JP2007009087A - Powder detergent composition with improved solubility at low temperatures - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder detergent composition capable of efficiently preventing the formation of detergent agglomerates that occur when washing is performed under low temperature water or in a state where stirring power is insufficient, and exhibits excellent solubility during washing. .
Surfactant particles (A) containing 10 to 40% of a surfactant and having an average particle size of 150 μm or more are provided.
Aluminosilicate particles (B) having an average particle size of less than 30 μm;
Containing composite particles (P) formed by surface treatment with particles (C) having an organic particle content of 50% or more and an average particle diameter of less than 30 μm and a contact angle of 50 ° or more,
The powder detergent composition whose relative area intensity ratio before and behind grinding | pulverization with IR intensity derived from the said organic substance and IR intensity derived from aluminosilicate is 1.01-20.
[Selection] Figure 2

Description

  The present invention relates to a powder detergent composition that has improved solubility in water at low temperatures and can be used for textiles such as clothing. Specifically, the present invention relates to a powder detergent composition containing composite particles obtained by surface-treating surfactant particles with aluminosilicate particles and organic matter-containing particles.

Conventionally, in order to solve various problems related to handling properties, disintegration, storage stability, solubility and the like of solid particles, a method of granulating solid particles with a water-soluble polymer compound (Patent Document 1), solid particles A method of covering the surface and the like (Patent Document 2) has been proposed.
In particular, in the field of powder detergent compositions, a phenomenon is often observed in which detergent particles containing a surfactant gel and agglomerate and remain dissolved during washing in winter. In recent years, the bath ratio has decreased due to the increase in the size of washing machines, and the amount of rinsing water has decreased due to the energy-saving design. In addition, methods of immersing and using powder detergent compositions have become widely used. . Therefore, it can be said that the detergent particles are likely to remain undissolved during washing using low-temperature water or washing with insufficient stirring power.
In order to solve this problem, a method of coating the surface of the detergent particles with a water-soluble polymer has been proposed (Patent Document 3).

On the other hand, a technique for blending various particles has been proposed in order to impart various functions to the powder detergent composition. In this case, the blended particles may affect each other, resulting in a problem that the solubility of the powder detergent is lowered. In particular, when a water-soluble inorganic compound is mixed with detergent particles in powder form, when the water-soluble inorganic compound comes into contact with water and hydrates, it aggregates violently with the detergent particles to form aggregates that remain undissolved. It was.
In order to solve this problem, a technique has been proposed in which detergent particles are coated with a nonionic surfactant and a water-soluble inorganic compound is coated with a water-soluble organic solution and / or solid powder (Patent Document 4).

As a coating technique, a water-insoluble powder or a granulated product such as a bleach activator is coated with a water-soluble polymer compound having a functional group that reacts with a polyvalent metal ion, and then a polyvalent metal ion. The technique (patent document 5, 6) which bridge | crosslinks with is proposed. These techniques are aimed at improving storage stability and shape stability when blended in a multi-aqueous composition.
Various coating techniques have been proposed for water-soluble inorganic compound particles intended to be mixed with granular detergent. For example, techniques have been proposed in which a water-soluble inorganic compound is granulated with a water-soluble polymer compound to improve the dissolution rate of granules and the dispersibility during washing (Patent Documents 7 and 8). In addition, water-soluble inorganic compounds may be mixed with a plurality of poorly water-soluble inorganic compounds such as alkali metal silicates, or may be compounded, or may be coated by spraying a concentrated silicate solution onto a water-soluble inorganic compound carrier. Etc. have been proposed (Patent Documents 9, 10, and 11). These coating techniques also focus on the contribution to improving the storage stability and detergency of particles.

On the other hand, a technique for coating an inorganic compound with a poorly water-soluble (organic) compound has been proposed to solve the problem relating to the solubility of the water-soluble inorganic compound. For example, as a technique for controlling the dissolution rate, a coating method using a higher alcohol has been proposed (Patent Document 12).
In addition, as a technique for improving the undissolved residue when washing with low-temperature water under conditions where stirring force is sufficiently applied, a method of coating with a fatty acid salt (Patent Documents 13 and 14), water-soluble alkali inorganic particles as an anionic surfactant A method of coating with an acid precursor and neutralizing at the same time has been proposed (Patent Documents 15 and 16).
Furthermore, as another coating technique in the field of powder detergent composition, a detergent composition having a fluidity improving effect and a fine powder formation inhibiting effect by coating a detergent component with an aluminosilicate and a water-soluble polymer, and silicon dioxide particles A granular detergent excellent in storage stability and coated with water-soluble polymer is proposed (Patent Documents 17 and 18).
In addition, anionic surfactants, nonionic surfactants, water-soluble inorganic compounds, and water-soluble binders such as polyethylene glycol that are usually used in powder detergent compositions are prepared in various combinations to prepare granules, such as enzymes and bleaching agents. A method for stabilizing the activity of the surfactant, a method for suppressing hydrolysis of the surfactant itself, and the like have been proposed (Patent Documents 19, 20, and 21).
Further, the granular material produced from the two-stage coating, wherein the first stage is a coating with a pulverized product of a detergent component and a detergent composition such as aluminosilicate, and the second stage is a coating with a coating agent containing a cellulose polymer and sugar. A detergent composition has been proposed (Patent Document 22).

