WO2018003905A1

WO2018003905A1 - Powdered detergent composition and method for producing same

Info

Publication number: WO2018003905A1
Application number: PCT/JP2017/023870
Authority: WO
Inventors: 陽一江端; 洋平野上; 高士小林
Original assignee: ライオン株式会社
Priority date: 2016-06-30
Filing date: 2017-06-29
Publication date: 2018-01-04
Also published as: JPWO2018003905A1; CO2019000751A2; CN109477034A

Abstract

Provided is a powdered detergent composition containing (A) a particle group of an α-sulfo fatty acid alkyl ester salt (α-SF salt) and (B) a particle group of an alkyl sulfate salt. The total content of pure α-SF salt in the particle group (A) and alkyl sulfate salt in the particle group (B) is 50 mass% or more, the content of alkyl sulfate salt in the particle group (B) is 1-100 parts by mass relative to 100 parts by mass of pure α-SF salt in the particle group (A), α-SF salt particles and alkyl sulfate salt particles are present as mutually independent particles, and excellent solidification suppression is achieved even if the concentration of α-SF salt is high.

Description

Powder detergent composition and method for producing the same

The present invention relates to a powder detergent composition and a method for producing the same. The powder detergent composition of the present invention is suitable as a powder detergent composition for addition to be blended into a powder detergent product together with other detergent components.
For example, the powder detergent composition of the present invention and other detergent components are suitably used in a method for producing a powder detergent product by dry mixing.
This application claims priority based on Japanese Patent Application No. 2016-131106 filed in Japan on June 30, 2016, the contents of which are incorporated herein by reference.

α-Sulfo fatty acid alkyl ester salts (hereinafter also referred to as α-SF salts) are widely used as surfactants to be blended in powder detergents for clothing.
In recent years, powder detergents have been produced by producing particles containing a high concentration of α-SF salt and mixing them with other detergent components.
However, there is a problem that the α-SF salt particles are easily solidified.
In order to solve this problem, Patent Document 1 proposes a method of suppressing solidification of a powder composition containing α-SF salt particles by coating α-SF salt particles with a coating agent and a liquid raw material. ing.

JP 2011-116807 A

However, the technique of Patent Document 1 still has room for improvement in terms of difficulty in solidification (inhibition of solidification). In particular, when the α-SF salt was contained at a high concentration, the solidification inhibition was not sufficient.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a powder detergent composition that has an α-SF salt at a high concentration and is excellent in inhibition of solidification, and a method for producing the same.

The present invention has the following aspects.
[1] A particle group (A) of an α-sulfo fatty acid alkyl ester salt and a particle group (B) of an alkyl sulfate salt, the pure component of the α-sulfo fatty acid alkyl ester salt in the particle group (A) and The total content of the alkyl sulfate in the particle group (B) is 50% by mass or more, and the pure content of the α-sulfo fatty acid alkyl ester salt in the particle group (A) is 100 parts by mass. A powder detergent composition wherein the alkyl sulfate in the particle group (B) is 1 to 100 parts by mass, and the α-sulfo fatty acid alkyl ester salt particles and the alkyl sulfate particles exist as independent particles, respectively. object.
[2] An α-sulfo fatty acid in the particle group (A), comprising an α-sulfo fatty acid alkyl ester salt particle group (A), an alkyl sulfate particle group (B), and an inorganic powder (C) The total content of the pure content of the alkyl ester salt and the alkyl sulfate salt in the particle group (B) is 50% by mass or more, and the pure content of the α-sulfo fatty acid alkyl ester salt in the particle group (A) The alkyl sulfate in the particle group (B) is 1 to 100 parts by mass with respect to 100 parts by mass, the content of the inorganic powder (C) is 1 to 30% by mass, and the α-sulfo A powder detergent composition, wherein the fatty acid alkyl ester salt particles and the alkyl sulfate particle are present as independent particles.
[3] The average particle size of the alkyl sulfate particle group (B) is 50 μm or more and less than 3 mm, and the average particle size of the inorganic powder (C) is 0.8 to 5 μm. Powder detergent composition.

[4] A method for producing a powder detergent composition according to [1], wherein the α-sulfo fatty acid alkyl ester salt particle group (A) and the alkyl sulfate salt group (B) are dry-mixed. A method for producing a detergent composition.
[5] A method for producing a powder detergent composition according to [2] or [3], wherein the α-sulfo fatty acid alkyl ester salt particles, alkyl sulfate particles, and inorganic powder are dry-mixed A method for producing a detergent composition.

[6] The content of particles having a particle size of 355 μm or less in the particle group (A) is 20 to 70% by mass with respect to the total mass of the particle group (A). Any powder detergent composition.
[7] A method for producing a powder detergent product by dry-mixing the powder detergent composition of [1] to [3] or [6] and other detergent components.

According to the present invention, it is possible to obtain a powder detergent composition that is excellent in the suppression of solidification while containing an α-SF salt at a high concentration.
Preferably, it is possible to obtain a powder detergent composition that suppresses powder adhesion (powder adhesion) to other materials and is excellent in suppression of solidification while containing α-SF salt at a high concentration.

