JP5315553B2 - Method for producing paste containing α-sulfo fatty acid alkyl ester salt - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing &alpha;-sulfo fatty acid alkyl ester salt-containing paste suited for producing powdery detergent composition from &alpha;-SF concentrate according to a spray drying method. <P>SOLUTION: The method of producing the &alpha;-sulfo fatty acid alkyl ester salt-containing paste having a water content of 23 to 32% comprises: a process (1) of mixing an &alpha;-sulfo fatty acid alkyl ester salt concentrate (a) having a water content of 6% or less, the &alpha;-sulfo fatty acid alkyl ester salt-containing paste (b) having a water content of 23 to 32% and/or water (c) to obtain a mixture (d) having a water content of 8 to 16%; and a process (2) of mixing the mixture (d) obtained in the process (1) and water (e) to obtain the &alpha;-sulfo fatty acid alkyl ester salt-containing paste (f) having a water content of 23 to 32%. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an α-sulfo fatty acid alkyl ester salt-containing paste. Specifically, a method for producing an α-sulfo fatty acid alkyl ester salt-containing paste having a specific gravity and viscosity suitable for producing spray-dried particles of the ester salt by diluting the α-sulfo fatty acid alkyl ester salt concentrate. About.

α-Sulfo fatty acid alkyl ester salts (α-SF) are widely used as surfactants for producing powder detergent compositions for clothing. Various methods for producing a powder detergent composition are known, and one of them is a spray drying method.
When producing a powder detergent composition from α-SF by a spray drying method, it is common to prepare a detergent slurry by using paste α-SF and mixing with a builder or the like. At this time, the detergent slurry may be prepared at a location far away from the location where the paste-like α-SF is produced. In that case, it is necessary to transport the paste α-SF not only in Japan and overseas but also overseas. However, since the paste-like α-SF is expensive to transport, the work is usually carried out such as transporting it as a concentrate and returning it to a paste before producing the powder detergent composition. As a method for concentrating α-SF, several methods have been known so far (Patent Documents 1 to 4).
Until now, in order to return the α-SF concentrate to the original paste state, the concentrate and water are put into a container almost simultaneously, and both are stirred and mixed to obtain moisture before concentration (23-32%). The paste is obtained by returning, or in the presence of the original paste before concentration (23-32%), the concentrate and water are alternately added and dissolved so as not to fall out of the range of moisture 23-32% There have been ways to increase it.
However, in this method, the mixture foams during stirring, and as a result, the specific gravity of the resulting α-SF-containing paste becomes lower than the value before concentration or the viscosity becomes higher than the value before concentration. There is a problem that it is not suitable for producing a powder detergent composition by a spray drying method.

JP 2004-210807 A International Publication No. 2004/111166 Pamphlet JP 2003-105396 A JP 2003-82395 A

  Therefore, an object of the present invention is to provide a method for producing an α-sulfo fatty acid alkyl ester salt-containing paste suitable for producing a powder detergent composition by a spray drying method from an α-SF concentrate.

As a result of intensive studies by the present inventors, it has been found that the object of the present invention can be achieved by increasing the water content of α-SF to a specific range and then setting the desired value.
That is, the present invention is a method for producing an α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 23 to 32%,
(1) (a) an α-sulfo fatty acid alkyl ester salt concentrate having a moisture content of 6% or less;
(b) mixing α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 23 to 32% and / or (c) water, and (d) obtaining a mixture having a moisture content of 8 to 16%, and (2) (D) the mixture obtained in step (1) and (e) water are mixed to obtain (f) an α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 23 to 32%,
The above manufacturing method is provided.

According to the production method of the present invention, it is possible to prevent foaming of the α-SF-containing paste during production. Therefore, the α-SF-containing paste obtained by the production method of the present invention has the same specific gravity and viscosity as those before concentration.
According to the production method of the present invention, it is also possible to suppress the paste from adhering to the stirring shaft during stirring. The α-SF-containing paste obtained by the production method of the present invention can be taken out from the container without being clogged at the discharge port.

  In the present invention, the α-sulfo fatty acid alkyl ester salt is represented by the following formula (1).

In the formula, R ¹ is a straight-chain or branched, preferably straight-chain alkyl or alkenyl group having 8 to 20, preferably 12 to 18, more preferably 12 to 16 carbon atoms,
R ² is a linear or branched, preferably linear alkyl or alkenyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 carbon atom, and M is an alkali metal, an ammonium salt or an amine salt. Preferably, it is an alkali metal, more preferably sodium or potassium.
When the carbon number of R ¹ is less than 8, detergency may be reduced, odor may be deteriorated, or the powder detergent composition may be easily solidified. If the carbon number of R ¹ exceeds 20, the detergency may be inferior.
Particularly preferred is a compound in which R ¹ is a linear or branched alkyl or alkenyl group having 12 to 16 carbon atoms, R ² is a methyl group, and M is sodium in the above formula.
In the present invention, the α-sulfo fatty acid alkyl ester can be used singly or as a mixture of two or more. A mixture is preferred.
The α-sulfo fatty acid alkyl ester salt used in the present invention can be produced by a known method, or a commercially available product can be used.

The (a) α-sulfo fatty acid alkyl ester salt concentrate having a water content of 6% or less used in the present invention is obtained by, for example, concentrating an α-SF-containing paste using the method described in International Publication No. 2004/111166 pamphlet. can get. The form of the concentrate is not particularly limited, and flakes, powders, and the like can be used. In the present invention, the moisture content of α-SF is a value measured with a Karl Fischer moisture meter.
The moisture of (b) used in the present invention is 23 to 32%. When the moisture is in this range, the paste has a viscosity of less than 200P and is easy to handle.
(C) Water used in the present invention includes pure water, ion-exchanged water, clean water, industrial water, and vapor generated from the thin film evaporator when preparing an α-SF concentrate using a vacuum thin film evaporator. Examples thereof include condensed water obtained by cooling.

