JP2003183699A - Powdery detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a powdery detergent composition for clothes, containing an oxygen-based bleaching agent and having excellent preservation stability. <P>SOLUTION: This powdery detergent composition contains (a) a detergent base, (b) a compound releasing hydrogen peroxide in an aqueous solution and (c) a compound generating an organic peracid by reacting with the hydrogen peroxide in the aqueous solution. The detergent base (a) is obtained by spray- drying a slurry containing (a1) a water-insoluble inorganic material and (a2) a specific water-soluble component, and comprises base granules having ≤2 mass% water content and a surfactant carried by the granules. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder detergent composition for clothes and a container powder detergent composition containing the composition in a container.

[0002]

2. Description of the Related Art In recent years, the washing situation has been strengthened by increasing the bulk density and usage of detergents, increasing the bath ratio (clothes / washing water) of washing machines, shortening the operating time, and lowering the agitation of power. Which may delay the dissolution of the detergent.

The designed cleaning power may not be fully exerted due to the delay in dissolution of the detergent.
The cleaning power for so-called stain stains such as food stains and plant stains may be reduced.

Therefore, it has been attempted to add a bleaching agent in order to improve the deterioration of the detergency of stains and stains caused by such washing conditions. The bleaching ingredients of bleaching agents are roughly classified into chlorine type and oxygen type, but even if applied to colored patterns, there is no discoloration, the fabric is not easily damaged, and the clothing is not easily yellowed. Oxygen is said to be suitable for incorporation into detergents. Then, in order to further improve the bleaching power, a bleach activator is used together with the oxygen-based bleaching agent.

However, oxygen-based bleaching agents and bleach activators are
There is a problem that it is decomposed due to moisture in the detergent, moisture absorption during storage, etc., and the activity decreases. Moreover, in the presence of zeolite and a trace amount of metals such as iron and copper, the activity of the oxygen-based bleaching agent is further accelerated because these act as catalysts. For this reason, although an oxygen-based bleaching agent has been used as a surface coating, it has not been sufficiently prevented from lowering the activity. If the oxygen-based bleaching agent can be stably blended in the detergent, bleaching can be performed at the same time as washing, which is convenient. Therefore, the development of a technique for enhancing the storage stability of the oxygen-based bleaching agent is strongly desired. There is.

[0006]

An object of the present invention is to contain an oxygen-based bleaching agent and to have storage stability (solubility, detergency,
It is intended to provide a powdered detergent composition for clothes and a detergent in a container which have excellent caking resistance and the like.

[0007]

According to the present invention, a slurry containing a water-insoluble inorganic substance (a1) and one or more water-soluble components (a2) selected from water-soluble polymers and water-soluble salts is spray-dried. Obtained water content (JIS K 3362:
Detergent base (a) [based on component (a)] having a surfactant supported on 2% by mass or less of base granules (according to the 1998 method for reducing heat loss), a compound (b) that releases hydrogen peroxide in an aqueous solution. ) [Hereinafter referred to as (b) component], and a powder detergent composition containing a compound (c) [hereinafter referred to as (c) component] that reacts with hydrogen peroxide in an aqueous solution to generate an organic peracid.

The present invention also provides a moisture vapor transmission rate (JIS Z 02
08: 1976) 15 to 50 g / m ² · 24 hr
The present invention relates to a powder detergent contained in a container in which the powder detergent composition according to the present invention is contained in a container having a container formed of the above member.

The present invention also provides the powder detergent composition of the present invention in a container containing calcium chloride and having a mass increase rate of 3 to 20 mass% when stored at 40 ° C. and 75% relative humidity for 120 hours. The present invention relates to a powder detergent contained in a container.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION <Component (a)> As described above, the component (a) is a specific detergent base in which a surfactant is supported on specific base granules having a water content of 2% by mass or less. From the viewpoint of storage stability, the water content of the base granules is preferably 1.5% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.

The water-insoluble inorganic substance (a1) preferably has an average primary particle size of 0.1 to 20 μm. Examples thereof include crystalline or amorphous aluminosilicates, silicon dioxide, and hydrated silicic acid. There are compounds, clay compounds such as pearlite, bentonite, etc., but crystalline or amorphous aluminosilicates, silicon dioxide, hydrated silicic acid compounds are preferable, and among them, sequestering ability of metal ion and supporting ability of surfactant. From the viewpoint of, crystalline aluminosilicate is preferable.