The powder detergent composition of the present invention is a powdery composition containing a particle group (A) of an α-sulfo fatty acid alkyl ester salt and a particle group (B) of an alkyl sulfate. Furthermore, the powdery composition containing inorganic powder (C) is preferable.

<Particle group of α-SF salt (A)>
The particle group (A) is a group of α-SF salt particles and is a cleaning component. The α-SF salt particles may contain impurities. The α-SF salt particles may contain moisture.
In addition to the α-sulfo fatty acid alkyl ester salt represented by the following formula (1), the α-SF salt particles include sulfate (sodium sulfate) which is an inevitable by-product in the production of the α-sulfo fatty acid alkyl ester salt. Etc.), an alkyl sulfate (such as sodium methyl sulfate), an α-sulfo fatty acid di-salt (such as α-sulfo fatty acid disodium salt), or an unreacted raw material. The α-sulfo fatty acid di-salt has a function as a surfactant.
In the present invention, the total content (mass%) of the α-sulfo fatty acid alkyl ester salt and the α-sulfo fatty acid di salt in the particle group (A) is regarded as a pure component. In addition, a pure part is measured by the measuring method of a pure part mentioned later.

The α-SF salt contained in the particle group (A) is represented by the following formula (1).
R ¹ —CH (SO ₃ M) —COOR ² (1)
[In the formula (1), R ¹ is a linear or branched alkyl group having 6 to 20 carbon atoms or a linear or branched alkenyl group having 6 to 20 carbon atoms, and R ² is , An alkyl group having 1 to 6 carbon atoms, and M is a counter ion. ]
The carbon number of R ¹ is preferably 8 to 18, and more preferably 12 to 16.
R ² preferably has 1 to 3 carbon atoms. Examples of R ² include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group, an ethyl group, and a propyl group are preferable because the detergency is further improved.
Examples of the counter ion (M) include alkali metal ions, protonated amines, ammonium and the like. Examples of the alkali metal that can be the counter ion include sodium and potassium. The amine that can be the counter ion may be any of primary to tertiary amines, and preferably has 1 to 6 carbon atoms in total. The amine may have a hydroxy group. Examples of such amines include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.
Among these, M is preferably an alkali metal ion, more preferably a sodium ion or a potassium ion.
One α-sulfo fatty acid alkyl ester salt contained in the α-SF salt particles may be used, or a mixture of two or more α-sulfo fatty acid alkyl ester salts having different carbon numbers for R ¹ may be used.
The α-SF salt particles constituting the particle group (A) may be one type or two or more types.
In the above-described alpha-SF salt, in the above general formula (1), the mass ratio of alpha-SF salt a carbon number of 16 alpha-SF salt and ^{R 1} a carbon number of 14 ^{R 1} is 40:60 Preferably it is ˜100: 0. Further, α-sulfo fatty acid methyl ester salt (MES salt) in which R ² is a methyl group is preferable, and M is preferably a sodium ion.

The content of pure α-SF salt with respect to the entire particle group (A) (total mass) is preferably 70% by mass or more, and more preferably 80% by mass or more. In addition to the α-SF salt, the particle group (A) includes sulfates (sodium sulfate, etc.), alkyl sulfates (sodium methyl sulfate, etc.) that are inevitable by-products in the production of α-sulfo fatty acid alkyl ester salts. , Α-sulfo fatty acid di-salt (such as α-sulfo fatty acid disodium salt) and water may be contained. Generally, the particle group (A) includes 60 to 98% by mass of α-SF salt, 1 to 10% by mass of α-sulfo fatty acid di-salt, and 1 to 10% by mass of alkyl sulfate.
The water content of the particle group (A) is preferably 10% by mass or less, and more preferably 5% by mass or less with respect to the total mass of the particle group (A). When the water content is in the above range, the adhesiveness at low temperature is easily suppressed, and the storage stability at low temperature is easily improved.
In this specification, the water content of the particle group (A) is a value measured by the Karl Fischer method.

The average particle diameter of the particle group (A) of the present invention is represented by a mass-based cumulative 50% diameter (mass median diameter) by a sieving method. Specifically, it is a value measured according to the following procedure.
The particles are classified using a 9-stage sieve and a saucer having openings of 1700 μm, 1400 μm, 1180 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm and 150 μm, respectively.
Classification operation is performed as follows. First, a sieve with a small opening is stacked on a tray in the order of a sieve with a large opening, and 100 g / times of particles are placed on the top of the top 1700 μm sieve, and a low-tap sieve shaker (Dalton Co., Ltd.) is covered. Manufactured, tapping: 125 times / minute, rolling: 250 times / minute) and vibrating for 3.5 minutes. Thereafter, the sample remaining on each sieve and the tray is collected for each sieve mesh. By repeating this classification operation, more than 1400 μm and less than 1700 μm (1400 μm.on), more than 1180 μm and less than 1400 μm (1180 μm.on), more than 1000 μm and less than 1180 μm (1000 μm.on), more than 710 μm and less than 1000 μm (710 μm.on) and more than 500 μm Each particle of 710 μm or less (500 μm.on), 355 μm or more (500 μm.on), 250 μm or more and 355 μm or less (250 μm.on), 150 μm or more and 250 μm or less (150 μm.on), dish to 150 μm or less (150 μm.pass) Obtain a diameter-classified sample. The mass frequency (%) is calculated using the obtained classification sample.
Let X be the mesh opening of the sieve, and Y be the sum of the mass frequency (%) of the classified sample collected on the sieve having the mesh opening X and X larger than X.
When log {log (100 / Y)} is plotted against logX, the slope of the least square approximation line is a, and the intercept is y (log is a common logarithm). However, the points where Y is 5% or less and Y is 95% or more are excluded from the plot.
An average particle diameter can be calculated | required by following Formula using these a and y.
Average particle diameter (mass 50% diameter) = 10 ^{((−0.521−y) / a)}

