JPWO2018003905A1 - Powder detergent composition and method for producing the same - Google Patents

Abstract

  The powder detergent composition comprises a particle group (A) of an α-sulfofatty acid alkyl ester salt (α-SF salt) and a particle group (B) of an alkyl sulfate, and the α-SF salt in the particle group (A) The total content of the pure portion of the polymer and the alkyl sulfate in the particle group (B) is 50% by mass or more, and the particle is based on 100 parts by mass of the pure portion of the α-SF salt in the particle group (A) The alkyl sulfate in the group (B) is 1 to 100 parts by mass, particles of the α-SF salt and particles of the alkyl sulfate exist as independent particles, and the concentration of the α-SF salt is high It is excellent in the suppression of solidification while containing

Description

The present invention relates to a powder detergent composition and a method of making the same. The powder detergent composition of the present invention is suitable as an additive powder detergent composition to be formulated into a powder detergent product along with other detergent ingredients.
For example, it can be suitably used in a method of producing a powder detergent product by dry mixing the powder detergent composition of the present invention and other detergent components.
Priority is claimed on Japanese Patent Application No. 2016-131106, filed June 30, 2016, the content of which is incorporated herein by reference.

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

JP, 2011-116807, A

However, the technique of Patent Document 1 still has room for improvement in terms of difficulty in solidifying (inhibition of solidifying). In particular, when the α-SF salt is contained at a high concentration, the inhibition of solidification is not sufficient.
This invention is made in view of the said situation, and aims at provision of the powder detergent composition which is excellent in the suppression property of solidification, containing the alpha-SF salt by high concentration, and its manufacturing method.

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, wherein the pure fraction of the α-sulfo fatty acid alkyl ester salt in the particle group (A) The total content with the alkyl sulfate in the particle group (B) is 50% by mass or more, and the above content relative to 100 parts by mass of the pure content of the α-sulfofatty acid alkyl ester salt in the particle group (A) Powder detergent composition, wherein the amount of the alkyl sulfate in the particle group (B) is 1 to 100 parts by mass, and the particles of the α-sulfofatty acid alkyl ester salt and the particles of the alkyl sulfate are independent of each other object.
[2] A particle group (A) of α-sulfo fatty acid alkyl ester salt, a particle group (B) of alkyl sulfate, and an inorganic powder (C), the α-sulfo fatty acid in the particle group (A) The total content of the pure component of the alkyl ester salt and the alkyl sulfate in the particle group (B) is 50% by mass or more, and the pure component of the α-sulfofatty acid alkyl ester salt in the particle group (A) The alkyl sulfate in the particle group (B) is 1 to 100 parts by mass, and the content of the inorganic powder (C) is 1 to 30% by mass with respect to 100 parts by mass, and the α-sulfo A powder detergent composition, wherein particles of a fatty acid alkyl ester salt and particles of the alkyl sulfate are present as independent particles.
[3] The average particle diameter of the particle group (B) of the alkyl sulfate is 50 μm or more and less than 3 mm, and the average particle diameter of the inorganic powder (C) is 0.8 to 5 μm. Powder detergent composition.

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

[6] The content of particles having a particle diameter 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] with other detergent components.

ADVANTAGE OF THE INVENTION According to this invention, the powder detergent composition which is excellent in the suppression property of solidification is obtained, although it contains (alpha) -SF salt in high concentration.
Preferably, while containing the α-SF salt at a high concentration, powder detergent composition (powder adhesion) to other materials can be suppressed, and a powder detergent composition having excellent solidification suppression property can be obtained.

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

<Particle Group of α-SF Salt (A)>
The particle group (A) is a group of particles of α-SF salt and is a cleaning component. The particles of the α-SF salt may contain impurities. The particles of the α-SF salt may contain water.
Particles of α-SF salt are sulfate (sodium sulfate), which is an unavoidable by-product in production of α-sulfofatty acid alkyl ester salt, in addition to α-sulfofatty acid alkyl ester salt represented by the following formula (1) Etc.), alkyl sulfates (such as sodium methyl sulfate), α-sulfo fatty acid disalts (such as α-sulfo fatty acid disodium salt), or unreacted raw materials. The α-sulfo fatty acid di salt has a function as a surfactant.
In the present invention, the total content (% by 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 part. In addition, pure content is measured by the measuring method of pure content of postscript.

