JP2005239836A - Powder cleaning composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder detergent composition having excellent washing performance when using hard water and having good powder physical properties such as caking resistance.
SOLUTION: (a) a polyoxyalkylene alkyl ether sulfate having a weight average addition mole number of 1 to 3 of alkylene oxide, (b) an alkyl sulfate ester salt, and (c) an α-sulfo fatty acid ester salt, each having a specific ratio A powder detergent composition having a surfactant equivalent content of 10 to 60% by mass, a builder content of 10 to 90% by mass, and a weight average particle size of 150 to 2000 μm.
[Selection figure] None

Description

  The present invention relates to a powder cleaning composition. Preferably, it is related with the powder cleaning composition for textiles used by melt | dissolving in water.

  The powder detergent composition is strongly directed to increase the bulk density and reduce the amount of use for the convenience of consumers. In addition, as a reduction in environmental burden, there is a demand for compact products and light packaging materials, and high bulk density detergents have become the mainstream. When making powder cleaners compact, inorganic salts such as mirabilite, which have a small cleaning effect, are added to large amounts in conventional low bulk density cleaners, and organic substances such as surfactants that are the main cleaning components As a result of the increase in the ratio, the detergent particles increased in plasticity, resulting in reduced productivity and caking problems during long-term storage.

  Surfactants blended in clothing detergents are compatible with various types of stains, and in order to obtain a synergistic effect with a plurality of surfactants, they are usually not a single type but a combination of several types of surfactants. The anionic surfactant and the nonionic surfactant are often used in combination.

  For example, high-concentration surfactant particles containing α-sulfo fatty acid ester salt and nonionic surfactant or / and polyethylene glycol in high concentration have been studied (for example, see Patent Document 1). However, since it is inferior in preventing re-contamination of solid particle dirt, there is a problem in using it as it is as a cleaning composition.

  Nonionic surfactants have high cleaning performance when hard water is used (hereinafter referred to as hard water resistance) and have a detergency suitable for use as a cleaning agent for clothing, but are liquid at room temperature. When the cleaning agent is stored for a long period of time, caking problems may occur due to the exudation of the liquid nonionic surfactant, which has been a limitation on production conditions.

  Therefore, high-concentration surfactant particles containing α-sulfo fatty acid ester salt and soap in a high concentration have been studied (for example, see Patent Document 2). However, there has been a problem that the particles become brittle over time, fine powder is generated, and the fluidity during use deteriorates.

  In addition, a detergent raw material containing a surfactant, a water-soluble carrier and a water-soluble structurant has been studied (see, for example, Patent Document 3). However, the cleaning performance is not sufficient, and there has been a problem in using it as it is as a cleaning composition.

  On the other hand, anionic surfactants typified by alkyl sulfate esters obtained by sulfating / neutralizing higher alcohols have been commercialized as powder products by drying their aqueous solutions. The alkyl sulfate ester salt has a problem in hard water resistance, and the cleaning performance is not sufficiently satisfactory, and there is a demand for improvement.

  In addition, polyoxyalkylene alkyl ether sulfate obtained by adding sulfoxide / neutralization to higher alcohol and then sulfating / neutralizing has a lower Kraft point relative to alkyl sulfate ester salts having the same carbon number, Since it has excellent low-temperature solubility and outstanding hard water resistance, it is used as a main base for liquid detergents and the like. However, due to the problem of poor caking properties peculiar to polyoxyalkylene alkyl ether sulfates, it has been extremely difficult to mix them in a powder cleaning composition.

For example, Patent Document 4 describes a method for producing an anionic activator granule. In Example 3 of Patent Document 1, a solid slurry having a solid content of 80% by mass of polyoxyethylene alkyl ether sulfate is dried. However, it was not possible to say that this granular material had a high water content of about 8% by mass, and was not a fluid granular material with improved caking properties.
JP-A-9-169999 Japanese Patent Laid-Open No. 9-20900 International Publication No. 00/31223 Pamphlet Japanese Patent Laid-Open No. 5-331496

  The subject of this invention is providing the powder detergent composition which was excellent in hard water resistance and improved powder characteristics, such as caking resistance.

The present invention
The surfactant equivalent described in JIS K 3362: 1998 is 10 to 60% by mass,
Containing 10 to 90% by mass of a builder,
The weight average particle size determined from the particle size measured by the sieving method using a sieving machine described in JIS K 3362: 1998 is 150 to 2000 μm.
A powder cleaning composition comprising:
(A) polyoxyalkylene alkyl ether sulfate (hereinafter referred to as component (a)) having 1 to 3 added moles of alkylene oxide (hereinafter referred to as AO), (b) alkyl sulfate ester salt (hereinafter referred to as ( b) component], (c) α-sulfo fatty acid ester salt (hereinafter referred to as component (c)), and the total amount of (a), (b), and (c) is equivalent to the surfactant. 60% by weight or more of the minute, (a) is 60% by weight or less in the anionic surfactant, (c) is 20 to 60% by weight in the anionic surfactant, (a) and (c) Powder cleaning agent having a mass ratio of 9/5 to 1/50 in (a) / (c) and 7/3 to 1/20 in (a) / (b) Relates to the composition.

  The powder detergent composition of the present invention is excellent in powder properties such as hard water resistance and caking resistance.

<(A) component>
The powder cleaning composition of this invention contains the polyoxyalkylene alkyl ether sulfate whose addition mole number of AO is 1-3 as (a) component. The content of the component (a) is preferably 0.1 to 36% by mass, and 0.5 to 30% by mass in the composition of the present invention in terms of washing performance, hard water resistance, caking resistance and productivity. More preferably, 1-20 mass% is still more preferable, and 3-15 mass% is especially preferable.

Examples of the component (a) include compounds represented by the general formula (I).
[R ¹ —O (AO) _n —SO ₃ ] _p M ¹ (I)
[Wherein, R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 3 indicating the added mole number of AO, M ¹ Is a cation, p is the valence of M ¹ , and n AOs may be the same or different. ]

In general formula (I), R ¹ is preferably an alkyl group having 10 to 18 carbon atoms. AO is preferably an oxyalkylene group having 2 to 3, particularly 2 carbon atoms. M ¹ is preferably an alkali metal atom such as Na or K, an alkaline earth metal atom such as Ca or Mg, or an alkanol-substituted or unsubstituted ammonium group, and more preferably an alkali metal atom, particularly Na. p is preferably 1 or 2, and more preferably 1.

<(B) component>
The powder detergent composition of the present invention contains an alkyl sulfate ester salt as the component (b). The content of the component (b) is preferably 0.1 to 30% by mass, and 0.5 to 25% by mass in the composition of the present invention in terms of washing performance, hard water resistance, caking resistance and productivity. More preferably, 1-20 mass% is still more preferable, and 3-15 mass% is especially preferable.

Examples of the component (b) include compounds represented by general formula (II).
_{^{[R 2 -O-SO 3]}} q M 2 (II)
[Wherein, R ² represents a linear or branched alkyl group having 8 to 20 carbon atoms, M ² represents a cation, q represents a valence of M ² , and n AOs may be the same or different. ]

In the general formula (II), R ² is preferably an alkyl group having 10 to 18 carbon atoms. M ² is preferably an alkali metal atom such as Na or K, an alkaline earth metal atom such as Ca or Mg, or an alkanol-substituted or unsubstituted ammonium group, and more preferably an alkali metal atom, particularly Na. q is preferably 1 or 2, and more preferably 1.

<(C) component>
The powder detergent composition of the present invention contains an α-sulfo fatty acid ester salt as the component (c). The content of the component (c) is preferably 0.1 to 36% by mass, more preferably 0.5 to 25% by mass in the composition of the present invention in terms of cleaning performance, caking resistance, and productivity. -20 mass% is still more preferable, and 3-15 mass% is especially preferable.

  (C) As a component, the compound represented by general formula (III) is mentioned, for example.