Among the water-soluble components (a2), examples of the water-soluble polymer include carboxylic acid type polymers, carboxymethyl cellulose, soluble starch, saccharides and the like. Among them, sequestering ability of metal ions, dispersing ability of solid dirt / particle dirt. In terms of anti-soil redeposition ability, a carboxylic acid polymer having a weight average molecular weight of 1,000 to 100,000 is preferable. Particularly, salts of acrylic acid-maleic acid copolymer and polyacrylic acid salts are preferable. Here, examples of the salt include sodium salt, potassium salt, and ammonium salt.

Among the water-soluble components (a2), the water-soluble salts include alkali metal salts such as carbonates, hydrogencarbonates, sulfates, hydrogensulfates, hydrochlorides or phosphates, ammonium salts, or amines. Examples thereof include water-soluble inorganic salts such as salts, and low-molecular-weight water-soluble organic acid salts such as citrate and fumarate. By blending the water-soluble salt, bubbles generated from the detergent particles are thermally expanded by heat of hydration and heat of dissolution generated by the reaction between the water-soluble salt and water, thereby promoting disintegration of the particles. More preferable.

The proportion of the water-insoluble inorganic substance (a1) in the base granules is preferably 20 to 90% by mass, more preferably 30 to 75% by mass, most preferably 40 to 70% by mass.
The ratio of the water-soluble component (a2) in the base granules is 1
0-80 mass% is preferable, 25-70 mass% is more preferable, 30-60 mass% is the most preferable. Especially (a
As 2), it is preferable to contain a water-soluble polymer and a water-soluble salt. Among them, the ratio of the water-soluble polymer in the base granules is preferably 2 to 30% by mass, more preferably 3 to 20% by mass, and 5 to 20% by mass. % Is most preferred. At this time, the ratio of the water-soluble salts in the base granules is preferably 5 to 78% by mass, more preferably 10 to 70% by mass, and 10 to 67% by mass.
Mass% is more preferable, 20-60 mass% is especially preferable, and 20-55 mass% is the most preferable. Within these ranges, the base granules have water-soluble components (a
A large amount of 2) is unevenly distributed, which is preferable in terms of solubility. The water-soluble component (a
The uneven distribution of 2) can be confirmed using, for example, a method (FT-IR / PAS) that uses Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy (PAS) together. This is the Applied Spectroscopy
vol. 47, 1311-1316 (1993), it is a method of analyzing the distribution state of the substance in the depth direction from the surface of the base granules, whereby uneven distribution can be confirmed.

In addition to these three components, the base granules may contain surfactants and auxiliary components such as fluorescent dyes, pigments and dyes suitable for detergent compositions.

The base granules are obtained by making various components into a slurry preferably having a water content of 30 to 60% by mass and then spray-drying. The temperature of the hot air during spray drying is preferably 200 to 300 ° C. from the viewpoint of solubility.

From the viewpoint of cleaning performance and solubility, the amount of the surfactant carried is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and 15 to 100 parts by mass of the base granules.
-65 parts by mass is more preferable, and 20-60 parts by mass is particularly preferable.

As the surfactant to be carried, anionic surfactant, nonionic surfactant, amphoteric surfactant,
One or a combination of two or more cationic surfactants may be mentioned, but anionic surfactants and nonionic surfactants are preferred.

The anionic surfactant has 1 carbon atom.
Sulfuric acid ester salt of alcohol of 0-18, carbon number 8-2
Sulfate ester of alcoholate of 0 alcohol,
Alkylbenzene sulfonate, paraffin sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt or fatty acid salt is preferable. Particularly in the present invention, the number of carbon atoms in the alkyl chain is 1.
0-14, more preferably 12-14 linear alkylbenzene sulfonate is preferred, and as the counterion,
Alkali metal salts and amines are preferable, and sodium and / or potassium, monoethanolamine and diethanolamine are particularly preferable.

As the nonionic surfactant, polyoxyalkylene alkyl (C8-20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (C8-20) phenyl ether, polyoxyalkylene sorbitan fatty acid (carbon Number 8-22) ester,
Polyoxyalkylene glycol fatty acid (C8 to C2
2) Ester and polyoxyethylene polyoxypropylene block polymer are preferable. In particular, the nonionic surfactant is preferably a polyoxyalkylene alkyl ether in which an alkylene oxide such as ethylene oxide or propylene oxide is added in an average of 4 to 20 mol to an alcohol having 10 to 18 carbon atoms. The nonionic surfactant has an HLB value (calculated by Griffin method) of 10.5 to 15.
It is preferably 0, more preferably 11.0 to 14.5.