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 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 And an alkyl group having 1 to 6 carbon atoms, and M is a counter ion. ]
8-18 are preferable and, as for carbon number of R < ¹ >, 12-16 are more preferable.
The number of carbon atoms in R ² is preferably 1 to 3. 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 which can be the counter ion include sodium and potassium. The amine capable of becoming 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. 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.
The α-sulfofatty acid alkyl ester salt contained in the particles of the α-SF salt may be one type, or a mixture of two or more types of α-sulfo fatty acid alkyl ester salts having different carbon numbers of R ¹ .
The particles of the α-SF salt 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 It is preferable that it is 100: 0. Further, an 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.

70 mass% or more is preferable, and, as for the content of the pure part of (alpha) -SF salt with respect to the whole (total mass) of particle group (A), 80 mass% or more is more preferable. In the particle group (A), in addition to the above-mentioned α-SF salts, sulfates (sodium sulfate etc.), alkyl sulfates (methyl sodium sulfate etc.) which are unavoidable by-products in production of α-sulfofatty acid alkyl ester salts , An α-sulfo fatty acid di salt (such as an α-sulfo fatty acid disodium salt) or water may be contained. In general, the particle group (A) contains 60 to 98% by mass of an α-SF salt, 1 to 10% by mass of an α-sulfo fatty acid disalt, and 1 to 10% by mass of an alkyl sulfate.
10 mass% or less is preferable with respect to the total mass of particle group (A), and, as for the water content of particle group (A), 5 mass% or less is more preferable. 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 enhanced.
In the present specification, the water content of the particle group (A) is a value measured by the Karl Fischer method.

The average particle size of the particle group (A) of the present invention is represented by the mass-based cumulative 50% diameter (mass median diameter) by sieving method. Specifically, it is a value measured according to the following procedure.
The classification operation of the particles is carried out using nine stages of sieves and trays 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, stack small sieves with large openings on the receiving tray in the order of large sieves, put 100 g / piece of particles from the top of the 1700 μm sieve on top, cover it, and cover with a low-tap sieve shaker (Dalton Co., Ltd. Made, tapping: 125 times / min, rolling: 250 times / min) and shake for 3.5 minutes. Thereafter, the samples remaining on the respective sieves and pans are collected every sieve. By repeating this classification operation, more than 1400 μm to less than 1700 μm (1400 μm. On), more than 1180 μm to less than 1400 μm (1180 μm. On), more than 1000 μm to 1180 μm (1000 μm. On), more than 710 μm to less than 1000 μm (710 μm. On), more than 500 μm Each particle of 710 μm or less (500 μm. On), 355 μm to 500 μm (355 μm. On), 250 μm to 355 μm or less (250 μm. On), 150 μm to 250 μm or less (150 μm. On), dish to 150 μm or less (150 μm. Pass) Obtain a classified sample of diameter. Mass frequency (%) is calculated using the obtained classified sample.
Let X be the mesh size of the sieve, and Y be the sum of mass frequencies (%) of the classified samples collected on the mesh sizes X and X larger than the mesh size.
The slope of the least squares approximate line when plotting log {log (100 / Y)} against log X is a, and the intercept is y (log is a common logarithm). However, points at which Y is 5% or less and Y is 95% or more are excluded from the above plot.
The average particle diameter can be determined by the following equation using a and y.
Average particle size (mass 50% diameter) = 10 ^{((−0.521−y) / a)}

  The average particle size of the particle group (A) is preferably 250 to 3000 μm, and more preferably 350 to 1000 μm. When the average particle size 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 diameter of the particle group (A) is 3000 μm or less, when the particle group (A) is blended in a powder detergent or the like, the difference with the particle diameters of other components becomes 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 classification operation described later in order to reduce the fine powder, the productivity is reduced.
In the present invention, the content of the fine powder of the particle group (A) (hereinafter, also referred to as a fine powder ratio) is not particularly limited. The content of the fine powder in the particle group (A) is preferably 70% by mass or less based on the total mass of the particle group (A) from the viewpoint of omitting the classification operation described later and enhancing the productivity. It is more preferable that it is 60 mass% or less, and it is further more preferable that it is 50 mass% or less. In addition, the content of the fine powder in the particle group (A) is preferably 20% by mass or more, and 30% by mass or more from the viewpoint that the solidification suppressing effect of the present invention can be more remarkably obtained. More preferable. On the other hand, when the content of the fine powder is large, the average particle size of the particle group (A) decreases. In addition, when the particle group (A) is blended in a powder detergent product, the difference between the particle diameter of the particle group (A) and the particle diameter of other components becomes large, which may cause problems such as separation. Therefore, it is preferable that content of the fine powder in particle group (A) is 50 mass% or less with respect to particle group (A) from this point.