However, it is difficult to say that the methods described in these documents are sufficient in the effect of suppressing the formation of detergent agglomerates and preventing the undissolved residue during washing using low-temperature water.
As described above, it is possible to efficiently prevent the formation of detergent agglomerates that occur when washing is performed in low-temperature water or with insufficient stirring power, and a granular detergent composition that exhibits excellent solubility during washing is desired. It was rare.

JP-A-3-53000 JP 2001-293354 A JP 7-242899 A JP 2002-266000 A Japanese National Patent Publication No. 11-514402 JP-A-63-130522 JP 63-20398 A Special table 2001-505240 gazette JP-A-8-60200 JP-A-4-275400 JP 2000-34496 A JP 2001-510501 A Japanese Patent Laid-Open No. 1-229098 Japanese Patent Laid-Open No. 10-237498 JP 2001-81498 A Japanese Patent Laid-Open No. 10-158699 JP 2000-505834 Gazette JP-A-6-172800 JP-A-6-192697 JP-A-4-345700 JP-A-3-265699 JP 2000-505834 Gazette

  Therefore, the present invention can efficiently prevent the formation of detergent agglomerates that occur when laundering in low-temperature water or with insufficient stirring power, and a powder detergent composition that exhibits excellent solubility during washing. The purpose is to provide.

That is, the present invention provides surfactant particles (A) containing 10 to 40% of a surfactant and having an average particle size of 150 μm or more.
Aluminosilicate particles (B) having an average particle size of less than 30 μm;
Containing composite particles (P) formed by surface treatment with particles (C) having a contact angle of 50 ° or more and containing 50% or more of organic matter and having an average particle size of less than 30 μm,
The relative area intensity ratio R1 / R2 represented by the following formula (1) is 1.01 to 20,
A powder detergent composition is provided.

R1 / R2 = (O1 / Z1) / (O2 / Z2) (1)

(In the formula, O1 represents the IR intensity derived from the organic substance in the particles (C) contained in the powder detergent composition, and Z1 represents the aluminosilicate particles (B) contained in the powder detergent composition. IR intensity derived from aluminosilicate, R1 represents relative area intensity O1 / Z1;
O2 represents the IR intensity derived from the organic substance in the particles (C) after grinding the powder detergent composition, and Z2 is the aluminosilicate in the aluminosilicate particles (B) after grinding the powder detergent composition. The IR intensity derived from the salt is represented, and R2 represents the relative area intensity O2 / Z2. )

  By this invention, the powder detergent composition excellent in the solubility to water at low temperature is obtained. The composition of the present invention is also easy to handle because dusting is suppressed. The composition of the present invention is also excellent in fluidity and non-solidifying property after long-term storage.

Surfactant particles (A)
Examples of the surfactant that can be used in the present invention include anionic surfactants and nonionic surfactants.
The anionic surfactant is not particularly limited as long as it is conventionally used as a detergent, and various anionic surfactants can be used. For example, the following can be mentioned.
(1) Linear or branched alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 18 carbon atoms
(2) C10-20 alkyl sulfate (AS) or alkenyl sulfate (3) C10-20 α-olefin sulfonate (AOS)
(4) C10-20 alkane sulfonate

(5) Alkyl ether added with ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less Sulfate (AES) or alkenyl ether sulfate (6) Ethylene oxide, propylene oxide, butylene having a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less Alkyl ether carboxylate or alkenyl ether carboxylate to which oxide or a mixture thereof is added (7) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms (8) C10 to 20 carbon atoms Higher fatty acid salt (9) C8 ~ 0 saturated or unsaturated α- sulfo fatty acids (alpha-SF) salt or a methyl, ethyl or propyl ester.
These anionic surfactants can be used singly or in appropriate combination of two or more.

Among these, (1) alkali metal salt of linear alkylbenzene sulfonic acid (LAS) (for example, sodium or potassium salt), (3) AOS, (5) AES, (8) alkali metal salt of higher fatty acid (for example, (9) α-SF alkali metal salts (for example, sodium or potassium salts).
Among them, an alkali metal salt of LAS having an alkyl group having 10 to 14 carbon atoms, an alkali metal salt of AOS having 12 to 18 carbon atoms, an alkali metal salt of a higher fatty acid salt having 12 to 18 carbon atoms, and 12 to 18 carbon atoms The alkali metal salt of α-SF is more preferred.