From the viewpoint of exerting detergency, the amount of the surfactant to be carried on the base granules used in the present invention is 1 to 60 per 100 parts by mass of the base granules. A mass part is preferable, 1-50 mass parts is more preferable, 3-40 mass parts is especially preferable. The supported amount of the nonionic surfactant is preferably 1 to 45 parts by mass, more preferably 1 to 35 parts by mass, and still more preferably 4 to 25 parts by mass with respect to 100 parts by mass of the base granules. The anionic surfactant and the nonionic surfactant may be used alone, but preferably they are mixed and used. Further, an amphoteric surfactant or a cationic surfactant can be used together depending on the purpose.

As a method for supporting the surfactant on the base granules, a granulator may be used, but it is preferable to use a stirrer for mixing in terms of solubility. It is preferable that the mixture is mixed under mild conditions so as not to collapse the pores described later.

The component (a) is preferably 1/10 or more of the particle size, more preferably 1/10 in the process of dissolving in water.
5 or more, more preferably 1/4 or more, particularly preferably 1
Emit bubbles with a diameter of / 3 or more. The bubbles are preferably released within 120 seconds when dissolved in water while still standing, and more preferably within 60 seconds, more preferably within 45 seconds. Further, the bubbles can be discharged as long as they have pores (single or plural) capable of discharging bubbles of a predetermined size, and the form and structure of particles are not particularly limited. The component (a) that releases such bubbles can be obtained, for example, by spray-drying the slurry and handling it so as not to crush the particles.

From the viewpoint of fluidity and non-caking property, the component (a) is preferably subjected to surface modification by supporting a surfactant on the base granules and then mixing it with a surface coating agent. The content of the surface coating agent in component (a) is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and even more preferably 5 to 25% by mass. As the surface coating agent, for example, aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, silicate compounds such as crystalline silicate, metal soap, powdered surfactant, etc. Examples thereof include fine powder, 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. Of these, water-insoluble inorganic substances are preferable, and crystalline aluminosilicate, amorphous aluminosilicate, and crystalline silicate are particularly preferable.

The equilibrium relative humidity of the component (a) at 40 ° C. is preferably 15 to 35%, more preferably 18 to 35% from the viewpoint of storage stability.
32% is more preferable, and 20-30% is further preferable.
This equilibrium relative humidity is measured as follows. In a 2.4 liter moisture-proof container, 600 g of component (a) and a polymer film humidity sensor (preferably Thandy, Th
ermo Recorder Rooster RH TR-72S and TR-
3110 temperature / humidity sensor combination) is put and sealed.
It is kept at 40 ° C. and stored for 24 hours. The humidity measurement value is read every 30 minutes, and the value at which there is no change is used as the equilibrium relative humidity. From the viewpoint of storage stability, the water content of the component (a) is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less.

The component (a) has a bulk density of preferably 600 g / L or more, more preferably 700 g / L, measured by the method specified by JIS K 3362, from the viewpoint of convenience and reduction of waste.
L or more is more preferable, and 800 g / L or more is further preferable. From the viewpoint of solubility, the bulk density is preferably 1600 g / L or less, more preferably 1300 g / L or less, and 10
It is more preferably 00 g / L or less.

The component (a) is JIS Z in terms of solubility.
After being vibrated for 5 minutes using a standard sieve of 8801, the average particle diameter determined from the mass fraction depending on the size of the sieve mesh is 150 to
700 μm is preferable, and more preferably 150 to 600
μm, and more preferably 180 to 500 μm. Further, in terms of solubility, the ratio of particles having a particle size of 177 to 350 μm is preferably 40% by mass or more, and more preferably 50% by mass or more in the component (a).

The ratio of the component (a) is preferably 50 to 99.5% by mass, and 60 to 9% by mass in the powder detergent composition from the viewpoint of cleaning performance.
99% by mass is more preferable, and 70 to 97% by mass is further preferable.

