WO2018003818A1

WO2018003818A1 - Coated α-sulfofatty-acid-alkyl-ester-salt particle group

Info

Publication number: WO2018003818A1
Application number: PCT/JP2017/023641
Authority: WO
Inventors: 渡辺　英明; 史也新倉; 鉱行埴原; 陽一江端; 高士小林; 洋平野上
Original assignee: ライオン株式会社
Priority date: 2016-06-30
Filing date: 2017-06-27
Publication date: 2018-01-04
Also published as: CN109415656A; JP2018002821A; CO2019000754A2; JP6774798B2

Abstract

Provided is a coated α-sulfofatty-acid-alkyl-ester-salt particle group: that is a group of coated α-sulfofatty-acid-alkyl-ester-salt particles in which α-sulfofatty-acid-alkyl-ester-salt particles (A) are coated by using a coating component (B) that contains one or more types of substances selected from a group including a calcium carbonate particle group (B1) and a zinc oxide particle group (B2); and that exhibits superior solidification suppression and odor suppression.

Description

Coated α-sulfo fatty acid alkyl ester salt particles

The present invention relates to a particle group of α-sulfo fatty acid alkyl ester salt coated with each particle. The coated α-sulfo fatty acid alkyl ester salt group of the present invention can be used by blending with other detergent components in a detergent product. For example, the coated α-sulfo fatty acid alkyl ester salt particles of the present invention and powders of 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. 2016-129039 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 detergent products have been manufactured by producing particles containing α-SF salt at a high concentration and powder-mixing them with other detergent components.
The α-SF salt particle group has a problem that it is easy to solidify. In Patent Document 1, the α-SF salt particles are coated with zeolite and further sprayed with a nonionic surfactant to suppress the solidification. An example is given.
In addition, the α-SF salt has a problem that it easily generates odor. By blending a fragrance when mixing the α-SF salt particles with other detergent components, the odor in the powder detergent product can be suppressed.

JP 2011-116807 A

However, there is no known method for suppressing odor generated during storage or transportation of α-SF salt particles, and countermeasures are required.
An object of the present invention is to provide a coated α-sulfo fatty acid alkyl ester salt particle group excellent in suppression of solidification (hard to solidify) and suppression of odor (low odor).

The present invention has the following aspects.
[1] A group of coated α-sulfo fatty acid alkyl ester salt particles in which α-sulfo fatty acid alkyl ester salt particles (A) are coated with a coating component (B), wherein the coating component (B) is calcium carbonate particles. A coated α-sulfo fatty acid alkyl ester salt particle group containing one or more selected from the group consisting of the group (B1) and the zinc oxide particle group (B2).
[2] The coated α-sulfo fatty acid according to [1], wherein the calcium carbonate particle group (B1) has a volume median diameter of 20 μm or less, and the zinc oxide particle group (B2) has a volume median diameter of 20 μm or less. Alkyl ester salt particle group.

[3] The total mass of the calcium carbonate particle group (B1) and the zinc oxide particle group (B2) is 50 to 100% by mass with respect to the total mass of the coating component (B). 2] coated α-sulfo fatty acid alkyl ester salt particles.
[4] The total mass of the calcium carbonate particle group (B1) and the zinc oxide particle group (B2) is 3 to 30% by mass with respect to the total mass of the coated α-sulfo fatty acid alkyl ester salt particle group. The coated α-sulfo fatty acid alkyl ester salt particle group according to any one of [1] to [3].
[5] A method for producing a detergent product, comprising mixing the coated α-sulfo fatty acid alkyl ester salt particles of any one of [1] to [4] and other detergent components.

The above-mentioned coated α-sulfo fatty acid alkyl ester salt particle group is excellent in solidification suppression and odor suppression.

<Coated α-sulfo fatty acid alkyl ester salt particles>
The coated α-sulfo fatty acid alkyl ester salt particle group (hereinafter also referred to as “coated α-SF salt particle group”) of the present invention comprises α-sulfo fatty acid alkyl ester salt particles (A) (hereinafter also referred to as component (A)). Is a group of coated α-sulfo fatty acid alkyl ester salt particles coated with coating component (B) (hereinafter also referred to as component (B)).
(B) A component contains 1 or more types chosen from the group which consists of a calcium carbonate particle group (B1) and a zinc oxide particle group (B2).
That component (A) is coated with component (B) means that particles of component (B) are attached around particles of component (A).

