WO2008075770A1

WO2008075770A1 - Aqueous surfactant solution and method for producing the same

Info

Publication number: WO2008075770A1
Application number: PCT/JP2007/074723
Authority: WO
Inventors: Takeshi Yamada; Fumiya Niikura; Hideo Andoh
Original assignee: Lion Corporation
Priority date: 2006-12-21
Filing date: 2007-12-21
Publication date: 2008-06-26
Also published as: MY157731A; JPWO2008075770A1; JP5222733B2

Abstract

Disclosed is an aqueous surfactant solution which is characterized by exhibiting fluidity even at room temperature, and containing 30-70% by mass of a mixture of an α-sulfofatty acid alkyl ester salt and an α-sulfofatty acid disalt, and 1-50% by mass of an unsaturated fatty acid having 10-22 carbon atoms relative to the mixture content. This aqueous surfactant solution is further characterized by having a pH of 3-8. Also disclosed is a method for producing such an aqueous surfactant solution.

Description

Specification

Surfactant aqueous liquid and method for producing the same

Technical field

The present invention relates to a surfactant aqueous solution containing a high concentration α-sulfo fatty acid alkyl ester salt and a method for producing the same.

Background art

[0002] a Sulfonate-based anionic surfactants such as sulfo fatty acid alkyl ester salts have high detergency, good biodegradability, and little impact on the environment. Therefore, they have high performance as detergent materials. In particular, it is often used in powder detergents for clothing.

By the way, the slurry of the anionic surfactant generally increases in viscosity as the concentration of the anionic surfactant increases, and when the concentration becomes about 30 to 40% by mass or more, the anionic surfactant becomes hexagonal. A structure is formed, resulting in a non-flowable gel. When this gel is heated under normal pressure to evaporate the water and concentrated, it will eventually become softer at a temperature of 50 to 100 ° C, the viscosity will decrease, and it will be somewhat fluid in a certain concentration range. It will be in a state with. If the concentration is continued further, the viscosity will rise again and the fluidity will be lost, such as changing to a solid state.

[0003] In such a state where there is no fluidity, there is a transportation cost that makes it difficult to transport by lorry or ship. For this reason, liquid detergents and the like have been particularly difficult to distribute overseas.

Therefore, Patent Document 1 describes that a high-concentration anionic surfactant and a sulfonic acid of an unsaturated fatty acid polyalkylene alkyl ester are added to the high-concentration anionic surfactant for the purpose of improving the high-viscosity, flowability and gelation upon dilution. Examples of adding salts or α-sulfo fatty acid polyalkylene alkyl ester salts are described.

Patent Document 2 includes a noion surfactant, a fatty acid containing 12 to 18 carbon atoms, an alkyl sulfate containing 12 to 18 carbon atoms, an unsaturated fatty acid sulfonate, and water. A concentrated aqueous surfactant mixture containing liquid and fluid is described. Patent Document 3 describes an example in which an unsaturated fatty acid glycerin ester is added as a viscosity reducing agent for the purpose of improving the fluidity of an alkyl sulfate paste.

Patent Document 1: JP-A-10-17898

Patent Document 2: Japanese Patent Publication No. 6-509133

Patent Document 3: Japanese Patent Publication No. 6-501726

[0004] However, in examples such as Patent Documents 1 to 3, although a viscosity reduction and fluidity improvement effect are observed at 40 ° C or higher, those effects are sufficiently achieved at room temperature, for example, about 25 to 30 ° C. There were times when it was not demonstrated in minutes. For this reason, an aqueous liquid containing an anionic surfactant, particularly an a-sulfo fatty acid alkyl ester salt at a high concentration, is usually in a poor fluid state at room temperature.

[0005] The present invention has been made in view of the above circumstances, and provides an aqueous surfactant liquid that exhibits fluidity even at room temperature and contains a high concentration α-sulfo fatty acid alkyl ester salt, and a method for producing the same. For the purpose.

Disclosure of the invention

Problems to be solved by the invention

[0006] As a result of intensive studies, the present inventors have found that the above problem can be solved by allowing an α-sulfo fatty acid alkyl ester salt and an α-sulfo fatty acid di salt to coexist with an unsaturated fatty acid. The headline and the present invention were completed.

That is, the aqueous surfactant liquid of the present invention comprises 30 to 70% by mass of a mixture of α-sulfo fatty acid alkyl ester salt and α-sulfo fatty acid di-salt; and! To 50% by mass based on the content of the mixture. It contains an unsaturated fatty acid having 10 to 22 carbon atoms, and ρ is 3 to 8.

Furthermore, it is preferable to contain an alcohol having 1 to 3 carbon atoms of 30% by mass or less based on the content of the mixture.

Means for solving the problem

[0007] Further, the method for producing the aqueous surfactant liquid according to the present invention is such that the mixture of α-sulfo fatty acid alkyl ester salt and α-sulfo fatty acid di-salt is 30 to 70% by mass and has 10 to 22 carbon atoms. So that the sum of the fatty acids is from! To 50% by weight, based on the content of the mixture; Is characterized by mixing α-sulfo fatty acid alkyl ester and unsaturated fatty acid and adjusting ρΗ to 3-8.

Furthermore, it is preferable to mix an alcohol having 1 to 3 carbon atoms of 30% by mass or less with respect to the content of the mixture.

Note that ρΗ is a measured value at a temperature of 50 ° C.

The invention's effect

[0008] According to the present invention, it is possible to provide an aqueous surfactant solution that exhibits fluidity even at room temperature and contains a high concentration α-sulfo fatty acid alkyl ester salt and a method for producing the same. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The aqueous surfactant liquid of the present invention comprises a mixture of α-sulfo fatty acid alkyl ester salt and α-sulfo fatty acid di-salt (hereinafter referred to as “MES salt”, α-sulfo fatty acid alkyl ester salt, and α-sulfo fatty acid alkyl ester of acid type). “MES”, a Sulfo fatty acid di-salt is sometimes referred to as “di-salt”) and unsaturated fatty acid having 10 to 22 carbon atoms, and has a pH of 3 to 8.

<a Mixture of Sulfo Fatty Acid Alkyl Ester Salt and α Sulfo Fatty Acid Di Salt> As the MES or MES salt used in the present invention, an α sulfo fatty acid alkyl ester or salt thereof generally proposed as an anionic surfactant Can be used. The α-sulfo fatty acid alkyl ester or salt thereof preferably used in the present invention includes a compound represented by the following general formula (I) (hereinafter referred to as α-sulfo fatty acid alkyl ester or salt (I)! ).

[0011] [Chemical 1]

Ο

R ¹ — CH— C II— Ο— R ₂ ² · · · (I)

S0 ₃ M

[Wherein R ¹ represents a linear or branched alkyl group or alkenyl group, R ² represents a linear or branched alkyl group, M represents a counter ion (sodium, potassium, etc. Alkaline metals, alkaline earth metals such as calcium, ammonium, alkanolamines such as ethanolamine, or hydrogen). ]

[0012] The alkyl group of R ¹ may be linear or branched, and preferably has 6 to 22 carbon atoms, more preferably 10 to 18 carbon atoms; preferable.

The alkenyl group for R ¹ may be linear or branched, and preferably has 6 to 22 carbon atoms, more preferably 10 to 18 carbon atoms, and more preferably 18 carbon atoms.

R ¹ is preferably an alkyl group. That is, the α-sulfo fatty acid alkyl ester or a salt thereof is preferably an α-sulfo saturated fatty acid alkyl ester or a salt thereof.

The alkyl group of R ² may be linear or branched, and preferably has from 3 to 3 carbon atoms, more preferably 1 or 2.

Any counter ion of the cocoon may be used as long as the compound represented by the general formula (I) forms a water-soluble salt. Examples of the water-soluble salt include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, and alkanolamine salts such as ammonium salt and ethanolamine salt. In the case of α-sulfo fatty acid alkyl ester, Μ represents hydrogen.

[0013] Further, the fatty acid of MES used in the present invention has 12, 14, 16 or 18 carbon atoms.

Here, when the carbon chain length of different MES fatty acids is single, the range in which the fluidity of the aqueous liquid is maintained becomes narrow. For example, if the MES fatty acids have a single carbon number of 16 and are single, the flow effect is exhibited when the MES concentration is in the range of 30-50% by mass.

The reason for this is thought to be that when the carbon chain length of the fatty acid of MES is single, it becomes easier to form a liquid crystal structure.

In addition, when multiple MESs with different carbon chain lengths are mixed, the range of MES concentrations that maintain the fluidity of the aqueous liquid is wider than when MESs with the same carbon chain length are mixed. For example, if the MES fatty acid has a carbon number of 16/18 = 80/20, the MES concentration is 30-55 mass%, and if the MES fatty acid has a carbon number of 16/18 = 60/40, the MES concentration is 30- 60% by mass, MES fatty acid carbon number is 14/16 = 70/30, MES concentration is 3 The fluidity of the aqueous liquid is maintained at 0 to 60% by mass.

The reason for this is thought to be that when MESs with different carbon chain lengths are included, the MES has a more regular crystal alignment than in the case of a single one, and forms a hexagonal liquid crystal.

This hexagonal phase exists in a liquid micelle state where the force S and MES concentrations vary depending on the carbon chain length ratio of MES, from 0 to 20 and 30%, and from around 20 and 30%. A gel-like, non-flowable hexagonal phase appears up to 0, 70%. Therefore, the key to MES production is to remove the difficult-to-operate hexagonal phase concentration range.