[Wherein, R ³ represents a linear or branched alkyl or alkenyl group having 10 to 22, preferably 12 to 18, and particularly preferably 14 to 18 carbon atoms. R ⁴ is a linear or branched alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. M ³ is an alkali metal or ammonium, and specific examples of the alkali metal include lithium, sodium, potassium, and the like. ]

  (C) A component is obtained by a well-known manufacturing method. For example, it can be produced by sulfonating a fatty acid ester obtained by reacting oil and fat with a lower alcohol with sulfuric anhydride and finally neutralizing with caustic alkali or the like. Examples of the raw oil and fat include coconut oil, palm kernel oil, pig oil, beef tallow, rice bran oil, palm oil, and fish oil.

<Powder cleaning composition>
From the viewpoint of productivity, solubility, and caking resistance, the amount corresponding to the surfactant described in JIS K 3362: 1998 in the composition of the present invention is preferably 15 to 50% by mass, and more preferably 20 to 40% by mass.

  Further, in terms of productivity, solubility, and caking resistance, the builder content in the composition of the present invention is preferably 25 to 80 mass%, more preferably 30 to 60 mass%, and more preferably 35 to 50 mass%. Further preferred. The builder preferably has at least one of a metal chelate action, an alkali buffer action, and a solid particle dispersion action.

  In addition, in terms of low-temperature solubility and detergency, the weight average particle size determined from the particle size measured by a sieving method using a sieving machine described in JIS K 3362: 1998 of the composition of the present invention is preferably 250 to 1800 μm. Preferably it is 300-1500 micrometers, More preferably, it is 300-1000 micrometers.

  The total amount of the component (a), the component (b), and the component (c) in the composition of the present invention is 65% corresponding to the surfactant in terms of productivity, detergency and caking resistance. % Or more, more preferably 70% by weight or more, still more preferably 75% by weight or more, and particularly preferably 80% by weight or more.

  In the composition of the present invention, it is preferable that 15 to 70% by mass, further 17 to 65% by mass, and particularly 20 to 60% by mass of the surfactant equivalent occupy the anionic surfactant.

  In addition, in terms of productivity and caking resistance, the component (a) in the anionic surfactant in the composition of the present invention is preferably 55% by mass or less, more preferably 50% by mass or less, and 45% by mass or less. Is more preferable, and 40% by mass or less is particularly preferable. Moreover, 5 mass% or more is preferable at the point of hard water resistance, 10 mass% or more is more preferable, 15 mass% or more is further more preferable, and 20 mass% or more is especially preferable.

  In addition, from the viewpoints of productivity, detergency and caking resistance, the component (c) in the anionic surfactant in the composition of the present invention is preferably 25 to 55% by mass, more preferably 28 to 50% by mass. 30 to 45% by mass is more preferable.

  Further, in terms of productivity, detergency and caking resistance, the mass ratio of the component (a) to the component (c) in the composition of the present invention is 8/5 to 1/30 in (a) / (c). Is preferable, 7/5 to 1/10 is more preferable, and 6/5 to 1/5 is still more preferable.

  Further, in terms of productivity, detergency and caking resistance, the mass ratio of the component (a) to the component (b) in the composition of the present invention is 7/3 to 1/20 in (a) / (b). Is preferable, 6/4 to 1/9 is more preferable, and 5/5 to 3/20 is still more preferable.

  In addition, the apparent density measured by the method described in JIS K 3362: 1998 of the composition of the present invention is preferably 300 to 1200 g / L, more preferably 400 to 1100 g / L in terms of low-temperature solubility, stability, and cleaning performance. 600 to 1000 g / L is more preferable, and 700 to 980 g / L is particularly preferable.

  Further, in terms of cleaning performance and damage, the pH of 0.05% by mass measured at 20 ° C. described in JIS K3362: 1998 of the composition of the present invention is preferably 8 to 12, more preferably 9 to 11.5. 9.5 to 11 are more preferable, and 10 to 11 are particularly preferable.

<(D) component>
The powder detergent composition of the present invention can contain a polyoxyalkylene alkyl ether sulfate having an added mole number of AO of 4 or more as the component (d) as long as the effects of the present invention are not impaired. The content of the component (d) is preferably 5% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and not contained in the composition of the present invention in terms of cleaning performance. Is particularly preferred.

Examples of the component (d) include compounds represented by the general formula (IV).
[R ⁵ —O (AO) _m —SO ₃ ] _r M ⁴ (IV)
[Wherein, R ⁵ is a linear or branched alkyl group having 8 to 20 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, m is an integer of 4 or more indicating the number of added moles of alkylene oxide, M ⁴ Represents a cation, r represents the valence of M ⁴ , and m AOs may be the same or different. ]

  In terms of productivity, detergency and caking resistance, the average added mole number of AO of the components (a), (b) and (d) is preferably 0.05-2, 1 is more preferable, and 0.2 to 0.8 is still more preferable. That is, it is preferable that the weight average value of the added mole number of AO based on the sum of the components (a), (b) and (d) in the composition is 0.05-2. In addition, (b) component is AO addition mole number = 0.

  When the component (d) is contained, the mass ratio between the total amount of (a) and (b) and (d) is [(a) + (b) in terms of washing performance, caking resistance, and productivity. )] / (D) is preferably 70/30 to 100/0, more preferably 80/20 to 100/0, and still more preferably 85/15 to 100/0.

<(E) component>
The powder cleaning composition of the present invention preferably contains a water-insoluble inorganic substance as the component (e) in terms of cleaning performance, caking resistance, and productivity, and the content thereof is in the composition of the present invention. 5 to 50% by mass, more preferably 8 to 45% by mass, particularly preferably 10 to 40% by mass, and most preferably 15 to 35% by mass. In addition, about (e) component, water-insoluble means that it does not melt | dissolve uniformly, even if it puts a sample equivalent to 0.1 mass% in 20 degreeC distilled water, and is stirred for 10 minutes. Moreover, these (e) components may be used as a builder.

  As the component (e), for example, crystalline aluminosilicate, amorphous aluminosilicate, silicon dioxide, hydrated silicate compound, talc, pyrophyllite, smectite (saponite, hectorite, soconite, stevensite, montmorillonite, Beidellite, nontronite, etc.), vermiculite, mica (phlogopite, biotite, chinwald mica, muscovite, paragonite, ceradonite, sea chlorite, etc.), chlorite (clinochlore, chamosite, nimite, penantite, sudite, donbasite) Etc.), brittle mica (Clintnite, Margarite, etc.), Sulite, Serpentine mineral (Antigolite, Lizardite, Chrysotile, Amesite, Clonsteadite, Burcellin, Greenerite, Garnierite, etc.), Kaolin Mineral (Kaori) Night, Ikkaito, nacrite, can be used clay minerals such as halloysite, etc.) and the like. For reasons such as not promoting the generation of undissolved residues, it is preferable to contain crystalline aluminosilicate and amorphous aluminosilicate, and more preferably to contain crystalline aluminosilicate. Moreover, 0.1-10 micrometers is preferable and, as for the weight average particle diameter of this aluminosilicate, 0.5-5 micrometers is more preferable. Suitable as the crystalline aluminosilicate is A-type zeolite (for example, trade name: “Toyo Builder”; manufactured by Tosoh Corporation, trade name: “synthetic zeolite”; manufactured by Nippon Builder Co., Ltd., trade name: “ VALFOR100 ”; PQ CHEMICALS (Thailand) Ltd., trade name:“ ZEOBUILDER ”; ZEOBILDER Ltd., trade name:“ VEGOBOND A ”; OMAN CHEMICAL INDUSTRIES LTD, trade name:“ THEICIC TELD ” It is also preferable in terms of sealing ability and economy. In addition, there are P type (for example, trade name “Ducil A24”, “ZSE064”, etc .; manufactured by Crosfield) and X type (for example, trade name: “WessalithXD”; manufactured by Degussa). The hybrid zeolite described in WO 98/42622 is also mentioned as a suitable crystalline aluminosilicate. Amorphous aluminosilicate and amorphous silica can also be used. For example, Japanese Patent Application Laid-Open No. 62-191417, page 2, lower right column, line 19 to page 5, upper left column, line 17 (particularly, the initial temperature is preferably in the range of 15 to 60 ° C.), Japanese Patent Application Laid-Open No. 62-191419. Amorphous aluminosilicate described in the second page, lower right column, line 20 to page 5, lower left column, line 11; JP-A-9-132794, column 17, line 46 to column 18, line 38; JP-A-7-10526, column 3, line 3 to column 5, line 9, JP-A-6-227811, column 2, line 15 to column 5, line 2, JP-A-8-119622 The amorphous aluminosilicate etc. which are described in 2nd column 18th line-3rd column 47th line can be mentioned. For example, “Toxeal NR” (manufactured by Tokuyama Soda Co., Ltd.), “Flowlite” (same as above), “TIXOLEX25” (manufactured by Han France Chemicals), “Silo Pure” (manufactured by Fuji Divison Co., Ltd.), etc. Can be used. In particular, those described in JP-A-6-179899, column 12, line 12 to column 13, line 1, column 17, line 34 to column 19, line 17 are suitable.