In step (1) of the present invention, (a) is mixed with (b) and / or (c) to obtain a mixture of (d) 8 to 16% moisture.
As a result of the study by the present inventors, the viscosity of α-SF tends to decrease as the amount of water increases, but after it reaches a minimum at around 12-14% moisture, it reaches a maximum at around 16% moisture, It was found that when the water content exceeded 16%, the water content dropped rapidly, and when the water content exceeded 22-23%, the water content became almost constant up to about 32% (see FIG. According to the stated viscosity measurement, water is gradually evaporated from a paste with a moisture content of 26%, and the viscosity of each moisture content up to 1.5% is measured).
Without being bound by any theory, when the α-SF concentrate is diluted to a paste with a moisture content of 23 to 32%, it defoams by passing through a state where the viscosity of the moisture content of 16% is maximized. It is estimated that the paste can be diluted to a paste having a good specific gravity and viscosity. Therefore, in the present invention, it is important that the water content of the mixture is 8 to 16%. If the water content of the mixture is less than 8%, the mixture may adhere to the stirring shaft during stirring and mixing.

The water content of the mixture is preferably 10 to 16%, and more preferably 12 to 16%.
When the water content of the mixture is less than 8%, the finally obtained (f) 23-32% water-containing α-SF-containing paste adheres to the stirring shaft during stirring or is taken out from the stirring container. There is a risk of clogging at the outlet. When the water content of the mixture exceeds 16%, (e) when mixed with water in the subsequent step (2), the mixture foams and is finally obtained. (F) α-SF having a water content of 23 to 32% There is a possibility that the specific gravity of the containing paste may decrease or the viscosity may increase.
The viscosity of the mixture at 70 ° C. is preferably 2000 to 4000 P, and more preferably 2000 to 3000 P. When the viscosity of the mixture is in such a range, it is preferable because mixing in the subsequent step (2) is facilitated.
The mixing temperature of (a) and (b) and / or (c) is preferably 60 to 90 ° C, more preferably 70 to 85 ° C. When the temperature is lower than 60 ° C., the viscosity of the mixture increases, and handling properties may be inferior. When the temperature exceeds 90 ° C., the mixture foams due to evaporation of water, and the specific gravity of the mixture may decrease or the viscosity may increase, resulting in poor handling properties.
The temperature of the mixture after mixing (a) with (b) and / or (c) is also preferably in the above range. It is more preferable to maintain the temperature of (b) and / or (c) before mixing with (a).

In the mixing order, (a) is preferably added to (b) and / or (c), and (a) is more preferably added to (b). When (a) is added to (b) and mixed, more (f) can be obtained. That is, the capacity of the mixing tank can be reduced.
When mixing (a) and (b) and / or (c), the total amount of (a) and the total amount of (b) and / or (c) can be mixed simultaneously, but (b) and It is preferable that the total amount of (c) is mixed while gradually adding (a).
When the mixture is prepared from (a) and (b), depending on the water content of (a) and (b), (a) and (b) are, for example, 5:95 in mass ratio. It can be prepared by mixing at a ratio of ˜50: 50.
When the mixture is prepared from (a) and (c), it can be prepared by mixing (a) and (c), for example, in a mass ratio of 5:95 to 15:85. it can.
When preparing the mixture using a blend of (b) and (c), depending on the amount of water in (b), (b) and (c) are, for example, 67:33 in mass ratio. The mixture is mixed at a ratio of ˜1: 99 to obtain an α-SF-containing paste having a water content of 50 to 50% or more, and the paste and (a) are, for example, in a mass ratio of 5:95 to 30:70 It can be prepared by mixing.

In step (2) of the present invention, (d) the mixture obtained in step (1) and (e) water are mixed to obtain (f) an α-SF-containing paste having a moisture content of 23 to 32%.
The water that can be used in this step is the same as the water that can be used in step (1). The temperature of water is preferably 20 to 90 ° C, more preferably 50 to 85 ° C, and further preferably 60 to 80 ° C. When the temperature of water is less than 20 ° C., the viscosity of the mixture with (d) increases, and the handling property may be lowered. If the temperature of the water exceeds 90 ° C, the mixture with (d) may foam. (D) When mixing a mixture and (e) water, (e) may be added to (d), or (d) may be added to (e). It is preferable to add (e) to (d). When (e) is added to (d) and mixed, mixing is completed quickly.
When mixing (d) and (e), the total amount of (d) and the total amount of (e) can be mixed at the same time, but mixing while gradually adding (e) to the total amount of (d) Alternatively, it is preferable to mix while gradually adding (d) to the total amount of (e).

Although depending on the amount of water in (d), (d) and (e) can be prepared by mixing (d) and (e), for example, in a mass ratio of 9:91 to 26:74. .
The mixing is preferably performed at a temperature of the mixture of (d) and (e) of 60 to 90 ° C, more preferably 70 to 85 ° C. If it is lower than 60 ° C., the viscosity may increase and the handling property may decrease. If the temperature exceeds 90 ° C., foaming due to water evaporation occurs, the specific gravity decreases, the viscosity increases, and the handling property may decrease.
The water content in (f) is 23 to 32%, preferably 24 to 28%, as in (b). If it is out of this range, the viscosity of (f) increases and the handling property may be lowered.