The average particle size of the coated α-SF salt particle group is preferably 250 μm to 3000 μm, and more preferably 350 μm to 1000 μm. When the average particle size of the particle group is 250 μm or more, the solidification property is more easily suppressed. When the average particle size of the particle group is 3000 μm or less, the difference from the particle size of other components does not become too large when blended in a powder detergent or the like, and problems such as separation are easily suppressed.

The average particle diameter of the coated α-SF salt particle group 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 bulk density of the coated α-SF salt particle group is preferably 0.55 to 0.75 kg / L, and more preferably 0.60 to 0.70 kg / L. When the bulk density of the particle group is in the preferred range, the solubility can be easily improved, and space can be saved when stored. The bulk density is measured according to JIS K3362: 1998.

<(A) component>
The component (A) is α-sulfo fatty acid alkyl ester salt particles.
Component (A) is a particle containing α-sulfo fatty acid alkyl ester salt (α-SF salt) at a high concentration, and contains 60% by mass or more of α-SF salt.
The content of the α-SF salt in the component (A) is preferably 70% by mass or more, and more preferably 80% by mass or more.
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.

The α-SF salt contained in the component (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 an alkyl group having 1 to 6 carbon atoms. And M is a counter ion. ]
In the present invention, it is excellent in suppression of odor as the number of carbon atoms of R ¹ in the formula (1) is large. Specifically, since the odor is stronger as the carbon number of R ¹ is larger, the odor suppression effect of the present invention is greater. In this respect, the carbon number of R ¹ is preferably 8 or more, and more preferably 12 or more. On the other hand, from the viewpoint of detergency, the carbon number of R ¹ is preferably 18 or less, and more preferably 16 or less.
R ¹ preferably has 8 to 18 carbon atoms, more preferably 12 to 16 carbon atoms.

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.
In the alpha-SF salt, the mass ratio of alpha-SF salt carbon number of ^{R 1} is 14 alpha-SF number of carbon atoms of salt and ^{R 1} is 16 40: be 0: 60 to 100 preferable. 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.
One α-SF salt may be used alone, or two or more α-SF salts may be used in combination.

In addition to the α-SF salt, component (A) includes sulfates (sodium sulfate, etc.), alkyl sulfates (sodium methyl sulfate, etc.), α-sulfo fatty acids that are by-produced during the synthesis of α-SF salt. By-products of di-salts (such as α-sulfo fatty acid disodium salt) and moisture may be contained. In general, the component (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 amount of water in component (A) is preferably 10% by mass or less, and more preferably 5% by mass or less.
When the water content in the component (A) is 10% by mass or less, the adhesiveness at a low temperature of the component (A) is easily suppressed, and the storage stability at a low temperature is easily improved.

The average particle size of the group (A) is preferably 250 to 3000 μm, more preferably 350 to 1000 μm. When the average particle size of the component (A) group is 250 μm or more, solidification of the coated α-SF salt particle group of the present invention is more easily suppressed. When the average particle size of the component group (A) is 3000 μm or less, when the coated α-SF salt particle group of the present invention is blended in a powder detergent or the like, the difference from the particle size of other components increases. However, separation is difficult to occur.
The average particle diameter of the component (A) group is a value determined by the same method as the average particle diameter of the coated α-SF salt particle group.

(A) A component can also be manufactured by a well-known method and can also use a commercial item.
The component (A) production method includes a step of preparing a paste containing an α-SF salt (paste preparation step), a step of preparing flakes from the paste (flaking step), and a step of preparing noodles from the flakes. (Noodle making process), the method of adjusting the pellet from the said noodle (pelletizing process), the method which grind | pulverizes the said flake, noodle, or a pellet and obtains a particle | grain (grinding process) is mentioned.
The noodle forming step and the pelletizing step are optional steps and may be omitted.
Further, after the pulverization step, a step of classifying the group of α-SF salt particles (classification step) may be provided. Furthermore, you may provide the process (aging process) of aging flakes, noodles, or a pellet after the said flaking process, noodle forming process, or pelletizing process.