In terms of cleaning performance and hard water resistance, the component (e) preferably contains an inorganic salt having a calcium capture amount of 200 to 600 CaCO ₃ mg / g. In terms of cleaning performance and hard water resistance, 1 to 38% by mass is preferable, 3 to 30% by mass is more preferable, 5 to 25% by mass is further preferable, and 8 to 20% by mass is particularly preferable. . The calcium capture amount is determined by the method described in JP-A-3-277696, page 3, lower right column, line 6 to page 4, upper left column, line 6 (however, an anionic surfactant is read as an inorganic salt). .

<Component (f)>
The powder cleaning composition of the present invention preferably contains a water-soluble inorganic salt as the component (f) in terms of cleaning performance, caking resistance, and productivity, and the content thereof is the composition of the present invention. Among them, 10 to 60% by mass is more preferable, 15 to 55% by mass is further preferable, 20 to 50% by mass is particularly preferable, and 25 to 45% by mass is most preferable. In addition, about (f) component, water solubility means that it will melt | dissolve uniformly, when a sample equivalent to 0.1 mass% is put into 20 degreeC distilled water and stirred for 10 minutes. Moreover, these (f) components may be used as a builder.

  Examples of the component (f) include water-soluble inorganic materials such as alkali metal salts such as carbonates, bicarbonates, sulfates, sulfites, hydrogen sulfates, hydrochlorides, and phosphates, ammonium salts, and amine salts. Examples include salts. Especially, it is preferable to contain carbonate and a sulfate, and it is more preferable to contain a sulfate.

  When the component (e) and the component (f) are contained, the mass ratio of the component (e) to the component (f) is (e) / (f) in terms of productivity, detergency and caking resistance. 10/1 to 1/10 is preferable, 8/1 to 1/8 is more preferable, 6/1 to 1/6 is still more preferable, and 4/1 to 1/4 is particularly preferable.

  From the viewpoint of productivity, detergency and caking resistance, the powder detergent composition of the present invention preferably has a water content of 0.1 to 8% by mass according to the superheat loss method described in JIS K 3362: 1998. 5-6 mass% is more preferable, and 1-5 mass% is still more preferable.

  In the composition of the present invention, surface modification may be performed in terms of fluidity and caking resistance. Examples of the surface modifier include aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, silicate compounds such as crystalline silicate compounds, metal soap, powder surfactants, etc. Fine powders, carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, water-soluble polymers such as polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof, and fatty acids. Aluminosilicates and crystalline silicates are more preferable, and aluminosilicates are more preferable.

  The content of the surface modifier is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less in the composition of the present invention from the viewpoint of storage stability. Moreover, 1 mass% or more in the cleaning agent of this invention is preferable at the point of surface modification, 3 mass% or more is more preferable, and 5 mass% or more is still more preferable.

<Other ingredients>
The powder cleaning composition of the present invention comprises (a) component, (b) component, (c) component, surfactants other than (d) component known in the field of clothing cleaning agents, (e) component, ( f) Builders other than ingredients, recontamination preventives (carboxymethylcellulose, etc.), bleaches, bleach activators, softeners, fluorescent brighteners, foam inhibitors (silicones, etc.), enzymes, enzyme stabilizers, coloring An agent, a fragrance | flavor, etc. can be contained.

  Examples of the surfactant other than the component (a), the component (b), the component (c), and the component (d) include those other than the component (a), the component (b), the component (c), and the component (d). Examples include anionic surfactants, nonionic surfactants, amphoteric surfactants, and one or more combinations of cationic surfactants. (A) Component, (b) Component It is preferable to use an anionic surfactant and a nonionic surfactant other than the components (c) and (d), and more preferably a nonionic surfactant. Further, amphoteric surfactants and cationic surfactants can be used in combination for the purpose.

  Examples of anionic surfactants other than the components (a), (b), (c), and (d) include alkylbenzene sulfonate, paraffin sulfonate, α-olefin sulfonate, α-sulfo Fatty acid salts or fatty acid salts are preferred. In the present invention, in particular, a fatty acid salt and a linear alkylbenzene sulfonate having an alkyl chain with 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms are preferred, and fatty acid salts are more preferred. The counter ion is preferably an alkali metal salt or an amine, particularly sodium and / or potassium, monoethanolamine or diethanolamine, and more preferably sodium and / or potassium. In view of caking resistance and productivity, it is preferable to contain a fatty acid salt in the powder detergent composition, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 18% by mass. 1 to 15% by mass is particularly preferable.

  Nonionic surfactants include polyoxyalkylene alkyl (carbon number 8-20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (carbon number 8-20) phenyl ether, polyoxyalkylene sorbitan fatty acid (carbon number 8-8). 22) Ester, polyoxyalkylene glycol fatty acid (carbon number 8 to 22) ester, and polyoxyethylene polyoxypropylene block polymer are preferable. In particular, as a nonionic surfactant, polyoxyalkylene alkyl ether obtained by adding 4 to 20 moles of AO such as ethylene oxide (hereinafter referred to as EO) or propylene oxide to alcohol having 10 to 18 carbon atoms is added. Is preferred. The nonionic surfactant preferably has an HLB value (calculated by the Griffin method) of 10.5 to 15.0, more preferably 11.0 to 14.5. From the viewpoint of caking resistance, cleaning performance, and productivity, the nonionic surfactant is preferably contained in the powder cleaning composition, more preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass. % Is more preferable, and 1 to 10% by mass is particularly preferable.

  Examples of builders other than the component (e) and the component (f) include organic builders. As the organic builder, aminocarboxylate, hydroxyaminocarboxylate, hydroxycarboxylate, cyclocarboxylate, ether carboxylate, and organic carboxylic acid (salt) polymer are preferable, and organic carboxylic acid (salt) polymer is preferable. Are more preferable. From the viewpoint of caking resistance, cleaning performance, and productivity, the composition of the present invention preferably contains an organic builder, and its content is more preferably 0.1 to 20% by mass in the composition. 5-15 mass% is still more preferable, and 1-10 mass% is especially preferable.

  Bleaching agents include compounds that release hydrogen peroxide in water. Carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct, tripolyphosphate / hydrogen peroxide adduct, pyrophosphate / Examples include hydrogen peroxide adducts, urea / hydrogen peroxide adducts, and the like. Among these, carbonate / hydrogen peroxide adduct and borate / hydrogen peroxide adduct are preferable, sodium carbonate / hydrogen peroxide adduct and sodium borate / hydrogen peroxide adduct are more preferable, and boric acid in terms of cleaning performance. Sodium / hydrogen peroxide adduct is more preferred. The composition of the present invention preferably contains a bleaching agent in terms of cleaning performance, and the content thereof is more preferably 0.1 to 20% by mass, and further 0.5 to 15% by mass in the composition. 1 to 10% by mass is preferable.

  The bleaching agent is preferably used together with the bleach activator in terms of washing performance. The mass ratio of the bleaching agent to the bleaching activator is more preferably 20/1 to 1/2, further preferably 10/1 to 2/3.

  Examples of the bleach activator include compounds that react with hydrogen peroxide in water to generate organic peracids. Glucose pentaacetate, triacetin, N, N, N commonly used in oxygen-based bleach-containing detergents Bleach activators such as', N'-tetraacetylethylenediamine and tetraacetylglycolyluril, and compounds represented by the following general formulas (1) to (4) can be used. In high temperature washing, N, N, N ′, N′-tetraacetylethylenediamine is preferred, and in low temperature washing, compounds represented by the following general formulas (1) to (4), among which the following general formulas (1) to (1) The compound represented by (2) is preferable in terms of cleaning performance.