Requires surfactants, builders, alkaline agents, enzymes, fluorescent brighteners, foam suppressants, fragrances, and dyes other than the α-sulfo fatty acid alkyl ester salts that are commonly used to produce powder detergent compositions By blending according to the above, it is possible to obtain a powder detergent composition by spray drying by an ordinary method from the α-SF-containing paste having a moisture content of 23 to 32% thus obtained.
In addition, the α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 23 to 32% obtained in the present invention is used for producing a powder detergent composition by a spray drying method, and can be used without any particular limitation. it can.
For example, it can be used in the following cases.
1: When mixed with an α-sulfo fatty acid alkyl ester salt-containing paste before concentration and used to produce an α-sulfo fatty acid alkyl ester salt-containing paste concentrate.
2: When used to produce an α-sulfo fatty acid alkyl ester salt-containing paste having a water content of more than 32% by further diluting with water.
3: Surfactants other than α-sulfo fatty acid alkyl ester salts usually used for producing liquid detergent compositions, builders, alkali agents, solvents, enzymes, fluorescent brighteners, preservatives, foam suppressants, When it is used to produce a liquid detergent composition by blending pH adjusters, fragrances, and dyes as required.

  First, (a) an α-SF concentrate having a moisture content of 6% or less and (b) an α-SF-containing paste having a moisture content of 23 to 32% were produced as follows. Unless otherwise specified, “%” represents mass%.

[Reference Example 1]
<Preparation of (b) α-SF-containing paste>
(Sulfonation process)
An apparatus having a capacity of 200 L, jacket cooling, and a reactor with a three-stage stirrer (material: SUS316L) provided with a circulation line to control the reaction temperature was used.
First, a fatty acid methyl ester (methyl palmitate (manufactured by Lion Corporation, product name: pastel M-16)) and methyl stearate (manufactured by Lion Corporation, product name: pastel M-180) as a raw material is a mass ratio of 6 / 4 mixture) was charged into the reactor, and 5% of finely powdered sodium sulfate (Na ₂ SO ₄ ) was added to the fatty acid methyl ester as a coloring inhibitor while stirring well.
While continuing stirring, the reaction temperature was 80 ° C., the circulation rate in the circulation line was 80 to 100 L / min, and SO ₃ gas (sulfonated gas) 110 to 120 m ³ (raw material methyl ester) diluted to 8% by volume with nitrogen gas. 1.2 times mol) was blown at a constant speed with a ring sparger over 1 hour. Further, aging was carried out for 30 minutes while maintaining at 80 ° C. to obtain a sulfonated product.

(Esterification process)
A three-stage stirred tank type with a jacket was used as the esterification reaction tank. Further, esterification was carried out by supplying methanol as a lower alcohol at 3.5 to 5.5 kg / hour while controlling the sulfonated product at 3 to 4% to obtain an esterified product. The reaction temperature for esterification was 80 ° C., and the aging time was 30 minutes.
(Neutralization process)
Next, the esterified product extracted from the esterification reaction tank was continuously supplied to the neutralization line at 130 to 135 kg / hour. The neutralization method employs the neutralization method described in JP-A-2001-64248, and a 25-35% sodium hydroxide aqueous solution is added at a rate of 50-60 kg / hour between the premixer and the neutralization mixer. A quantitative feed was made to allow continuous neutralization. Then, the neutralized product of the esterified product that had been neutralized in advance and the esterified product were thoroughly mixed with a premixer, and then mixed with an aqueous sodium hydroxide solution to obtain a neutralized product.
The amount of the pre-neutralized product circulating through the loop was 15 to 25 times the total of the esterified product and the aqueous alkali solution to be added. The neutralization temperature was controlled at 70 ° C. by adjusting the water temperature in the heat exchanger of the loop circuit. The residence time of the neutralized product was 20 minutes. A pH control system was installed in the circulation loop, and the feed rate (feed amount) of the aqueous sodium hydroxide solution was controlled by a feedback controller that adjusts the feed rate of the aqueous sodium hydroxide solution. The pressure inside the circulation loop was 4 kgf / cm ² .

(Bleaching process)
Subsequently, the said neutralized material was supplied to the bleaching agent mixing line at the supply rate of 180-200 kg / hour. The bleaching agent mixing line was a circulation loop system equipped with a circulation line having a heat exchanger. Then, 35% hydrogen peroxide solution is supplied at a rate of 3.5 to 7.5 kg / hour (1 to 2% in a pure amount with respect to AI (active ingredient: α-SF)), and bleaching supplied from a circulation line. Thoroughly mixed with the neutralized product (pre-bleached product). The amount of loop circulation was 15 times the amount of neutralized product newly added to the preliminary bleached product, and the pressure in the circulation loop pipe was 4 kgf / cm ² . Further, the temperature of the circulation loop was adjusted to 80 ° C. by a heat exchanger, and the residence time of the circulation loop was 10 minutes.
Subsequently, it introduce | transduced into the bleaching line of a distribution pipe system, bleaching was advanced, and the alpha-SF containing paste was obtained. The bleaching line was a jacketed double tube, and the temperature and pressure could be adjusted. The flow of the bleaching agent mixture was a piston flow, the pressure was adjusted to 4 kgf / cm ² , the temperature was adjusted to 80 ° C., and the residence time was 180 minutes.
The water content of the obtained α-SF-containing paste was measured with a Karl Fischer moisture meter and found to be 25%. The specific gravity was 0.90 g / cc (temperature 75 ° C.), and the viscosity was 110 P (temperature 69 ° C.).