<Component (b)> Examples of compounds that release hydrogen peroxide in an aqueous solution include carbonate / hydrogen peroxide adducts, borate / hydrogen peroxide adducts, tripolyphosphate / hydrogen peroxide adducts, Examples include pyrophosphate / hydrogen peroxide adducts, urea / hydrogen peroxide adducts, and the like. Among these, carbonate
Hydrogen peroxide adduct, borate / hydrogen peroxide adduct are preferred, sodium carbonate / hydrogen peroxide adduct, sodium borate / hydrogen peroxide adduct are more preferred, and sodium carbonate / hydrogen peroxide adduct in terms of cleaning performance The thing is more preferable.

The component (b) can be improved in storage stability by being coated with an inorganic salt and / or a polymer or the like. Above all, it is more preferable to coat with borate, silicate, sulfate or carbonate. When the component (b) is used as particles containing the component (b), the coating amount is preferably 5 to 20% by mass in the particles in terms of stability and solubility. Further, a stabilizer, a dissolution accelerator, a chelating agent, etc. which have been conventionally known may be contained in the particles. Among them, chlorides, ureas, anionic surfactants and nonionic surfactants are preferable from the viewpoint of solubility, and the ratio thereof is preferably 0.1 to 5% by mass in the particles.

The powder detergent composition of the present invention preferably contains the component (b) in an amount of 0.1 to 8% by mass, more preferably 0.5 to 5% by mass, from the viewpoints of cleaning performance and cleaning efficiency. ~
3.5% by mass is more preferable, and 1.5 to 2.8% by mass is particularly preferable.

<Component (c)> As a compound which reacts with hydrogen peroxide in an aqueous solution to generate an organic peracid, glucose pentaacetate, triacetin, N, N, which are generally used in detergents containing an oxygen-based bleaching agent. , N ′, N′-tetraacetylethylenediamine, tetraacetylglycolyluril, and other bleach activators can be used, but from the viewpoint of effect, the compounds represented by the general formulas (1) to (4) are Particularly preferred.

[0033]

[Chemical 1]

[In the formula, R ¹ is an alkyl group having 4 to 13 carbon atoms, preferably 10 to 13 carbon atoms, and R ² is 5 to 1 carbon atoms.
3, preferably 7 to 11 alkyl groups, M represents a hydrogen atom or an alkali metal, alkaline earth metal, ammonium or alkanol ammonium. ]

[0035]

[Chemical 2]

[Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ ,
R ¹⁰ is a methyl group, an ethyl group or a hydroxyethyl group, R ⁸ is an alkylene group having 2 to 10 carbon atoms, and X ⁻ is an anion (preferably a halogen ion, an alkyl group having 1 to 3 carbon atoms). (Sulfate ion, fatty acid ion having 1 to 12 carbon atoms, phosphate ion, sulfate ion). ].

The powder detergent composition of the present invention preferably contains 0.1 to 5 mass% of the component (c). . From the viewpoint of cleaning performance and cleaning efficiency, 0.5 to 3 mass% is preferable, and
8-2 mass% is more preferable.

The component (c) is preferably a granulated product containing a surfactant and a binder in terms of solubility and stability. From the standpoint of granulation, anionic surfactants are more preferable as the surfactant, and the number of carbon atoms is 10 from the viewpoint of improving solubility.
To 18 alkyl sulfate ester salts, especially sodium lauryl sulfate ester, sodium myristyl sulfate ester, or polyoxyethylene having an alkyl group having 10 to 18 carbon atoms (average number of moles of ethylene oxide added (hereinafter referred to as E
1-10, especially 1-5] alkyl ether sulfate, especially polyoxyethylene (EOp)
2-5) The blending of sodium lauryl ether sulfate and polyoxyethylene (EOp2-5) sodium myristyl ether sulfate is more preferable. As the binder, polyethylene glycol having an average molecular weight of 2000 to 20000 and a fatty acid having 8 to 20 carbon atoms are more preferable, and the weight average molecular weight of polyethylene glycol is preferably 4000 to 10000, more preferably 4000 to 8000. Also, the carbon number of fatty acids is
It is preferably 10-18, more preferably 12-18. Further, the fatty acid may be in the state of sodium or potassium soap. In the particles containing the component (c), the surfactant is preferably 1 to 40% by mass, and the binder is
0.5-30 mass% is preferable. Further, an acidic substance may be added for the purpose of further improving the stability. Examples of the acidic substance include one or more organic carboxylic acids selected from succinic acid, maleic acid, fumaric acid, citric acid, glycolic acid and p-hydroxybenzoic acid.