The average particle size of the particle group (A) is preferably 250 to 3000 μm, more preferably 350 to 1000 μm. When the average particle diameter of the particle group (A) is 250 μm or more, solidification of the powder detergent composition of the present invention is more easily suppressed. When the average particle size of the particle group (A) is 3000 μm or less, when the particle group (A) is blended with a powder detergent or the like, the difference from the particle size of other components does not become too large, and separation hardly occurs. .

The particle group (A) may contain particles having a particle diameter of 355 μm or less (hereinafter also referred to as “fine powder”). If the content of fine powder is large, solidification tends to proceed during storage. On the other hand, if a large amount of fine powder is removed by a classification operation to be described later in order to reduce the fine powder, productivity is lowered.
In the present invention, the content of the fine powder of the particle group (A) (hereinafter also referred to as fine powder ratio) is not particularly limited. From the point that the classification operation described later can be omitted and productivity can be improved, the content of fine powder in the particle group (A) is preferably 70% by mass or less based on the total mass of the particle group (A). It is more preferably 60% by mass or less, and further preferably 50% by mass or less. Moreover, from the point which can acquire the solidification inhibitory effect of this invention more notably, it is preferable that content of the fine powder in a particle group (A) is 20 mass% or more, and it is 30 mass% or more. More preferred. On the other hand, when there is much content of fine powder, the average particle diameter of particle group (A) will become small. In addition, when the particle group (A) is blended in a powder detergent product, the difference in particle diameter between the particle group (A) and other components may increase, resulting in problems such as separation. For this reason, the content of fine powder in the particle group (A) is preferably 50% by mass or less with respect to the particle group (A).

It is known that the particle group (A) containing an α-SF salt has a metastable crystal state and a stable crystal state formed by crystallizing the particle group (A). .
The stable crystalline state particle group (A) (hereinafter also referred to as “stable solid”) is solidified more than the metastable crystalline state particle group (A) (hereinafter also referred to as “metastable solid”). It is known that it is excellent in the suppression property (see International Publication No. 2009/054406).

Generally, metastable solids are not easily formed from high-purity α-SF salt. However, when an α-SF salt is obtained by using a fatty acid alkyl ester as a starting material through the production method described later, usually by-products such as alkyl sulfates and α-sulfo fatty acid di-salts are used in addition to the α-SF salt. Arise. When such a by-product is contained in the particle group (A), the α-SF salt-containing solid substance tends to be in a metastable state.

The present invention includes an α-SF salt particle group (A) and an alkyl sulfate particle group (B), wherein the α-SF salt particles and the alkyl sulfate particles are independent particles. Therefore, even if the particle group (A) is a metastable solid, good solidification inhibition can be obtained.
Therefore, as the particle group (A), a metastable solid may be used, or a stable solid may be used. From the viewpoint that the aging step can be omitted and productivity can be improved, it is preferable to use a metastable solid as the particle group (A).

<Method for Producing Particle Group (A)>
The particle group (A) (hereinafter also referred to as the component (A)) can be produced by a known method, or a commercially available product can be used.
For example, a step of preparing a paste containing α-SF salt (pasting step), a step of preparing flakes from the paste (flaking step), a step of preparing noodles from the flakes (noodle forming step), the noodles The method which has the process (pulverization process) which pulverizes the said flakes, noodle, or a pellet and obtains a particle (pulverization process) is mentioned.
The above (noodle making process) and (pelletizing process) are optional processes and may be omitted. Moreover, you may provide the process (classification process) of classifying a particle group after the said (pulverization process). Furthermore, after the above (flaking process), (noodle forming process) or (pelletizing process), a process of aging flakes, noodles or pellets (aging process) may be provided.

(Aging process)
By performing the aging step, the crystal state of the α-SF salt particles can be converted from a metastable state (metastable solid) to a stable state (stable solid). By converting a metastable solid to a stable solid, the solidification inhibition is further improved.
Methods for converting metastable solids to stable solids are known, and examples of such methods include the following methods (I-1) to (I-3).
(I-1) A method of maintaining a metastable solid at a pressure of 30 ° C. or higher and 200000 Pa or lower for at least 48 hours.
(I-2) A method of maintaining a melt obtained by melting a metastable solid at a temperature not lower than the melting point of the metastable solid and not higher than the melting point of the stable solid for 5 minutes or more.
(I-3) For a melt obtained by melting a metastable solid, a shearing force at a shear rate of 100 (1 / s) or more at a temperature not lower than the melting point of the metastable solid and not higher than 80 ° C. How to give.
Metastable solids and stable solids can be easily distinguished by thermal analysis using a differential scanning calorimeter. 100 × S1 / S2 where S1 is the heat absorption peak area at 50 to 130 ° C. and S2 is the heat absorption peak area at 0 to 130 ° C., which is observed when thermal analysis is performed with a differential scanning calorimeter. The value of crystallinity (unit:%) is less than 50% for metastable solids and 50% or more for stable solids.