The composition of the obtained α-SF-containing paste was measured by the following method.
[Anionic surfactant concentration (total concentration of α-sulfo fatty acid methyl ester sodium salt and α-sulfo fatty acid disodium salt (di-Na salt)]]
0.3 g of paste was accurately weighed into a 200 mL volumetric flask, and ion exchange water (distilled water) was added up to the marked line and dissolved by ultrasonic waves. After dissolution, it is cooled to about 25 ° C., 5 ml of this is taken into a titration bottle with a whole pipette, 25 ml of MB indicator (methylene blue) and 15 ml of chloroform are added, and further 5 ml of 0.004 mol / L benzethonium chloride solution is added. Titrated with 0.002 mol / L sodium alkylbenzene sulfonate solution. In the titration, the titration bottle was capped and shaken vigorously and allowed to stand, and the end point was the point where both layers had the same color tone against a white plate. Similarly, a blank test (the same test as described above except that no bleached product was used) was performed, and the concentration was calculated from the difference in titer.

[Ratio of di-Na salt in anionic surfactant]
Di-Na salt standards 0.02, 0.05, and 0.1 g were accurately weighed into a 200 mL volumetric flask, added with about 50 mL of water and about 50 mL of ethanol, and dissolved using ultrasonic waves. After dissolution, the mixture was cooled to about 25 ° C., and methanol was accurately added up to the marked line to obtain a standard solution.
About 2 mL of this standard solution was filtered using a 0.45 μm chromatographic disk and then subjected to high performance liquid chromatography under the following measurement conditions to prepare a calibration curve from the peak area.
(High-performance liquid chromatography measurement conditions)
-Apparatus: LC-6A (manufactured by Shimadzu Corporation).
Column: Nucleosil 5SB (manufactured by GL Sciences Inc.).
-Column temperature: 40 ° C.
Detector: differential refractive index detector RID-6A (manufactured by Shimadzu Corporation).
Mobile phase: 0.7% sodium perchlorate in H ₂ O / CH ₃ OH = 1/4 (volume ratio) solution.
-Flow rate: 1.0 mL / min.
Injection volume: 100 μL.

Next, 1.5 g of paste was accurately weighed into a 200 mL volumetric flask, and about 50 mL of water and about 50 mL of ethanol were added and dissolved using ultrasonic waves. After dissolution, the mixture was cooled to about 25 ° C., and methanol was accurately added up to the marked line to make a test solution.
About 2 mL of the test solution was filtered using a 0.45 μm chromatographic disk, then analyzed by high performance liquid chromatography under the same measurement conditions as above, and the di-Na salt in the sample solution was analyzed using the calibration curve created above. The concentration was determined.
The ratio (mass%) of the di-Na salt in the α-SF-containing paste was calculated from the calculated di-Na salt concentration and the anionic surfactant concentration determined above.

[Sodium sulfate (sodium nitrate) concentration and sodium methyl sulfate (methyl sulfate) concentration (mass%)]
Accurately measure 0.02, 0.04, 0.1, and 0.2g each of sodium methylsulfate and sodium sulfate standard products in a 200 mL volumetric flask, add ion-exchanged water (distilled water) to the marked line, It was dissolved using ultrasonic waves. After dissolution, the mixture was cooled to about 25 ° C. and used as a standard solution. About 2 mL of this standard solution was filtered using a 0.45 μm chromatographic disk, followed by ion chromatography under the following measurement conditions, and a calibration curve was prepared from the peak areas of sodium methyl sulfate and sodium sulfate standard solutions.
(Ion chromatography measurement conditions)
-Apparatus: DX-500 (manufactured by Nippon Dionex).
-Detector: Electrical conductivity detector CD-20 (manufactured by Nippon Dionex).
-Pump: IP-25 (manufactured by Nippon Dionex).
-Oven: LC-25 (manufactured by Nippon Dionex).
-Integrator: C-R6A (manufactured by Shimadzu Corporation).
Separation column: AS-12A (manufactured by Nippon Dionex).
Guard column: AG-12A (manufactured by Nippon Dionex).
Eluent: 2.5 mM Na ₂ CO ₃ /2.5 mM NaOH / 5% (volume) acetonitrile aqueous solution.
-Eluent flow rate: 1.3 mL / min.
・ Regenerating solution: pure water.
-Column temperature: 30 ° C.
-Loop volume: 25 μL.

Next, 0.3 g of paste is accurately weighed into a 200 mL volumetric flask, ion-exchanged water (distilled water) is added up to the marked line, and dissolved using ultrasonic waves. After dissolution, the solution was cooled to about 25 ° C. and used as a test solution.
About 2 mL of the test solution was filtered using a 0.45 μm chromatographic disk, and then analyzed by ion chromatography under the same measurement conditions as described above. Using the calibration curve created above, the sodium methylsulfate concentration in the sample solution and The sodium sulfate concentration was determined, and the sodium methyl sulfate concentration and the sodium sulfate concentration (mass%) in the α-SF-containing paste sample were calculated.
The results are shown in Table 1.

<(A) Preparation method of flakes>
Vacuum thin film evaporator (vertical control, heat transfer area: 0. 0%) equipped with a stirring blade rotating a paste containing 26% of α-SF (raw material) at a rotation speed of 1,060 rpm and a tip speed of about 12 m / sec. 5 m ² , inner diameter: 204 mm, clearance between heat transfer surface and blade tip: 2-4 mm, inner wall heating temperature 120 ° C., vacuum degree 0.007-0.014 MPa (absolute pressure) To produce an α-SF-containing concentrate having a water content of 4.0% or less. A MONO pump (manufactured by Hyojin Equipment Co., Ltd.) was used as a discharge pump from the vacuum thin film evaporator. Thereafter, the obtained concentrate was cooled and solidified to 20 to 30 ° C. using a steel belt double cooler (Nihon Belting Co., Ltd.) to obtain flakes.

[Example 1]
The α-SF-containing paste obtained in [Reference Example 1] was previously charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the paste temperature reached 70 ° C. or higher, α-SF flakes having a water content of about 2% obtained according to Reference Example 1 were charged and mixed until the water content of the mixture of paste and flakes in the container was about 15%. At this time, care was taken so that the temperature of the mixture did not fall below 60 ° C. After completion of the addition, the mixture was mixed for about 5 minutes until uniform, and then hot water of 70 ° C. or higher was added and mixed to obtain an α-SF-containing paste having a moisture content of about 27%. The properties of the obtained paste are as shown in Table 2.