The nonionic surfactant is not particularly limited as long as it is conventionally used as a detergent, and various nonionic surfactants can be used. For example, the following can be mentioned.
(10) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms Ether Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(11) Polyoxyethylene alkyl (or alkenyl) phenyl ether

(12) An alkylene oxide added with an alkylene oxide between ester bonds of a long-chain fatty acid alkyl ester, for example, a fatty acid alkyl ester alkoxylate represented by the following general formula (1)

R ¹ CO (OA) _n OR ² (1)

(In the formula, R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, or a mixture thereof, preferably 2 -3 represents an alkylene oxide addition unit, and n represents the average number of moles of alkylene oxide added, generally 3 to 30, preferably 5 to 20. R ² represents a substituent having 1 to 3 carbon atoms. (The lower (C1-C4) alkyl group which may have is shown.)
(13) Polyoxyethylene sorbitan fatty acid ester (14) Polyoxyethylene sorbite fatty acid ester (15) Polyoxyethylene fatty acid ester (16) Polyoxyethylene hydrogenated castor oil (17) Glycerin fatty acid ester

Among these, (10) polyoxyethylene alkyl (or alkenyl) ether or polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or lower and an HLB of 9 to 16, and (12) ethylene to fatty acid methyl ester Fatty acid methyl ester ethoxylate to which oxide is added or fatty acid methyl ester ethoxypropoxylate to which ethylene oxide and propylene oxide are added to fatty acid methyl ester is preferable.
Among these, (10) a polyoxyethylene alkyl ether having a melting point of 50 ° C. or less and an HLB of 9 to 16 and (12) a fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to a fatty acid methyl ester having 12 to 18 carbon atoms are more preferable. .
The content of the surfactant in the surfactant particles (A) is 10 to 40%, preferably 15 to 40%, and most preferably 18 to 35%.
When an anionic surfactant and a nonionic surfactant are used in combination, the anionic surfactant and the nonionic surfactant are preferably used in a mass ratio of 10: 1 to 1:10.

The surfactant particles (A) contain an inorganic compound, a water-soluble polymer compound, a dissolution accelerator and the like in addition to the surfactant.
Examples of inorganic compounds include sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, non-crystalline layered sodium silicate, etc., neutral salts such as sodium sulfate, Orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate and other phosphates, crystalline aluminosilicate, amorphous aluminosilicate, and the like can be used. Among these, sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate, sodium aluminosilicate, and sodium sulfate are preferable. Sodium carbonate, potassium carbonate, sodium silicate, sodium aluminosilicate, and sodium sulfate are more preferable.
The content of the inorganic compound in the surfactant particles (A) is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and most preferably 25 to 50%.
The water-soluble polymer compound is preferably an acrylic acid polymer compound or a cellulose polymer compound, and includes an acrylic acid polymer, an acrylic acid / maleic acid copolymer, carboxymethyl cellulose (CMC), and a hydroxyalkyl cellulose. Derivatives and polyacetal carboxylates are more preferred. An acrylic acid / maleic acid copolymer having a weight average molecular weight of 1000 to 80000 is particularly preferred. Polyethylene glycol having a weight average molecular weight of 1000 to 20000 is also preferred.

The content of the water-soluble polymer compound in the surfactant particles (A) is preferably 0.1 to 10% by weight, and preferably 0.2 to 7% by weight.
Benzene having a short chain alkyl having 1 to 5 carbon atoms such as potassium carbonate, inorganic ammonium salts such as ammonium sulfate and ammonium chloride, sodium p-toluenesulfonate, sodium xylenesulfonate, sodium cumenesulfonate, etc. Water-soluble substances such as sulfonate, sodium benzoate, sodium benzenesulfonate, sodium chloride, citric acid, D-glucose, urea, and sucrose can be used. Of these, potassium carbonate and sodium chloride are preferable, and potassium carbonate is more preferable.
The content of the dissolution accelerator in the surfactant particles (A) is preferably 1 to 15% by weight, and more preferably 2 to 10% by weight.
In addition, a swellable water-insoluble substance, an antistatic agent, a recontamination preventing agent, an extender, a reducing agent, and a bleach activating catalyst can be contained. For example, citrate, aminocarboxylate, and hydroxyaminocarboxylate are preferable.

The average particle diameter of the surfactant particles (A) is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, and most preferably 300 to 700 μm. When the average particle diameter is in such a range, it is preferable in terms of solubility. In addition, in this specification, a particle diameter can be measured by the method as described in an Example.
The bulk density of the detergent particles (A) is preferably from 0.4~1.2g / cm ^3, more preferably from 0.5 to 1.0 g / cm ^3, from 0.7 to 0 Most preferably, it is .9 g / cm ³ . It is preferable that the bulk density is in such a range because the volume per box can be reduced. In the present specification, the bulk density can be measured according to JIS K 3362.
The water content of the surfactant particles (A) is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and 6 to 8% in terms of solubility and storage stability. Most preferably. In the present specification, the moisture content can be measured by an infrared moisture meter (such as a product of Kett).
In the powder detergent composition of the present invention, the surfactant particles (A) are preferably contained in an amount of 60% by mass or more, more preferably 70% by mass or more, and most preferably 70% by mass.

  Surfactant particle (A) can be manufactured by the following method, for example. That is, the raw powder and binder components (surfactant, water, liquid polymer component, etc.) are kneaded and kneaded, then extruded and granulated, and the solid detergent obtained after kneading and kneading. Kneading and crushing granulation method to crush and granulate, Stirring granulation method to add a binder component to the raw material powder and stir with a stirring blade to granulate, Spray the binder component while rolling the raw material powder It can be produced by a tumbling granulation method for granulation, a fluidized bed granulation method in which a liquid binder is sprayed and granulated while fluidizing the raw material powder.