<Alkyl sulfate particle group (B)>
The particle group (B) (hereinafter also referred to as the component (B)) is a group of alkyl sulfate particles, and contributes to suppression of solidification of the powder detergent composition containing the particle group (A). Alkyl sulfate is a component that contributes to improving foaming when using powder detergent products. The alkyl sulfate particles may contain impurities in addition to the alkyl sulfate. The alkyl sulfate particles may contain moisture.
The alkyl sulfate is represented by the following formula (2).
R ³ -OSO ₃ M ′ (2)
[In formula (2), R ³ is a linear or branched alkyl group or a linear or branched alkenyl group having 6 to 20 carbon atoms of 6 to 20 carbon atoms, M 'is Counter ion. ]
R ³ preferably has 8 to 18 carbon atoms, more preferably 12 to 16 carbon atoms. R ³ is preferably a linear alkyl group or alkenyl group.
Examples of the counter ion (M ′) include alkali metal ions, protonated amines, ammonium ions, and the like. Examples of the alkali metal that can be the counter ion include sodium and potassium. Examples of the amine that can be a counter ion include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.
Among these, the counter ion (M ′) is preferably an alkali metal ion, more preferably a sodium ion or a potassium ion.
Particularly preferred alkyl sulfates are those in which R ³ is a linear or branched alkyl group or alkenyl group having 12 to 16 carbon atoms, and M ′ is a sodium ion.

The alkyl sulfate contained in the alkyl sulfate particles may be one kind or a mixture of two or more kinds of alkyl sulfates having different carbon numbers for R ³ .
The number of alkyl sulfate particles constituting the particle group (B) may be one, or two or more.
70 mass% or more is preferable and, as for content of the alkyl sulfate (pure part) with respect to the whole (total mass) of particle group (B), 80 mass% or more is more preferable.
The water content of the particle group (B) is preferably 10% by mass or less, and more preferably 5% by mass or less with respect to the total mass of the particle group (B). When the water content is in the above range, the adhesiveness at low temperature is easily suppressed, and the storage stability at low temperature is easily improved.
The average particle size of the particle group (B) is preferably 50 μm or more and less than 3 mm, more preferably 60 μm or more and less than 1 mm. It is excellent in the solidification suppression effect as it is more than the said lower limit. When the powder detergent composition of the present invention is blended into a powder detergent product together with other detergent components, the particle size difference from other detergent components does not become too large and separation is unlikely to occur.
In the present invention, the average particle diameter of the particle group (B) is represented by a volume-based median diameter measured by a dry method using a laser diffraction / scattering apparatus.
The particle group (B) can be produced by a known method such as reacting a raw natural higher alcohol with sulfuric anhydride. It can also be obtained from commercial products.

<Inorganic powder (C)>
Inorganic powder (C) (hereinafter also referred to as component (C)) includes zeolite, sodium carbonate, calcium carbonate, magnesium carbonate, alkaline earth metal carbonate, amorphous silica, white carbon, sodium silicate, silicic acid. Examples thereof include silicates such as calcium and magnesium silicate, viscous minerals such as talc and bentonite, titanium dioxide, sodium sulfate, potassium sulfate and sodium tripolyphosphate. Among these, zeolite, calcium carbonate, amorphous silica, and white carbon are preferable.
Zeolite is a general term for crystalline aluminosilicates. As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, but crystalline aluminosilicate (zeolite) is preferable from the viewpoint of cation exchange ability, and A-type, X-type, and Y-type. P-type zeolite is preferred. In particular, A-type zeolite is preferable.
The inorganic powder (C) contributes to suppression of solidification of the powder detergent composition containing the particle group (A). Inorganic powder (C) may be used individually by 1 type, and may use 2 or more types together.
The average particle size of the inorganic powder (C) is preferably 0.8 to 5 μm, more preferably 0.8 to 3.8 μm. It is excellent in the solidification suppression effect of a powder detergent composition as it is in said range.
In the present invention, the average particle diameter of the inorganic powder (C) is represented by a volume-based median diameter measured by a dry method using an apparatus by a laser diffraction / scattering method.

<Content of each component>
The total content of the α-SF salt in the particle group (A) and the alkyl sulfate in the particle group (B) is 50% by mass or more based on the total mass of the powder detergent composition.
When the inorganic powder (C) is included, the total amount of the α-SF salt in the particle group (A) and the alkyl sulfate salt in the particle group (B) with respect to the total mass of the powder detergent composition. The content is 50% by mass or more, and the content of the inorganic powder (C) is 1 to 30% by mass.
The powder detergent composition may contain, as an optional component, other particle groups that do not fall under any of the components (A) to (C) as long as the effects of the present invention are not impaired. Other particle groups can be appropriately selected from known particle groups contained in powder detergent products.
The content of the other particle group is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and may be zero with respect to the total mass of the powder detergent composition.
The total of the components (A) to (C) and other particle groups is 100% by mass with respect to the total mass of the powder detergent composition.