[Classification process]
In the classification step, the particle size of the group of the component (A) is adjusted to a desired range using a classification device. The classifying device is not particularly limited, and a known classifying device can be used, but a sieve is preferably used. Among the sieves, a gyro sieve, a flat sieve and a vibrating sieve are preferable. The gyro-type sieve is a sieve that gives a horizontal circular motion to a slightly inclined plane sieve. A plane sieve is a sieve that gives a reciprocating motion almost parallel to the surface of a slightly inclined plane sieve. The vibrating sieve is a sieve that gives a rapid vibration in a direction substantially perpendicular to the sieve surface. It is preferable that the time for sieving is 5 seconds or more. A tapping ball can also be used to improve the sieving efficiency.

In general, the group of the component (A) before the classification step is different depending on the production conditions, but particles having a particle size of 355 μm or less (hereinafter also referred to as “fine powder”) are the total of the group of the component (A). 30 mass% or more is contained with respect to mass.
When there is much content of the fine powder in the group of (A) component, solidification will advance easily during preservation | save. Therefore, in order to suppress solidification, a classification process is performed to adjust the amount of fine powder in the group of component (A). For example, the content of fine powder in the group of components (A) is adjusted to be less than 20% by mass with respect to the total mass of the group of components (A).
However, in the present invention, by suppressing the solidification by coating the component (A) with the component (B), the fine powder in the group of the component (A) is added to the group of the component (A). Even when the content is 20% by mass or more based on the total mass, it is possible to obtain a coated α-SF salt particle group excellent in solidification inhibition.
Therefore, in this invention, content of the fine powder in the group of (A) component is not specifically limited. From the viewpoint that the classification operation can be omitted and productivity can be improved, the content of fine powder in the group of components (A) is preferably 70% by mass or less with respect to the total mass of the group of components (A). , 60% by mass or less is more preferable, and 50% by mass or less is more preferable. Moreover, from the point which can acquire the solidification inhibitory effect of this invention more effectively, content of the fine powder in the group of (A) component is 20 mass% or more with respect to the total mass of the group of (A) component. It is preferable that the content is 30% by mass or more. On the other hand, when there is much content of fine powder, the average particle diameter of the group of (A) component will become small. Moreover, when the group of (A) component is mix | blended with a powder detergent product, the difference of the particle size of (A) component and the particle size of another component becomes large, and problems, such as isolation | separation, may arise. Therefore, from this point, the content of fine powder in the group of components (A) is preferably 50% by mass or less with respect to the total mass of the group of components (A).

[Aging process]
The flakes, noodles, pellets and particles containing the α-SF salt (hereinafter collectively referred to as “α-SF salt-containing solid”) have a metastable crystalline state and a solid containing the α-SF salt. It is known that there exists a stable crystal state formed by crystallizing an object.
An α-SF salt-containing solid in a stable crystalline state (hereinafter also referred to as “stable solid”) is an α-SF salt-containing solid in a stable state (hereinafter also referred to as “metastable solid”). It is known that it is more excellent in suppressing the solidification (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 through the above-mentioned steps using a fatty acid alkyl ester as a starting material, usually by-products such as alkyl sulfate and α-sulfo fatty acid di-salt are produced in addition to the α-SF salt. . If such a by-product is contained in the α-SF salt-containing solid, the α-SF salt-containing solid tends to be in a metastable state.

In the aging step, the metastable solid is converted into a stable solid.
Methods for converting a metastable solid to a stable solid are known, and examples 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 more and 20000 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) 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.

In the present invention, since the suppression of solidification can be enhanced by coating the component (A) with the component (B), even if the component (A) is a metastable solid, good suppression of solidification is achieved. can get.
Therefore, as the component (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 component (A).
Whether component (A) is a metastable solid or a stable solid can be easily discriminated from both X-ray diffraction measurement and microscopic observation in addition to the differential scanning calorimetry measurement (International Publication No. 2009). / 054406).