Aluminosilicate particles (B)
As an aluminosilicate used in the present invention, a preferable aluminosilicate includes the following general formula (I):

_{^{x 1 (M 2 O) ·}} Al 2 O 3 · y 1 (SiO 2) · w 1 (H 2 O) (I)

(In the formula, M represents an alkali metal atom such as sodium or potassium, x ¹ , y ¹ and w ¹ represent the number of moles of each component, and generally x ¹ is 0.7 to 1.5, y ^1. Is a number from 0.8 to 6, and w ¹ is an arbitrary positive number.)
A crystalline aluminosilicate represented by the following general formula (II) or (III):

_{^{x 2 (M 2 O) ·}} Al 2 O 3 · y 2 (SiO 2) · w 2 (H 2 O) (II)

(In the formula, M represents an alkali metal atom such as sodium or potassium, x ² , y ² and w ² represent the number of moles of each component. In general, x ² is 0.7 to 1.2, y ^2. 1.6 to 2.8, w ² represents 0 or any positive number.)

_{^{x 3 (M 2 O) ·}} Al 2 O 3 · y 3 (SiO 2) · z 3 (P 2 O 5) · w 3 (H 2 O) (III)

(In the formula, M represents an alkali metal atom such as sodium or potassium, x ³ , y ³ , z ³ and w ³ represent the number of moles of each component, and generally x ³ is 0.2 to 1.1. , y ³ is 0.2 to 4.0, z ³ is 0.001 to 0.8, w ³ represents 0 or any positive number.)
Amorphous aluminosilicate represented by the following. Among these, it is preferable to be represented by the formula (I), and A type zeolite and P type zeolite are particularly preferable. A-type zeolite is more preferable.
In the present invention, instead of aluminosilicate particles (B), smectites such as montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite; sericite, illite, muscovite, phlogopite, etc. Mica; or clay minerals such as vermiculite, chlorite, pyrophyllite, talc, kaolin mineral, serpentine, sepiolite, allophane, and hydrotalcite can also be used.

In the powder detergent composition of the present invention, the content of the aluminosilicate particles (B) is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, and most preferably 1.5% by mass. It is.
Commercially available products can be used as they are for the aluminosilicate particles (B) used in the present invention. For example, a product sold under the trade name Shilton B by Mizusawa Chemical Co., Ltd. can be used.
The average particle diameter of the aluminosilicate particles (B) is less than 30 μm, preferably 0.1 to 10 μm, more preferably 0.3 to 7 μm. It is preferable that the average particle size is in such a range because it does not remain in the washed clothes.
The primary particle size of the aluminosilicate particles (B) is preferably 1/5 or less of the surfactant particles (A), and the primary particle size is 1/10 or less of the particles (A). More preferred. It is preferable that the primary particle size is in such a range because it can exist stably with respect to the surfactant particles A.
The primary particle diameter means a particle diameter in a liquid paraffin solvent under stirring, and can be measured by a particle size analyzer or the like.
The aluminosilicate particles (B) may contain components such as moisture and trace amounts of impurities generated in the production process, but are preferably 5% or less with respect to the total amount of the particles (B).

Particle (C)
Examples of the organic substance include fatty acids such as saturated or unsaturated fatty acids having 10 to 20 carbon atoms, specifically lauric acid, palmitic acid, stearic acid, etc .; higher fatty acid dicarboxylic acids such as dicarboxylic acids of the higher fatty acids; higher alcohols such as Saturated or unsaturated alcohol having 12 to 22 carbon atoms, specifically 1 mol ethylene oxide adduct of hexadecanol, 1 mol ethylene oxide adduct of octadecanol, etc .; HLB 5 or less, preferably 3 or less higher alcohol or higher fatty acid Alkylene oxide adducts such as the above higher alcohols or higher fatty acid ethylene oxide, propylene oxide adducts, specifically 1 mol ethylene oxide adducts of palmitic acid; higher fatty acid esters such as higher fatty acids and lower alcohols Esters, specifically Palmi Phosphate methyl esters; and higher fatty acid glycerides, specifically can be used lauric acid, palmitic acid, mono- such as stearic acid, a di- or triglyceride. If present, it can also be used in the form of a salt. Examples of the counter ion forming the salt include ions of alkali metals such as sodium and potassium, ions of alkaline earth metals such as calcium, and the like. Of these, fatty acids (salts) are preferred, lauric acid, palmitic acid, stearic acid and the like are preferred, and lauric acid is most preferred.
The content of the organic substance in the particles (C) is preferably 55% by mass or more, and more preferably 60% by mass or more. It is preferable that the organic content is in such a range because hydrophobicity can be effectively imparted to the composite particles P.
The particles (C) can contain a surfactant and an optional component of the particles (A) in addition to the organic substance.