It is known that a particle group (A) containing an α-SF salt has a metastable crystalline state and a stable crystalline state formed by crystallizing the particle group (A). .
And, the particle group (A) in stable crystalline state (hereinafter also referred to as "stable solid") is solidified more than the particle group (A) in metastable state (hereinafter referred to as "metastable solid") Are known to be excellent in the inhibitory properties of (see WO 2009/054406).

  In general, metastable solids are less likely to be formed from high purity α-SF salts. However, when fatty acid alkyl ester is used as a starting material and α-SF salt is obtained through the below-mentioned production method, usually, in addition to α-SF salt, by-products such as alkyl sulfate and α-sulfo fatty acid di salt are It occurs. When such a by-product is included in the particle group (A), the α-SF salt-containing solid tends to be in a metastable state.

In the present invention, particles of α-SF salt particles (A) and particles of alkyl sulfate (B) are contained, and particles of α-SF salt and particles of alkyl sulfate are independent of each other. Since the suppression of solidification can be enhanced by the presence as P., even if the particle group (A) is a metastable solid, good suppression of solidification can be obtained.
Therefore, as the particle group (A), a metastable solid may be used or a stable solid may be used. It is preferable to use a metastable solid as the particle group (A) from the viewpoint of omitting the ripening step and increasing the productivity.

<Production Method of Particle Group (A)>
The particle group (A) (hereinafter, also referred to as 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 an α-SF salt (pasting step), a step of preparing flakes from the paste (flaking step), a step of preparing noodles from the flakes (noodleing step), the noodles And the step of preparing pellets (pelletizing step), and the step of pulverizing the flakes, noodles or pellets to obtain particles (pulverizing step).
The above (noodleing step) and (pelletizing step) are optional steps and may be omitted. Moreover, you may provide the process (classification process) which classifies particle groups after the above (grind process). Furthermore, after the above (flaking step), (noodleing step) or (pelletizing step), a step (aging step) of aging the flakes, noodles or pellets may be provided before the grinding step.

(Aging process)
By performing the aging step, the crystalline state of the particles of the α-SF salt can be converted from a metastable state (metastable solid) to a stable state (stable solid). Converting a metastable solid to a stable solid further improves the inhibition of solidification.
The method of converting a metastable solid into a stable solid is known, and such methods include, for example, the following methods (I-1) to (I-3).
(I-1) A method of maintaining a metastable solid at a pressure of 30 ° C. or more and 200,000 Pa or less 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) With respect to a melt obtained by melting a metastable solid, shear force is applied at a shear rate of 100 (1 / s) or higher at a temperature of 80 ° C. or higher and a temperature above the melting point of the metastable solid How to give.
A metastable solid and a stable solid can be easily distinguished by thermal analysis using a differential scanning calorimeter. When the heat absorption peak area at 50 to 130 ° C. observed when thermal analysis is performed by a differential scanning calorimeter is S1, and the heat absorption peak area at 0 to 130 ° C. is S2, it is determined by 100 × S1 / S2. The value of crystallinity (unit:%) is less than 50% for a metastable solid and 50% or more for a stable solid.