The content of the component (A) in the coated α-sulfo fatty acid alkyl ester salt particles (hereinafter also referred to as “coated α-SF salt particles”), in which the component (A) is coated with the component (B), The amount is preferably 70 to 97% by mass, more preferably 75 to 93% by mass, and still more preferably 80 to 90% by mass with respect to the SF salt particles.
When the content of the component (A) is not less than the lower limit of the above range, when the coated α-SF salt particles are blended into a powder detergent product, the degree of freedom in blending other components other than the coated α-SF salt particles It becomes easy to keep. Further, when the content of the component (A) is not more than the upper limit of the above range, it is easy to obtain a solidification suppressing effect and an odor suppressing effect.

<(B) component>
The component (B) is a coating component. The component (B) is selected from the group consisting of the calcium carbonate particle group (B1) (hereinafter also referred to as the (B1) component) and the zinc oxide particle group (B2) (hereinafter also referred to as the (B2) component). Includes more than species. The component (B) may include other particles that are neither calcium carbonate particles nor zinc oxide particles.
Other particles include inorganic builder particles such as zeolite, sodium sulfate, and sodium sulfite, alkaline agent particles such as sodium carbonate and potassium carbonate, polymer builder particles such as cationized cellulose, powdered cellulose, and sodium polyacrylate. Etc.
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.
When other particles are used, any one of them may be used, or two or more kinds may be used in combination.

When the component (B) includes one or both of the component (B1) and the component (B2), solidification of the coated α-SF salt particle group is suppressed and odor is suppressed. Further, the components (B1) and (B2) do not cause stickiness on the surface of the coated α-SF salt particles, and do not impair the handling properties of the coated α-SF salt particles.
The total mass of the component (B1) and the component (B2) is preferably 50 to 100% by mass and more preferably 70 to 100% by mass with respect to the total mass of the component (B). It is excellent in the solidification inhibitory effect and the odor inhibitory effect as it is more than the said lower limit.
The lower limit of the total mass of the component (B1) and the component (B2) is preferably 3% by mass and more preferably 5% by mass with respect to the total mass of the coated α-SF salt particle group. 7 mass% is more preferable, and 10 mass% is particularly preferable. The upper limit is preferably 30% by mass, more preferably 25% by mass, and even more preferably 20% by mass.
A preferable numerical range of the total mass of the component (B1) and the component (B2) with respect to the total mass of the coated α-SF salt particle group is 3% by mass to 30% by mass, 5% by mass to 30% by mass, 7 mass% or more and 30 mass% or less, 7 mass% or more and 25 mass% or less, and 10 mass% or more and 20 mass% or less are mentioned. When the total mass of the component (B1) and the component (B2) is 3% by mass or more, a solidification suppressing effect and an odor suppressing effect are sufficiently obtained. Further, when the total mass of the component (B1) and the component (B2) is 30% by mass or less, when the coated α-SF salt particle group is added to the powder detergent, other than the coated α-SF salt particles It becomes easy to maintain the freedom of blending the ingredients.

In the present invention, the average particle diameter of the component (B) is represented by a volume-based cumulative 50% diameter (volume median diameter) measured by a wet method using a laser diffraction / scattering apparatus.
The volume median diameter of the component (B1) or the component (B2) is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, particularly preferably 5 μm or less, and particularly preferably 4 μm or less. Most preferably, it is 3 μm or less. When the amount is not more than the above upper limit value, the effect of suppressing solidification and the effect of suppressing odor can be sufficiently obtained. As the volume median diameter is smaller, the solidification suppressing effect and the odor suppressing effect are further enhanced.
On the other hand, the lower limit of the volume median diameter of the component (B1) or the component (B2) is preferably 20 nm from the viewpoints of practicality and availability. Preferred numerical ranges of the volume median diameter of each of the component (B1) or the component (B2) are 20 nm to 20 μm, 20 nm to 10 μm, 20 nm to 8 μm, 20 nm to 5 μm, 20 nm to 4 μm, and 20 nm or more. 3 micrometers or less are mentioned.

When the component (B) includes a group of other particles, the lower limit of the volume median diameter of the group of other particles is preferably 20 nm from the viewpoint of practicality and availability. The upper limit is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less from the viewpoint of suppressing solidification.
The volume median diameter of the component (B) can be adjusted using a known classifier such as a sieve.