[In the formula, R ¹¹ is preferably an alkyl group having 4 to 13 carbon atoms (more preferably 10 to 13), R ¹² is preferably an alkyl group having 5 to 13 carbon atoms (more preferably 7 to 11), and M is A hydrogen atom or an alkali metal, alkaline earth metal, ammonium or alkanolamine is shown. When M is a hydrogen atom, an alkali metal, ammonium or alkanolamine, n is 1, and when M is an alkaline earth metal, n is 2. ]

[In the formula, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ , R ²⁰ are a methyl group, an ethyl group, and a hydroxyethyl group, respectively, and R ¹⁸ is an alkylene group having 2 to 10 carbon atoms. And X ^m− represents an anion (preferably a halogen ion, an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, a phosphate ion, or a sulfate ion). m is the valence of the anion. ]

  The composition of the present invention preferably contains a bleach activator in terms of cleaning performance, and the content thereof is more preferably 0.05 to 20% by mass, and 0.1 to 15% by mass in the composition. % Is more preferable, and 0.5 to 10% by mass is particularly preferable.

  In addition, the composition of the present invention contains (a) component and (b) component in terms of productivity and caking resistance, and (c) a granulated product substantially free of component (A), It is preferable to contain a granulated product (B) containing the component (a), the component (b) and the component (c), wherein the component (c) is 50% by mass or more of the surfactant in the granulated product. . It is more preferable to contain both the granulated product (A) and the granulated product (B). Moreover, each granulated material can also use multiple things from which a composition differs.

<Granulated product (A)>
The powder detergent composition of the present invention contains (a) component, (b) component, (e) component, (f) component, and (d) component in terms of productivity and caking resistance. The granulated product (A) which does not substantially contain the component (c) may be contained. Here, “substantially free of component (c)” means that the component (c) is not present in the granulated product (A) or is negligible even if it is present. Means that the component (c) is less than 1% by mass in the surfactant of the granulated product (A).

  The weight average particle diameter of the granulated product (A) is preferably 150 to 2000 μm, more preferably 200 to 1500 μm, and still more preferably 300 to 1000 μm from the viewpoint of caking resistance and productivity.

  The apparent density of the granulated product (A) measured by the method described in JIS K 3362: 1998 is preferably 300 to 1200 g / L, more preferably 400 to 900 g / L in terms of caking resistance and productivity. 500 to 800 g / L is more preferable.

  From the viewpoint of caking resistance and productivity, the equivalent of the surfactant described in JIS K 3362: 1998 in the granulated product (A) is preferably 60 to 98% by mass, more preferably 65 to 98% by mass, and 70 to 70%. 96 mass% is still more preferable, 75-94 mass% is especially preferable, and 80-92 mass% is the most preferable.

  From the viewpoint of caking resistance and productivity, the component (a) in the granulated product (A) is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, still more preferably 10 to 50 mass%, 15-40 mass% is especially preferable.

  From the viewpoint of caking resistance and productivity, the component (b) in the granulated product (A) is preferably 10 to 95 mass%, more preferably 20 to 90 mass%, still more preferably 30 to 85 mass%, 40-80 mass% is especially preferable.

  In terms of productivity, the component (d) in the granulated product (A) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 15% by mass, and 0 to 10% by mass. % Is particularly preferred.

  In terms of hard water resistance, caking resistance, and productivity, the mass ratio of (a) component, (b) component, and (d) component in the granulated product (A) is [(a) + (d)]. / [(B)] is preferably 70/30 to 5/95, more preferably 60/40 to 10/90, and still more preferably 50/50 to 15/85.

  In terms of washing performance, caking resistance, and productivity, the weight average added mole number of AO based on the sum of the components (a), (b) and (d) in the granulated product (A) is 0. 0.05 to 2 is preferable, 0.1 to 1 is more preferable, and 0.2 to 0.8 is still more preferable.

  In terms of cleaning performance, powder properties, and productivity, the mass ratio of the total amount of the component (a) and the component (b) in the granulated product (A) and the component (d) is [(a) + (b )] / (D), preferably 70/30 to 100/0, more preferably 80/20 to 100/0, and still more preferably 85/15 to 100/0.

  In terms of cleaning performance and solubility, the total amount of the component (a), the component (b) and the component (d) in the granulated product (A) is preferably 50 to 98% by mass, more preferably 60 to 96% by mass. Preferably, 70 to 94% by mass is more preferable, and 80 to 92% by mass is particularly preferable.

  From the viewpoint of caking resistance and productivity, the granulated product (A) contains the component (e) and / or the component (f), and the total content thereof is 1 in the granulated product (A). -38 mass% is preferable, 3-30 mass% is still more preferable, 5-25 mass% is especially preferable, and 8-20 mass% is the most preferable. In particular, it is preferable to contain the component (e) in terms of productivity and solubility.

  In view of caking resistance and productivity, the content of the component (e) in the granulated product (A) is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, and 5 to 20% by mass. Is particularly preferred.

  In addition, from the viewpoint of caking resistance and productivity, the content of the component (f) in the granulated product (A) is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, and 0 5 to 10% by mass is particularly preferable.

  In terms of productivity, caking resistance and solubility, the granulated product (A) is a powder containing the component (e) and / or component (f) under reduced pressure in a granulator having a stirring blade and a crushing blade. A paste containing (a) component, (b) component, and (d) component, if necessary, or a mixture thereof (for example, (a) paste containing (a) component, (b) component) Paste containing, combination of paste containing component (d), combination of paste containing one of (a) component (a), component (b), component (d) and paste containing the other two (B) A paste including all of the components (a), (b), and (d), and a step of granulating at the same time as drying is preferable.

  From the viewpoint of fluidity and caking resistance of the finally obtained detergent composition particles, the granulated product (A) may be subjected to surface modification. Examples of the surface modifier include aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, silicate compounds such as crystalline silicate compounds, metal soap, powder surfactants, etc. Fine powders, carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, water-soluble polymers such as polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof, and fatty acids. Aluminosilicates and crystalline silicates are more preferable, and aluminosilicates are more preferable. The content of the surface modifier is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less in the granulated product (A) of the present invention from the viewpoint of storage stability. Moreover, 1 mass% or more in the granulated material (A) of this invention is preferable at the point of surface modification, 3 mass% or more is more preferable, and 5 mass% or more is still more preferable.

  The granulated product (A) of the present invention is obtained by drying and granulating a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste obtained by the method shown in the following step 1 by a known method as shown in step 2. Can be obtained.

Step 1: Preparation of polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste

In order to prepare the polyoxyalkylene alkyl ether sulfate-containing aqueous solution, the following methods (1) to (3) are exemplified.
(1) A method of sulfating and neutralizing an AO adduct of a higher alcohol obtained by adding AO to an alcohol having 8 to 20 carbon atoms (hereinafter referred to as a higher alcohol) so as to have a weight average addition mole number of 0.05 to 2. .
(2) A method in which a higher alcohol and an AO adduct of a higher alcohol are mixed so that the AO weight average addition mole number of the mixture is 0.05 to 2, and then sulfated and neutralized.
(3) A method in which a higher alcohol and an AO adduct of a higher alcohol are separately sulfated and neutralized in advance so that the AO weight average addition mole number of the mixture is 0.05-2.

  Sulfation and neutralization can be performed by known methods. The sulfating agent used for sulfation is preferably sulfur trioxide or chlorosulfonic acid. When using sulfur trioxide gas, it is usually diluted with an inert gas, preferably dry air or nitrogen, and a sulfur trioxide gas concentration of 1 to 8% by volume, preferably 1.5 to 5% by volume of gas. Used as a mixture. Examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, sodium carbonate and the like.

  The unreacted content contained in the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste of the present invention is not preferable because it causes a decrease in purity and the caking property of the powder. Is acceptable, and more preferably 2% by mass or less. Here, the unreacted component includes alcohol, alkoxylate that has not been sulfated, and a small amount of hydrocarbon and wax by-produced from the reaction.