The contact angle of the particles (C) is preferably 60 ° or more, more preferably 70 ° or more, and most preferably 80 ° or more. In the present invention, the contact angle can be measured with a contact angle meter or the like. When the contact angle is in such a range, it is preferable because hydrophobicity can be effectively imparted to the composite particles P.
The average particle size of the particles (C) is preferably from 0.1 to 10 μm, and more preferably from 0.1 to 5 μm. It is preferable that the average particle diameter of the particles (C) is in such a range because the particles (C) can exist stably with respect to the surfactant particles A.
The particle (C) may contain a surfactant, an optional component of the particle (A), and the like as long as the effects of the present invention are not impaired.
The amount of the particles (C) in the powder detergent composition of the present invention is preferably 0.001 to 5% by mass, more preferably 0.1 to 3% by mass, and 0.1 to 1% by mass. % Is most preferred.
The particles (C) can be produced by pulverizing an organic substance. Moreover, it can manufacture by making sodium carbonate particle | grains, sodium sulfate particle | grains, etc. which are normally used as a builder into a core particle, coating this with an organic substance using a stirring granulator etc., and grind | pulverizing as needed. The pulverization can usually be performed using a pin mill or the like.

<Optional component>
The powder detergent composition of the present invention can optionally contain components usually contained in the powder detergent composition in addition to the particles (A) to the particles (C). Examples of such components include builder granules, enzyme particles, bleach particles, bleach activator particles, fragrances, dyes, pigments and the like.
The builder granules are preferably contained in an amount of 10 to 40% by mass with respect to the composition of the present invention. More preferably, it is 12-30 mass%, More preferably, it is 15-20 mass%.
Enzyme particles and the like vary depending on the effect of each component, but are preferably contained in an amount of 0.01 to 10% with respect to the powder detergent composition of the present invention. Specifically, 0.2 to 1.5% by mass of enzyme particles, 2 to 10% by mass of bleach particles, and 1 to 5% by mass of bleach activator particles are preferable. As the enzyme, protease, amylase, lipase, cellulase and the like can be used.
These optional components are also usually contained in the composition of the present invention in the form of particles (sometimes referred to as “(D) particles”), but the average particle size is from the viewpoint of solubility and product appearance. It is preferable that the particle size is the same as that of the surfactant particles (A). The difference between the bulk density of the surfactant particles (A) and the bulk density of the (D) particles is preferably within ± 0.3, within ± 0.25, from the viewpoint of classification during production and transportation. Is more preferred, and most preferred is comparable.

<Manufacture of composite particles (P)>
The composite particles (P) of the present invention can be produced, for example, by mixing a predetermined amount of (A) to (C) particles in a horizontal cylindrical rolling mixer for a predetermined time.

<Measurement method of relative area intensity>
The present invention is derived from the IR intensity (O1) derived from the organic substance in the particles (C) contained in the powder detergent composition and the aluminosilicate in the aluminosilicate particles (B) contained in the powder detergent composition. Relative area strength (R1 = O1 / Z1) with IR strength (Z1), IR strength (O2) derived from organic matter in particles (C) after grinding powder detergent composition and powder detergent composition ( The ratio (R1 / R2) of the relative area strength (R2 = O2 / Z2) to the IR strength (Z2) derived from the aluminosilicate in the aluminosilicate particles (B) after grinding A) is 1 .01-20.
The relative area intensity (O1 / Z1, O2 / Z2) of the IR intensity (O1, O2) of the organic substance and the IR intensity (Z1, Z2) of the crystalline aluminosilicate is, for example, Fourier transform infrared spectroscopy (FT-IR) Or photoacoustic spectroscopy (PAS) in combination (hereinafter abbreviated as “FT-IR / PAS”). The distribution state of the target substance (organic matter and aluminosilicate) in the depth direction from the surface of the sample can be confirmed by FT-IR / PAS.
By comparing the relative area intensity of the characteristic peak of the organic substance to the characteristic peak of the aluminosilicate obtained for each of the case of measuring the powder detergent composition while maintaining the structure and the case of measuring in a uniform state after grinding. Structural features of the powder detergent composition can be identified. R1 / R2 means the mass ratio of the aluminosilicate particles (B) and the organic particles (C) on the surface of the powder detergent composition (P), and the larger this value, the greater the value on the surface of the composite particles (P). It means that the mass ratio of the organic particles (C) to the existing aluminosilicate particles (B) is large.
By measuring the relative area strength, it is possible to confirm the characteristics of the surface of the powder detergent composition even if the surfactant particles (A) contain particles (B) and particles (C).
R1 / R2 is preferably 1.03 to 10, more preferably 1.05 to 1.5, and most preferably 1.05 to 1.15. When R1 / R2 is in such a range, it is preferable because the solubility in water at low temperatures is excellent.
Without being bound by any theory, the optimal ratio of the hydrophobic particles present on the surface of the surfactant particles to the crystalline aluminosilicate particles is determined by the cold water between the particles containing the surfactant particles. It is considered that aggregation can be suppressed by suppressing the permeation of the resin and delaying the gelation.