In the coated α-SF salt particles, the area covered with the component (B) is preferably 30% or more, more preferably 50% or more, relative to the surface area of the component (A). % Or more is more preferable, and it may be 100%.
The ratio (coverage) of the coated area to the surface area of the component (A) is determined by, for example, coating α-SF salt particles using a microscope (manufactured by Asahi Optical Instruments Co., Ltd., Handi Scope TM), a scanning electron microscope (for example, (S-2380N, manufactured by Hitachi, Ltd.) and an energy dispersive X-ray analyzer (for example, EMAX-7000, manufactured by Horiba, Ltd.), and can be confirmed by image processing or surface elemental analysis.

<Method for Producing Coated α-SF Salt Particles>
The coated α-SF salt particle group can be produced by a method having a step (coating step) of coating the component (A) with the component (B).
The method of coating the component (A) with the component (B) is not particularly limited, and examples thereof include a method in which the component (A) and the component (B) are charged into a mixer and mixed (dry mixing).
Either the component (A) or the component (B) may be charged first into the mixer, or both may be charged simultaneously.
Although it does not specifically limit as said mixer, The mixer used for dry-type mixing is preferable, for example, horizontal cylindrical mixers, container rotary mixers, such as V-type mixer, a stirring mixer, etc. are mentioned.

The coated α-SF salt particles of the present invention can be used in a detergent product together with other detergent components.
For example, it is suitably used in a method for producing a powder detergent product by dry-mixing the coated α-SF salt particles of the present invention and powders of other detergent components.
As other detergent components, known components blended in powder detergent products can be used. Specific examples include anionic surfactants such as linear alkylbenzene sulfonic acid metal salts, α-olefin sulfonic acid metal salts, alkyl sulfate metal salts, and soap metal salts; nonionic surfactants such as alkylene oxide adducts of higher alcohols; Surfactant; Cationic surfactant; Inorganic builder such as zeolite, sodium sulfate and sodium sulfite; Alkaline agent such as sodium carbonate and potassium carbonate; Fluorescent agent; Bleach agent; Bleach activator; Enzyme; Polymerized builders such as cationized cellulose, powdered cellulose, and sodium polyacrylate.

The content of the coated α-SF salt particle group with respect to the total mass of the powder detergent product is not particularly limited, but is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, and 5 to 40%. More preferably, it is% mass. When it is in the preferable range, solidification of the powder detergent product is easily suppressed, and the fluidity is easily improved.
The coated α-SF salt particle group of the present invention is not limited to a powder detergent, and may be blended in, for example, a tablet-like or sheet-like solid detergent or a liquid detergent.

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 crystallinity of component (A)]
A DSC 6220 manufactured by SII was used as a differential scanning calorimeter. 20g of a sample is pulverized with a trio blender (manufactured by Trio Science), 5-30mg of the pulverized product is placed in a silver sample pan, heated from 0 ° C to 130 ° C at a rate of 2 ° C / min, and subjected to thermal analysis. did.
S1 / S2 × 100 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. at this time, and this was defined as the crystallinity (unit:%).
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 was 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. was defined as S1. When an exothermic peak was observed at 0 to 130 ° C., 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.

[Measuring method of average particle diameter (volume median diameter) of component (B)]
The measurement was performed by a wet method using a particle size distribution measuring apparatus (LS13320, manufactured by Beckman Coulter, Inc.) using a laser diffraction / scattering method. The particle diameter at the point of 50% in the cumulative volume distribution curve in which the total volume of the particle size distribution determined on a volume basis was 100% was defined as the volume median diameter.
The preparation method of the measurement solution is as follows. First, the sample was dispersed in isopropyl alcohol as a solvent so that the concentration was 0.5% by mass. Next, a solution obtained by subjecting this solution to ultrasonic treatment for 30 minutes was used as a measurement solution.

[Evaluation of inhibition of solidification]
80 g of the coated α-SF salt particle group of each example as a sample is placed in a cylindrical cell having an inner diameter of 50 mm and a height of 100 mm, and left standing at a load of 2 kg for 1 week in an atmosphere of 40 ° C. It was. The molded body is taken out, and the detection part is lowered from the upper part at a condition of 5.32 mm / second using IMDA FORCE GAUGE (model No., main body: MX-500N, detection part: ZP-500N), and the upper surface of the molded body The load was gradually applied to the whole, and the maximum load (kgf) applied until the molded body broke was measured. The measurement was performed five times for each sample, and the average value was obtained. It can be evaluated that the smaller the measured value of the maximum load is, the more excellent the suppression of solidification is.