[Example 2]
The α-SF-containing paste obtained in [Reference Example 1] was previously charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the paste temperature reached 70 ° C. or higher, α-SF flakes having a water content of about 2% obtained according to Reference Example 1 were charged and mixed until the water content of the mixture of paste and flakes in the container was about 8%. At this time, care was taken so that the temperature of the mixture did not fall below 60 ° C. After completion of the addition, the mixture was mixed for about 5 minutes until uniform, and then warm water of 70 ° C. or higher was added and mixed to obtain an α-SF-containing paste having a water content of about 25%. The properties of the obtained paste are as shown in Table 2.

[Examples 3 to 5]
The α-SF-containing paste obtained in [Reference Example 1] was previously charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the paste temperature reached 70 ° C. or higher, α-SF flakes having a moisture content of about 2% obtained according to Reference Example 1 were charged and mixed until the mixture moisture of the paste and flakes in the container was about 12%. At this time, care was taken so that the temperature of the mixture did not fall below 60 ° C. After completion of the addition, the mixture was mixed for about 5 minutes until uniform, and then warm water of 70 ° C. or higher was added and mixed to obtain an α-SF-containing paste having a moisture content of about 24-31%. The properties of the obtained paste are as shown in Table 2.

Example 6
Warm water was previously charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the hot water temperature reached 70 ° C. or higher, α-SF flakes having a water content of about 2% obtained according to Reference Example 1 were charged and mixed until the water content of the mixture of hot water and flakes in the container was about 16%. At this time, care was taken so that the temperature of the mixture did not fall below 60 ° C. After completion of the addition, the mixture was mixed for about 5 minutes until uniform, and then hot water of 70 ° C. or higher was added and mixed to obtain an α-SF-containing paste having a moisture content of about 27%. The properties of the obtained paste are as shown in Table 3.

Example 7
The α-SF-containing paste obtained in [Reference Example 1] was previously charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the paste temperature reached 70 ° C. or higher, α-SF flakes having a water content of about 2% obtained according to Reference Example 1 were charged and mixed until the water content of the mixture of paste and flakes in the container reached 10%. At this time, care was taken so that the temperature of the mixture did not fall below 60 ° C. After completion of the addition, the mixture was mixed until it became uniform for about 5 minutes, and then condensed water heated to 70 ° C. or higher was added and mixed to obtain an α-SF-containing paste having a water content of about 26%. The properties of the obtained paste are as shown in Table 3. Condensed water was obtained by the following method.
<Method for preparing condensed water>
When the concentrate is prepared by the vacuum thin film evaporator, the vapor generated from the thin film evaporator is condensed in a shell and tube type condenser through which cooling water having a temperature of about 15 ° C. is passed, and is condensed in a lower container. The collected liquid was used as condensed water.

Example 8
Condensed water was previously charged into an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the condensed water temperature reached 70 ° C. or higher, α-SF flakes having a water content of about 2% obtained according to Reference Example 1 were charged and mixed until the water content of the mixture of condensed water and flakes in the container was 15%. At this time, care was taken so that the temperature of the mixture did not fall below 60 ° C. After completion of the addition, the mixture was mixed until it became uniform for about 5 minutes, and then condensed water heated to 70 ° C. or higher was added and mixed to obtain an α-SF-containing paste having a water content of about 25%. The properties of the obtained paste are as shown in Table 3.

[Examples 9 to 10]
The α-SF-containing paste obtained in [Reference Example 1] was previously charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the paste temperature reached 70 ° C. or higher, the concentrate generated in the initial stage of concentration was charged, and the mixture was charged and mixed until the water content of the mixture became about 9%. At this time, care was taken so that the temperature of the mixture did not fall below 60 ° C. After completion of the addition, the mixture is mixed for about 5 minutes until uniform, and then condensed water (Example 9) or warm water (Example 10) warmed to 70 ° C. or higher is added and mixed to obtain an α having a water content of about 26 to 27%. -A paste containing SF was obtained. The properties of the obtained paste are as shown in Table 3. Moreover, the adjustment method of the concentrate generate | occur | produced in the initial stage of concentration is shown below.
<Preparation method of concentrate generated at the initial stage of concentration>
Vacuum thin film evaporator (vertical controller, heat transfer area) equipped with a stirring blade rotating the α-SF-containing paste obtained in Reference Example 1 at a rotation speed of 1,060 rpm and a tip speed of about 12 m / sec. : 0.5 m ² , inner diameter: 204 mm, clearance between heat transfer surface and blade tip: 2 to 4 mm, inner wall heating temperature 120 ° C., vacuum degree 0.007 to 0.014 MPa (manufactured by Hitachi, Ltd.) (Absolute pressure). At that time, an α-SF-containing concentrate having a water content of about 3% or more discharged in the initial stage of concentration was recovered and used as a concentrate generated in the initial stage of concentration. A MONO pump (manufactured by Hyojin Equipment Co., Ltd.) was used as a discharge pump from the vacuum thin film evaporator.