[0014] The di-salt is a by-product obtained in the process of producing the MES salt as described later, and is represented by the following general formula (II).

[0015] [Chemical 2]

[Wherein, R ¹ and M are the same as R ¹ and M in the above formula (I), respectively. ]

[0016] The content of the mixture of the MES salt and di-salt in the surfactant aqueous liquid of the present invention is 30 to 70% by mass, preferably 30 to 60% by mass, based on the total mass of the surfactant aqueous liquid. More preferred is 30-50% by mass. If the content of the mixture of MES salt and di-salt is less than 30% by mass, the economic effect in transportation and storage will be insufficient because the content of MES salt is low. On the other hand, when the content of the mixture of MES salt and di-salt exceeds 70%, the fluidity of the aqueous surfactant solution is lowered, and it becomes difficult to maintain the fluidity at room temperature, for example, 30 ° C.

[0017] Note that the MES salt and di-salt are those in which the compound M represented by the general formulas (I) and (II) is an alkali metal such as sodium or potassium, an alkaline earth metal such as calcium, or ammonium. This refers to those substituted with alkanolamines such as hum and ethanolamine, and does not include those substituted with hydrogen.

In addition, MES salts and di-salts with a pH of 3 to 8 are composed of an alkaline salt and hydrogen as the counter ion of M. Force that can be a mixture of substituted S, M When the amount of unsaturated fatty acid added to a mixture of MES salt and di-salt is calculated, all counter ions of M are replaced with alkaline salt (Ie, the molecular weight of the MES salt required for AI measurement described below is assumed to be 100% salt). When the counter ion of M consists of a plurality of salts, the content of each salt can be measured, and the molecular weight of the MES salt can be determined from the ratio.

[0018] <Unsaturated fatty acid>

The unsaturated fatty acid has 10 to 22 carbon atoms, preferably 16 to 20 carbon atoms, and more preferably 18 carbon atoms.

The unsaturated fatty acid may have one unsaturated bond or two or more unsaturated bonds. Such unsaturated fatty acids include force proleic acid, 9-undecylenic acid, 10-undecylenic acid, 2 lauroleic acid, lindenoleic acid, 5 lauroleic acid, 11 lauroleic acid, zudic acid, 5 myristoleic acid, myristoleic acid, 2 palmitoleic acid, 7 palmitoleic acid, zomarinic acid, trans-9-palmitoleic acid, petroselinic acid, petroselinic acid, oleic acid, linolenolic acid, linolenic acid, elaidic acid, basenic acid, codoic acid, gondoic acid, trans Examples thereof include gondonic acid, gallic acid, and brassic acid, and oleic acid, linoleic acid, and linolenic acid are particularly preferable.

The above unsaturated fatty acids can be used alone or in combination of two or more.

The unsaturated fatty acid used in the present invention is represented by R ³ —COOH (R ³ is an unsaturated, linear or branched hydrocarbon group having 9 to 21 carbon atoms), and has surface activity. If it is acidic in the aqueous agent solution, the aqueous surfactant solution can exhibit fluidity. Therefore, even if it is an alkaline and solid carboxylate, it can be used as the unsaturated fatty acid of the present invention if it is acidified in the aqueous surfactant solution by adjusting the pH. From the viewpoint of operation during the production of aqueous liquids, acidic and liquid unsaturated fatty acids are preferred.

[0019] The content of the unsaturated fatty acid in the aqueous surfactant solution of the present invention is from! To 50% by mass, preferably from 3 to 20% by mass, based on the content of the mixture of the MES salt and di-salt. 5 to 20% by mass is more preferable. Unsaturated fatty acid content relative to MES salt and di-salt mixture content When the force is less than mass%, the effect of the present invention is sufficiently obtained. On the other hand, if the unsaturated fatty acid content exceeds 50% by mass with respect to the content of the mixture of MES salt and di-salt, the effect reaches its peak, and the upper limit of MES salt that can be incorporated into the surfactant aqueous solution is lowered. Therefore, it is not economically preferable. Therefore, the content of unsaturated fatty acid is optimally 5 to 20% by mass with respect to the content of the mixture of MES salt and di-salt, and excellent fluidity at 25 to 30 ° C, particularly 30 ° C. Preferred to have! / ,.

[0020] <Optional component>

The aqueous surfactant liquid of the present invention preferably further contains an alcohol having 1 to 3 carbon atoms. Alcohol is not an essential component, but the inclusion of alcohol reduces the viscosity of MES and further improves the fluidity of the aqueous surfactant liquid at 30 ° C.

The alcohol may be a monohydric alcohol or a polyhydric alcohol. Examples of monohydric alcohols having 1 to 3 carbon atoms include methanol, ethanol, n-propanol and isopropanol. Examples of the polyhydric alcohol having 1 to 3 carbon atoms include ethylene glycol and propylene glycol.

As alcohol, monohydric alcohol is preferable, and ethanol and isopropanol are particularly preferable. The above alcohols can be used singly or in combination of two or more.

When the alcohol is added to the surfactant aqueous liquid of the present invention, the content thereof is 30% by mass or less with respect to the content of the mixture of the MES salt and the di-salt, and 20% by mass or less is preferable 10% by mass. % Or less is more preferable. Even if the alcohol content exceeds 30% by mass with respect to the content of the mixture of MES salt and di-salt, the effect reaches its peak, and the upper limit of MES salt that can be added to the surfactant aqueous solution is lower. Is not preferable.

[0021] In addition to the above, the aqueous surfactant solution of the present invention is further influenced by the effects of pH adjusters, preservatives, antioxidants and metal ions described later (decomposition and color tone of surfactants) as necessary. If necessary, a chelating agent or the like may be added and blended as necessary.

Examples of the antioxidant include dibutylhydroxytoluene (BHT), isopropyl taenoate, ascorbic acid, tocopherol, sodium erythorbate and the like. Examples of the chelating agent include ethylenediamine tetraacetate, kenate, methylglycine diacetate, and tritrimethyl triacetate.

[0022] <pH characteristics>

The surfactant aqueous liquid of the present invention contains a balanced amount of water in addition to the components described above. The “balance amount” in the present invention means the content of water in the aqueous surfactant liquid adjusted so that the total content of each component other than water and water is 100% by mass.

[0023] The aqueous surfactant solution has a pH (measurement temperature: 50 ° C) of 3 to 8, preferably 4 to 7, more preferably 4 to 6. A pH below 3 is not preferred because MES and MES salts deteriorate under strong acidic conditions. On the other hand, when the pH exceeds 8, as the alkalinity increases, the liquid unsaturated fatty acid becomes a solid salt, so that the fluidity of the aqueous surfactant liquid decreases. Therefore, when the pH of the aqueous surfactant liquid is 3-8, it is preferable because it has excellent fluidity at 25-30 ° C, especially 30 ° C.

[0024] The pH of the liquid composition can be adjusted, for example, by blending a pH adjuster.

The pH adjuster is not particularly limited and can be appropriately selected according to the purpose. For example, hydrochloric acid, dilute hydrochloric acid, sulfuric acid, dilute sulfuric acid, citrate, glycine, succinic acid, acetic acid, tartaric acid, D-tartaric acid, lactic acid , Glacial acetic acid, fumaric acid, propionic acid, maleic acid, DL-malic acid, aspartic acid, glutamic acid, adipic acid, darconic acid, boric acid, valeric acid, butyric acid, isobutyric acid, methylbutyric acid, sodium hydroxide, water Examples include potassium oxide, magnesium hydroxide, and sodium hydrogen carbonate. Among these, sodium hydroxide is preferable when adjusting pH by mixing a sulfonic acid slurry of MES and an unsaturated fatty acid. On the other hand, when a slurry of a neutralized product of MES (ie, MES salt) and an unsaturated fatty acid are mixed, sulfuric acid and citrate are preferred as pH adjusting agents if pH adjustment is necessary. The above pH adjusters can be used alone or in combination of two or more.

[0025] <Fluidity>

The aqueous surfactant liquid of the present invention preferably has fluidity at 25 to 30 ° C.

Whether the aqueous surfactant liquid is “fluid” or not is determined by placing the aqueous surfactant liquid in a glass bottle and placing it under a temperature condition of, for example, 30 ° C. and tilting the glass bottle 90 degrees. It can be evaluated by the time from when the aqueous activator moves through the glass bottle until the upper surface becomes horizontal.

The aqueous surfactant liquid of the present invention is, for example, an aqueous slurry of a predetermined amount of a mixture of MES salt and di-salt, or MES, a predetermined amount of unsaturated fatty acid having 10 to 22 carbon atoms, and other optional ones as necessary. It can be produced by adjusting the pH to 3 to 8 with a pH adjusting agent after adding and mixing the components or simultaneously with mixing.

As an aqueous slurry of a mixture of MES salt and di-salt, or MES, a commercially available product may be used, or a product produced by a production method as described later may be used.

The concentration and temperature of the MES salt in the aqueous slurry to which the unsaturated fatty acid having 10 to 22 carbon atoms is added are such that the aqueous slurry is fluid when mixed with the unsaturated fatty acid under the temperature conditions at the time of mixing. It is preferable that the concentration and the temperature be such that the composition has a softness that can be stirred. When the aqueous slurry force S is applied, the unsaturated fatty acid having 10 to 22 carbon atoms is easily dispersed in the aqueous slurry, and the fluidity at 25 to 30 ° C, particularly 30 ° C is maintained. It is fully demonstrated.