  The effective component of the neutralized product obtained by the above method is preferably 30% by mass or less, or 60 to 80% by mass from the viewpoint of handling properties. Among these, the active ingredient 60 to 80% by mass becomes a paste and exhibits fluidity. Therefore, preparing this relatively high-concentration paste during neutralization reduces the energy load during drying, More preferred.

  In the present invention, a water-soluble inorganic salt may be present in the product. Representative examples of the water-soluble inorganic salt include sodium chloride, sodium sulfate, sodium carbonate and the like. These water-soluble inorganic salts may be added as they are, but may be by-produced by reaction. For example, when NaClO (sodium hypochlorite) is added to a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste for the purpose of improving the hue, NaCl (sodium chloride) is by-produced. Although use is limited, sodium hypochlorite can be added in this way, and sodium chloride can also be by-produced as an inorganic salt.

  The obtained polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste is subjected to the next step 2.

Step 2: Drying and granulating step Step 2 is a step of drying and granulating the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste prepared in Step 1 under various conditions. Sometimes it happens.

  As a drying means, in order to suppress degradation of quality such as hydrolysis due to heating of the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste, drying under vacuum is preferable. Furthermore, in view of the foaming property specific to polyoxyalkylene alkyl ether sulfate and pulverization at the end of drying, a continuous or batch-type vacuum dryer having a stirring blade and a pulverizer or a drying process capable of obtaining an equivalent effect is preferable. Examples of the continuous dryer include rotating thin film evaporators such as Contro, Cebucon [trade name, manufactured by Hitachi, Ltd., trade name], Smith thin film evaporator [manufactured by Shinko Pantech Co., Ltd.], and the like. . In the case of these continuous dryers, a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste can be continuously charged into a rotary thin film evaporator under reduced pressure to obtain a dried product. Examples of the batch dryer include a mixer vacuum dryer (SV mixer) manufactured by Shinko Pantech Co., Ltd., a microwave granulator / dryer manufactured by Fukae Powtech Co., Ltd., and Tanabe Wiltech Co., Ltd. And the like. Among these, a microwave granulator / dryer which is easy to perform step 1 in the same tank and can be dried and granulated in step 2 is particularly preferable because the load on the equipment is small.

  As drying conditions at this time, drying at a degree of vacuum at which the temperature of the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste becomes 80 ° C. or lower reduces heat history and suppresses degradation of quality such as decomposition. To preferred.

As a more specific drying method, a method of drying the polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste obtained in Step 1 by any of the following methods (4) to (6) can be mentioned.
(4) A polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste, or a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste and a mixture of an alkyl sulfate ester salt-containing aqueous solution, paste, or powder are mixed with a stirring blade and / or a solution. A method in which batch drying is performed in a batch vacuum dryer having a crusher and drying is performed under reduced pressure.
(5) In a batch type vacuum dryer having a stirring blade and / or a crusher, an anionic surfactant powder is charged in advance to such an extent that a stirring and crushing effect can be obtained, and then the powder in the machine under reduced pressure. A method of drying by supplying an aqueous solution or paste containing a polyoxyalkylene alkyl ether sulfate at a supply rate such that the body maintains a powder state. As the anionic surfactant powder prepared in advance at this time, the anionic surfactant powder and alkyl sulfate salt powder obtained in the present invention are used in combination, or only alkyl sulfate salt powder is used. May be.
(6) A method in which a polyoxyalkylene alkyl ether sulfate-containing aqueous solution or paste is continuously charged into a rotary thin film evaporator under reduced pressure and dried.

  The granulated product (A) in the present invention can be further granulated as needed, but there is no particular limitation on the granulator that can be used at that time, for example, a stirring tumbling granulator (Fukae Powtech Co. ), Manufactured by Tanabe Wiltech Co., Ltd.), etc., and can be granulated by adding water, a polyoxyalkylene alkyl ether sulfate-containing aqueous solution, etc. as a binder. Can be obtained.

<Granulated product (B)>
The powder detergent composition of the present invention contains (a) component, (b) component, (c) component, (e) component, and (f) component in terms of productivity and caking resistance, ) A granulated product which may contain components, and in the surfactant in the granulated product, (c) is contained in an amount of 50% by mass or more, further 60 to 100% by mass, particularly 65 to 95% by mass. The granulated product (B) to be contained can be contained. The content of the granulated product (B) is preferably 50 to 95% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass in the composition of the present invention. Moreover, when both a granulated material (A) and a granulated material (B) are contained, both total content is 5-99 mass% in the composition of this invention, Furthermore, 10-95 mass% is preferable. .

  From the viewpoint of caking resistance and productivity, the weight average particle diameter of the granulated product (B) is preferably 150 to 2000 μm, more preferably 200 to 1500 μm, and further preferably 300 to 1000 μm. The apparent density of the granulated product (B) measured by the method described in JIS K 3362: 1998 is preferably 300 to 1200 g / L, more preferably 400 to 900 g / L in terms of caking resistance and productivity. 500 to 800 g / L is more preferable.

  From the viewpoint of caking resistance and productivity, the equivalent of the surfactant described in JIS K 3362: 1998 in the granulated product (B) is preferably 10 to 60% by mass, more preferably 13 to 50% by mass, 15 -40 mass% is still more preferable.

  From the viewpoint of caking resistance and productivity, the granulated product (B) preferably contains the component (e) and / or the component (f), and the total content thereof is 30 to 70% by mass. Is preferable, 35-65 mass% is still more preferable, and 40-60 mass% is especially preferable.

  From the viewpoint of caking resistance and productivity, the content of the component (e) in the granulated product (B) is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 40% by mass. preferable.

  From the viewpoint of caking resistance and productivity, the content of the component (f) in the granulated product (B) is more preferably 10 to 60% by mass, further preferably 15 to 50% by mass, and more preferably 20 to 40% by mass. Particularly preferred.

  The granulated product (B) may be a granulated product obtained by spray-drying the slurry containing the component (c), or a granulated product obtained by performing compaction granulation after spray-drying, etc. (A), (b), (c) in the powder raw material containing the component (e) and / or the component (f) in a granulator having a stirring blade and a crushing blade in terms of caking property and solubility. It is preferable to manufacture by the manufacturing method including the process of adding the paste containing this.

  From the viewpoint of fluidity of the detergent particles and caking resistance, the granulated product (B) may be subjected to surface modification. Examples of the surface modifier include aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, silicate compounds such as crystalline silicate compounds, metal soap, powder surfactants, etc. Fine powders, carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, water-soluble polymers such as polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof, and fatty acids. Aluminosilicates and crystalline silicates are more preferable, and aluminosilicates are more preferable. The content of the surface modifier is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less in the granulated product (B) of the present invention from the viewpoint of storage stability. Moreover, 1 mass% or more in the granulated material (B) of this invention is preferable at the point of surface modification, 3 mass% or more is more preferable, and 5 mass% or more is still more preferable.

<Granulated product (A) 1>
While adjusting the drying conditions such that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the operation product temperature is 70 ± 1 ° C., the alkyl (carbon number 12 to 16) sodium sulfate salt (hereinafter, the alkyl sulfate ester salt is referred to as AS. (Indicated) containing paste (active ingredient 73 mass%) and polyoxyethylene (EO weight average addition mole number 1) alkyl (carbon number 12-16) ether sulfate sodium salt (hereinafter, polyoxyalkylene alkyl ether sulfate is referred to as ES) A vacuum dryer having an internal volume of 2500 L (Fukae Pautech Co., Ltd.), a paste prepared by mixing an aqueous solution containing 25% by mass of the active ingredient with a mass ratio of the active ingredient of AS: ES = 85: 15. ), FDM-1200JE] at an average addition rate of 150 kg / Hr, agitator rotation speed: 55 r / min, chopper rotation speed: 2000 r / min in, the average clearance between the stirring blade and the wall surface: granulating conditions 5.5 mm, dried and subjected to granulation at the same time, to obtain a granulated product 600 kg. Furthermore, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having a weight average particle size of 120 μm.