The method for obtaining R1 / R2 will be described below using sodium oleate as an organic substance as an example.
After adding a predetermined amount of aluminosilicate particles (B) and (C) sodium oleate to the surface of the surfactant particles, the surfactant particles (A) are mixed by mixing in a horizontal cylindrical rolling mixer for 1 minute. A powder detergent composition is obtained by preparing and mixing arbitrary components as needed. The obtained powder detergent composition is filled into a PAS cell. On the other hand, the powder detergent composition is sufficiently pulverized with an agate mortar or the like to obtain a uniform state (until there are no particles having a particle size of 74 μm or more), and is filled in another PAS cell. This is used as a comparative sample. As the PAS cell, for example, Photoacoustics Model 300 type photoacoustic detector manufactured by MTEC can be used.
The FT-IR / PAS is measured by using, for example, a Spectrum One type infrared spectrophotometer manufactured by PERKIN ELMER. The measurement conditions are, for example, a resolution of 8 cm ⁻¹ , a scan speed of 0.20 cm / sec, and a total of 16 times.
In the PAS spectrum of the powder detergent composition, the characteristic peaks of sodium oleate and crystalline aluminosilicate are 1560 cm ⁻¹ (reverse symmetric stretching vibration of —COO—) and 1009 cm ⁻¹ (reverse symmetric stretching of Si—O—Si), respectively. Read the area or intensity of these peaks as vibration).
For the peak area, the area of the portion surrounded by the base line connecting the valleys at both ends of the peak and the line indicating the peak shape is read. When calculating the IR intensity, if the overlap of peaks is significant and it is difficult to calculate the peak area, the intensity up to the intersection of the peak top, the perpendicular drawn from that point, and the base line connecting the valleys at both ends of the peak is calculated. It is good also as IR intensity of each component.

<Production of surfactant particles (A)>
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. To this, surfactant excluding α-SF-Na and nonionic surfactant and PEG # 6000 were added and stirred for 10 minutes. Subsequently, MA (acrylic acid / maleic acid copolymer sodium salt) and a fluorescent agent were added. After further stirring for 10 minutes, a part of the powder A-type zeolite (2.0% equivalent amount (vs. each particle, the same applies hereinafter) for the addition during kneading, 3.2% equivalent amount for the grinding aid, Sodium carbonate, potassium carbonate, and sodium sulfite were added except 5% equivalent amount of each type A zeolite for surface coating. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size of 320 μm and a bulk density of 0.30 g / Spray dried particles with cm ³ and 5% moisture were obtained.
On the other hand, an aqueous slurry of α-SF-Na (moisture concentration 25%) obtained by sulfonating and neutralizing the fatty acid ester of the raw material was mixed with a part of the nonionic surfactant (25 relative to α-SF-Na). %) Was added and concentrated under reduced pressure with a thin film dryer until the water content was 11% to obtain a mixed concentrate of α-SF-Na and a nonionic surfactant.
The above-mentioned spray-dried particles, this mixed concentrate, 2.0% equivalent of type A zeolite, 0.5% equivalent of the remaining nonionic surfactant and water except for spray addition, and continuous kneader (Kurimoto Co., Ltd.) (Kakosho, KRC-S4 type) was kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a surfactant-containing kneaded product. This surfactant-containing kneaded product was cut with a cutter while extruding it with a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die having a hole diameter of 10 mm (cutter peripheral speed was 5 m / s) A pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.
Next, 3.2% equivalent amount of particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and coexisting with cold air (10 ° C., 15 m / s) The powder was pulverized using a Fitz mill (manufactured by Hosokawa Micron Co., Ltd., DKA-3) arranged in series at the bottom (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation Number: 1st stage / 2nd stage / 3rd stage are all 4700 rpm).
<Production of particles (C)>
According to the composition shown in Table 3, Coroplex 160Z (fine pulverization pin mill) was used, and pulverization was performed at a supply rate of 100 kg / hr and a mill disk peripheral speed of 85 m / sec to prepare particles (C).

<Manufacture of powder detergent composition>
Filling rate of 30 with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7 L, clearance between inner wall surface: 20 mm, height: 45 mm) (A) particles, (B) particles, and particles (C) were added under the conditions described in the table under the conditions of volume%, rotational speed 22 rpm, and 25 ° C., and 0.5% equivalent nonionic surfactant to the total amount. The particles were obtained by rolling for 1 minute while spraying the fragrance and surface modifying.
In order to color a part of the obtained particles, the surfactant-containing particles are transported at a speed of 0.5 m / s on the belt conveyor (the height of the surfactant-containing particle layer on the belt conveyor is 30 mm, the layer width) 300 mm) A 20% aqueous dispersion of the dye was sprayed on the surface.
Thereafter, an enzyme and other powder components were mixed in the horizontal cylindrical rolling mixer to obtain a powder detergent composition.

<Measurement of average particle size>
Surfactant particles (A)
About each sample and its mixture, classification operation was performed using the 9-stage sieve and saucer of 1680 micrometers, 1410 micrometers, 1190 micrometers, 1000 micrometers, 710 micrometers, 500 micrometers, 350 micrometers, 250 micrometers, and 149 micrometers. In the classification operation, a sieve with a small opening is stacked on a tray in the order of a large opening, and a base sample of 100 g / time is placed on the top of the top 1680 μm sieve. Attached to Iida Seisakusho Co., Ltd., Tapping: 156 times / minute, Rolling: 290 times / minute), and after vibrating for 10 minutes, the sample remaining on each sieve and the saucer was collected for each sieve, The mass of was measured.
When the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle size (weight: 50%) was calculated by the following equation, where c% was the cumulative mass frequency from the sieve to the aμm sieve and d% was the mass frequency on the aμm sieve.