<Particle Group of Alkyl Sulfate (B)>
The particle group (B) (hereinafter also referred to as component (B)) is a group of particles of alkyl sulfate and contributes to suppression of solidification of the powder detergent composition containing the particle group (A). In addition, alkyl sulfate is a component that contributes to the improvement of foaming when using a powder detergent product. The particles of alkyl sulfate may contain impurities in addition to the alkyl sulfate. The particles of alkyl sulfate may contain water.
The alkyl sulfate is represented by the following formula (2).
R ³ −OSO ₃ M ′ (2)
[In Formula (2), R ³ represents 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 M ′ represents It is a counter ion. ]
The number of carbon atoms of R ³ is 8 to 18 is preferable, 12 to 16 is more preferable. R ³ is preferably a linear alkyl group or an alkenyl group.
Examples of the counter ion (M ′) include alkali metal ions, protonated amines, ammonium ions and the like. Examples of the alkali metal which can be the counter ion include sodium and potassium. Examples of the amine which can be the counter ion include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.
Among these, the counter ion (M ′) is preferably an alkali metal ion, and 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 or alkenyl group having 12 to 16 carbon atoms, and M ′ is a sodium ion.

The alkyl sulfate contained in the particles of the alkyl sulfate may be one type, or may be a mixture of two or more types of alkyl sulfates having different carbon numbers of R ³ .
The number of particles of the alkyl sulfate 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.
10 mass% or less is preferable with respect to the total mass of particle group (B), and, as for the water content of particle group (B), 5 mass% or less is more preferable. 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 enhanced.
The average particle diameter of the particle group (B) is preferably 50 μm or more and less than 3 mm, and more preferably 60 μm or more and less than 1 mm. It is excellent in the control effect of solidification as it is more than the above-mentioned lower limit. When the powder detergent composition of the present invention is formulated into a powder detergent product together with other detergent components as the above upper limit value or less, the difference in particle size with other detergent components becomes too large and separation hardly occurs.
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 an apparatus by a laser diffraction / scattering method.
The particle group (B) can be produced by a known method such as, for example, reacting natural higher alcohols as raw materials with sulfuric anhydride. It can also be obtained from commercial products.

<Inorganic powder (C)>
As the inorganic powder (C) (hereinafter, also referred to as component (C)), zeolite, sodium carbonate, calcium carbonate, magnesium carbonate, alkaline earth metal carbonate, amorphous silica, white carbon, sodium silicate, silicic acid Examples thereof include calcium, silicates such as magnesium silicate, viscosity minerals such as talc and bentonite, titanium dioxide, sodium sulfate, potassium sulfate, sodium tripolyphosphate and the like. Among these, zeolite, calcium carbonate, amorphous silica and white carbon are preferable.
Zeolite is a generic term for crystalline aluminosilicates. As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, but from the viewpoint of cation exchange ability, crystalline aluminosilicate (zeolite) is preferable, and A-type, X-type and Y-type are preferable. And P-type zeolites are preferable. In particular, A-type zeolite is preferred.
The inorganic powder (C) contributes to suppression of solidification of the powder detergent composition containing the particle group (A). The inorganic powder (C) may be used alone or in combination of two or more.
0.8-5 micrometers is preferable and, as for the average particle diameter of inorganic powder (C), 0.8-3.8 micrometers is more preferable. It is excellent in the inhibitory effect of solidification 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 pure portion 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 contained, the total of the pure portion of the α-SF salt in the particle group (A) and the alkyl sulfate in the particle group (B) with respect to the total mass of the powder detergent composition. Content is 50 mass% or more, and content of inorganic powder (C) is 1-30 mass%.
The powder detergent composition may contain, as an optional component, another particle group which does not correspond to any of the components (A) to (C) as long as the effects of the present invention are not impaired. As other particle groups, they can be appropriately selected and used from known particle groups contained in powder detergent products.
The content of the other particle groups 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 the other particle groups is 100% by mass based on the total mass of the powder detergent composition.

In the embodiment where the powder detergent composition contains the components (A) to (C) and does not contain other particle groups, the pure of the α-SF salt in the particle group (A) with respect to the total weight of the powder detergent composition It is preferable that content of the sum total of the amount and the alkyl sulfate in particle | grain group (B) is 50-99 mass%, and content of an inorganic powder (C) is 1-30 mass%.
More preferably, the total content of the pure portion of the α-SF salt in the particle group (A) and the alkyl sulfate in the particle group (B) is 65 to 95 mass based on the total mass of the powder detergent composition. %, And the content of the inorganic powder (C) is 5 to 20% by mass.
In the embodiment comprising the components (A) to (C) and the other particle groups, the pure portion of the α-SF salt in the particle groups (A) and the particle groups (B) with respect to the total mass of the powder detergent composition Content of the total of the alkyl sulfate of 50% by mass to less than 95% by mass, the content of the inorganic powder (C) is 5 to 20% by mass, and the content of the other particle groups is more than zero It is preferable that it is -20 mass%.