  200 kg of the above powder raw material is put into a vacuum dryer with a capacity of 2500 L [FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.] so that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the product temperature is 70 ± 1 ° C. While adjusting to dry conditions, alkyl (carbon number 12-16) sodium sulfate (AS) -containing paste (active ingredient 73 mass%) and polyoxyethylene (EO weight average addition mole number 1) alkyl (carbon number 12-12) 16) An ether sulfate sodium salt (ES) -containing aqueous solution (active ingredient 25% by mass) and a paste prepared by mixing the active ingredient so that the mass ratio of AS: ES = 85: 15 is averaged 150 kg / Hr in the dryer. , And granulated simultaneously with drying under the conditions of agitator rotation speed: 55 r / min, chopper rotation speed: 2000 r / min, EO weight average Pressurizing mole number was obtained granulated product polyoxyethylene alkyl sulfate sodium salt 0.25. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 3% by mass. The zeolite was 3% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite is added to the obtained granulated product, and the zeolite is uniformly coated on the granulated product, and a granular granulated product having a weight average particle size of 950 μm and an apparent density of 650 g / L by vibrating sieve. (A) 1 was obtained. The composition of the granulated product (A) 1 is as follows: (a) component: 10.4% by mass, (b) component: 74.3% by mass, (d) component: 2.8% by mass, (e) component: 10 0.8 mass%, component (f): 0.9 mass%, and the balance water (100 mass% in total).

<Granulated product (A) 2>
While adjusting the drying conditions such that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the operation product temperature is 70 ± 1 ° C., the alkyl (carbon number 12 to 16) sodium sulfate (AS) -containing paste (active ingredient 73 mass) %) And polyoxyethylene (EO weight average addition mole number 1) alkyl (carbon number 12 to 16) ether sulfate sodium salt (ES) -containing aqueous solution (active ingredient 25 mass%), the mass ratio of the active ingredient is AS : The paste mixed so that ES = 55: 45 was dropped into a vacuum dryer (Fukae Pautech Co., Ltd., FDM-1200JE type) having a dryer internal volume of 2500 L at an average addition rate of 150 kg / Hr, and the agitator was rotated. Number: 55 r / min, chopper rotation speed: 2000 r / min, average clearance between stirring blades and wall surface: granulation at the same time as drying under granulation conditions of 5.5 mm, 6 To obtain a granulated product of 0kg. Further, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having a weight average particle size of 100 μm.

  200 kg of the above powder raw material is put into a vacuum dryer with a capacity of 2500 L [FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.] so that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the product temperature is 70 ± 1 ° C. While adjusting to dry conditions, alkyl (carbon number 12-16) sodium sulfate (AS) -containing paste (active ingredient 73 mass%) and polyoxyethylene (EO weight average addition mole number 1) alkyl (carbon number 12-12) 16) An ether sulfate sodium salt (ES) -containing aqueous solution (active ingredient 25% by mass) and a paste prepared by mixing the active ingredient so that the mass ratio of AS: ES = 55: 45 is 150 kg / Hr on average in the dryer. , And granulated simultaneously with drying under the conditions of agitator rotation speed: 55 r / min, chopper rotation speed: 2000 r / min, EO weight average Pressurizing mole number was obtained granulated product polyoxyethylene alkyl sulfate sodium salt is 0.75. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 10% by mass. The zeolite was 3% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite is added to the obtained granulated product, and the zeolite is uniformly coated on the granulated product, and a granular granulated product having a weight average particle size of 920 μm and an apparent density of 680 g / L by vibrating sieve. (A) 2 was obtained. The composition of the granulated product (A) 2 is as follows: (a) component: 36.6% by mass, (b) component: 48.1% by mass, (d) component: 2.8% by mass, (e) component: 10 0.8 mass%, component (f): 0.9 mass%, and the balance water (100 mass% in total).

<Granulated product (A) 3>
While adjusting the drying conditions such that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the operation product temperature is 70 ± 1 ° C., the paste containing alkyl (carbon number 12-18) sodium sulfate (AS) (active ingredient 73 mass) %) And polyoxyethylene (EO weight average addition mole number 2) alkyl (carbon number 12 to 18) ether sulfate sodium salt (ES) containing aqueous solution (active ingredient 25 mass%), the mass ratio of the active ingredient is AS : The paste mixed so that ES = 85: 15 was dropped into a vacuum dryer (Fukae Pautech Co., Ltd., FDM-1200JE type) having an internal volume of 2500 L at an average addition rate of 150 kg / Hr, and the agitator was rotated. Number: 55 r / min, chopper rotation speed: 2000 r / min, average clearance between stirring blades and wall surface: granulation at the same time as drying under granulation conditions of 5.5 mm, 6 To obtain a granulated product of 0kg. Furthermore, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having a weight average particle size of 120 μm.

  200 kg of the above powder raw material is put into a vacuum dryer with a capacity of 2500 L [FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.] so that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the product temperature is 70 ± 1 ° C. While adjusting to dry conditions, alkyl (carbon number 12-18) sodium sulfate (AS) -containing paste (active ingredient 73 mass%) and polyoxyethylene (EO weight average addition mole number 2) alkyl (carbon number 12-12) 18) A paste prepared by mixing an aqueous solution containing sodium sulfate sodium salt (ES) (active ingredient 25% by mass) so that the mass ratio of the active ingredient is AS: ES = 85: 15 is averaged 150 kg / Hr in the dryer. , And granulated simultaneously with drying under the conditions of agitator rotation speed: 55 r / min, chopper rotation speed: 2000 r / min, EO weight average Pressurizing mole number was obtained granulated product polyoxyethylene alkyl sulfate sodium salt 0.5. The water content was 1% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 7% by mass. The zeolite was 3% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite is added to the obtained granulated product, and the zeolite is uniformly coated on the granulated product, and the granulated product having a weight average particle size of 960 μm and an apparent density of 710 g / L by vibrating sieve. (A) 3 was obtained. The composition of the granulated product (A) 3 is (a) component: 10.4% by mass, (b) component: 74.3% by mass, (d) component: 2.8% by mass, (e) component: 10 0.8 mass%, component (f): 0.9 mass%, and the balance water (100 mass% in total).

<Granulated product (A) 4>
While adjusting the drying conditions so that the jacket temperature is 85 ° C, the pressure is 4.0 kPa, and the operating product temperature is 70 ± 1 ° C, higher alcohols (12 to 16 carbon atoms) and higher alcohols (12 to 16 carbon atoms) Polyoxyethylene (EO weight average addition mole number 0. 0) obtained by sulfating the raw material which mix | blended the ethoxylate which added 1 mol of EO weight average in the ratio of 75/25, and then neutralizing with sodium hydroxide aqueous solution. 25) Alkyl (carbon number 12 to 16) ether sulfate sodium salt-containing paste (active ingredient 72% by mass) in a vacuum dryer (Fukae Powtech Co., Ltd., FDM-1200JE type) with an internal volume of 2500 L on average 150 kg / Hr The agitator rotation speed was 55 r / min, the chopper rotation speed was 2000 r / min, and the average clearance between the stirring blade and the wall surface was 5.5 mm. Depending on the conditions, drying and subjected to granulation at the same time, to obtain a granulated product 600 kg. Further, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having a weight average particle size of 100 μm.

  200 kg of the above powder raw material is put into a vacuum dryer with a capacity of 2500 L [FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.] so that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the product temperature is 70 ± 1 ° C. The raw material which mix | blended higher alcohol (C12-16) and the ethoxylate which added 1 mol of weight average EO to higher alcohol (C12-16) in the ratio of 75/25, adjusting to various drying conditions. Of polyoxyethylene (EO average addition mole number 0.25) alkyl (carbon number 12 to 16) ether sulfate sodium salt obtained by sulfation, and then neutralization with aqueous sodium hydroxide solution (active ingredient 72% by mass) ) In the dryer at an average addition rate of 150 kg / Hr, under the conditions of agitator rotation speed: 55 r / min, chopper rotation speed: 2000 r / min. Performs granulation simultaneously with 燥 to obtain granules of polyoxyethylene alkyl sodium sulfate EO weight average addition mole number of 0.25. The water content was 1% by mass. The zeolite was 3% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 4% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite is added to the obtained granulated product, the zeolite is uniformly coated on the granulated product, and the granulated product having a weight average particle size of 1160 μm and an apparent density of 670 g / L by vibrating sieve. (A) 4 was obtained. The composition of the granulated product (A) 4 is as follows: (a) component: 19.1% by mass, (b) component: 65.6% by mass, (d) component: 2.8% by mass, (e) component: 10 0.8 mass%, component (f): 0.9 mass%, and the balance water (100 mass% in total).