<Other Ingredients> As other ingredients, powder detergent compositions include builder, alkaline agent, water-soluble polymer, anti-soil redeposition agent, softening agent, optical brightening agent, foam known in the field of detergents. A control agent, an enzyme, an enzyme stabilizer, a coloring agent, a fragrance and the like can be contained.

As the inorganic builder, crystalline aluminosilicate, amorphous aluminosilicate, crystalline sodium silicate,
Examples thereof include sodium tripolyphosphate, sodium pyrophosphate, and the like, and crystalline aluminosilicate is more preferable from the viewpoints of environmental impact and cleaning performance. From the viewpoint of cleaning performance, the ratio of the inorganic builder is preferably 10 to 50% by mass in the composition, and 1
5-40 mass% is more preferable.

Examples of the alkaline agent include carbonates, silicates, amines (alkylamines, alkanolamines, etc.) and the like, and carbonates and silicates are more preferable. From the viewpoint of cleaning performance, the proportion of the alkaline agent in the composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

Examples of the water-soluble polymer include carboxylic acid type polymers, carboxymethyl cellulose, soluble starch and sugars. Among them, a carboxylic acid-based polymer having a weight average molecular weight of 1,000 to 100,000 is preferable from the viewpoints of sequestering ability of metal ions, dispersing ability of solid stains / particle stains and preventing redeposition. Particularly, salts of acrylic acid-maleic acid copolymer and polyacrylic acid salts are preferable. Here, examples of the salt include sodium salt, potassium salt, and ammonium salt. From the viewpoint of cleaning performance, the proportion of the water-soluble polymer in the composition is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass.

<Powder Detergent Composition> The powder detergent composition of the present invention is JIS K 336 in terms of convenience and waste reduction.
The bulk density measured by the method specified in 2 is 600 g /
L or more is preferable, 700 g / L or more is more preferable,
800 g / L or more is more preferable. From the viewpoint of solubility, the bulk density is preferably 1600 g / L or less and 1300 g / L.
g / L or less is more preferable, and 1000 g / L or less is further preferable.

The powder detergent composition of the present invention, in terms of detergency and solubility, was vibrated for 5 minutes using a standard sieve of JIS Z 8801, and then averaged from the mass fraction depending on the size of the sieve mesh. The particle size is preferably 150 to 700 μm,
More preferably 150 to 600 μm, still more preferably 1
It is 80 to 500 μm.

From the viewpoint of storage stability, the water content of the powder detergent composition of the present invention is preferably 5% by mass or less, and 0.1 to 5% by mass.
Is more preferable, 0.5 to 3 mass% is further preferable,
0.5 to 2.5 mass% is particularly preferable.

<Container> The container used for the powdered detergent of the present invention has a moisture permeability (according to JIS Z 0208: 1976) of 15 to 50 g in view of storage stability and economy.
/ M ² · 24 hr is preferably a container having a containing portion made of a member, and the water vapor transmission rate is 20 to 50 g / m ² · 24 hr.
Is more preferable, and 20-40 g / m ² · 24 hr is even more preferable. Here, the member means a member corresponding to the thickness and form of the container of the final product, and the moisture permeability is measured on the surface of the container in contact with the powder detergent composition.

The container used for the powdered detergent of the present invention has a mass increase rate of 3 to 2 when it contains calcium chloride and is stored at 40 ° C. and 75% relative humidity for 120 hours.
A container of 0 mass% is preferable from the viewpoint of storage stability and economy, and the mass increase rate is more preferably 5 to 15 mass%, further preferably 5 to 10 mass%. Here, JIS K8124: 1994 (reagent for drying) is used as calcium chloride.

As the container used for the powder detergent, there are known plastic containers formed by injection molding or the like, pillow packages formed by plastic films, gusset packages, pouch packages, standing pouch packages, and the like. On the other hand, a box-shaped container made of pulp is also known because of its low price, ease of manufacturing / molding, printability, and the like. In recent years, from the viewpoint of saving plastic resources and environmental protection, it has been demanded to reduce the amount of plastic materials used, and a container made of pulp is preferable from the viewpoint of easy reuse and disposal of resources. . The amount of pulp in the container is 30% by mass
The above is preferable, 30 to 99 mass% is more preferable, and 5
0 to 98 mass% is more preferable, and 60 to 95 mass% is particularly preferable. The strength of the container can be improved by incorporating the plastic sheet into the container, by providing it inside or outside. Further, the moisture permeability and the mass increase rate can be adjusted by changing the type and thickness of the plastic sheet.