[Reference Example 2]
Instead of the 200 L reactor of Reference Example 1, a falling film reactor (hereinafter referred to as a reactor) was used for the sulfonation reaction. The SO ₃ gas, dry air (dew point: -55 ° C.) the SO ₂ with was used as the SO ₃ by catalytic oxidation.
SO ₃ gas diluted to a SO ₃ concentration of 8% with the raw material fatty acid methyl ester and dry air was fed from the upper part to the lower part of the reactor so as to contact in parallel flow. At this time, the SO ₃ gas was supplied so that the amount of SO ₃ was 1.2 times the molar amount of the raw material. The reaction temperature in the reactor was 80 ° C., the reaction time was 15 seconds, and the reaction pressure was 10 kPa.
Next, the reaction product discharged from the outlet of the reactor is supplied to a continuous multistage reaction tank in which two tanks are arranged in series together with fine powdered sodium sulfate (Na ₂ SO ₄ ) as a coloring inhibitor. Aging was performed at 80 ° C. and an average residence time of 90 minutes. After esterification, an α-SF-containing paste was obtained according to [Reference Example 1]. Thereafter, α-SF flakes having a moisture content of about 2% were obtained according to Reference Example 1 (Flake Preparation Method).

Example 11
The α-SF-containing paste obtained in [Reference Example 2] was previously charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the paste temperature reached 70 ° C. or more, the α-SF flakes having a water content of about 2% obtained in [Reference Example 2] were charged and mixed until the water content of the mixture of paste and flakes in the container was about 9%. did. At this time, care was taken so that the temperature of the mixture did not fall below 60 ° C. After completion of the addition, the mixture was mixed for about 5 minutes until uniform, and then warm water of 70 ° C. or higher was added and mixed to obtain an α-SF-containing paste having a water content of about 26%.
The properties of the obtained paste are as shown in Table 3.

[Reference Example 3]
After introducing 20% by mass of methanol to 100% by mass of the α-sulfo fatty acid methyl ester obtained according to the sulfonation step of [Reference Example 2], this mixture and 5.7% by mass of 35% hydrogen peroxide were mixed with a mixer. Were introduced into a continuous loop reactor equipped with a heat exchanger and bleached.
Next, 31% by mass of 27% NaOH aqueous solution, 19% by mass of water and 6% by mass of methanol are added to 100% by mass of the bleached product obtained in a loop type continuous neutralization apparatus using a mixing mixer and a heat exchanger. The pH was adjusted to 7 by introduction, and an α-SF containing composition was obtained. Furthermore, the α-SF-containing composition was used as a raw material surfactant aqueous solution and the apparatus shown in FIG. 2 (1. Heater, 2. Pressure control valve, 3. Flash can: capacity 30 L, 4. Circulation pump, 5. Recycle flash evaporation was performed with a condenser to remove the lower alcohol, and an α-SF-containing paste was obtained. Thereafter, α-SF flakes having a moisture content of 2% were obtained in accordance with (Flake Preparation Method) in [Reference Example 1].

Example 12
The α-SF-containing paste obtained in [Reference Example 3] was previously charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the paste temperature reached 70 ° C. or higher, the α-SF flakes having a water content of about 2% obtained in [Reference Example 3] were charged and mixed until the water content of the mixture of paste and flakes in the container was about 8%. did. At this time, care was taken so that the temperature of the mixture did not fall below 60 ° C. After completion of the addition, the mixture was mixed for about 5 minutes until uniform, and then warm water of 70 ° C. or higher was added and mixed to obtain an α-SF-containing paste having a water content of about 25%. The properties of the obtained paste are as shown in Table 3.

[Comparative Example 1]
An α-SF-containing paste was prepared according to [Example 1] except that α-SF flakes having a water content of about 2% were added and mixed so that the water content of the mixture was about 4%, and α-SF having a water content of about 25% was prepared. A containing paste was obtained. The properties of the obtained paste are as shown in Table 2. Although the paste had good properties, it resulted in adhesion to the stirring shaft.
[Comparative Example 2]
The α-SF-containing paste obtained in Reference Example 1 was charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the paste temperature reached 70 ° C. or higher, flakes having a water content of about 2% obtained according to Reference Example 1 and hot water were added and mixed while adjusting the water content of the mixture to about 23 to 32%. Finally, the moisture was adjusted to obtain an α-SF-containing paste having a moisture content of about 26%. The properties of the obtained paste are as shown in Table 2. As a result, a paste having a low specific gravity and a high viscosity was obtained.

[Comparative Example 3]
In an approximately 100 L container equipped with a stirrer, the α-SF concentrate obtained previously in [Reference Example 1] (liquid before flaking, moisture 2.4%) was charged, and the paddle rotation speed was 105 rpm. Agitation was started at a jacket temperature of 80 ° C. Thereafter, warm water of 60 ° C. or higher was added and mixed to obtain an α-SF-containing paste having a water content of about 25%. The properties of the obtained paste are as shown in Table 3. Although the physical properties of the paste were good, it resulted in adhesion to the stirring shaft and clogging of the discharge port.
[Comparative Example 4]
The α-SF-containing paste obtained in [Reference Example 1] was previously charged in an approximately 100 L container equipped with a stirrer, and stirring was started at a paddle rotation speed of 105 rpm and a jacket temperature of 80 to 90 ° C. When the paste temperature reached 70 ° C. or higher, the concentrate generated in the initial stage of concentration described in [Examples 9 to 10] and hot water were added and mixed while adjusting the mixture moisture to about 23 to 32%. The water content of the actually obtained mixture was 22%. Finally, the moisture was adjusted to obtain an α-SF-containing paste having a moisture content of about 26%. The properties of the obtained paste are as shown in Table 3. As a result, a paste having a low specific gravity and a high viscosity was obtained.

<Analysis method>
[Moisture measurement method]
The moisture content of the α-sulfo fatty acid alkyl ester salt-containing paste or concentrate was measured using a Karl Fischer moisture meter (“MKC-210” manufactured by Kyoto Electronics Industry Co., Ltd.). Specifically, 10 to 100 mg of a sample was dissolved in a Karl Fischer reagent at atmospheric temperature, and measurement was started according to a conventional method. The measurement was automatically stopped as the electrode reaction ended. The amount of sample input was input to the Karl Fischer moisture meter touch panel to calculate the amount of moisture.