<Granulated product (A) 5>
While adjusting the drying conditions so that the jacket temperature is 85 ° C, the pressure is 4.0 kPa, and the operating product temperature is 70 ± 1 ° C, higher alcohol (carbon number 14-18) and higher alcohol (carbon number 14-18) Polyoxyethylene (EO weight average addition mole number 0. 0) obtained by sulfating the raw material which mix | blended the ethoxylate which added 2 mol of EO weight average in the ratio of 75/25, and then neutralizing with sodium hydroxide aqueous solution. 5) Alkyl (carbon number 14-18) ether sulfate sodium salt-containing paste (active ingredient 72% by mass) in a vacuum dryer (Fukae Pautech Co., Ltd., FDM-1200JE type) with an internal capacity of 2500 L on average 150 kg / Hr The agitator rotation speed is 55 r / min, the chopper rotation speed is 2000 r / min, and the average clearance between the stirring blade and the wall surface is 5.5 mm. By drying and subjected to granulation at the same time, to obtain a granulated product 600 kg. Further, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) together with 10% by mass of zeolite with respect to the granulated product to obtain a powder raw material having a weight average particle size of 80 μm.

  200 kg of the above powder raw material is put into a vacuum dryer with a capacity of 2500 L [FDM-1200JE type, manufactured by Fukae Pautech Co., Ltd.] so that the jacket temperature is 85 ° C., the pressure is 4.0 kPa, and the product temperature is 70 ± 1 ° C. The raw material which mix | blended higher alcohol (C14-C18) and the ethoxylate which added 2 mol of EO to the higher alcohol (C14-C18) weight average in the ratio of 75/25, adjusting to various drying conditions. Of polyoxyethylene (EO weight average addition mole number 0.5) alkyl (carbon number 14-18) ether sulfate sodium salt obtained by sulfation, and then neutralization with aqueous sodium hydroxide solution (active ingredient 72 mass) %) Was dropped into the dryer at an average addition rate of 150 kg / Hr, and the agitator rotation speed was 55 r / min and the chopper rotation speed was 2000 r / min. Drying and subjected to granulation at the same time, EO weight average addition mole number was obtained granules polyoxyethylene alkyl sulfate sodium salt 0.5. The water content was 1% by mass. The zeolite was 3% by mass. The content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO was 8% by mass. Moreover, sodium sulfate was 1 mass%. Thereafter, 8% by mass of zeolite is added to the obtained granulated product, and the zeolite is uniformly coated on the granulated product, and the granulated product having a weight average particle size of 980 μm and an apparent density of 650 g / L by vibrating sieve. (A) 5 was obtained. The composition of the granulated product (A) 5 is as follows: (a) component: 19.1% by mass, (b) component: 65.6% by mass, (d) component: 2.8% by mass, (e) component: 10 0.8 mass%, component (f): 0.9 mass%, and the balance water (100 mass% in total).

<Granulated product (B) 1>
After preparing a detergent slurry with an alkyl group having 12 to 14 carbon atoms of α-sulfo fatty acid methyl ester sodium, sodium carbonate, zeolite, sodium sulfite and sodium sulfate so that the slurry moisture is 50% by mass, a countercurrent type is prepared. Using a spray drying tower, it was dried to a moisture content of 4% by mass. The temperature of the hot air used is 380 ° C. The obtained dried product, polyoxyethylene alkyl ether having an alkyl group having 12 to 14 carbon atoms and an EO weight average addition mole number of 7 and water are introduced into a continuous kneader (Kurimoto Iron Works KRC Kneader # 2 type). A uniform kneaded product was obtained. A perforated plate having 80 holes of 5 mmφ was installed at the discharge port of this kneader, and the kneaded product was made into 5 mmφ × 10 mm cylindrical pellets (Fuji Powder Co., Ltd., Petterter EXDF-60). The pellets were introduced into a crusher (Okada Seiko Co., Ltd., Espeed Mill ND-10 type) together with 15 ° C. cooling air. At the same time, zeolite having a weight average particle diameter of 1 μm was added as a grinding aid. The crusher was a 15 cm long cutter rotated at 3000 rpm with 4 stages of cross, and the screen was punched metal with a diameter of 2 mmφ and a hole area ratio of 20%. Next, the particles that passed through the pulverizer were separated from the cooling air and surface-modified with 3% by mass of zeolite having a weight average particle diameter of 1 μm to obtain a granulated product (B) 1 having an apparent density of 760 g / L. The composition of the granulated product (B) 1 is that α-sulfo fatty acid methyl ester sodium having 12 to 14 carbon atoms in the alkyl group: 15% by mass, sodium carbonate: 20% by mass, zeolite: 30% by mass, sodium sulfite: 1 The polyoxyethylene alkyl ether having an alkyl group having 12 to 14 carbon atoms and an EO weight average added mole number of 7: 5% by mass and water: 4% by mass were obtained.

<Granulated product (B) 2>
Α-sulfo fatty acid methyl ester sodium having 14 to 18 carbon atoms of saturated fatty acid residue, higher (13 carbon atoms) alcohol polyoxyethoxylate (EO weight average addition mole number 25), 4,4′-bis (4- Amino-6-morpholino-1,3,5-triazinylamino) stilbene disulfonic acid (Whiteex SA), 4,4′-bis (2-sulfostyryl) biphenyl disodium (Tinopearl CBS-X), sodium sulfate The solid content concentration of 80% by mass paste and powder builder consisting of potassium carbonate, sodium carbonate, zeolite and fine particle silica are continuously added to a turbulator (manufactured by Hosokawa Micron Co., Ltd.) for stirring granulation operation. After carrying out, Fitzmill (Hosozo) together with 8% by mass of zeolite having a weight average particle diameter of 2 μm with respect to the obtained granulated product. Crushed under the condition of a screen diameter of 1.5 mm and surface-modified with 3% by mass of zeolite having a weight average particle diameter of 1 μm, a weight average particle diameter of 450 μm, a Tyler mesh 9 # residual amount of 3 A granulated product (B) 2 having a mass%, a 150 # passing mass of 6 mass%, and an apparent density of 780 g / L was obtained. The composition of the granulated product (B) 2 is as follows: sodium α-sulfo fatty acid methyl ester having a saturated fatty acid residue of 14 to 18 carbon atoms: 22% by mass, higher (13 carbon atoms) alcohol polyoxyethoxylate (EO weight average) Number of added moles 25): 5% by mass, 4,4′-bis (4-amino-6-morpholino-1,3,5-triazinylamino) stilbene disulfonic acid (Whiteex SA): 0.2% by mass 4,4′-bis (2-sulfostyryl) biphenyl disodium (Tinopearl CBS-X): 0.3% by mass, sodium sulfate: 8% by mass, potassium carbonate: 20% by mass, sodium carbonate: 20% by mass, Zeolite: 20% by mass, fine particle silica: 2% by mass, water: 2.5% by mass.

<Granulated product (B) 3>
An α-sulfo fatty acid methyl ester sodium salt having a saturated fatty acid residue of 14 to 18 and a solid content concentration of 75% by mass consisting of sodium sulfate and sodium sulfate, and a powder consisting of potassium carbonate and sodium carbonate are combined with a vertical kneader (( (Made by Dalton Co., Ltd.) was mixed and mixed at 60 ° C., and then molded with a pelleter (Fuji Powdal Co., Ltd.). After adding 7% by mass of finely powdered sodium carbonate (particle size: 10 μm) as a grinding aid to this kneaded product, it was pulverized by Fitzmill (manufactured by Hosokawa Micron Corporation) to obtain a powder having a particle size of 500-600 μm. The compound was obtained. Subsequently, the powdered product thus obtained was mixed and kneaded using a continuous kneader (manufactured by Kurimoto Industry Co., Ltd.) so as to have the following composition together with the zeolite and other components subjected to spray drying. After adding 7% by mass of finely powdered sodium carbonate (particle size 10 μm) as a grinding aid to the obtained kneaded product, the mixture is pulverized with Fitzmill (manufactured by Hosokawa Micron Corporation), and detergent particles with a particle size of 440 μm Got. Further, the detergent particles were surface-modified with 2% by mass of zeolite to produce a granulated product (B) 3 having an apparent density of 850 g / L. The composition of the granulated product (B) 3 is as follows: sodium α-sulfo fatty acid methyl ester having 14 to 18 carbon atoms: 20% by mass, potassium carbonate: 15% by mass, sodium carbonate: 15% by mass, zeolite: 28% by mass, Sodium sulfite: 1% by mass, sodium sulfate: 18% by mass, and water: 3% by mass.