Mixing is a batch-type kettle, which can be performed using a stirrer that supports high viscosity. A continuous online mixer installed on the way with recycling pipes (trade name “Mildaichi”, manufactured by Ebara Corporation) ), Homomixer (for example, manufactured by Primix Co., Ltd.), centrifugal centrifugal pump (for example, manufactured by Shin Nippon Machinery Co., Ltd.), static tube mixer (trade name "Static Mixer", manufactured by Noritake Company Limited) , Manufactured by Kenix Co., Ltd.) etc.

[A Method for Producing Sulfo Fatty Acid Alkyl Ester or its Salt]

The MES salt can be obtained by sulfonating a fatty acid alkyl ester to obtain a sulfonated product, and then aging and neutralizing the sulfonated product. For example, the above MES or MES salt (I) can be obtained with the ability S to obtain a fatty acid alkyl ester represented by the following general formula (III) as a raw material.

[0028] [Chemical 3]

[Wherein, R ¹ and R ² are the same as R ¹ and R ² in the above formula (I), respectively. ]

[0029] Specific examples of fatty acid alkyl esters include animal fats such as beef tallow and fish oil lanolin; plant fats derived from coconut oil, palm oil, soybean oil, etc .; from the oxo method of α-olefin Examples include derived synthetic fatty acid alkyl esters.

More specifically, methyl dodecanoate, ethyl dodecanoate or propyl dodecanoate; methyl stearate, ethyl stearate or propyl stearate; hardened fish oil fatty acid methyl, hardened fish oil fatty acid ethyl or hardened fish oil fatty acid propyl; palm oil fatty acid methyl Examples include chill, palm oil fatty acid ethyl, or palm oil fatty acid propyl; palm kernel oil fatty acid methyl, palm kernel oil fatty acid ethyl, or palm kernel oil fatty acid propyl.

Any one of these fatty acid alkyl esters may be used alone, or two or more thereof may be used in combination.

[0030] The fatty acid alkyl ester preferably has an iodine value of 0.5 or less, more preferably 0.1 or less. The lower the iodine value, the more effectively the coloration in the sulfonation process can be reduced and the color tone of the resulting MES or MES salt becomes better.

As the fatty acid alkyl ester, in particular, a saturated fatty acid alkyl ester (for example, ^{one in} which R ¹ in the formula (III) is an alkyl group) is preferably used.

[0031] Hereinafter, an example of a method for producing an MES salt will be described more specifically.

(Sulfonation process)

This is a step of sulfonating fatty acid alkyl ester as a raw material with gaseous sulfuric anhydride.

A known method can be used for sulfonation of the fatty acid alkyl ester. For example, thin film type sulfonation method, tank type sulfonation method, etc. can be employed.

When the fatty acid alkyl ester is brought into contact with gaseous sulfuric anhydride, SO is first inserted into the alkoxy group portion of the fatty acid alkyl ester to produce a SO 1 molecule adduct.

3 3

Next, SO is inserted into the α-position of the SO 1 molecule adduct to produce an SO 2 molecule adduct.

3 3 3

Then, SO is released from the alkoxy group part of the SO 2 molecule adduct, and a It is thought that acid alkyl ester (MES, M in the above general formula (I) is hydrogen) is formed.

[0032] Examples of the sulfonated gas include SO gas containing SO, fuming sulfuric acid, and the like.

3 3

SO gas is preferred.

Three

As the sulfonated gas, in particular, dehumidified air so that the SO concentration is 1 to 40% by volume

Three

A sulfonated gas diluted with an inert gas such as nitrogen or nitrogen is preferred. SO concentration

When it is 3% by volume or more, the volume of the sulfonated gas falls within an appropriate range, and the capacity of the apparatus used for sulfonation can be reduced. If it is 40% by volume or less, an excessive sulfonation reaction is difficult to occur, so that a by-product is difficult to be produced, and the color tone of the product is also good.

In particular, in order to suppress color tone deterioration of α-sulfo fatty acid alkyl ester, the SO concentration in the sulfonated gas is preferably 1 to 30% by volume.

Three

The amount of the sulfonated gas used is preferably 1.0 to 2.0 times mole amount, more preferably 1.0 to 1.7 times mole amount, particularly preferably the amount of the fatty acid alkyl ester used as a raw material. Is 1. 05-1. 5 times the molar amount. 1. Sulfonation reaction proceeds sufficiently when the amount is more than 0 times the molar amount, and excessive sulfonation reaction hardly occurs when the amount is less than 2.0 times the molar amount. Moreover, the color tone of the product is also good.

[0033] The sulfonation of MES may be carried out by dispersing a coloring inhibitor described below in the raw material.

As the coloring inhibitor, for example, organic acid salts and inorganic sulfates can be used, and inorganic sulfates are preferably used. Among organic acid salts and inorganic sulfates, monovalent metal salts are preferred.

Examples of the metal constituting the monovalent metal salt include alkali metals such as sodium, potassium, and lithium.

Examples of the organic acid salt include sodium formate, potassium formate, and sodium acetate.

The inorganic sulfate is preferably a monovalent metal salt and a powdered inorganic salt, and examples thereof include sodium sulfate, potassium sulfate, and lithium sulfate. Inorganic sulfate is a coloring inhibitor. Since it is a low-cost and high-efficiency component, it is a component that is blended in detergents. Therefore, when using the MES salt in detergent applications, it is preferable not to remove the inorganic sulfate in the MES salt.

The average particle size of the coloring inhibitor is preferably 250 m or less, more preferably 100 m or less. During the reaction, the color inhibitor, for example, inorganic sulfate, is hardly dissolved in the raw material liquid phase so that the surface thereof is slightly dissolved, and is dispersed in the raw material liquid phase. Therefore, the smaller the average particle diameter, the larger the contact area between the coloring inhibitor and the raw material liquid phase, and the dispersibility of the coloring inhibitor particles in the raw material liquid phase is improved, thereby further enhancing the coloring suppression effect. it can. The addition amount of the coloring inhibitor is preferably 30% by mass or less, more preferably 0.5 to 20% by mass, and particularly preferably 3 to 20% by mass with respect to 100% by mass of the fatty acid alkyl ester as a raw material. . If the addition amount of the coloring inhibitor exceeds 30% by mass, the effect of inhibiting coloring is saturated, which is not preferable.

[0034] (Aging process)

In this sulfonation, the reaction proceeds rapidly until the formation of the above-mentioned SO 2 molecule adduct.

Three

The SO force from the SO 2 molecule adduct is desorbed from the SI molecule and becomes a MES.

3 3

Therefore, it is necessary to age.

Here, “aging” means holding the reaction product at a predetermined aging temperature for a predetermined time. The aging temperature is 70 to 100 ° C, preferably 80 to 90 ° C. When the temperature is 70 ° C or higher, the reaction proceeds rapidly. When the temperature is 100 ° C or lower, the product is hardly colored. The aging reaction time is 1 to 120 minutes, preferably 30 to 90 minutes.

[0035] (Esterification process)

Esterification is performed by adding alcohol to the reaction product after the aging step.

This esterification step is carried out as necessary but not essential.

If SO 2 molecule adduct remains in the reaction product, esterify with alcohol

Three

As a result, the elimination of SO introduced into the alkoxy group is further promoted, and the MES

Three

The degree is improved.

The alcohol used in the esterification step is preferably one having 1 to 3 carbon atoms, particularly the carbon of the alcohol residue of the starting fatty acid alkyl ester (eg, O—R ² in formula (III)). Those equal to the number are preferred. For example, when a fatty acid alkyl ester having 1 to 3 carbon atoms in the general formula (III) is used, the alcohol used in the esterification step preferably has 1 to 3 carbon atoms.

The reaction temperature is preferably 50 to 100 ° C, more preferably 50 to 90 ° C. The reaction time is preferably 5 to 120 minutes.

[0036] (Neutralization process)

Next, a neutralization step of neutralizing the reaction product containing MES obtained by the aging or esterification is performed. This gives you the power to obtain MES salt.

Neutralization can be performed by adding an alkali to the reaction product.

According to this method, the alkali used at this time is preferably used as an aqueous solution, whereby a paste of MES salt can be obtained.

Examples of the aqueous alkali solution include aqueous solutions of alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates, alkaline earth metal hydroxides, alkanolamines such as ammonia and ethanolamine, and the like. .

[0037] If the reaction solution is strongly alkaline, the ester bond of the MES salt tends to be cleaved! /. When the ester bond is cleaved, a by-product such as a di-salt represented by the general formula (II) is generated. Therefore, the MES salt is obtained in a mixture with the di-salt.

By the way, since di-salt hardly contributes to cleaning performance, it is desirable to suppress the by-product. Therefore, neutralization is preferably performed under acidic or weak alkaline conditions (pH 4 to 9), and more preferably under acidic or neutral conditions (pH 4 to 7).

Furthermore, after neutralizing a part of the reaction product obtained in the aging step or the esterification step in advance, the obtained neutralized product and an unneutralized sulfonated product are mixed, and the mixture is mixed. Therefore, it is preferable to neutralize under acidic conditions. Thereby, cleavage of the ester bond and alkali by-product can be effectively suppressed.