<Evaluation method>
[Viscosity measurement]
A cylindrical stainless steel sample container (internal volume 1 L (diameter: about 10.5 cm, height: about 11.55 cm)) is filled with the pastes of Examples and Comparative Examples, and Brookfield type (B type) viscometer ((stock) ) Viscosity was measured using Tokyo Keiki Co., Ltd. The viscosity of 200 [P] or less is 20 rpm, rotor No. 4 and 200 [P] or more, 10 rpm, rotor No. It is a measured value after 1 minute under each condition of 7. Based on the obtained value, the following criteria were evaluated.
<Evaluation criteria>
Very good: Less than 100 [P]
Good: Less than 100 to 200 [P]
Slightly poor: Less than 200 to 500 [P]
Defect: 500 [P] or more

[Specific gravity measurement]
In order to prevent air from entering the paste of the example and comparative example into a cylindrical stainless steel sample container (internal volume 1L (diameter: approx. 10.5cm, height: approx. 11.55cm)) whose exact internal volume is known After satisfying the wear and measuring the weight, the weight per cc was calculated. The evaluation criteria are as follows.
<Evaluation criteria>
Very good: 0.8 [g / cc] or more
Good: 0.7 to less than 0.8 [g / cc]
Slightly poor: Less than 0.6 to 0.7 [g / cc]
Defect: Less than 0.6 [g / cc]

[Manufacturability evaluation method]
Evaluation was performed according to the following criteria.
<Evaluation criteria>
A: Paste does not adhere to the stirring shaft, and there is no clogging at the discharge port.
○: The paste adhered to the stirring shaft,
Even if the preparation is repeated three times without removing the adhesion, the adhesion does not grow,
No clogging at the outlet
Δ: The paste adheres to the stirring shaft,
When the preparation was repeated three times without removing the adhesion, the adhesion grew.
No clogging at the outlet
X: The paste adheres to the stirring shaft,
If the preparation is repeated three times without removing the adhesion, the adhesion grows, and
There is also clogging at the outlet

Formulation Example 1
Using the α-SF-containing paste obtained in [Example 1], spray-dried particles having the compositions shown in Table 4 were obtained.

  The components shown in Table 5 were dry mixed with the spray-dried particles shown in Table 4 to obtain a granular detergent composition.

Formulation Example 2
Using the α-SF-containing paste obtained in [Example 1], a liquid detergent composition having the composition shown in Table 6 was obtained.

[Reference Example 4]
The fatty acid methyl ester of the raw material of [Reference Example 1] was methyl palmitate (product name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (product name: Pastel M-180, manufactured by Lion Corporation). The α-SF-containing paste was obtained according to [Reference Example 1] except that the mixture was changed to a mixture having a mass ratio of 8/2. The composition of the obtained α-SF-containing paste was measured in the same manner as in [Reference Example 1]. The results are shown in Table 7. Thereafter, α-SF flakes having a moisture content of about 2% were obtained in accordance with (Flake Preparation Method) in [Reference Example 1].

[Reference Example 5]
The fatty acid methyl ester of the raw material of [Reference Example 1] was methyl palmitate (product name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (product name: Pastel M-180, manufactured by Lion Corporation). The α-SF-containing paste was obtained according to [Reference Example 1] except that the mixture was changed to a mixture having a mass ratio of 9/1. The composition of the obtained α-SF-containing paste was measured in the same manner as in [Reference Example 1]. The results are shown in Table 8. Thereafter, α-SF flakes having a moisture content of about 2% were obtained in accordance with (Flake Preparation Method) in [Reference Example 1].

Example 13
[Alpha] -SF containing about 26% moisture according to [Example 3] except that the α-SF containing paste and [alpha] -SF flakes obtained in [Reference Example 4] were used and the mixture moisture was about 12%. A paste was obtained. Properties of the obtained paste are as shown in Table 9.
Example 14
[Alpha] -SF containing about 25% moisture according to [Example 3] except that the α-SF containing paste and [alpha] -SF flakes obtained in [Reference Example 5] were used and the mixture moisture was about 12%. A paste was obtained. Properties of the obtained paste are as shown in Table 9.
Example 15
An α-SF-containing paste having a moisture content of about 26% was obtained according to Example 6 except that the α-SF flakes obtained in [Reference Example 4] were used and the moisture content of the mixture was about 16%. Properties of the obtained paste are as shown in Table 9.

Example 16
An α-SF-containing paste with a moisture content of about 26% was obtained according to Example 6 except that the α-SF flakes obtained in [Reference Example 5] were used and the moisture content of the mixture was about 16%. Properties of the obtained paste are as shown in Table 9.
Example 17
According to [Example 10], α-SF having a water content of about 24% was used except that the α-SF-containing paste and α-SF concentrate obtained in [Reference Example 4] were used and the water content of the mixture was about 9%. A containing paste was obtained. Properties of the obtained paste are as shown in Table 9.
Example 18
[Alpha] -SF having a water content of about 24% according to [Example 10] except that the [alpha] -SF-containing paste and [alpha] -SF concentrate obtained in [Reference Example 5] were used and the water content of the mixture was about 9%. A containing paste was obtained. Properties of the obtained paste are as shown in Table 9.