[Evaluation of odor control]
(1) Measurement of deodorization rate 3 g of a sample was put in a 20 mL vial and sealed, and allowed to stand in a constant temperature bath at 40 ° C. for 60 minutes, and then the components contained in the headspace part were analyzed by GC-MS. .
That is, the components contained in the head space part were subjected to solid-phase microextraction fiber (manufactured by Spelco, product name: SPME fiber, film thickness: 65 μm, PDMS / DVB (divinylbenzene dispersed polydimethylsiloxane) under the condition of 40 ° C. ) For 30 minutes.
For the solid-phase microextraction fiber after extraction, a methyl alkyl ketone (alkyl group is C6 to C15) contained in the headspace using GC-MS (manufactured by Agilent Technologies, product name: Agilent 7890 / 5975C) under the following conditions: The component analysis was conducted.
Total peak area value (Xa) of methyl alkyl ketone (alkyl group is C6-C15) component when only component (A) before coating is used as a sample, and methyl when sample of coated α-SF salt particle group is used as a sample The total peak area value (Xb) of the alkyl ketone (alkyl group is C6 to C15) component was measured, and the deodorization rate (unit:%) was calculated by the following formula (I).
Deodorization rate (unit:%) = (Xb) / (Xa) × 100
(Measurement condition)
Column: HP-INNOWAX (length: 30 m, inner diameter: 0.25 mm, film thickness: 0.25 μm),
Measurement temperature: After holding at 35 ° C. for 3 minutes, the temperature is raised to 205 ° C. at 40 ° C./min, and further to 250 ° C. at 10 ° C./min.
Carrier gas: helium,
Inlet temperature: 250 ° C
Interface temperature: 250 ° C
Injection method: pulsed splitless.

(2) Sensory evaluation 40 g of the sample coated α-SF salt particle group (25 ° C.) was filled into a 120 mL capacity glass bottle to prepare an evaluation sample. The sensory evaluation by the expert panel was implemented about the fragrance of the evaluation sample. The odor of only component (A) before coating was evaluated according to the following criteria as a control.
A: There is a deodorizing effect.
B: Slight deodorizing effect.
C: Slight deodorizing effect.
D: No deodorizing effect.

(Raw materials used)
<(A) component>
(A-1): a group of α-SF salt particles produced in Production Example 1 below, crystallinity 75% (stable solid), average particle size 450 μm, fine powder rate 30% by mass, moisture 2% by mass. In the α-SF salt in the particles, in the general formula (1), R ¹ is an alkyl group having 14 to 16 carbon atoms, R ² is a methyl group, and M is a sodium ion.

<(B) component>
[Calcium carbonate particles (B1)]
8 types of calcium carbonate particles with different volume median diameters (volume median diameter 13.2 μm (special grade, manufactured by Kanto Chemical Co., Ltd.), volume median diameters 7.9 μm, 4.3 μm, 2.6 μm, 1.7 μm 1.1 μm, 0.2 μm (both manufactured by Shiroishi Kogyo Co., Ltd.) and volume median diameter of 2.1 μm (manufactured by Sankyo Seiko Co., Ltd.) were used.
[Zinc oxide particles (B2)]
Zinc oxide particles (volume median diameter 1.1 μm (manufactured by Kanto Chemical Co., Ltd., special grade)) were used.
[Other group of particles]
Zeolite particle group: A type zeolite particle group (manufactured by Guangzhou, 4A zeolite (trade name)) is pulverized and classified to adjust the volume median diameter to 1.6 μm or 3.8 μm.
Bentonite particle group: Refined bentonite particles (Kunimine Industries, Ltd., Kunipia F (trade name)) were pulverized and classified to adjust the volume median diameter to 1.3 μm or 2.2 μm.