The neutralization temperature is preferably 30 to 140 ° C, more preferably 40 to 70 ° C.

[0038] The concentration of the aqueous alkali solution used for neutralization varies depending on the type of alkali used, preferably about 2 to 50 mass%, more preferably 15 to 50 mass%. If the content is 50% by mass or less, hydrolysis of the produced MES salt can be suppressed. Alkaline water When the concentration of the liquid is 2% by mass or more, it is easy to adjust the MES salt content in the resulting neutralized product. The neutralized product obtained by the production method as described above, that is, the aqueous slurry of MES salt is usually in the form of a paste. The smaller the MES salt content, the lower the viscosity, and the higher the content, the higher the viscosity. There is. Therefore, the viscosity of the aqueous slurry can be adjusted by adjusting the content of the MES salt in the neutralized product.

[0039] (Bleaching process)

In the above production method, if necessary, the MES salt may have a color tone close to white or before or after the neutralization step described above! /.

Examples of the treatment for making the color tone close to white include a whitening treatment using a bleaching agent such as hydrogen peroxide. Such treatment may be performed before the neutralization step or after the neutralization step.

[0040] [Method for producing surfactant aqueous liquid]

Three typical methods for producing an aqueous surfactant liquid are shown below.

(Production Example 1; Production method of adjusting pH by mixing MES and unsaturated fatty acid)

The MES bleached product obtained above (sulfonated, esterified and then bleached sulfonic acid), the above unsaturated fatty acid and water, and a mixture of MES salt and di-salt is 30 to 70% by mass. A saturated fatty acid is mixed so as to be 1 to 50% by mass with respect to the content of the mixture to prepare a blend, and the pH is adjusted to 3 to 8 at 50 ° C with the above pH adjuster. The preparation temperature is not necessarily 50 ° C as long as the above composition is in a fluid state and can be uniformly dispersed.

In this method, an aqueous surfactant solution containing a MES salt is finally obtained. Therefore, the blending amount of MES in this method shall be indicated by the final mixture of MES salt and di-salt. That is, the blending amount of MES is determined by calculating so that the content of the mixture of MES salt and di-salt in the surfactant aqueous solution is 30 to 70% by mass.

Similarly, the amount of unsaturated fatty acid is also determined by calculating 1 to 50% by mass with respect to the finally obtained mixture of MES salt and di-salt.

[0041] (Production Example 2; Production method of adjusting pH by mixing a mixture of MES salt and di-salt and unsaturated fatty acid) A mixture of the MES salt and di-salt obtained above (neutralized sulfonic acid neutralized after sulfonation, esterification and bleaching treatment), the above unsaturated fatty acid and water, and the mixture is 30 ~ 70% by mass, blended so that the unsaturated fatty acid is 1-50% by mass with respect to the content of the above mixture to make a blend, and with the above pH adjuster, the pH is adjusted to 3-8 at 50 ° C. Prepare. The preparation temperature is not necessarily 50 ° C as long as the above composition is in a fluid state and can be uniformly dispersed.

[0042] (Production Example 3; Production method of adjusting pH by mixing a mixture of MES salt and di-salt and unsaturated fatty acid)

The mixture of MES salt and di-salt obtained above (neutralized sulfonic acid that was bleached after sulfonation, esterification and neutralization), the above unsaturated fatty acid and water were mixed into 30 ~ 70% by mass, blended so that unsaturated fatty acid is 1-50% by mass with respect to the content of the above mixture to make a blend, and with the above pH adjuster, it becomes pH 3-8 at 50 ° C Prepare to. The preparation temperature is not necessarily 50 ° C as long as the above composition is in a fluid state and can be uniformly dispersed.

[0043] The MES salt-containing product obtained by the production method as described above contains by-products such as the above-mentioned di-salts in addition to the MES salt itself.

By-products include the above-mentioned di-salts, methyl sulfate, ethyl sulfate, pyl sulfate, lower intermediate carboxylic acids or their esters, ketones, aldehydes and other organic substances; sodium sulfate and other inorganic substances Is mentioned.

[0044] Among the above-mentioned by-products, the di-salt has a function as a surfactant, although its function is lower than that of the MES salt.

Therefore, in the MES salt-containing product produced as described above, the active ingredient (AI) content as a surfactant is determined as the content of a mixture of MES salt (pure) and di-salt.

Yes

The AI content in the MES salt-containing product is preferably 35 to 90% by mass, more preferably 60 to 90% by mass, preferably 10 to 90% by mass with respect to the total mass of the MES salt-containing product. preferable. When it is 10% by mass or more, production efficiency is improved, and when it is 90% by mass or less, handling properties are excellent. [0045] As described above, the surfactant aqueous liquid of the present invention comprises 30-70% by mass of a mixture of α-sulfo fatty acid alkyl ester salt and α-sulfo fatty acid di-salt, which is a cation surfactant! It is contained in a high content and has a strength of 25 to 30 ° C.! /, And it is fluid under the temperature conditions of room temperature. Therefore, transportation by lorry, ship, etc. is easy, and transportation costs can be reduced. In addition, it is expected that the use of a-sulfo fatty acid alkyl ester salts will be further expanded because it can be easily applied to liquid detergent aqueous solutions.

Example

[0046] The ability to explain the present invention in more detail with reference to the following examples The present invention is not limited to these examples. In the examples, “%” indicates mass% unless otherwise specified. Hereinafter, α-sulfo fatty acid methyl ester salt may be abbreviated as MES salt, and α-sulfo fatty acid dinatrium salt may be abbreviated as di-salt.

The measurement methods used in the following examples and comparative examples are as follows.

[0047] [Method of measuring AI (mixture of MES salt and di-salt) content]

About 0.3 g of the sample is accurately weighed into a 200 ml volumetric flask, and ion-exchanged water (distilled water) is added up to the marked line and dissolved with ultrasound to make the test solution. After dissolution, cool to approximately 25 ° C, take 5 ml of this solution into a titration bottle with a whole pipette, add 25 ml of MB (methylene blue) indicator and 15 ml of black mouth form, and add another 0.004 mol / l benzethonium chloride solution. Add 5 ml and titrate with 0.002 ml / l sodium alkylbenzenesulfonate solution. Titrate each time the bottle is stoppered and shaken vigorously and allowed to stand, with the end point being the same color on both layers against a white plate. Similarly, perform a blank test (the same test as above except that the sample is not used), determine the AI concentration in the test solution from the difference in titration amount, and calculate the AI content (mass%) in the sample from that value. .

[0048] [Measurement method of ratio of di-salt in AI]

Di-salt standard 0.02, 0.05, and 0.1 g are accurately weighed into a 200 ml volumetric flask, and about 50 ml of water and about 50 ml of ethanol are added and dissolved using ultrasound. After dissolution, cool to about 25 ° C, add methanol exactly to the marked line, and use this as the standard solution. After filtering about 2 ml of this standard solution using a 0.45 πι chromatodisc, perform high-performance liquid chromatography under the following measurement conditions to create a calibration curve from the peak area. (High-performance liquid chromatography measurement conditions)

• Equipment: LC 6 A (manufactured by Shimadzu Corporation)

• Column: nucleosil 5SB (manufactured by GL Sciences)

• Column temperature: 40 ° C

• Detector: Differential refractive index detector RID— 6 A (manufactured by Shimadzu Corporation)

• Mobile phase: 0.7% sodium perchlorate in H 2 O / CH 1/4 = 1/4 solution

twenty three

• Direct flow: 1. OmL / min

• Injection amount: 100

[0049] Next, about lg of the sample is accurately weighed into a 200 ml volumetric flask, about 50 ml of water and about 50 ml of ethanol are added and dissolved using ultrasonic waves. After dissolution, cool to about 25 ° C, add methanol exactly to the marked line, and use this as the test solution.

About 2 ml of the test solution was filtered using a 0.45 πι chromatodisc, analyzed by high performance liquid chromatography under the same measurement conditions as above, and using the calibration curve created above, the di-salt concentration in the test solution was analyzed. , Calculate the di-salt content in the sample, and determine the proportion (mass%) of the di-salt in the soot.

[0050] [Method for measuring sodium sulfate content and methyl sulfate content]

Weigh accurately the standard products of mirabilite and methyl sulfate in 0 · 02, 0.04, 0.1 and 0.2g respectively into a 200 ml volumetric flask, add ion-exchanged water (distilled water) to the marked line, Dissolve using waves. After dissolution, cool to about 25 ° C and use this as the standard solution.

About 2 ml of this standard solution is filtered using a 0.45 m chromatographic disk, followed by ion chromatography under the following measurement conditions to create a calibration curve from the peak areas of methyl sulfate and mirabilite standard solution.

(Ion chromatography measurement conditions)

'Device: DX-500 (Nippon Dionex)

• Detector: Electrical conductivity detector CD-20 (Nippon Dionex)

• Pump: IP-25 (Nippon Dionex)

• Oven: LC 25 (Nippon Dionex)

'Integrator: C—R6 A (manufactured by Shimadzu Corporation) • Separation column: AS—12A (Nippon Dionex)

• Guard column: AG-12A (Nippon Dionex)

'Eluent: 2.5 mM Na 2 CO 2 /2.5 mM NaOH / 5% acetonitrile solution

twenty three

• Eluent flow rate: 1.3 mL / min

• Reclaimed liquid: pure water

• Column temperature: 30 ° C

• Loop capacity: 25〃 L

[0051] Next, approximately 0.3 g of the sample is accurately weighed into a 200 ml volumetric flask, ion-exchanged water (distilled water) is added up to the marked line, and dissolved using ultrasound. After dissolution, cool to about 25 ° C and use this as the test solution.

