: Ca ion content 10 ppb or more and less than 20 ppb (Good)

[0127] C: Ca ion content 20 ppb or more and less than 50 ppb (possible)

[0128] D: Ca ion content 50 ppb or higher (not allowed)

[0129] (Evaluation criteria for Fe ions (aqueous solution equivalent))

[0130] A: Fe ion content less than 10 ppb (Excellent)

[0131] B: Fe ion content 10 ppb or more and less than 20 ppb (Good)

[0132] C: Fe ion content 20 ppb or more and less than 50 ppb (possible)

[0133] D: Fe ion content 50 ppb or higher (not allowed)

[0134] Refining amount per unit time

[0135] In contact process 2 and contact process 3, the amount of purification per hour was measured in terms of solid content for 100 ml of ion exchange resin. The measured amount of purification was evaluated according to the following evaluation criteria.

[0136] A: Tablet weight 10 g or more (Excellent)

[0137] B: Tablet weight 5 g or more and less than 10 g (Good)

[0138] C: Tablet weight less than 5 g (possible)

[0139]

[0140] In Examples 1 to 32, the chloride ion content in the aqueous solution of the purified organic sulfonic acid compound was reduced to less than 100 ppm. Regarding each metal content, the Na ion content was reduced to less than 80 ppb. The K ion, Ca ion, and Fe ion content were reduced to less than 50 ppb. Furthermore, in Examples 1 to 19 and 21 to 32, the purification amount per unit time was 5 g or more in both Contact Process 2 and Contact Process 3. In Example 20, the solution concentration of the organic sulfonic acid compound in contact with the exchange resin in both Contact Process 2 and Contact Process 3 was low. Therefore, the purification amount per unit time did not exceed 5 g. However, the evaluation of the chloride ion content and each metal content was excellent. On the other hand, in Comparative Example 1, Contact Process 2 was not performed. Therefore, the chloride ion content was 100 ppm or more. In Comparative Example 2, Contact Process 2 was performed after Contact Process 3. Consequently, the chloride ion content was 100 ppm or higher. In Comparative Example 3, Contact Process 3 was not performed. Consequently, the content of each metal ion was not sufficiently reduced. In Comparative Example 4, a mixed phase of anion exchange resin and cation exchange resin was used in Contact Process 2. Consequently, neither the chloride ion content nor the content of each metal ion was sufficiently reduced. In Comparative Example 5, the column was filled with both resins so that the anion exchange resin and the cation exchange resin were in contact during Contact Process 2. That is, the anion exchange resin and the cation exchange resin were not separated from each other. Consequently, the chloride ion content was not sufficiently reduced. Furthermore, regarding the content of each metal, the Na ion content was 50 ppb or higher and less than 80 ppb. The K ion content, Ca ion content, and Fe ion content were 20 ppb or higher and less than 50 ppb.

Claims

Claim 1 A method for manufacturing an organic sulfonic acid compound comprising a reaction process 1, a contact process 2, and a contact process 3, wherein in the reaction process 1, an organic sulfonic acid compound is synthesized using a reaction base containing a chlorine-based compound, and the organic sulfonic acid compound contains chlorine and a metal derived from the reactants by the synthesis, wherein in the contact process 2, a solution of the organic sulfonic acid compound obtained in the reaction process 1 is contacted with an anion exchange resin, and in the contact process 3, the solution of the organic sulfonic acid compound that has passed through the contact process 2 is contacted with a cation exchange resin, and wherein the anion exchange resin of the contact process 2 and the cation exchange resin of the contact process 3 are spaced apart from each other. Claim 2 A method for preparing an organic sulfonic acid compound according to claim 1, wherein the organic sulfonic acid compound is a surfactant. Claim 3 A method for producing an organic sulfonic acid compound according to claim 1, wherein in the contact process 2, the solution having an organic sulfonic acid compound concentration of 1 to 50 mass% is in contact with the anion exchange resin. Claim 4 A method for producing an organic sulfonic acid compound according to claim 1, wherein in the contact process 3, the solution having an organic sulfonic acid compound concentration of 1 to 40 mass% is in contact with the cation exchange resin. Claim 5 In claim 1, in the contact process 2, the solution has a space velocity (SV) of 0.3 to 4.9 h -1 A method for manufacturing an organic sulfonic acid compound, wherein the compound comes into contact with the anion exchange resin. Claim 6 In claim 1, in the contact process 3, the solution has a space velocity (SV) of 0.3 to 4.9 h -1 A method for preparing an organic sulfonic acid compound in contact with the above-mentioned cation exchange resin.

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