(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 were added in an amount of 5% by mass of the fatty acid methyl ester mixture. While stirring, 110 kg of SO ₃ gas (sulfonated gas) diluted to 4% by volume with nitrogen gas was bubbled into the mixture and reacted at a constant rate over 3 hours. The reaction temperature was kept at 80 ° C.
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 the bleaching agent mixing line, and 35% hydrogen peroxide solution was supplied in an amount of 1 to 2% by mass with respect to the α-SF salt in terms of pure component, While maintaining, the mixture was mixed and bleached 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 crushed using a crusher (manufactured by Nippon Belting Co., Ltd.). To obtain α-SF salt-containing flakes.

[Aging process]
The α-SF salt-containing flakes were maintained at 30 ° C. and 12000 Pa for 720 hours to convert the α-SF salt-containing flakes into stable solids.
[Noodle making process]
The α-SF salt flakes were heated to obtain a melt having a temperature of 60 to 63 ° C. This melt was charged into a KRC kneader (S2 type, manufactured by Kurimoto Seiko Co., Ltd.) in which warm water of 51 ° C. was passed through the jacket at 600 to 800 g / min, and kneaded at a rotational speed of 86 rpm for 0.5 minutes. Thereafter, the melt taken out from the kneader was passed through a pelleter double to form a noodle shape.
[Pelletization process]
The noodles were crushed using nibra (manufactured by Hosokawa Micron Corporation) to obtain pellets.
[Crushing process]
The obtained pellets were put into a speed mill and pulverized with a processing capacity of 200 kg / hr, a peripheral speed of 32 m / s, and a screen hole diameter of 2.5 mm to obtain a group of α-SF salt particles.

<Examples 1 to 16>
Examples 1 to 11 are examples, and examples 12 to 16 are comparative examples.
According to the composition shown in Table 1, the component (A) and the component (B) were charged into a container rotary mixer and mixed to obtain a coated α-SF salt particle group. In Example 16, the component (A) was used as it was. In the table, when there is a blank blending component, the blending component is not blended.
The solidification inhibitory property and odor inhibitory property of the coated α-SF salt particles in each example were evaluated by the above methods. The evaluation results are shown in Table 1.

From the results in Table 1, the coated α-SF salt particle groups of Examples 1 to 11 are excellent in solidification suppression and odor suppression.
In Examples 12 and 13 in which the component (B) does not contain any of the component (B1) and the component (B2) and the zeolite particle group is used instead, the solidification suppression property was good, but the odor suppression property was good. Inferior.
In Examples 14 and 15, in which the component (B) does not contain any of the components (B1) and (B2) and bentonite particles are used instead, the suppression of solidification is good although the suppression of odor is good. Inferior.

The above-mentioned coated α-sulfo fatty acid alkyl ester salt particle group is excellent in solidification suppression and odor suppression.
The above-mentioned coated α-sulfo fatty acid alkyl ester salt particles are mixed with other detergent components and used for the production of detergent products.

Claims

a group of coated α-sulfo fatty acid alkyl ester salt particles in which α-sulfo fatty acid alkyl ester salt particles (A) are coated with a coating component (B);
A coated α-sulfo fatty acid alkyl ester salt particle group, wherein the coating component (B) contains one or more selected from the group consisting of a calcium carbonate particle group (B1) and a zinc oxide particle group (B2).
The coated α-sulfo fatty acid alkyl ester according to claim 1, wherein the calcium carbonate particle group (B1) has a volume median diameter of 20 µm or less, and the zinc oxide particle group (B2) has a volume median diameter of 20 µm or less. Salt particle group.
The coating α- according to claim 1, wherein the total mass of the calcium carbonate particle group (B1) and the zinc oxide particle group (B2) is 50 to 100 mass% with respect to the total mass of the coating component (B). Sulfo fatty acid alkyl ester salt particles.
The total mass of the calcium carbonate particle group (B1) and the zinc oxide particle group (B2) is 3 to 30% by mass with respect to the total mass of the coated α-sulfo fatty acid alkyl ester salt particle group. The coated α-sulfo fatty acid alkyl ester salt particle group as described.
A method for producing a detergent product, comprising mixing the coated α-sulfo fatty acid alkyl ester salt particles according to any one of claims 1 to 4 and other detergent components.