About 2 ml of the test solution was filtered using a 0.45 πι chromatodisc, analyzed by ion chromatography under the same measurement conditions as above, and using the calibration curve created above, the concentration of mirabilite in the sample solution and Obtain the methyl sulfate concentration, and calculate the sodium sulfate content and methyl sulfate content (% by mass) in the sample.

If necessary, calculate the content for soot from the sodium sulfate content and methyl sulfate content in the obtained sample and the soot content obtained above.

[0052] [ρΗ measurement method]

When measuring ρΗ, it shall be performed under the following conditions. Note that rho calibration is performed at 50 ° C.

Five.

(pH measurement conditions)

• Equipment: pH METER MODEL “pH81” (manufactured by Tokyo Glass Instrument Co., Ltd.)

• pH calibration: pH 4, 7, 9 standard buffer (manufactured by Pure Chemical Co., Ltd.) is used.

[0053] Here, main samples used in the following production examples are shown below.

(Unsaturated fatty acid)

.Oleic acid: Pure Chemical Co., Ltd. (grade 1)

• Linoleic acid: manufactured by Kanto Chemical

• Linolenic acid: manufactured by Kanto Chemical Co., Inc.

(alcohol) • Ethanol: Made by Pure Chemical (1st grade)

'Isopronol (IPA): Pure Chemicals (special grade)

[Production Example 1 of Surfactant Aqueous Solution: Mixture of MES salt and di-salt of fatty acid 16, 18 [C16 / C18 = 100/0 (mass ratio)] and unsaturated fatty acid to adjust pH Production method]

(Sulfonation process)

The sulfonation reaction was performed using a continuous film reactor.

Fatty acid methyl ester prepared from palm oil as raw material (16 fatty acid methyl ester (carbon number of R ^{1 in} the above general formula (I): 14, carbon number of R ² : 1, molecular weight: 270) and carbon number) A mixture with 18 fatty acid methyl esters (R ^{1 in} the above general formula (I): 16, carbon number of R ² : 1, molecular weight: 298); C16 / C18 = 100/0 (mass ratio) (Lion A chemical company, molecular weight: 270) was used.

SO gas (sulfonated gas) diluted to 8% by volume with nitrogen gas is fatty acid methyl ester

Three

Supply to 1.2 times moles of raw material (fatty acid methyl ester supply: 162. Og / min, SO supply: 40. Og / min), sulfonation reaction for 30 minutes at 80 ° C reaction temperature The line

Three

I got it.

Thereafter, 3.9% by mass of fine powdered sodium sulfate was added to the produced sulfonic acid, and aging was performed for 30 minutes while maintaining the temperature at 80 ° C.

(Esterification)

Next, 0.18 kg of methanol was added to 6.0 kg of aging sulfonic acid, and esterification was performed at a reaction temperature of 80 ° C. for 30 minutes.

(Neutralization process)

Next, the esterification product is continuously supplied to the neutralizer at 150 g / min, and 27.5% aqueous sodium hydroxide solution is quantitatively supplied at a rate of 62.3 g / min to continuously neutralize. did. The neutralization temperature was controlled at 70 ° C, and the residence time of the neutralized product was 20 minutes. The pH of the obtained neutralized product was 6.0 (measurement temperature: 50 ° C).

(Bleaching process) Next, 0.143 kg of 35% hydrogen peroxide was added with mixing, the temperature was adjusted to 80 ° C. with a jacket, and a bleaching reaction was carried out for 7 hours.

The MES salt thus obtained was a mixture of AI content = 68.0%, sodium sulfate content = 3.3% to AI, methyl sulfate content = 6.7% to AI with di-salt. The proportion of di-salt in AI was 6.2%.

[0055] <Test 1 1: Surfactant aqueous solution containing 35% by mass ^^ 3 salt and di-salt mixture (Sample 1 one;! To 1 20); 30% by mass ^^ 3 salt and di-salt mixture Surfactant aqueous solution containing (sample 1 21); 50% by weight ^^ 3 salt aqueous solution containing salt and di-salt (sample 1 22); 55% by weight ^^ 3 salt and di-salt mixture Surfactant aqueous solution containing (sample 1 23); 75% by weight surfactant aqueous solution containing a mixture of MES salt and di-salt (sample 1 24)>

(Adjustment of surfactant aqueous solution)

Bleached mixture of MES salt and di-salt (AI content = 68.0% by mass) 51.5 g was placed in a 200 mL glass container and heated to about 50 ° C.

Next, while stirring with a nozzle blade, add the unsaturated fatty acid and alcohol in the amount shown in Table 1 (mass% vs. mixture of MES salt and di-salt) and add 10% aqueous sodium hydroxide or 10% aqueous sulfuric acid. Thus, each sample (surfactant aqueous solution) shown in Table 1 was prepared by adjusting the pH shown in the table (measurement temperature: 50 ° C) and finally making a total amount of 100 g with a balanced amount of water.

[0056] (Evaluation of fluidity)

Transfer some of these to a 50 mL lidded glass bottle (35 mm diameter, 60 mm height), hold at 50 ° C overnight (about 10-50 hours), then transfer to a 30 ° C constant temperature bath. After holding in the bath for 1 day, when each glass bottle is tilted 90 degrees (leveled) at a temperature of 30 ° C, the aqueous surfactant solution moves through the glass bottle and the top surface becomes horizontal. Time was measured and evaluated according to the following criteria. The results are shown in Table 1.

As evaluation criteria, ◎: less than 30 seconds, ○: 30 to; less than 180 seconds, Δ: 180 seconds or more to less than 10 minutes, X: 10 minutes or more (solidification).

[0057] [Table 1]

[0058] <Test 1 2: Surfactant aqueous solution containing a mixture of 40% by mass ^^ 3 salt and di-salt>

(Adjustment of surfactant aqueous solution)

A mixture of bleached MES salt and di-salt (AI content = 68.0% by mass) was prepared in the same manner as in Test 1-1 except that 58.8 g was used. In addition, the fluidity of the aqueous surfactant solution was evaluated in the same manner as in Test 1-1 (Result: Table 2).

[0059] (Appearance evaluation)

In addition, the presence or absence of liquid separation of the surfactant aqueous solution and crystal precipitation was evaluated according to the following criteria.

That is, as evaluation criteria for liquid separation, the evaluation was as follows: ○: no separation, X: separation. In addition, as evaluation criteria for crystal precipitation, the evaluation was as follows: ○: no crystal precipitation, X: crystal precipitation (Results: Table 2).

[0060] (Viscosity measurement)

In addition, the viscosity of the surfactant aqueous solution can be measured using a viscometer (BH type for high viscosity manufactured by Toki Sangyo, No.

6 or No. 7 rotor) at a predetermined temperature and 20 rpm for 30 seconds (result: Table 2).

[0061] [Table 2]

Note) Sample: pH 6; Fluidity 'Separability' Crystal precipitation: 30 ° C, observed after 1 day; Viscosity measurement: 5

Measured at 0 ° C, then cooled to 30 ° C and measured

[0062] <Test 1 3: Surfactant aqueous solution containing a mixture of 50% by mass ^^ 3 salt and di-salt>

(Adjustment of surfactant aqueous solution)

It was prepared in the same manner as in Test 1-1 except that 73.5 g of a mixture of bleached MES salt and di-salt (AI content = 68.0% by mass) was used. In addition, the fluidity of the surfactant aqueous liquid was evaluated in the same manner as in Test 1-1. The liquid separation of the surfactant aqueous liquid, the presence or absence of crystal precipitation, and the viscosity were evaluated in the same manner as in Test 1-2. (Results: Table 2).

[0063] [Production Example 2 of Surfactant Aqueous Solution: Mixture of MES Salt and Di Salt of Fatty Acids 16 and 18 [C 16 / C 18 = 90/10 (mass ratio)], and Unsaturated Fatty Acid Manufacturing method to mix and adjust pH]

<Adjustment of MES salt> (Sulfonation process)

The sulfonation reaction is carried out using a tank reactor (10L capacity, jacket cooling, glass with a stirrer

)

Fatty acid methyl ester prepared from palm oil as raw material (16 fatty acid methyl ester (carbon number of R ^{1 in} the above general formula (I): 14, carbon number of R ² : 1, molecular weight: 270) and carbon number) Mixture with 18 fatty acid methyl esters (R ^{1 in} the above general formula (I): 16, carbon number of R ² : 1, molecular weight: 298); C16 / C18 = 90/10 (mass ratio) Lion Chemical 5. Okg (average molecular weight: 272.8) was charged into the reactor, and while stirring, 5% of fine powdered sodium sulfate (average particle size 50 am) was added as a coloring inhibitor. .

While continuing to stir, while maintaining the reaction temperature at 80 ° C by heat removal control, SO gas (sulfonated gas) diluted to 8% by volume with nitrogen gas (1.2 times mole to raw material,

Three

SO conversion value: 1. 76 kg) was blown at a constant speed over 1 hour to carry out sulfonation reaction. So

Three

Thereafter, aging was further performed for 30 minutes while maintaining the temperature at 80 ° C.