The alkyl sulfate in the particle group (B) is 1 to 100 parts by mass, preferably 5 to 100 parts by mass, with respect to 100 parts by mass of the pure component 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. A powder detergent product in which the powder detergent composition is blended, as well as the effect of suppressing solidification of the powder detergent composition being 1 part by mass or more of the alkyl sulfate relative to 100 parts by mass of the pure content of the α-SF salt It excels in the foaming improvement effect at the time of using.
The powder detergent composition having 100 parts by mass or less of alkyl sulfate relative to 100 parts by mass of the pure portion of the α-SF salt sufficiently contains the pure portion of the α-SF salt which is a detergent component.
Moreover, from the point which is excellent in the suppression property of powder adhesion, the one where there is little content of alkyl sulfate is preferable. By setting it as the above-mentioned preferable range, the suppression of solidification of the present invention and the suppression of powder adhesion can be balanced.

<Powder detergent composition>
In one aspect of the present invention, the powder detergent composition is produced by a method of dry-mixing the particle group (A), the particle group (B) and any other particle group at a predetermined blending ratio.
In yet another embodiment comprising inorganic powder (C), the powder detergent composition comprises particles (A), particles (B), inorganic powder (C) and any other particles. It is manufactured by a method of dry mixing at a predetermined blending ratio.
As a method of dry mixing, for example, a method of charging and mixing powder can be used. As an apparatus for mixing powders, any apparatus used for dry mixing can be used without particular limitation. Specific examples thereof 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 particles of α-SF salt (one particle constituting particle group (A)) and the particle of alkyl sulfate (one particle constituting particle group (B)) are independent of each other. Present as particles. In the present invention, “being present as independent particles” means a state of being mixed in a state where the original particle shape before mixing is substantially maintained, as in the case of dry mixing. For example, it includes a state in which particles of alkyl sulfate are attached around the particles of the α-SF salt which maintains the particle shape before mixing. On the other hand, it does not include those which are mixed and regranulated so that the particles do not maintain the particle shape before mixing. The particles of the inorganic powder (C) may be present in a state of being attached to the surface of particles other than the inorganic powder (C), or may be present without being attached, but from the viewpoint of solidification inhibition It is preferable to be present in the state of being attached to the surface of the particles of the SF salt or the particles of the alkyl sulfate.

(how to use)
The powder detergent composition of the present invention is suitable as an additive powder detergent composition to be formulated into a powder detergent product along with other detergent ingredients.
For example, it can be suitably used in a method of producing a powder detergent product by dry mixing the powder detergent composition of the present invention and other detergent components.
Other detergent ingredients may be known ingredients that are formulated into powder detergent products. Specific examples include surfactants that do not fall under either the particle group (A) or the particle group (B); inorganic builders such as sodium sulfate and sodium sulfite; alkaline agents such as sodium carbonate and potassium carbonate; fluorescent agents; Agents; bleaches; agents; perfumes; dyes; softeners; polymeric builders such as cationic cellulose, powdered cellulose, sodium polyacrylate and the like.
The content of the α-SF salt is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and still 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 by way of examples, but the present invention is not limited by the following description.

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

(1) Measurement method of pure content Weigh accurately about 0.2 g of the sample into a 200 mL volumetric flask, add ion-exchanged water (distilled water) up to the marked line, and dissolve the sample in ion-exchanged water with ultrasound. The After dissolution, cool to about 25 ° C, take 5 mL of this aqueous sample solution into a titration bottle with a whole pipet, add 25 mL of methylene blue indicator and 15 mL of chloroform, and add 5 mL of a 0.004 mol / L benzethonium chloride solution. The solution was titrated with a 0.002 mol / L sodium alkylbenzene sulfonate solution. In each case, the titration bottle was stoppered and shaken vigorously, and then allowed to stand. The point at which both layers separated with the white plate as the background had the same color was defined as the end point.
Similarly, a blank test (same test as described above except that the sample was not used) was carried out, and the content of the pure portion in the sample was calculated from the following formula from the difference of the titration amount of the sodium alkylbenzene sulfonate solution.
Pure content (mass%) = (titrated value in blank test (mL)-titrated amount (mL)) x 0.002 (mol / L) x molecular weight of α-SF salt / (sampling amount (g) × 5 (mL) / 200 (mL) / 10