[0049]

Example 1 (1) Production of powder detergent composition A slurry having a solid content of 50% by mass was spray-dried at a hot air temperature of 250 ° C. to obtain the following base granules I and II. Next, the base granules I or II were loaded with a surfactant mixed solution and further surface-modified to obtain the following detergent bases I and II. next,
Detergent Base I or II and the following (b) component-containing particles:
The powder (c) component-containing particles, the enzyme-containing particles, and the fragrance were mixed to obtain a powder detergent composition.

<Base granule I> The composition is as follows: sodium polyacrylate (weight average molecular weight 10,000) 7% by mass, sodium carbonate 26% by mass, sodium sulfate 20% by mass,
6 mass% of sodium chloride, 0.5 mass% of fluorescent dye, 40 mass% of zeolite, and 0.5 mass% of water. Chinopearl CBS-X (manufactured by Ciba Geigy) was used as the fluorescent dye. As the zeolite, 4A type zeolite (manufactured by Tosoh Corporation) was used.

<Base Granule II> The composition is linear alkyl (10 to 13 carbon atoms) sodium benzenesulfonate 1
% By mass, sodium polyacrylate (weight average molecular weight 1
0000) 5% by mass, sodium carbonate 26% by mass, sodium sulfate 10% by mass, sodium chloride 6% by mass, fluorescent dye 0.5% by mass, zeolite 50% by mass, water 0.5% by mass. The same fluorescent dye and zeolite as those used for the base granules I were used.

<Detergent base I> 100 parts by mass of base granules I was put into a Loedige mixer (manufactured by Matsusaka Giken Co., Ltd., capacity 20 L, with a jacket), and a spindle (150 rpm)
Under stirring, 20 parts by mass of a nonionic surfactant, 22 parts by mass of linear alkyl (10 to 13 carbon atoms) benzenesulfonate sodium, 4 parts by mass of sodium fatty acid (14 to 18 carbon atoms), polyethylene glycol (weight average Molecular weight 8
500) A mixed solution of 2 parts by mass and 4 parts by mass of water was added over 3 minutes, and then stirred for 5 minutes. Furthermore, 20 parts by weight of crystalline sodium silicate and 10 parts of zeolite are added to this mixer.
A mass part was added and surface coating was performed. The nonionic surfactant is an alkyl group having 12 to 16 carbon atoms and EOp.
A polyoxyethylene alkyl ether of 6.0 was used. As the crystalline sodium silicate, powder SKS-6 (manufactured by Hoechst Tokuyama Corp.) was used.

The detergent base I obtained has a bulk density of 810 g.
/ L, the average particle size is 270 μm, and the ratio of particles having a particle size of 177 to 350 μm is 55% by mass, and bubbles having a particle size of 1/3 or more were released from the inside of the particles during the process of dissolving in water. Also,
The equilibrium relative humidity was 25% (40 ° C).

<Detergent base II> 100 parts by mass of base granules II were put into a Lodige mixer (manufactured by Matsusaka Giken Co., Ltd., capacity 20 L, with jacket), and the nonionic surfactant 10 was added under stirring of the main shaft (150 rpm). Parts by mass, straight-chain alkyl (carbon number 10 to 13) sodium benzenesulfonate 2
6 parts by mass, fatty acid (C14-18) sodium 4 parts by mass, polyethylene glycol (weight average molecular weight 850
0) A mixed solution of 2 parts by mass and 3 parts by mass of water was added over 3 minutes, and then stirred for 5 minutes. Furthermore, 20 parts by mass of crystalline sodium silicate and 10 parts by mass of zeolite were charged into this mixer to perform surface coating. The same nonionic surfactant and crystalline sodium silicate as those used in detergent base I were used.

The detergent base II obtained has a bulk density of 850 g.
/ L, the average particle size was 320 μm, and the ratio of particles having a particle size of 177 to 350 μm was 55% by mass, and bubbles having a particle size of 1/3 or more were released from the inside of the particles during the process of dissolving in water. Also,
The equilibrium relative humidity was 25% (40 ° C).