(Esterification process)

Next, 180 g of methanol was added to the reactor to carry out esterification. The esterification was carried out at a reaction temperature of 80 ° C and a reaction time of 30 minutes.

(Neutralization process)

Next, the product of the esterification step was continuously supplied to the neutralizer at 154.5 g / min, and a 27.5% aqueous sodium hydroxide solution was quantitatively supplied at a rate of 61.8 g / min. Neutralized continuously. The neutralization temperature was controlled at 70 ° C, and the residence time of the neutralized product was 20 minutes. The pH of the obtained neutralized product was 6.9 (measurement temperature: 50 ° C.).

(Bleaching process)

Next, 6.0 kg of this neutralized product was charged into a stirring tank equipped with a 10 L jacket, and 171.4 g of 35% aqueous hydrogen peroxide was added with mixing to carry out a bleaching reaction. The bleaching reaction was carried out at a bleaching time of 5 hours with the jacket adjusted to a floating temperature of 80 ° C.

The bleached MES salt thus obtained was a mixture of di-salt with AI content = 70.0%, sodium sulfate content = 2.9% vs. AI, methyl sulfate content = 6.6% vs. AI. . The proportion of di-salt in AI was 5.1%. [0064] <Test 2-1: Aqueous surfactant aqueous solution containing a mixture of 40 mass% ^^ 3 salt and di-salt>

(Adjustment of surfactant aqueous solution)

A mixture of bleached MES salt and di-salt (AI content = 70.0% by mass) was prepared in the same manner as in Test 1-1 except that 57.lg was used. Further, the fluidity of the surfactant aqueous liquid was evaluated in the same manner as in Test 1-. The liquid separation of the surfactant aqueous solution, the presence or absence of crystal precipitation, and the viscosity were evaluated in the same manner as in Test 1-2. (Results: Table 3).

[0065] <Test 2-2: Surfactant aqueous solution containing a mixture of 50 mass% ^^ 3 salt and di-salt>

(Adjustment of surfactant aqueous solution)

A mixture of bleached MES salt and di-salt (AI content = 70.0% by mass) was prepared in the same manner as in Test 1-1 except that 71.4g was used and 7 was used. Further, the fluidity of the surfactant aqueous liquid was evaluated in the same manner as in Test 1-. The liquid separation of the surfactant aqueous solution, the presence or absence of crystal precipitation, and the viscosity were evaluated in the same manner as in Test 1-2. (Results: Table 3).

[0066] [Table 3]

Measured at 0 ° C, then cooled to 30 ° C and measured

[Production Example 3 of Surfactant Aqueous Solution; Mixture of MES Salt and Di-Salt with 16 and 18 [C 16 / C 18 = 80/20 (mass ratio) of Fatty Acids] and Unsaturated Fatty Acid Manufacturing method to adjust] <Adjustment of MES salt>

(Sulfonation process)

)

Fatty acid methyl ester prepared from palm oil as raw material (16 fatty acid methyl ester (carbon number of R ^{1 in} the above general formula (I): 14, carbon number of R ² : 1, molecular weight: 270) and carbon number) Mixture with 18 fatty acid methyl esters (R ^{1 in} general formula (I): 16 carbon atoms, R ² carbon atoms: 1, molecular weight: 298); CI 6 / C18 = 80/20 (mass ratio) Lion Preparation was carried out under the same conditions as in Production Example 2, except that Chemical Corporation, average molecular weight: 281.2) was used.

The bleached MES salt thus obtained was a mixture of di-salt with AI content = 69.0%, sodium sulfate content = 3.2% vs AI, methyl sulfate content = 6.0% vs AI. . The proportion of di-salt in AI was 4.7%.

[0068] <Test 3-1: Aqueous surfactant aqueous solution containing a mixture of 40 mass% ^^ 3 salt and di-salt>

(Adjustment of surfactant aqueous solution)

A mixture of bleached MES salt and di-salt (AI content = 70.0% by mass) was prepared in the same manner as in Test 1-1 except that 57.2g was used. In addition, the fluidity of the surfactant aqueous liquid was evaluated in the same manner as in Test 1-1. The liquid separation of the surfactant aqueous liquid, the presence or absence of crystal precipitation, and the viscosity were evaluated in the same manner as in Test 12 (Result: Table 4).

[0069] [Table 4]

Measured at 0 ° C, then cooled to 30 ° C and measured

[0070] <Test 3—2: Surfactant aqueous solution containing a mixture of 45% by weight ^^ 3 salt and di-salt (Sample 2 one;! ~ 2-20); 30% by weight ^^ 3 salt and di-salt Surfactant aqueous solution (sample 2 21) containing 50 wt% ^^ 3 salt and disalt mixture (sample 2-22); 55 wt% ^^ 3 salt and dihydrate Surfactant aqueous solution containing a mixture of salts (Sample 2-23); Surfactant aqueous solution containing a mixture of 75% by weight MES salt and di-salt (Sample 2-24)>

(Adjustment of surfactant aqueous solution)

Prepared in the same manner as in Test 1-1 except that 64.3 g of a mixture of bleached MES salt and di-salt (AI content = 70.0% by mass) was used. In addition, the fluidity of the aqueous surfactant solution was evaluated in the same manner as in Test 1-1 (Result: Table 5).

[0071] [Table 5]

[0072] <Test 3-3: Aqueous surfactant aqueous solution containing a mixture of 50% by mass ^^ 3 salt and di-salt>

A mixture of bleached MES salt and di-salt (AI content = 70.0 mass%) was prepared in the same manner as in Test 1-1 except that 71.4 g was used. In addition, the fluidity of the surfactant aqueous liquid was evaluated in the same manner as in Test 1-1. The liquid separation of the surfactant aqueous liquid, the presence or absence of crystal precipitation, and the viscosity were evaluated in the same manner as in Test 12 (Result: Table 4).

[0073] [Production Example 4 of Aqueous Surfactant Liquid; Mixture of MES Salt and Disalt with 16 and 18 [C 16 / C 18 = 60/40 (mass ratio)] of Fatty Acid, and Unsaturated Fatty Acid Manufacturing method to mix and adjust pH]

<Adjustment of MES salt> (Sulfonation process)

The sulfonation reaction was carried out in a tank reactor (200 L capacity, made of SUS3 16L with jacket cooling / stirring device).

First, fatty acid methyl ester prepared from palm oil as the raw material (16 fatty acid methyl ester (carbon number of R ^{1 in} the above general formula (I): 14, carbon number of R ² : 1, molecular weight: 270)) And a fatty acid methyl ester having 18 carbon atoms (R ^{1 in} the above general formula (I): 16 carbon atoms, R ² carbon number: 1, molecular weight: 298); CI 6 / C18 = 60/40 (mass) Ratio) Made by Lion Chemical Co., Ltd.) 85kg (average molecular weight: 281.2) is charged into the reactor, and while stirring, 5% of fine powdered mirabilite (average particle size 50 am) is added as a coloring inhibitor. did.

While continuing to stir and maintain the reaction temperature at 80 ° C by heat removal control, SO gas (sulfonated gas) diluted to 8% by volume with nitrogen gas 102m ³ (1.2 relative to the raw material)

Three

Double mole, SO equivalent value: 29.0 kg) is blown at a constant speed over 1 hour with a rings spurger

Three

Then, sulfonation reaction was performed. Thereafter, aging was performed for 30 minutes while maintaining the temperature at 80 ° C.

(Esterification process)

Next, 4.5 kg of methanol was added to the reactor to perform esterification. The esterification was carried out at a reaction temperature of 80 ° C and a reaction time of 30 minutes.

(Neutralization process)

Next, the product of the esterification step is continuously fed to the neutralizer at 2.63 kg / min, and 27.5% aqueous sodium hydroxide solution is quantitatively fed at a rate of 1.06 kg / min. , Continuously neutralized. The neutralization temperature was controlled at 70 ° C, and the residence time of the neutralized product was 20 minutes. The pH of the obtained neutralized product was 6.5 (measurement temperature: 50 ° C.).

(Bleaching process)

Next, 82 kg of this neutralized product was charged into a 200 L jacketed stirring tank, and 1.6 kg of 35% hydrogen peroxide solution (corresponding to a pure HO content of 1.0% with respect to the AI content) was added with mixing. Bleaching

twenty two

Reaction was performed. The bleaching reaction was carried out at a bleaching time of 7 hours by adjusting the bleaching temperature to 80 ° C using a jacket.

The bleached MES salt thus obtained has an AI content of 70.0% and a sodium sulfate content. = 3.0% AI, methyl sulfate content = 6.5% AI mixture of di-salts. The proportion of di-salt in AI was 4.8%.

[0074] <Test 4 1: Aqueous surfactant liquid containing a mixture of 40% by mass ^^ 3 salt and di-salt>

(Adjustment of surfactant aqueous solution)

A mixture of bleached MES salt and di-salt (AI content = 70.0 mass%) 57.2 g was placed in a 200 mL glass container and heated to about 50 ° C.

Next, in Table 6 while stirring at a rotation speed of 3000 rpm with a homomixer (made by Tokushu Kika Kogyo Co., Ltd .: Τ · Κ. Robomitas, stirring unit: Τ · ホモ. Add the unsaturated fatty acid and alcohol in the amount shown (% by mass to the mixture of MES salt and di-salt) and add 10% aqueous sodium hydroxide or 10% sulfuric acid to the pH shown in Table 6 (measurement temperature: 50 ° C). Each sample (surface active agent aqueous solution) shown in Table 6 was prepared with a final balance of water and lOOg, and the same evaluation as in Production Example 2 was performed (Result: Table). 6).