(Measuring method of moisture: Karl Fischer method)
The sample was broken into pieces and crushed. About 0.05 g of this pulverized material was collected, the water content in the pulverized material was measured using a Karl Fischer moisture meter MKC-210 (manufactured by Kyoto Denshi Kogyo Co., Ltd.), and the water content (mass%) in the sample was calculated.

(Method of measuring crystallinity)
A DSC 6220 manufactured by SII was used as a differential scanning calorimeter. 20 g of a sample was ground with a trio blender (manufactured by Trio Science Co., Ltd.), 5 to 30 mg of it was placed in a silver sample pan, the temperature was raised from 0 ° C. to 130 ° C. at a rate of 2 ° C./min, and thermal analysis was performed.
100 * S1 / S2 was calculated | required from heat absorption peak area S1 in 50-130 degreeC at this time, and heat absorption peak area S2 in 0-130 degreeC, and this was made into crystallinity degree (unit:%). The value of crystallinity (unit:%) is less than 50% for a metastable solid and 50% or more for a stable solid.
The area S1 and the area S2 were obtained by performing “automatic division integration” processing using software attached to the differential scanning calorimeter. When an exothermic peak is observed at 50 to 130 ° C., a 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 the exothermic peak is 0 to 130 ° C. When it recognizes, the value which deducted the absolute value of the exothermic peak area from the heat absorption peak area in 0-130 ° C was made into S2.

(Measurement method of fine powder rate)
The sample was sieved using a 355 μm sieve, and the fine powder ratio (unit: mass%) was calculated from the amount of fine powder passed through the sieve according to the following equation.
Fine powder rate = (mass of fine powder passing through sieve / total mass of sieved sample) × 100
(Method of measuring average particle size of particle group (B), inorganic powder (C))
Dry measurement was carried out using a particle size distribution measuring apparatus (LS 13 320, manufactured by Beckman Coulter, Inc.) by a laser diffraction / scattering method, and the volume-based median diameter was defined as the average particle size.

(Evaluation method of 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 at rest at a load of 2 kg for 1 week in an atmosphere of 40 ° C. to obtain a cylindrical molded body.
The molded body is taken out, and the detection portion is lowered from above at a condition of 5.32 mm / sec using FORCE GAUGE made by IMADA (model No., main body: MX-500N, detection portion: ZP-500N), and the upper surface of the molded body A 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 determined. In addition, with respect to the molded object whose largest load exceeds 50 kgf, it measured on the said conditions using IMADA FORCE GAUGE (model No., main body: MX-5000N, detection part: ZTS-5000N).
The smaller the maximum load, the better the control of solidification.

(Evaluation method of suppression of powder adhesion)
80 g of the sample is placed in a cylindrical cell (Plamold (φ 50 × 100 (mm), made by Floric Co., Ltd.) with an inner diameter of 50 mm and a height of 100 mm, and left standing for 1 week under a load of 2 kg at 40 ° C. It was set as a cylindrical-shaped molded object.
The molded body was taken out, and the adhesion state of the powder to the cylindrical cell wall surface was visually evaluated.
<Evaluation criteria>
・ ・ ・ ... no adhesion of powder on cell wall.
○: adhesion of powder is observed on part of the cell wall surface.
X: adhesion of powder is observed on the entire cell wall surface.