Aluminosilicate particles (B)
For the average particle size, a volume-based average particle size was determined using LS-230 Particle Size Analyzer manufactured by Coulter.
Particle (C)
For the average particle size, a volume-based average particle size was determined using LS-230 Particle Size Analyzer manufactured by Coulter.
<Contact angle measurement method>
Sample adjustment: Double-sided tape was attached to a slide glass, and particles (C) were spread over, and then excess powder was removed.
Measurement method: Water at a temperature of 20 ° C. was dropped onto the sample, and the contact angle after 30 seconds was measured with an automatic contact angle meter (CA-QI series, manufactured by Kyowa Interface Science). The average of five measurements was taken as the contact angle.
<Calculation method of relative area intensity ratio R1 / R2>
The obtained powder detergent composition was filled in a PAS cell. As the PAS cell, a Photoacoustics Model 300 photoacoustic detector manufactured by MTEC was used.
Measurement of FT-IR / PAS was performed by using a Spectrum One type infrared spectrophotometer manufactured by PERKIN ELMER. The measurement conditions were a resolution of 8 cm ⁻¹ , a scan speed of 0.20 cm / sec, and a total of 16 times.
In the PAS spectrum of the powder detergent composition, the characteristic peaks of sodium laurate and crystalline aluminosilicate are 1560 cm ⁻¹ (reverse symmetrical stretching vibration of —COO—) and 1009 cm ⁻¹ (reverse symmetrical stretching of Si—O—Si), respectively. As the vibration), the area of these peaks was read and used as the IR intensity of each component.
In addition, the peak area read the area of the part enclosed by the base line which connected the trough of the both ends of a peak, and the line which shows a peak shape.
The IR intensity derived from the organic substance in the particles (C) contained in the powder detergent composition read from the above is O1, and is derived from the aluminosilicate in the aluminosilicate particles (B) contained in the powder detergent composition. The IR intensity was Z1, and the relative area intensity R1 = O1 / Z1 was calculated.
Similarly, the powder detergent composition was sufficiently pulverized with an agate mortar or the like to obtain a uniform state (until particles having a particle size of 74 μm or more disappeared), and filled in another PAS cell, which was used as a comparative sample. For this comparative sample, the IR intensity derived from the organic matter in the particles (C) after grinding the powder detergent composition by the same operation is O2, and in the aluminosilicate particles (B) after grinding the powder detergent composition The IR intensity derived from the aluminosilicate was Z2, and the relative area intensity R2 = O2 / Z2 was calculated.
From the above R1 and R2, the ratio R1 / R2 of the relative area intensity was calculated using the above formula (1).

<Measurement of bulk density>
The bulk density was measured according to JIS K3362.
<Evaluation of solubility (low-temperature aggregation)>
Place 30.0 g of powder detergent composition in an aggregated state near one outer periphery of the fan-shaped depression divided into four parts of the pulsator of Mitsubishi Electric's two-tank washing machine CW-C30A1. (50% by weight of cotton underwear, 50% by weight of polyester / cotton blended underwear) is poured into the washing tub, and 30 L of tap water of 5 ° C. is poured at a flow rate of 10 L / min so that the detergent is not directly exposed to water. It was allowed to stand later. After 3 minutes from the start of water injection, stirring was started with a soft water flow, and after stirring for 3 minutes, the water was drained, and the state of the powder detergent composition remaining in the clothing and the washing tub was visually determined according to the following evaluation criteria. Evaluation criteria ◎, ○, and △ were considered acceptable. The “aggregate” described below refers to a lump having a diameter of 3 mm or more in which detergent particles are aggregated.
〔Evaluation criteria〕
A: There is no aggregate.
○: There is almost no aggregate.
Δ: A small amount of aggregate remains.
X: A large amount of aggregate remains.

<Dust generation evaluation method>
A Shibata digital dust indicator is set on the top of a 50cm high, 30cm vertical and horizontal sealed container, and 30g of the detergent composition is dropped from the height of 50cm. After the drop, the maximum dust generation count (cpm; count per minute) ). The relationship between the number of dust generation counts and the degree of dust generation is as follows.
◎: 20 cpm or less ○: 20 cpm or more, 50 cpm or less Δ: 50 cpm or more, 100 cpm or less ×: 100 cpm or more

FIG. 1 shows the relationship between the amount of particles (C) and the solubility and dust generation with respect to the total amount of aluminosilicate particles (B) and particles (C), and FIG. 2 shows R1 / R2 and solubility. The relationship between dust generation is shown.
From FIG. 1, it can be seen that the solubility improves as the blending amount of the C particles increases, whereas the dust generation tends to deteriorate as the blending amount of the C particles increases.
From FIG. 2, it can be seen that the more C particles are present on the surface of the P particles, the better the solubility is. However, when there is an excessive amount, the dust generation tends to deteriorate.