[0075] <Test 4 1 2: Surfactant aqueous solution containing a mixture of 50% by mass ^^ 3 salt and di-salt>

Mix the MES salt and di-salt mixture to 71.5 g, add the unsaturated fatty acid and alcohol in the amount shown in Table 6 (mass% vs. MES salt and di-salt mixture), and balance the amount of water. Each sample was prepared in the same manner as in Test 4-1, except that the total amount was adjusted to lOOg, and the same evaluation was performed (Result: Table 6).

[0076] [Table 6]

Measured at 0 ° C, then cooled to 30 ° C and measured

[0077] <Test 4 3: Surfactant aqueous solution containing a mixture of 55% by weight ^^ 3 salt and di-salt (Sample 3-1 to Sample 3-20); 30% by weight of ^^ 3 salt and di-salt Surfactant aqueous solution containing a mixture (Sample 3-21); 60% by weight ^^ 3 Surfactant aqueous solution containing a mixture of salt and di-salt (Sample 3-22); 65% by weight ^^ 3 salt Surfactant aqueous solution containing a mixture of di-salts (Sample 3-1 to Sample 3-20); Surfactant aqueous solution containing a mixture of 75% by weight ^^ 3 salt and di-salt (Sample 3-24)> MES The mixture of salt and di-salt was concentrated and dried at 70 ° C to AI = 89.0%, and then pulverized into fine particles to facilitate dissolution in water. The amount of the fine particles is 61.8 g, and the amount of unsaturated fatty acid and alcohol shown in Table 7 (mass% vs. mixture of MES salt and di-salt) is added, and the total amount is 100 g with a balanced amount of water. Except for adjustment, each sample was prepared and fluidity was evaluated in the same manner as in Test 1-1 (Result: Table 7).

[0078] [Table 7]

[Production Example 5 of Surfactant Aqueous Solution] Mixture of MES salt and di-salt of 16 and 18 [C16 / C18 = 60/40 (mass ratio) of fatty acid] and unsaturated fatty acid to adjust pH Production method]

(Sulfonation process)

First, fatty acid methyl ester prepared from palm oil as a raw material (16 carbon number fatty acid methyl ester (carbon number of R ^{1 in} the above general formula (I): 14, carbon number of R ² : 1, molecular weight: 270 And a fatty acid methyl ester having 18 carbon atoms (R ^{1 in} the above general formula (I): 16 carbon atoms, R ² carbon number: 1, molecular weight: 298); CI 6 / C18 = 60/40 ( (Mass ratio); manufactured by Lion Chemical Co., Ltd. ) 85 kg (average molecular weight: 281.2) was charged into the reactor, and while stirring, 5% of fine powdered sodium sulfate (average particle size 50 am) was added as a coloring inhibitor to the raw material.

Three

(Esterification process)

(Neutralization process)

(Bleaching process)

twenty two

The bleached MES salt thus obtained was a mixture of di-salt with AI content = 70.0%, sodium sulfate content = 1.8% vs. AI, methyl sulfate content = 6.3% vs. AI. . The proportion of di-salt in AI was 4.3%.

(Adjustment of surfactant aqueous solution) A mixture of bleached MES salt and di-salt (AI content = 70.0 mass%) 57.2 g was placed in a 200 mL glass container and heated to about 50 ° C.

Next, in Table 8 while stirring at a rotation speed of 5000 rpm with a homomixer (made by Tokushu Kika Kogyo Co., Ltd .: Τ · Κ.Robomitas, stirring section: Τ · Κ. Add the unsaturated fatty acid and alcohol of the indicated blending amount (mass% vs. MES salt and di-salt) and add 10% aqueous sodium hydroxide or 10% sulfuric acid to the pH shown in Table 8 (measurement temperature: 50 ° C) Each sample (surfactant aqueous solution) shown in Table 8 was prepared by adjusting the total amount to 100 g with a balance amount of water.

[0081] (Evaluation of fluidity)

Transfer some of these to a 50 mL glass bottle with a lid (bottom 35 mm, height 60 mm), hold at 50 ° C overnight (about 10-50 hours), then transfer to a 30 ° C thermostatic bath. After holding in the bath for 3 days, when each glass bottle is tilted 90 degrees under a temperature of 30 ° C, the time when the aqueous surfactant solution moves through the glass bottle and the top surface becomes horizontal is measured. Evaluation was made according to the following criteria. The results are shown in Table 8.

Evaluation criteria are as follows: ◎: less than 30 seconds, ○: 30 to less than 180 seconds, △: 180 seconds or more to less than 10 minutes, X: 10 minutes or more (solidification).

[0082] [Table 8]

[0083] <Test 5—2: Surfactant aqueous solution containing a mixture of 50% by mass ^^ 3 salt and di-salt (Sample 5)

5-23)]

Mix the mixture of MES salt and di-salt to 71.5 g, add unsaturated fatty acid and alcohol in the amount shown in Table 2 (mass% vs. mixture of MES salt and di-salt), and balance the amount of water. Except for adjusting the total amount to 100 g, each sample was prepared and fluidity was evaluated in the same manner as in Test 5-1. The results are shown in Table 9.

[0084] [Table 9Ί

[Production Example 6 of Aqueous Surfactant Liquid; Production Method of Adjusting pH by Mixing MES of Fatty Acids 16 and 18 and Unsaturated Fatty Acid]

20kg of the product (MES) that passed through the sulfonation process and esterification process in Production Example 5 was separated and charged into a 50L jacketed stirring tank, and 35% hydrogen peroxide solution 0.57kg (the pure content of HO with respect to the MES mass) (Corresponding to 1.0%) was added with mixing to carry out a bleaching reaction. Bleaching reaction

twenty two

The bleaching temperature was adjusted to 80 ° C with a jacket and the bleaching time was 3 hours.

When the bleached MES thus obtained was neutralized, the AI content = 69.8%, sodium sulfate content = 1.9% vs. AI, methyl sulfate content = 6.4% vs. AI, and di-salt. mixture It was a thing. The ratio of di-salt in AI was 4.4%. Based on this analysis value, the amount of unsaturated fatty acid and the like added to sulfonic acid (MES) was calculated in terms of the final MES salt and di-salt mixture.

[0086] <Test 6—1: Surfactant aqueous solution containing a mixture of 60% by mass ^^ 3 salt and di-salt (Sample 6-1— 6-23)>

(Adjustment of surfactant aqueous solution)

Bleached MES (AI content = 97.1 mass%) 58.2 g (60. Og if converted to a mixture of MES and di-salts) is placed in a 200 mL glass container and heated to about 50 ° C. Warm up. Next, while stirring at a rotational speed of 5000 rpm with a homomixer (made by Tokushu Kika Kogyo Co., Ltd .: Τ · Κ. Robomitas, stirring part: Τ · ホ. Unsaturated fatty acids and alcohol in the indicated amounts (mass% vs. MES salt and di-salt mixture) were added. Next, the pH (measurement temperature: 50 ° C) shown in Table 10 was adjusted with 10% aqueous sodium hydroxide solution, and finally the total amount was adjusted to 100 g with a balanced amount of water. Each sample shown in Table 10 (surfactant aqueous solution) Liquid) was prepared.

[0087] (Evaluation of fluidity)

The fluidity was evaluated in the same manner as in Test 5-1. The results are shown in Table 10.

[0088] [Table 10]

[Production Example 7 of Surfactant Aqueous Solution] Mixing MES salt and di-salt with 14 and 16 [C14 / C16 = 30/70 (mass ratio)] of fatty acid and unsaturated fatty acid to adjust pH Production method]

(Sulfonation process)

The sulfonation reaction was conducted in a film reactor (made of glass, inner diameter 8 mm, film length 1.5 m).

Fatty acid methyl ester prepared from palm oil as raw materials (14 fatty acid methyl ester (carbon number of R ^{1 in} the above general formula (I): 12, carbon number of R ² : 1, molecular weight: 242)) and charcoal C16 / C16 = 30/70 (mass ratio) Lion Chemical Co., Ltd., a mixture of 16 fatty acid methyl esters with a prime number of 16 (R ^{1 in} general formula (I): carbon number of 1, carbon number: 1, molecular weight: 270) Made by company. ) (Average molecular weight: 261.6) was used.

Supply SO gas (sulfonated gas) diluted to 8% by volume with nitrogen gas while maintaining the reaction temperature at 80 ° C by heat removal control so that it is 1.2 times moles of the raw material (raw material supply)

Three

Supply rate: 157 · Og / min, SO conversion straight: 40 · Og / min)

Three

went. Thereafter, aging was further performed for 30 minutes while maintaining the temperature at 80 ° C.

(Esterification 'bleaching process)

Next, 1.1 kg of methanol was added to 5.5 kg of aged sulfonic acid to carry out esterification. The esterification was carried out at a reaction temperature of 80 ° C.

Next, 0.394 kg of 35% hydrogen peroxide solution was added with mixing to carry out a bleaching reaction. The bleaching reaction was carried out at a bleaching time of 7 hours with the jacket adjusted to a bleaching temperature of 80 ° C.