In an embodiment in which the powder detergent composition contains the components (A) to (C) and does not contain other particle groups, the purity of the α-SF salt in the particle groups (A) relative to the total mass of the powder detergent composition The total content of the component and the alkyl sulfate in the particle group (B) is preferably 50 to 99% by mass, and the content of the inorganic powder (C) is preferably 1 to 30% by mass.
More preferably, the total content of the α-SF salt in the particle group (A) and the alkyl sulfate in the particle group (B) is 65 to 95% by mass with respect to the total mass of the powder detergent composition. %, And the content of the inorganic powder (C) is 5 to 20% by mass.
In an embodiment including the components (A) to (C) and other particle groups, the pure α-SF salt in the particle group (A) and the particle group (B) with respect to the total mass of the powder detergent composition The total content of alkyl sulfates is 50% by mass or more and less than 95% by mass, the content of the inorganic powder (C) is 5 to 20% by mass, and the content of other particle groups is more than zero. It is preferably ˜20% by mass.

The alkyl sulfate in the particle group (B) is 1 to 100 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the α-SF salt in the particle group (A). 5 to 50 parts by mass is more preferable, 5 to 40 parts by mass is further preferable, and 5 to 20 parts by mass is particularly preferable. When the alkyl sulfate salt is 1 part by mass or more with respect to 100 parts by mass of the pure α-SF salt, the powder detergent composition is excellent in suppressing the solidification of the powder detergent composition, and the powder detergent composition is blended with the powder detergent composition. Excellent foaming effect when using.
The powder detergent composition in which the alkyl sulfate is 100 parts by mass or less with respect to 100 parts by mass of the pure α-SF salt sufficiently contains the pure α-SF salt as a detergent component.
In addition, it is preferable that the content of the alkyl sulfate is smaller from the viewpoint of excellent powder adhesion suppression. By setting it as the said preferable range, it becomes what balanced the suppression of solidification of this invention, and the suppression of powder adhesion.

<Powder detergent composition>
In one aspect of the present invention, the powder detergent composition is produced by a method in which the particle group (A), the particle group (B), and any other particle group are dry-mixed at a predetermined blending ratio.
Furthermore, in another aspect containing inorganic powder (C), the powder detergent composition comprises particle group (A), particle group (B), inorganic powder (C), and any other particle group. It is manufactured by a method of dry mixing at a predetermined blending ratio.
As a dry mixing method, for example, a method in which powder is charged and mixed can be used. As an apparatus for mixing powder, any apparatus can be used without particular limitation as long as it is an apparatus used for dry mixing. Specific examples include, but are not limited to, a container-rotating cylindrical mixer, a V-type mixer, and a stirring granulator.
In the powder detergent composition of the present invention, the α-SF salt particles (one particle constituting the particle group (A)) and the alkyl sulfate particle (one particle constituting the particle group (B)) are independent of each other. Exist as particles. In the present invention, the term “existing as an independent particle” means a state in which the original particle shape before mixing is generally maintained as in the case of dry mixing. For example, it includes a state in which alkyl sulfate particles are adhered around α-SF salt particles that have generally maintained the particle shape before mixing. On the other hand, particles that are kneaded and re-granulated to such an extent that the particles do not maintain the particle shape before mixing are not included. The particles of the inorganic powder (C) may be present on the surface of the particles other than the inorganic powder (C), or may be present without adhering, but from the viewpoint of suppressing solidification, α- It is preferably present in a state of adhering to the surface of SF salt particles or alkyl sulfate particles.

(how to use)
The powder detergent composition of the present invention is suitable as a powder detergent composition for addition to be blended into a powder detergent product together with other detergent components.
For example, the powder detergent composition of the present invention and other detergent components are suitably used in a method for producing a powder detergent product by dry mixing.
As other detergent components, known components blended in powder detergent products can be used. Specific examples include surfactants that do not fall into either particle group (A) or particle group (B); inorganic builders such as sodium sulfate and sodium sulfite; alkaline agents such as sodium carbonate and potassium carbonate; fluorescent agents; bleaching Agents; bleach activators; enzymes; fragrances; dyes; softeners; polymer builders such as cationized cellulose, powdered cellulose and sodium polyacrylate.
The content of α-SF salt is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and even more preferably 1 to 20% by mass with respect to the total mass of the powder detergent product.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

<Measurement method / Evaluation method>
(Method for measuring the content of pure α-SF salt in the particle group (A))
The total content of α-sulfo fatty acid alkyl ester salt and α-sulfo fatty acid di-salt was measured by the method (1) below, and the content was determined as the pure content.