(Raw material used)
<Particle group (A)>
(A-1): A particle group of an α-SF salt produced in the following Production Example 1, 91% by mass of a pure component, 2% by mass of water, and a metastable solid having a crystallinity of 30 to 35%.
(A-2): A particle group of an α-SF salt produced in the following Production Example 2, 91 mass% pure, 2 mass% water, metastable solid with a crystallinity of 30 to 35%.
(A-3): The particle group of the α-SF salt produced in the following Production Example 3, 91% by mass of pure component, 2% by mass of water, stable solid with 70% to 80% of crystallinity.
(A-4): particle group of α-SF salt produced in the following Production Example 4, stable solid with 91% by mass of pure water, 2% by mass of water, and 70% to 80% of crystallinity.
The α-sulfofatty acid alkyl ester salts in (a-1) to (a-4) are each an alkyl group in which R ¹ is a C 14-16 carbon atom, R ² is a methyl group in the general formula (1). It is a compound in which M is a sodium ion. The crystalline states (a-1) to (a-4), the fine particle ratio, and the average particle size are shown in Tables 1 and 2.

<Particle Group of Alkyl Sulfate (B)>
(B-1): sodium lauryl sulfate (Texapon OC-P, BASF), pure 94% by mass.
(B-2): sodium lauryl sulfate (Shanghai YouYang Indastrial), pure 95% by mass.
(B-3): sodium lauryl sulfate (EMAL 10P HD, Kao), 98% by mass in pure part.
(B-4): sodium lauryl sulfate (EMERSENSE AS 956-P, Emery), pure 95% by mass.
The average particle diameters of (b-1) to (b-4) are shown in Tables 1 and 2.
<Inorganic powder (C)>
(C-1): A-type zeolite (4A zeolite manufactured by Thai Silicate Chemical Co., Ltd.). The average particle diameter of (c-1) is shown in Tables 1 and 2.
(C-2): A-type zeolite (4A zeolite manufactured by Chalco). The average particle diameter of (c-2) is shown in Tables 1 and 2.

(Production Example 1: Production of (a-1))
[Paste formation process]
80:20 (Mass ratio) of methyl palmitate (Lion Corporation, trade name "Pastel M-16") and methyl stearate (Lion Corporation, trade name "Pastel M-180") Mixed as.
In a 1 kL reactor equipped with a stirrer, 330 kg of the fatty acid methyl ester mixture and anhydrous sodium sulfate as a coloring inhibitor are added in an amount of 5% by mass of the fatty acid methyl ester mixture, and while stirring, nitrogen While bubbling, 110 kg of SO ₃ gas (sulfonated gas) diluted to 4% by volume with gas was blown at a constant speed for reaction for 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 above reaction product was transferred to an esterification tank, and 14 kg of methanol was supplied to carry out an esterification reaction at 80 ° C. After completion of the reaction, the esterified product was withdrawn from the esterification tank, and was neutralized continuously by adding an equivalent aqueous sodium hydroxide solution with a line mixer.
Next, this neutralized product is injected into the bleaching agent mixing line, and a 35% by weight aqueous hydrogen peroxide solution is supplied in an amount of 1 to 2% by mass with respect to the α-SF salt in terms of pure part. The mixture was mixed and bleached while keeping the temperature at .degree. C. to obtain an .alpha.-SF salt-containing paste.

[Flake process]
The obtained paste containing α-SF salt is introduced into a vacuum thin film evaporator (heat transfer surface: 4 m ² , manufactured by Ballestra) at 200 kg / hr, inner wall heating temperature 100 to 160 ° C., vacuum degree 0.01 to 0 The solution was concentrated at .03 MPa and taken out as a melt at a temperature of 100 to 130.degree.
This molten material is cooled to 20-30 ° C. in 0.5 minutes using a belt cooler (made by Nippon Belting Co., Ltd.), and further containing α-SF salt by using a crusher (made by Nippon Belting Co., Ltd.) I got the flakes.
[Crushing process]
The said (alpha) -SF salt containing flakes were thrown into the grinder (Fitzmill), and it ground at 1300 rpm, and obtained the particle group of (alpha) -SF salt.

[Classification process]
The resulting particles of the α-SF salt were sieved using a 355 μm sieve, and the fine powder passing through the sieve was cut. Next, the cut fine powder was reduced (mixed) to particles of an α-SF salt so as to have a fine powder ratio of 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 carried out so that the fine powder ratio was 40%.

(Production Example 3: Production of (a-3))
In Production Example 1, the following ripening step was performed between the flaking step and the grinding step. Other than that was carried out similarly to manufacture example 1, and prepared crystallinity degree (a-3) higher than (a-1).
[Aging process]
The alpha-SF salt containing flakes 600 kg, was packed in a flexible container bag of 1 m ^3, that was maintained for 4 weeks at 30 ° C. or higher environment.