(Neutralization process)

Next, the product of the esterification step is continuously supplied to the neutralizer at 183.8 g / min, and a 27.5% aqueous sodium hydroxide solution is quantitatively supplied at a rate of 62.3 g / min. , Continuously neutralized. The neutralization temperature was controlled at 70 ° C, and the residence time of the neutralized product was 20 minutes. The pH of the obtained neutralized product was 6.8 (measurement temperature: 50 ° C).

(Concentration process)

Subsequently, it concentrated at 70 degreeC with the evaporator.

The bleached MES salt thus obtained was a mixture of di-salt with AI content = 69.0%, sodium sulfate content = 1.5% vs AI, methyl sulfate content = 4.2% vs AI . The ratio of di-salt in AI was 3.5%.

(Adjustment of surfactant aqueous solution)

It was prepared in the same manner as in Test 1-1 except that 58.0 g of a mixture of bleached MES salt and di-salt (AI content = 69.0% by mass) was used. In addition, the fluidity of the surfactant aqueous liquid was evaluated in the same manner as in Test 1-1. The liquid separation of the surfactant aqueous liquid, the presence or absence of crystal precipitation, and the viscosity were evaluated in the same manner as in Test 1-2 (Result: Table 11). [0091] <Test 7—2: Surfactant aqueous solution containing a mixture of 50 mass% £ 3 salt and di-salt> (Preparation of surfactant aqueous solution)

A mixture of bleached MES salt and di-salt (AI content = 69.0 mass%) was prepared in the same manner as in Test 1-1 except that 72.4 g was used. In addition, the fluidity of the surfactant aqueous liquid was evaluated in the same manner as in Test 1-1. The liquid separation of the surfactant aqueous solution, the presence or absence of crystal precipitation, and the viscosity were evaluated in the same manner as in Test 1-2 (Result: Table 11).

[0092] [Table 11]

Note) Sample: pH 6; Fluidity · Separability · Crystal precipitation: 30 ° C, observed after 1 day; Viscosity measurement: 5

Measured at 0 ° C, then cooled to 30 ° C and measured

[0093] <Prescription example; >

Using Samples 11 and 12, spray-dried particles having the composition shown in Table 12 were obtained.

[0094] [Table 12

[0095] The spray-dried particles shown in Table 12 were dry-mixed with the ingredients shown in Table 13 to obtain a granular detergent composition.

[0096] [Table 13]

The raw materials used are shown below.

• Hydrogen peroxide solution: Pure Chemical Co., Ltd., first grade reagent, aqueous solution containing 35% by mass hydrogen peroxide.

• Carbonated Na: grain ash (manufactured by Soda Ash Japan Co., Ltd.)

• Optical brightener: Chino Pearl CBS— X (Ciba Specialty Chemicals)

• Hydroxylation Na: Flakes, sex soda (manufactured by Tsurumi Soda Co., Ltd.)

• LAS H: Linear alkyl benzene sulfonic acid (manufactured by Lion Corporation, Rypon LH-200) (AV value (mg of potassium hydroxide required to neutralize LAS-H) = 180 · 0) In Fig. 4, the composition is expressed as LAS-Na neutralized with Na hydroxide in the slurry before spray drying.

• STPP: Sodium tripolyphosphate (manufactured by Taiyo Chemical Co., Ltd.)

• Na pyrophosphate: Sodium pyrophosphate (anhydrous) (Phosphorus Chemical Co., Ltd.)

'Silica Na: S50 ° Sodium Silicate No. 1 (Nippon Chemical Industry Co., Ltd.) (SiO 2 / Na 2 O molar ratio = 2

twenty two

.15)

• Polyacrylic acid Na: Aqualic DL—453 (manufactured by Nippon Shokubai Co., Ltd.) (pure content 35% by weight aqueous solution)

• Acrylic acid / maleic acid copolymer Na: Aqualic TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% by weight aqueous solution)

• Nonionic surfactant: Polyoxyethylene alkyl ether (manufactured by Lion Corporation, 12 to 14 carbon atoms of alkyl group, average number of moles of ethylene oxide added 8)

-Zeolite: Type A zeolite (pure 47.5% by mass) (manufactured by Nippon Chemical Industry Co., Ltd.)

• Carbonate K: Potassium carbonate (powder) (Asahi Glass Co., Ltd.)

• Sulphite Na: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.)

• Na sulfate: neutral anhydrous sodium sulfate AO (manufactured by Shikoku Kasei Co., Ltd.)

• Ishizuchi: Fatty acid sodium with 12 to 18 carbon atoms (67% pure by weight, titer 40 to 45 ° C, molecular weight 289)

Enzyme 1: Sabinase 18T (Novozymes Japan Co., Ltd.)

• Bleach particles: Sodium percarbonate (Mitsubishi Gas Chemical Co., Ltd., SPC-D)

• Bleach activator particles: Bleach activation described in Examples of JP-A-2007-153596 Granule G

• Perfume 1: A perfume composition consisting of the following:

Decanal 0.5%, Otananal 0.3%, Hexylcinnamic aldehyde 10.0%, Dimethenolevenno Recanolevi 'Ninole Sete 卜 8.0%, Lemon 3.0%, Liria Inore 6.0%, Lila Monole 2.0%, Linaronore 5.0%, F: Nino Ethinole Noreno Monole 7.5%, Tonalide 2.0%, o-tert butylcyclohexyl acetate 3.0%, Galaxolide Benzylbenzoate 2. 0% Rinasu one Honoré 2.5%, Gerani old Nore 1.0 ^_0/0, shea Bok Roneronore 2.0%, di Yasumoranji 2 · 0%, methyl dihydro Jiyasu antimonate 5.0%, Tabineoru 1.0 %, main Chinoreyonon 3.0%, Sechinoresedoren 5.0%, Remo two Bok Rinore 1.0 ^_0/0, Funoreite Bok 1.0 ^_0/0, Oribon 1, 5%, benzoin 1 2.0%, cis one 3 Hexenol 0.5%, Coumarin 2.0%, Damasenone 0.2%, Damascon 0.3%, Helicopter Narore 1 - 5 ^_0/0, helicopter old tropine 1, 5% § varnish aldehyde 2-5% gamma prime Undekarakuton 0 - 8%, Bagudanoru 1, 2% tri Puranore 0.5 ^_0/0, styrallyl Honoré acetate 1 . 5 ^_0/0, Caron 0.1 ^_0/0, Pentarido 3.0 ^_0/0, Kisadesen 2 on 2, 9 percent to old hexa, ethylene brassylate 6.2 2%

In addition,% of a fragrance | flavor component shows% in a fragrance | flavor composition.

• AES (C12 / 14-E02.5): Polyoxyethylene alkyl ether sulfate Na (manufactured by Lion Corporation, alkyl group having 12 to 14 carbon atoms, average added mole number of ethylene oxide 2.5).

• Monoethanolamine: Made by Nippon Shokubai Co., Ltd.

• Propylene glycol: manufactured by Showa Denko K.K.

Enzyme ² : Evalase 16L (Novozymes Japan Co., Ltd.)

• C 12/14 fatty acid: Choshi fatty acid (Nippon Yushi Co., Ltd.)

• Chenic acid: manufactured by Fuso Chemical Industry Co., Ltd.

• Dye: Green 201, manufactured by Hagi Kasei Co., Ltd.

'Preservative: Caisson CG—ICP (ROHM' and 'Haas' Japan)

• Antifoaming agent: Palmitic acid (manufactured by NOF Corporation)

• pH adjuster:

• Perfume 2: Table in JP 2002-146399; ;! ~ Perfume composition A described in 18 [0100] As is apparent from the above results, the surfactant aqueous solution containing a mixture of MES salt and di-salt of each blending amount, unsaturated fatty acid, and alcohol and having a pH adjusted to 3 to 8 Also showed fluidity.

On the other hand, the aqueous surfactant solution adjusted so that the pH was higher than 8 had no fluidity in any case.

In particular, an aqueous surfactant solution having a mixture of MES salt and di-salt of 60% by mass had solidified.

As described above, the aqueous surfactant solution of the present invention contained a mixture of α-sulfo fatty acid alkyl ester salt and _α -sulfo fatty acid di-salt in high concentration and exhibited fluidity even at 30 ° C.

Industrial applicability

[0101] According to the present invention, it is possible to provide an aqueous surfactant solution that exhibits fluidity even at room temperature and contains a high concentration of α-sulfo fatty acid alkyl ester salt and a method for producing the same.

Claims

The scope of the claims

[1] a 30 to 70% by mass of a mixture of a sulfo-fatty acid alkyl ester salt and an α-sulfo fatty acid di-salt; and a content of the mixture; A surfactant aqueous liquid characterized by containing ρΗ in the range of 3-8.

[2] The surfactant aqueous liquid according to [1], further comprising an alcohol having 1 to 3 carbon atoms of 30% by mass or less based on the content of the mixture.

[3] a 30 to 7 mixture of sulfo-fatty acid alkyl ester salt and α-sulfo fatty acid di-salt

Mix the above-mentioned mixture or α-sulfo fatty acid alkyl ester and unsaturated fatty acid so that 0% by mass of unsaturated fatty acid having 10 to 22 carbon atoms is in the content of said mixture; And ρΗ is adjusted to 3 to 8, a method for producing an aqueous surfactant liquid.

[4] The method for producing an aqueous surfactant liquid according to claim 3, further comprising mixing an alcohol having 1 to 3 carbon atoms of 30% by mass or less with respect to the content of the mixture.