<Particle (b) Containing Component I> Sodium carbonate / hydrogen peroxide adduct (bleaching agent particles described in paragraph 0019 of JP-A-2000-256699).

<Part (b) component-containing particles II> Sodium borate / hydrogen peroxide adduct (except that the sodium carbonate / hydrogen peroxide adduct is replaced with a sodium borate / hydrogen peroxide adduct, JP-A 2000-256699). Paragraph 0019 of the publication
Obtained in the same manner as the bleach particles described.

<Particle (c) Containing Particle I> Granulated product of sodium lauroyloxybenzene sulfonate (JP-A-200)
Bleach activator particles described in paragraph 0018 of 0-256699).

<Component (c) Containing Particle II> Granules of decanoyloxybenzoic acid (except that sodium lauroyloxybenzenesulfonate was replaced with decanoyloxybenzoic acid, paragraph 001 of JP 2000-256699 A).
Obtained in the same manner as the bleaching activator particles described in 8).

<Particles Containing Enzyme> Cellulase K
3-26499 gazette), Lipolase 100T
(Manufactured by Novo Co.) at a mass ratio of 3: 1.

<Powder detergent composition I> Detergent base I 95
% By mass, 2.8% by mass of the component (b) -containing particle I, (c)
1.2 mass% of the component-containing particles I, 0.5 mass% of the enzyme-containing particles, and 0.5 mass% of the fragrance were mixed to obtain a powder detergent composition I.

<Powder detergent composition II> 95% detergent base I
Mass%, 2.5 mass% of the component (b) -containing particle II, (c)
Powder-detergent composition I obtained by mixing 1.5 mass% of component-containing particles II, 0.5 mass% of enzyme-containing particles, and 0.5 mass% of fragrance.
Got I.

<Powder Detergent Composition III (Comparative Example)> 10% by mass of linear alkyl (C10 to C13) sodium benzene sulfonate, linear alkyl (C10 to C13) benzene sulfonic acid based on detergent base 6% by mass of potassium, 10% by mass of sodium ethyl ester of α-sulfofatty acid (derived from palm oil), 3% by mass of polyoxyethylene alkyl ether (C12 of alkyl group, EOp6), polyethylene glycol (weight average molecular weight of 850).
0) 1% by mass, zeolite 10% by mass, acrylic acid-maleic acid copolymer (weight average molecular weight 70000, acrylic acid / maleic acid = 3/7 molar ratio) 3% by mass, fatty acid sodium (derived from beef tallow) 4% by mass, 1 No. 1 sodium silicate, 15 mass% sodium carbonate, 5 mass% sodium sulfate, and 0.3 mass% fluorescent dye are prepared, and a slurry (solid content 50 mass%) is prepared, spray-dried and spray-dried composition. I got a thing. To this, 3% by mass of crystalline sodium silicate and 13% by mass of sodium carbonate were charged into a ribbon mixer on the basis of the mass of the detergent base and mixed. The obtained mixture was extruded into a columnar shape having a diameter of 10 mm by a pre-extrusion type twin-screw type extrusion granulator (Pellettor Double: manufactured by Fuji Paudal Co., Ltd.) for consolidation. The obtained pellets were pulverized and granulated with 5% by mass of zeolite in a flash mill (manufactured by Fuji Paudal Co., Ltd.) for surface coating. After removing coarse particles from the granulated product, the granulated product was transferred to a V blender and mixed with 5% by mass of zeolite to obtain a detergent base III having a water content of 5.7% by mass.

95% by weight of detergent base III, 2.8% by weight of component (b) -containing particle I, and 1. 8% of (c) component-containing particle I.
2% by mass, 0.5% by mass of enzyme-containing particles, and 0.5% of fragrance.
5% by mass was mixed to obtain a powder detergent composition III. The equilibrium relative humidity of this powder detergent composition III was 40% (40 ° C.). The same components as those used in the production of the detergent base III, which were the same as those used in the detergent bases I and II, were used.

<Powder detergent composition IV (comparative example)> A powder detergent composition IV was obtained in the same manner as the powder detergent composition I except that the water content of the base granules I was changed to 3% by mass.

(2) Production of powder detergent in a container Powder detergent compositions I to III and the following containers I to III are shown in Table 1.
The combination was used to obtain a powdered detergent in a container. The filling amount of the composition into the container was 1.2 kg.