(1) Method for measuring pure content About 0.2 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 the sample is dissolved in ion-exchanged water with ultrasound. It was. After dissolution, it is cooled to about 25 ° C., 5 mL of this sample aqueous solution is taken into a titration bottle with a whole pipette, 25 mL of methylene blue indicator and 15 mL of chloroform are added, and further 5 mL of 0.004 mol / L benzethonium chloride solution is added, Titration was performed with a 0.002 mol / L sodium alkylbenzenesulfonate solution. In each titration, the titration bottle was capped and shaken vigorously, then allowed to stand, and the end point was the point where both layers separated against a white plate became the same color.
Similarly, a blank test (the same test as described above except that no sample was used) was performed, and the pure content in the sample was calculated from the following formula from the difference in titration of the sodium alkylbenzenesulfonate solution.
Pure content (% by mass) = (Titration (mL) −Titration (mL) in blank test) × 0.002 (mol / L) × molecular weight of α-SF salt / (sampled amount (g)) × 5 (mL) / 200 (mL)) / 10

(Moisture measurement method: Karl Fischer method)
The sample was pulverized into a pulverized product. About 0.05 g of this pulverized product was sampled, the moisture in the pulverized product was measured using a Karl Fischer moisture meter MKC-210 (manufactured by Kyoto Electronics Industry Co., Ltd.), and the moisture (mass%) in the sample was calculated.

(Measurement method of crystallinity)
A DSC 6220 manufactured by SII was used as a differential scanning calorimeter. A 20 g sample was pulverized with a trio blender (manufactured by Trio Science Co., Ltd.), 5-30 mg of the sample was put in a silver sample pan, heated from 0 ° C. to 130 ° C. at a rate of 2 ° C./min, and subjected to thermal analysis.
100 × S1 / S2 was determined from the heat absorption peak area S1 at 50 to 130 ° C. and the heat absorption peak area S2 at 0 to 130 ° C., and this was defined as the crystallinity (unit:%). The value of crystallinity (unit:%) is less than 50% for metastable solids and 50% or more for stable solids.
The area S1 and the area S2 were obtained by performing an “automatic division integration” process using software attached to the differential scanning calorimeter. When an exothermic peak is observed at 50 to 130 ° C., the value obtained by subtracting the absolute value of the exothermic peak area from the heat absorption peak area at 50 to 130 ° C. is S1, and an exothermic peak is observed at 0 to 130 ° C. When it was observed, the value obtained by subtracting the absolute value of the exothermic peak area from the heat absorption peak area at 0 to 130 ° C. was defined as S2.

(Measurement method of fine powder rate)
The sample was sieved using a sieve having an opening of 355 μm, and the fine powder ratio (unit: mass%) was calculated from the amount of fine powder passed through the sieve by the following formula.
Fine powder ratio = (mass of fine powder passed through sieve / total mass of sample passed through sieve) × 100
(Measuring method of average particle diameter of particle group (B) and inorganic powder (C))
Dry measurement was performed using a particle size distribution measuring apparatus (LS13320, manufactured by Beckman Coulter, Inc.) using a laser diffraction / scattering method, and the volume-based median diameter was defined as the average particle diameter.

(Evaluation method for inhibition of solidification)
80 g of a sample was placed in a cylindrical cell having an inner diameter of 50 mm and a height of 100 mm, and left to stand for 1 week under a load of 2 kg in an atmosphere of 40 ° C. to obtain a cylindrical molded body.
The molded body is taken out, and the detection part is lowered from the upper part under the condition of 5.32 mm / second using FORADA GAUGE (Model No., main body: MX-500N, detection part: ZP-500N) manufactured by IMADA, and the upper surface of the molded body The load was gradually applied to the whole, and the maximum load (unit: kgf) applied until the molded body broke was measured. This measurement was performed three times and the average value was obtained. Incidentally, for a molded body having a maximum load exceeding 50 kgf, measurement was performed under the same conditions as described above using FORGA GAUGE (model No., main body: MX-5000N, detection unit: ZTS-5000N) manufactured by IMADA.
The smaller the maximum load, the better the suppression of solidification.

(Evaluation method for suppression of powder adhesion)
80 g of sample is put in a cylindrical cell (Plamold (φ50 × 100 (mm)), manufactured by Floric Co., Ltd.) with an inner diameter of 50 mm and a height of 100 mm, and left at 40 ° C. and a load of 2 kg for 1 week. A cylindrical shaped body was obtained.
The molded body was taken out, and the adhesion state of the powder on the cylindrical cell wall surface was visually evaluated.
<Evaluation criteria>
◎ ・・・ No adhesion of powder on the cell wall.
○: Powder adheres to a part of the cell wall.
X: Adherence of powder is observed on the entire cell wall surface.