(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 carried out so that the fine powder ratio was 40%.

Examples 1 to 14
The powder group (A), the particle group (B) and the inorganic powder (C) were mixed into the container rotary mixer according to the formulations shown in Tables 1 and 2 and dry mixed to produce a powder detergent composition.
With respect to the obtained powder detergent composition, the inhibition of solidification and the inhibition of powder adhesion were evaluated by the methods described above. The results are shown in Tables 1 and 2 (the same applies hereinafter).

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

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

From the results of Tables 1 and 2, in the powder detergent compositions of Examples 1 to 15, solidification was further suppressed as compared with Comparative Example 3.
Comparison of Examples 1 to 3 with Comparative Example 1, Examples 4 to 8 with Comparative Example 6 and Examples 9 and 10 with Comparative Example 2 improves the solidifying property by blending the particle group (B). I understand.
Comparing Examples 1 to 3 with Examples 4, 5 and 7, respectively, it is understood that the suppression of solidification is further improved by making the crystalline state of the particle group (A) a stable solid.
From the results of Examples 11 to 14 and Comparative Example 4, 1 part by mass or more of the alkyl sulfate in the particle group (B) is based on 100 parts by mass of the pure portion of the 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 becomes.
When Examples 9 and 10 and Comparative Example 2 are compared, the solidifying property is improved by blending the particle group (B) even when the fine powder ratio of the particle group (A) is as high as 40%, and in particular, the particle group ( It can be seen that the larger the average particle diameter of B), the greater the improvement effect.
When Example 15 and Comparative Example 3 are compared, it can be seen that, even when the fine particle rate of the particle group (A) is as high as 40%, the solidifying property is improved by blending the particle group (B).
From the results of Examples 11 to 14, it is understood that the effect of improving the solidifying property is higher as the content of the particle group (B) is larger, and the powder adhesion is suppressed as the content of the particle group (B) is smaller. That is, by setting the content of the particle group (B) in an appropriate range, it is possible to achieve both the suppression of solidification and the suppression of powder adhesion.

The above-mentioned powder detergent composition is excellent in the inhibition of solidification while containing the α-SF salt at a high concentration.
The above-mentioned powder detergent compositions are suitably used together with other detergent ingredients for the production of powder detergent products.

Claims (5)

a particle group of an α-sulfo fatty acid alkyl ester salt (A) and a particle group of an alkyl sulfate (B),
The total content of the pure component of the α-sulfofatty acid alkyl ester salt in the particle group (A) and the alkyl sulfate in the particle group (B) is 50 mass based on the total mass of the powder detergent composition. % Or more,
The amount of the alkyl sulfate in the particle group (B) is 1 to 100 parts by mass with respect to 100 parts by mass of the pure portion of the α-sulfofatty 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 are present as independent particles. particles of an α-sulfo fatty acid alkyl ester salt (A), particles of an alkyl sulfate (B), and inorganic powder (C),
The total content of the pure component of the α-sulfofatty acid alkyl ester salt in the particle group (A) and the alkyl sulfate in the particle group (B) is 50 mass based on the total mass of the powder detergent composition. % Or more,
The amount of the alkyl sulfate in the particle group (B) is 1 to 100 parts by mass with respect to 100 parts by mass of the pure portion of the α-sulfofatty 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 are present as independent particles.   The powder detergent composition according to claim 2, wherein the average particle diameter of the particle group (B) is 50 μm or more and less than 3 mm, and the average particle diameter of the inorganic powder (C) is 0.8 to 5 μm. A method of producing a powder detergent composition according to claim 1, comprising
The manufacturing method of the powder detergent composition which dry-mixes particle group (A) of the said (alpha) -sulfo fatty-acid alkylester salt, and particle group (B) of the said alkyl sulfate. A method of producing the powder detergent composition according to claim 2 or 3,
The manufacturing method of the powder detergent composition which dry-mixes particle group (A) of the said (alpha) -sulfo fatty-acid alkylester salt, particle group (B) of the said alkyl sulfate, and the said inorganic powder (C).