<Container I> A pillow packaging container made of stretched nylon / linear low-density polyethylene film (polyethylene inner surface). The water vapor transmission rate of the film forming the housing portion is 5 g / m ² · 24 hr, and the mass increase rate of the container is 3% by mass.
Is less than.

<Container II> A carton container made of a three-layer material in which polyethylene is sanded with coated cardboard. The water vapor transmission rate of the three-layer material forming the container is 35 g / m ² · 24 h
r, the mass increase rate of the container is 7.5% by mass.

<Container III> A carton container made of a three-layer material obtained by sanding polyethylene with coated cardboard. The water vapor transmission rate of the three-layer material forming the container is 60 g / m ² · 24.
hr, the mass increase rate of the container is over 20 mass%.

(3) Evaluation After storing the powdered detergent in a container prepared above under the following conditions, JIS K3362:
Effective oxygen (O) (%) was calculated by the method described in 1998 “7.9 Quantification of Peroxide Salt”. The residual ratio of available oxygen after storage was calculated based on that before storage. The results are shown in Tables 1 and 2.
Shown in.

<Storage method I> The temperature was kept constant at 30 ° C. and the humidity was kept at 40% RH for 24 hours.
Humidity 80% RH over time, then humidity 80% RH
Kept for 24 hours, then over 40 hours humidity 40% RH
The environment was repeatedly changed, and it was stored for 3 months.

<Storage method II> Temperature 40 ° C., humidity 65% R
Stored in a room with constant H for 2 days, then temperature 5 ℃, humidity 7
The sample was moved to a room with a constant 5% RH and stored for 2 days, and then the sample was transferred to a room with a constant temperature of 40 ° C. and a relative humidity of 65% RH, which was repeatedly stored for 1 month.

[0073]

[Table 1]

From Table 1, it can be seen that in Test Examples 1-1 and 1-2 using the powder detergent composition of the present invention, the residual ratio of available oxygen is high.

[0075]

[Table 2]

From Table 2, it can be seen that when the powder detergent composition of the present invention is contained, the container II has the highest effect regardless of the storage conditions.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 3/39 C11D 3/39 11/00 11/00 17/04 17/04 (72) Inventor Hitoshi Tanimoto 1334 Minato Minato, Wakayama City, Kao Co., Ltd. (72) Inventor Osamu Yamaguchi 1334 Minato, Wakayama City, Wakayama Prefecture Kao Co., Ltd. (72) Hiroshi Nishimura, 1334 Minato, Wakayama City, Wakayama Lab. F term (reference) 3E068 AA22 AC09 CC02 CC22 CE01 CE02 CE03 EE23 EE24 4H003 AB03 AB19 AC08 BA09 BA21 BA27 DA01 EA12 EA15 EA16 EA19 EA28 EB09 EB22 EB30 EB36 EC01 EC03 EE05 FA09 FA43

Claims (5)

[Claims] 1. A water content (JIS K 3362) obtained by spray-drying a slurry containing a water-insoluble inorganic substance (a1) and one or more water-soluble components (a2) selected from water-soluble polymers and water-soluble salts. : Detergent base (a) in which a surfactant is supported on 2% by mass or less of base granules (according to the weight loss method described in 1998), a compound (b) that releases hydrogen peroxide in an aqueous solution, and a peroxide in an aqueous solution. A powder detergent composition containing a compound (c) which reacts with hydrogen oxide to generate an organic peracid. 2. The detergent base (a) has an equilibrium relative humidity of 15
The powder detergent composition according to claim 1, wherein the powder detergent composition has a content of ˜35% (40 ° C.). 3. The powder detergent according to claim 1, wherein the detergent base (a) is a particle capable of releasing bubbles having a diameter of 1/10 or more of the particle diameter from the inside of the particle in the process of being dissolved in water. Composition. 4. Water vapor transmission rate (JIS Z 0208: 1976)
The powdered detergent contained in a container, wherein the powdered detergent composition according to any one of claims 1 to 3 is contained in a container having an accommodation part made of a member of 15 to 50 g / m ² · 24 hr. 5. A mass increase rate of 3 to 2 when calcium chloride is contained and stored at 40 ° C. and 75% relative humidity for 120 hours.
A powdered detergent in a container, wherein the powdered detergent composition according to any one of claims 1 to 3 is contained in a container of 0% by mass.