(Raw materials used)
<Particle group (A)>
(A-1): α-SF salt particle group produced in Production Example 1 below, metastable solid having a purity of 91% by mass, moisture of 2% by mass, and crystallinity of 30 to 35%.
(A-2): Metastable solid of α-SF salt particles produced in Production Example 2 below, pure content of 91% by mass, moisture of 2% by mass, and crystallinity of 30 to 35%.
(A-3): α-SF salt particles produced in Production Example 3 below, a stable solid having a purity of 91% by mass, moisture of 2% by mass, and crystallinity of 70% to 80%.
(A-4): α-SF salt particles produced in Production Example 4 below, a stable solid having a purity of 91% by mass, moisture of 2% by mass and crystallinity of 70% to 80%.
The α-sulfo fatty acid alkyl ester salts in (a-1) to (a-4) are all represented by the general formula (1), wherein R ¹ is an alkyl group having 14 to 16 carbon atoms, R ² is a methyl group, A compound in which M is a sodium ion. Tables 1 and 2 show the crystal states, fine powder ratios, and average particle sizes of (a-1) to (a-4).

<Alkyl sulfate particle group (B)>
(B-1): Sodium lauryl sulfate (Texapon OC-P, BASF), pure content 94% by mass.
(B-2): Sodium lauryl sulfate (Shanghai YouYang Industrial), pure content 95% by mass.
(B-3): Sodium lauryl sulfate (EMAL 10P HD, Kao), pure content 98% by mass.
(B-4): Sodium lauryl sulfate (EMERSENSE AS 956-P, Emery), pure content 95% by mass.
Tables 1 and 2 show the average particle sizes of (b-1) to (b-4).
<Inorganic powder (C)>
(C-1): Type A zeolite (4A zeolite manufactured by Thai Silicate Chemical Co.). The average particle size of (c-1) is shown in Tables 1 and 2.
(C-2): A-type zeolite (4A zeolite manufactured by Chalco). The average particle size of (c-2) is shown in Tables 1 and 2.

(Production Example 1: Production of (a-1))
[Paste making process]
Methyl palmitate (product name “Pastel M-16” manufactured by Lion Corporation) and methyl stearate (product name “Pastel M-180” manufactured by Lion Corporation) are 80:20 (mass ratio). Mixed.
Into a reactor having a capacity of 1 kL equipped with a stirrer, 330 kg of the fatty acid methyl ester mixture and anhydrous sodium sulfate as a coloring inhibitor in an amount of 5% by mass of the fatty acid methyl ester mixture were added while stirring. While bubbling 110 kg of SO ₃ gas (sulfonated gas) diluted to 4% by volume with gas, the reaction was blown at a constant rate over 3 hours. The reaction temperature was kept at 80 ° C. The molar ratio of sulfonated gas to fatty acid methyl ester mixture (sulfonated gas / fatty acid methyl ester mixture) was 1.10.
The reaction product was transferred to an esterification tank, 14 kg of methanol was supplied, and an esterification reaction was performed at 80 ° C. After completion of the reaction, the esterified product was withdrawn from the esterification tank, and an equivalent amount of aqueous sodium hydroxide solution was added with a line mixer for continuous neutralization.
Next, this neutralized product was poured into a bleaching agent mixing line, and hydrogen peroxide solution having a concentration of 35% by mass was supplied in an amount of 1 to 2% by mass with respect to the α-SF salt in terms of pure content. The mixture was mixed and bleached while maintaining at 0 ° C. to obtain an α-SF salt-containing paste.

[Flakeing process]
The obtained α-SF salt-containing paste was introduced into a vacuum thin film evaporator (heat transfer surface: 4 m ² , manufactured by Ballestra) at 200 kg / hr, an inner wall heating temperature of 100 to 160 ° C., and a degree of vacuum of 0.01 to 0 It was concentrated at 0.03 MPa and taken out as a melt having a temperature of 100 to 130 ° C.
This melt is cooled to 20-30 ° C. for 0.5 minutes using a belt cooler (manufactured by Nippon Belting Co., Ltd.) and further contains α-SF salt using a crusher (manufactured by Nippon Belting Co., Ltd.). I got flakes.
[Crushing process]
The α-SF salt-containing flakes were charged into a pulverizer (Fitzmill) and pulverized at 1300 rpm to obtain α-SF salt particles.

[Classification process]
The obtained α-SF salt particles were sieved using a sieve having an opening of 355 μm, and the fine powder that passed through the sieve was cut. Next, the cut fine powder was reduced (mixed) to a particle group of α-SF salt so that the fine powder ratio was 15% to obtain (a-1).

(Production Example 2: Production of (a-2))
(A-2) was prepared in the same manner as in Production Example 1 except that the classification step was performed so that the fine powder ratio was 40%.

(Production Example 3: Production of (a-3))
In Production Example 1, the following aging step was performed between the flaking step and the pulverizing step. Otherwise, in the same manner as in Production Example 1, (a-3) having a crystallinity higher than (a-1) was prepared.
[Aging process]
600 kg of α-SF salt-containing flakes were filled into a 1 m ³ flexible container bag and maintained in an environment of 30 ° C. or higher for 4 weeks.

(Production Example 4: Production of (a-4))
(A-4) was prepared in the same manner as in Production Example 3, except that the classification step was performed so that the fine powder ratio was 40%.

<Examples 1 to 14>
The particle group (A), the particle group (B), and the inorganic powder (C) having the formulations shown in Tables 1 and 2 were charged into a container rotary mixer and dry-mixed to produce a powder detergent composition.
About the obtained powder detergent composition, the inhibitory property of solidification and the inhibitory property of powder adhesion were evaluated by said method. The results are shown in Tables 1 and 2 (the same applies hereinafter).