<Granulated product (C)>
Detergent in which α-sulfo fatty acid methyl ester sodium having 12 to 14 carbon atoms in alkyl group, fatty acid sodium having 12 to 18 carbon atoms, sodium carbonate, zeolite, sodium sulfite and sodium sulfate is made to have a slurry water content of 50% by mass. After preparing the slurry, it was dried using a countercurrent spray drying tower. The temperature of the hot air used is 380 ° C. The obtained dried product, alkyl (carbon number 12 to 16) sodium sulfate (AS) -containing paste (active ingredient 73% by mass) and polyoxyethylene (EO weight average addition mole number 1) alkyl (carbon number 12 to 16) ) Continuous kneader (Kurimoto Tekko KRC Kneader #) with paste mixed with ether sulfate sodium salt (ES) -containing aqueous solution (25% by mass of active ingredient) so that mass ratio of active ingredient is AS: ES = 85: 15 2 type) to obtain a uniform kneaded product. A perforated plate having 80 holes of 5 mmφ was installed at the discharge port of this kneader, and the kneaded product was made into 5 mmφ × 10 mm cylindrical pellets (Fuji Powder Co., Ltd., Petterter EXDF-60). The pellets were introduced into a crusher (Okada Seiko Co., Ltd., Espeed Mill ND-10 type) together with 15 ° C. cooling air. At the same time, zeolite having a weight average particle diameter of 1 μm was added as a grinding aid. The crusher was a 15 cm long cutter rotated at 3000 rpm with 4 stages of cross, and the screen was punched metal with a diameter of 2 mmφ and a hole area ratio of 20%. Next, the particles that passed through the pulverizer were separated from the cooling air and surface-modified with zeolite having a weight average particle diameter of 1 μm to obtain a granulated product (C) having an apparent density of 830 g / L. The composition of the granulated product (C) is as follows: sodium α-sulfo fatty acid methyl ester having 12 to 14 carbon atoms in the alkyl group: 8 mass%, sodium fatty acid having 12 to 18 carbon atoms: 7 mass%, sodium carbonate: 20 mass% %, Zeolite: 30% by mass, sodium sulfite: 1% by mass, sodium sulfate: 23% by mass, alkyl (carbon number 12 to 16) sodium sulfate (AS) and polyoxyethylene (EO weight average addition mole number 1) alkyl (C12-16) Mixture of ether sulfate sodium salt (ES) (content of polyoxyethylene alkyl ether sulfate added with 4 mol or more of EO is 3 mass% in the mixture): 7 mass%, water: 4 It was mass%.

<Builder particles 1>
A pre-feed granule (manufactured by Tokuyama Siltech Co., Ltd.) was used.

<Builder particles 2>
Sodium sulfate produced by recrystallization was sieved with a 1400 μm JIS standard sieve, and the part passing through the sieve was designated as builder particles 2. The particles had a particle size of 710 μm or more of 32% by mass, a particle of 500 μm or more of 72% by mass, and a weight average particle size of 602 μm.

<Bleach particle 1>
Sodium borate / hydrogen peroxide adduct

<Bleach particle 2>
Sodium carbonate / hydrogen peroxide adduct, sodium percarbonate; bleaching agent particles described in paragraph 0019 of JP-A No. 2000-256699)

<Bleaching activator particles 1>
N, N, N ′, N′-tetraacetylethylenediamine

<Bleaching activator particles 2>
Granulated product of sodium lauroyloxybenzenesulfonate (bleaching agent particles described in paragraph 0018 of JP-A-2000-256699)

<Bleaching activator particles 3>
Instead of sodium lauroyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate was used, and bleaching activator particles 3 were obtained by the same adjustment method as bleaching activator particles 2.

<Example>
The powder cleaning composition shown in Table 1 was prepared using the above components and the components in Table 1, and the following evaluations were performed. The results are shown in Table 1.

[Detergency evaluation]
(Preparation of a collar fabric) A collar fabric described in JIS K3362: 1998 is prepared.
(Cleaning conditions and evaluation method) The cleaning powers of the detergent compositions in Table 1 and the index detergents for determining cleaning power were compared in accordance with the cleaning power evaluation method for synthetic detergents for clothing described in JIS K 3362: 1998. The use concentration of the cleaning composition in Table 1 was 0.5 g / L. However, the calcium chloride dihydrate used in the water used was 270 mg / L.
◎: Superior to index detergent ○: Slightly superior to index detergent △: Equivalent to index detergent ×: Inferior to index detergent

[Caking resistance]
Using a two-type filter paper defined by JIS P 3801 (for example, “Qualitative No. 2 filter paper” manufactured by Toyo Roshi Kaisha, Ltd.), a container having an open top of length × width × height = 10 cm × 6 cm × 4 cm is made. 100 g of a sample is put in this box, and a total mass of 15 g + 250 g of an acrylic resin plate and a lead plate (or iron plate) is placed thereon. This is left in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 80%, and the caking state is determined after 7 days. The determination is performed by obtaining the passage rate as follows. The higher the pass rate is, the higher the caking resistance is, which is a preferable physical property for the cleaning agent particle group. As for the pass rate, the sample after the test is gently opened on a sieve (aperture 4760 μm defined in JIS Z 8801), the weight of the passed powder is measured, and the pass rate for the sample after the test is obtained.

(note)
* 1: The total amount of surfactant is the sum of the amount of surfactant in the composition, and is shown as approximating the amount corresponding to the surfactant described in JIS K 3362: 1998.

Claims (6)

The surfactant equivalent described in JIS K 3362: 1998 is 10 to 60% by mass,
Containing 10 to 90% by mass of a builder,
The weight average particle size determined from the particle size measured by the sieving method using a sieving machine described in JIS K 3362: 1998 is 150 to 2000 μm.
A powder cleaning composition comprising:
(A) polyoxyalkylene alkyl ether sulfate having 1 to 3 added moles of alkylene oxide, (b) alkyl sulfate ester salt, (c) α-sulfo fatty acid ester salt, (a), (b) And the total amount of (c) is 60% by mass or more corresponding to the surfactant, (a) is 60% by mass or less in the anionic surfactant, and (c) is in the anionic surfactant. The mass ratio of (a) to (c) is 9/5 to 1/50, and the mass ratio of (a) to (b) is (a) / ( Powder cleaning composition which is 7/3 to 1/20 in b).   Further, (d) a polyoxyalkylene alkyl ether sulfate having an addition mole number of alkylene oxide of 4 or more, and the weight of the addition mole number of alkylene oxide based on the sum of (a), (b) and (d) The powder cleaning composition according to claim 1, wherein the average value is 0.05-2.   The powder cleaning agent according to claim 2, wherein the mass ratio of the total amount of (a) and (b) to (d) is 70/30 to 100/0 in terms of [(a) + (b)] / (d). Composition.   The powder cleaning composition according to any one of claims 1 to 3, comprising (e) 5 to 50% by mass of a water-insoluble inorganic substance and (f) 10 to 60% by mass of a water-soluble inorganic salt.   A granulated product containing (a), (b), (e) and (f), which is substantially free of (c) (A), and (a), (b), A granulated product containing (c), (e) and (f), both of the granulated product (B) containing 50% by mass or more of (c) in the surfactant in the granulated product The powder cleaning composition of Claim 4 containing this.   In a granulator in which the granulated product (A) has a stirring blade and a crushing blade, a paste containing (a) and (b) is added to the powder raw material containing the component (e) and / or the component (f). The powder detergent composition according to claim 5, which is a granulated product obtained by a production method including a step of adding.