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.
-Carbonic acid Na: grain ash (manufactured by Soda Ash Japan)
・ Fluorescent whitening agent: Chino Pearl CBS-X (manufactured by Ciba Specialty Chemicals)
・ Na hydroxide: Flaked caustic soda (manufactured by Tsurumi Soda Co., Ltd.)
LAS-H: linear alkylbenzene sulfonic acid (manufactured by Lion Corporation, Raipon LH-2)
00) (AV value (mg of potassium hydroxide required to neutralize 1 g of LAS-H) = 180
. 0) In Table 4, LAS- neutralized with Na hydroxide in the slurry before spray drying.
The composition is expressed as Na, and in Table 6, the composition is expressed as LAS-H.
STPP: sodium tripolyphosphate (manufactured by Taiyo Chemical Industry Co., Ltd.)
・ Pyrophosphate Na: Sodium pyrophosphate (anhydrous) (Phosphorus Chemical Co., Ltd.)
Silicate Na: S50 ° sodium silicate No. 1 (manufactured by Nippon Chemical Industry Co., Ltd.) (SiO2 / Na2O molar ratio = 2.15)
-Polyacrylic acid Na: Aqualic DL-453 (manufactured by Nippon Shokubai Co., Ltd.) (pure 35 mass% aqueous solution)
-Acrylic acid / maleic acid copolymer Na: Aqualic TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40 mass% aqueous solution)

Α-SF-Na: α-SF-containing paste obtained in Example 1 Nonionic surfactant 1: Ethylene oxide average 1 of Diador 13 (manufactured by Mitsubishi Chemical Corporation)
5-mol adduct / zeolite: A-type 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.)
・ Sulfuric acid Na: neutral anhydrous sodium sulfate A0 (manufactured by Shikoku Kasei Co., Ltd.)
Soap: Fatty acid sodium having 12 to 18 carbon atoms (67 mass% pure, 40 to 45 ° C. titer)
, Molecular weight 289)
Enzyme 1: Sabinase 18T (Novozymes Japan Co., Ltd.)
・ Bleaching agent particles: Sodium percarbonate (manufactured by Mitsubishi Gas Chemical Co., Inc., SPC-D)
Bleach activator particles: Bleach activator granulated product G described in Examples of JP-A-2007-153596

Fragrance 1: A fragrance composition comprising the following composition: Decanol 0.5%, Octanal 0.3%, Hexylcinnamic aldehyde 10.0%, Dimethylbenzylcarbinyl acetate 8.0%, Lemon oil 3.0%, Lilyal 6.0%, Lyral 2.0%, Linalol 5.0%, Phenylethyl alcohol 7.5%, Tonalide 2.0%, o-tert-butylcyclohexyl acetate 3.0%, Galaxolide benzylbenzoate 2.0 %, Linascol 2.5%, Geraniol 1.0%, Citronellol 2.0%, Jasmolange 2.0%, Methyldihydrojasmonate 5.0%, Terpineol 1.0%, Methylionone 3.0%, Acetyl Drain 5.0%, Remononitrile 1.0%, Fluitate 1.0%, Oligorib 1.5%, Benzoy 1.0%, cis-3-hexenol 0.5%, coumarin 2.0%, damasenone 0.2%, damascon 0.3%, helional 1.5%, heliotropin 1.5%, anisaldehyde2. 5%, Gamma-undecalactone 0.8%, Bagdanol 1.2%, Tripral 0.5%, Stylaryl acetate 1.5%, Caron 0.1%, Pentalide 3.0%, Oxahexadecen-2-one 2.9%, ethylene brush rate 6.2%
In addition,% of a fragrance | flavor component shows% in a fragrance | flavor composition.

Nonionic surfactant 2: polyoxyethylene alkyl ether (manufactured by Lion Co., Ltd., having 12 to 14 carbon atoms in the alkyl group, average number of moles of ethylene oxide added 8)
・ AES (C12 / 14-EO2.5): Polyoxyethylene alkyl ether sulfate Na (Lion Corporation)
Manufactured, carbon number of alkyl group 12-14, average number of added moles of ethylene oxide 2.5).
Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.
・ Propylene glycol: manufactured by Showa Denko K.K.
Enzyme 2: Evalase 16L (Novozymes Japan Co., Ltd.)
・ C12 / 14 fatty acid: Isogo fatty acid (manufactured by NOF Corporation)
Citric acid: manufactured by Fuso Chemical Industry Co., Ltd.
-Dye: Green 201, manufactured by Sakai Kasei Co., Ltd.
-Antiseptic: Caisson CG-ICP (Rohm and Haas Japan Co., Ltd.)
-Antifoaming agent: palmitic acid (manufactured by NOF Corporation)
・ PH adjuster: sulfuric acid (manufactured by Toho Zinc Co., Ltd.)
Perfume 2: Perfume composition A described in Tables 11 to 18 of JP-A-2002-146399

(D) It is a graph which shows the measured value of the viscosity in each water | moisture content of a mixture. It is an example of the flow which manufactures the concentrate of (alpha) -SF.

Explanation of symbols

1 Heater 2 Pressure Control Valve 3 Flash Can 4 Circulation Pump 5 Condenser

Claims (3)

A method for producing an α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 23 to 32 mass% ,
(1) (a) an α-sulfo fatty acid alkyl ester salt concentrate having a moisture content of 6 % by mass or less;
(b) a 23-32 % by mass moisture-containing α-sulfo fatty acid alkyl ester salt-containing paste and / or (c) water was mixed at a temperature of 60-90 ° C. , and (d) the moisture was 8-16 % by mass. A step of obtaining a mixture having a temperature of 60 to 90 ° C , and (2) (d) the mixture obtained in the step (1) and (e) water having a temperature of 60 to 80 ° C at a temperature of 60 to 90 ° C. (F) a step of obtaining an α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 23 to 32 % by mass ,
The manufacturing method characterized by including. The process according to claim 1, wherein a viscosity at 70 ° C. of the (d) is characterized in that it is a 2000～4000P. The method according to claim 1 or 2 , wherein (a) is added to (b) and mixed in the step (1).

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