The raw materials used in the examples are shown below.
Surfactant particles (A)
<Surfactant>
Α-SF-Na: 14 carbon atoms: sodium salt of α-sulfo fatty acid methyl ester having carbon number 16 = 18: 82 (manufactured by Lion Corporation, AI = 70%, the remainder is unreacted fatty acid methyl ester, sodium sulfate , Methyl sulfate, hydrogen peroxide, water, etc.)
LAS-K: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Lypon LH-200 (manufactured by Lion) LAS-H pure 96%) 48% hydroxylated during preparation of surfactant composition Neutralize with aqueous potassium). The compounding quantity in Table 1 shows the mass% as LAS-K.
AOS-K: α-olefin sulfonate potassium having an alkyl group having 14 to 18 carbon atoms (manufactured by Lion Corporation)
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: C12: 11.7%, C14: 0.4%, C16: 29.2%, C18F0 (stearic acid): 0.7%, C18F1 (oleic acid): 56.8%, C18F2 (linoleic acid): 1.2%, molecular weight: 289)
Nonionic surfactant: ECOROL 26 (alcohol having an alkyl group having 12 to 16 carbon atoms manufactured by ECOGREEN) adduct with an average of 15 moles of ethylene oxide (pure content: 90%, melting point: 43 ° C., HLB 15.4)

<Water-soluble polymer>
MA agent: acrylic acid / maleic acid copolymer Na salt, Aqualic TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution)
・ PEG # 6000: Polyethylene glycol manufactured by Lion Corporation, trade name PEG # 6000M
<Inorganic compounds>
・ Type A zeolite: Shilton B (manufactured by Mizusawa Chemical Co., Ltd., 80% pure)
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd., average particle size 490 μm, bulk density 1.30 g / cm ³ )
・ Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.)
・ Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.)
<Others>
-Dye: Ultramarine (Daiichi Seika Kogyo Co., Ltd., Ultramarine Blue)
Fragrance A: Fragrance composition A shown in JP-A-2002-146399 [Table 11] to [Table 18]
Fragrance B: Fragrance composition B shown in JP-A-2002-146399 [Table 11] to [Table 18]
-Fluorescent agent: Chinopearl CBS-X (Ciba Specialty Chemicals) / Chinopearl AMS-GX (Ciba Specialty Chemicals) = 3/1 (mass ratio) mixture

Aluminosilicate particles (B)
・ Type A zeolite: Shilton B (manufactured by Mizusawa Chemical Co., Ltd., 80% pure)
・ P-type zeolite: DOUCIL A24 (Ineos Silica)

Particle (C)
<Organic>
-Lauric acid: manufactured by NOF Corporation, NAA-122, melting point 43 ° C
Palmitic acid methyl ester: manufactured by Lion Corporation, pastel M-16, melting point 30 ° C.
<Others>
Sodium carbonate: grain ash (Asahi Glass Co., Ltd. average particle size 320 μm, bulk density 1.07 g / cm ³ )
(D) Particles / enzyme particles A: Cannase 12T (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12T (Novozymes) / Cellzyme 0.7T (Novozymes) = 5/2/1/2 (mass ratio) Mixture of enzyme particles B: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12T (Novozymes) / Cellzyme 0.7T (Novozymes) = 5/2/1/2 (mass ratio) -Surface-treated inorganic compound particles: produced according to production method 1 described on pages 39 to 40 of WO 2004/094313.
・ Bleaching agent: Mitsubishi Gas Chemical Co., Ltd., sodium percarbonate, SPC-D, effective oxygen amount 13.2%, average particle size 760 μm
Bleach activator: Bleach activator granulated product produced according to the method for preparing Bleach activator granulated product A described in page 55 of International Publication WO 2004/094313.

The relationship between the quantity of particle | grains (C) with respect to the total amount of aluminosilicate particle | grains (B) and particle | grains (C), solubility, and dust generation property is shown. The relationship between R1 / R2 and solubility is shown.

Claims (3)

Surfactant particles (A) containing 10 to 40% of a surfactant and having an average particle size of 150 μm or more, aluminosilicate particles (B) having an average particle size of less than 30 μm,
Containing composite particles (P) formed by surface treatment with particles (C) having an organic substance content of 50% or more and an average particle size of less than 30 μm and a contact angle of 50 ° or more;
The relative area intensity ratio R1 / R2 represented by the following formula (1) is 1.01 to 20,
Powder detergent composition.

R1 / R2 = (O1 / Z1) / (O2 / Z2) (1)

(Where
O1 represents the IR intensity derived from the organic substance in the particles (C) contained in the powder detergent composition, and Z1 represents the aluminosilicate in the aluminosilicate particles (B) contained in the powder detergent composition. Represents the derived IR intensity, R1 represents the relative area intensity O1 / Z1;
O2 represents the IR intensity derived from the organic substance in the particles (C) after grinding the powder detergent composition, and Z2 is the aluminosilicate in the aluminosilicate particles (B) after grinding the powder detergent composition. The IR intensity derived from the salt is represented, and R2 represents the relative area intensity O2 / Z2. )   (C) Organic substance of component is a fatty acid and / or its salt, The powder detergent composition of Claim 1 characterized by the above-mentioned.   The powder detergent composition according to claim 1 or 2, wherein R1 / R2 is 1.03 to 10.

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