<Example 15>
Example 15 is an example which does not contain inorganic powder (C).
With the formulation shown in Table 2, the particle group (A) and the particle group (B) are put into a container rotary mixer in the same manner as in Example 1 and dry mixed to produce a powder detergent composition. Evaluation was performed in the same manner.
<Comparative Examples 1, 2, 4, 6>
Comparative Examples 1, 2, 4, and 6 are examples that do not contain the particle group (B).
In the same manner as in Example 1, the particle group (A) and the inorganic powder (C) having the composition shown in Table 2 were put into a container rotary mixer and dry-mixed to produce a powder detergent composition. And evaluated in the same manner.

<Comparative Example 3>
Comparative Example 3 is an example not containing the particle group (B) and the inorganic powder (C).
The powder detergent composition consisting only of the particle group (A) shown in Table 2 was evaluated in the same manner as in Example 1.
<Comparative Example 5>
Comparative Example 5 is an example not containing the particle group (A) and the inorganic powder (C).
The powder detergent composition consisting only of the particle group (B) shown in Table 2 was evaluated in the same manner as in Example 1.

From the results shown in Tables 1 and 2, solidification of the powder detergent compositions of Examples 1 to 15 was further suppressed as compared with Comparative Example 3.
When Examples 1 to 3 and Comparative Example 1, Examples 4 to 8 and Comparative Example 6, and Examples 9 and 10 and Comparative Example 2 are compared, the solidification property is improved by adding the particle group (B). I understand.
Comparing Examples 1 to 3 with Examples 4, 5, and 7 respectively, it can be seen that solidification inhibition is further improved by making the crystal state of the particle group (A) a stable solid.
From the results of Examples 11 to 14 and Comparative Example 4, the alkyl sulfate in the particle group (B) is 1 part by mass or more with respect to 100 parts by mass of the pure α-SF salt in the particle group (A). It turns out that the inhibitory effect of solidification is acquired by mix | blending so that it may become.
When Examples 9 and 10 are compared with Comparative Example 2, even when the fine particle ratio of the particle group (A) is as high as 40%, the solidification property is improved by blending the particle group (B), and particularly the particle group ( It can be seen that the improvement effect is larger when the average particle size of B) is larger.
When Example 15 and Comparative Example 3 are compared, it can be seen that solidification improves by blending the particle group (B) even when the fine particle ratio of the particle group (A) is as high as 40%.
From the results of Examples 11 to 14, it can be seen that the larger the content of the particle group (B), the higher the effect of improving the solidification property, and the lower the content of the particle group (B), the more the powder adhesion is suppressed. That is, by setting the content of the particle group (B) in an appropriate range, it is possible to achieve both solidification inhibition and powder adhesion inhibition.

The above-mentioned powder detergent composition is excellent in the suppression of solidification while containing α-SF salt at a high concentration.
The above-mentioned powder detergent composition is blended with other detergent components and used suitably for the production of powder detergent products.

Claims

particle group (A) of α-sulfo fatty acid alkyl ester salt and particle group (B) of alkyl sulfate salt,
The total content of the α-sulfo fatty acid alkyl ester salt in the particle group (A) and the alkyl sulfate salt in the particle group (B) is 50% by mass with respect to the total mass of the powder detergent composition. % Or more,
The alkyl sulfate in the particle group (B) is 1 to 100 parts by mass with respect to 100 parts by mass of the α-sulfo fatty acid alkyl ester salt in the particle group (A),
A powder detergent composition, wherein the particles of the α-sulfo fatty acid alkyl ester salt and the particles of the alkyl sulfate salt are present as independent particles.
α-sulfo fatty acid alkyl ester salt particle group (A), alkyl sulfate particle group (B), and inorganic powder (C),
The total content of the α-sulfo fatty acid alkyl ester salt in the particle group (A) and the alkyl sulfate salt in the particle group (B) is 50% by mass with respect to the total mass of the powder detergent composition. % Or more,
The alkyl sulfate in the particle group (B) is 1 to 100 parts by mass with respect to 100 parts by mass of the α-sulfo fatty acid alkyl ester salt in the particle group (A),
The content of the inorganic powder (C) is 1 to 30% by mass with respect to the total mass of the powder detergent composition,
A powder detergent composition, wherein the particles of the α-sulfo fatty acid alkyl ester salt and the particles of the alkyl sulfate salt are present as independent particles.
The powder detergent composition according to claim 2, wherein the particle group (B) has an average particle size of 50 µm or more and less than 3 mm, and the inorganic powder (C) has an average particle size of 0.8 to 5 µm.
A method for producing a powder detergent composition according to claim 1, comprising:
A method for producing a powder detergent composition, comprising dry mixing the particle group (A) of the α-sulfo fatty acid alkyl ester salt and the particle group (B) of the alkyl sulfate.
A method for producing a powder detergent composition according to claim 2 or 3,
A method for producing a powder detergent composition, wherein the α-sulfo fatty acid alkyl ester salt particle group (A), the alkyl sulfate salt group (B), and the inorganic powder (C) are dry-mixed.