JP5785747B2 - Granular detergent composition - Google Patents

Description

  The present invention relates to granular detergent compositions.

In addition to surfactants, granular detergent compositions containing bleaching components such as sodium percarbonate particles are expected to remove not only sebum stains but also stain stains when washing clothes and the like.
However, according to the knowledge of the present inventors, even when washing is performed using a detergent containing a bleaching component, stain stains containing phenolic pigments such as black tea and red wine may be darkly colored if the washing time is insufficient. is there. Even if the color develops, if the washing time is extended, the washing can be performed by the bleaching effect, but it tends to cause dissatisfaction with the washing effect.

Generally, alkaline agents such as carbonates and bicarbonates are used in detergent compositions. For example, the following Patent Documents 1 to 3 are given as conventional techniques in which sodium bicarbonate is contained in the granular detergent composition, but none of them describes a stain stain cleaning.
Patent Document 1 is intended to improve the low-temperature solubility of granular detergent compositions, and in the examples, mixed particles obtained by granulating maleic acid: carbonate: bicarbonate in a ratio of 40:20:40 are granulated. The example which mix | blended 2-10% is described. It is described that a bleaching agent may be included as an optional component. The bicarbonate used in the examples is anhydrous sodium bicarbonate having a particle size distribution of 400-1200 μm.

  Patent Document 2 is intended to improve the solubility of a granular detergent composition. In addition to a base powder containing a detergent active ingredient, sodium salt, potassium salt of citric acid, sulfuric acid, carbonic acid, bicarbonate or silicic acid, It is described that 5 to 20% by weight of filler particles made of a magnesium salt or a mixture thereof may be blended, and that a bleaching agent may be included as an optional component. At least 20% of the filler particles have either a particle size of less than 150 μm or greater than 1180 μm, and the average particle size of the filler particles is 50 μm or more.

Patent Document 3 aims to improve the low-temperature solubility of the granular detergent composition, and includes a particle group (a) having a surfactant carrying ability of a specific value or more and a circularity of the particles of a specific value or more. A water-soluble salt particle group (b) having an aspect ratio of a specific value or more is mixed with a liquid surfactant-containing composition, and a surfactant is added to these particle groups (a) and (b). A method for producing detergent particles to be carried is described.
As the water-soluble salts of the particle group (b), at least one selected from the group consisting of sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium sulfate, sodium sesquicarbonate and sodium tripolyphosphate is described.
Further, it is described that a bleaching agent may be included as an optional component.

Special table 2003-524672 Japanese Patent No. 4033895 Japanese Patent No. 3828489

  The present invention has been made in view of the above circumstances, and has a good cleaning effect on sebum stains, and stain stains containing phenolic pigments such as black tea and red wine do not darkly develop and are good for stain stains. An object is to provide a granular detergent composition having a cleaning effect.

In order to solve the above problems, the granular detergent composition of the present invention is a granular detergent composition containing the following components (A) to (C), and the component (A) is contained in the entire granular detergent composition. 50 to 90% by mass, the total of component (B) and component (C) is 10 to 50% by mass, and the mass ratio (C) / (B) of component (B) to component (C) is 0.15 to 0.15. It is 1.00.
Component (A): Surfactant-containing particles containing an alkali metal carbonate.
Component (B): Sodium hydrogen carbonate particles.
Component (C): Sodium percarbonate particles.

In the component (B), the particles having a particle size of less than 150 μm are less than 20% by mass, the particles having a particle size of 600 μm or more are substantially not contained, and the average particle size is preferably from 150 to 350 μm. .
Furthermore, it is preferable to contain carboxymethylcellulose as a component (D).

  According to the present invention, there is a good cleaning effect on sebum stains, stain stains containing phenolic pigments such as black tea and red wine do not darkly develop, and granularity that has a good cleaning effect on stain stains A detergent composition is obtained.

<Component (A)>
Component (A) is a surfactant-containing particle containing an alkali metal carbonate. That is, the component (A) is particles containing an alkali metal carbonate and a surfactant. Component (A) does not contain sodium bicarbonate and does not contain sodium percarbonate.
As the surfactant, components known as surfactants to be blended in the granular detergent composition can be appropriately used. As the alkali metal carbonate, a known alkali metal carbonate as a detergency builder can be appropriately used.
Moreover, it is preferable to mix | blend other detergency builders which are neither an alkali metal carbonate nor sodium hydrogencarbonate as another component. Furthermore, the well-known arbitrary component mix | blended with a granular detergent composition can also be suitably contained in the range which does not impair the stability of a component (A). Each component will be described later.

Component (A) preferably contains 10 to 70% by mass of alkali metal carbonate in the particles and 10% by mass or more of surfactant.
When the content of the alkali metal carbonate is in the above range, good detergency is easily obtained. A more preferable range is 30 to 60% by mass.
When the content of the surfactant in the component (A) is 10% by mass or more, a good cleaning effect is easily obtained. 15 mass% or more is more preferable. The upper limit of the content of the surfactant is preferably 35% by mass or less, and more preferably 30% by mass or less in terms of balance with other components.

The component (A) preferably has a slower dissolution rate in water than the component (B). When the component (A) has a slower dissolution rate, it is easy to obtain a good cleaning effect for stain stains containing phenolic pigments. The dissolution rate of component (A) can be adjusted by the particle bulk density and / or particle size. The bulk density and particle diameter of the particles can be adjusted according to the production conditions of the surfactant-containing particles as the component (A).
The bulk density of the component (A) is not particularly restricted, 600 g / dm ³ or more, more preferably 700~1200g / dm ^3, more preferably from 800~1200g / dm ^3. When the bulk density of the component (A) is 600 g / dm ³ or more, the dissolution rate tends to be slower than that of the component (B). If it is 1200 g / dm ³ or less, there is little concern that it will remain undissolved during cleaning.
The average particle diameter of the component (A) is not particularly limited, but is preferably 200 to 1500 μm, more preferably 250 to 1000 μm, and particularly preferably 300 to 700 μm. When the average particle size of the component (A) is in the above range, there is little concern that it will remain undissolved during washing, and the dissolution rate tends to be slower than that of the component (B). The average particle diameter is a value measured by the following method.

[Average particle size]
The average particle diameter in the present invention is measured by a classification operation using a 9-stage sieve having openings of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm and a tray. In the classification operation, a small sieve sieve is stacked on a tray in the order of a large sieve sieve, and a sample of 100 g / time is placed on the top of the top 1680 μm sieve, the lid is capped, and a low-tap sieve shaker (stock) (Made by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute) After shaking for 10 minutes, the sample remaining on each sieve and the saucer was collected for each sieve, Measure the mass. Then, when the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is “a μm”, and the opening of the sieve that is one step larger than a μm is “ bμm ”, the integrated value of the mass frequency from the tray to the aμm sieve is“ c% ”, and the mass frequency on the aμm sieve is“ d% ”. %) To obtain the average particle diameter of the sample.

The water content of the component (A) is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and more preferably 5.5 to 8.5% by mass from the viewpoint of achieving both solubility and storage stability. Further preferred.
Content of the component (A) in a granular detergent composition is 50 mass% or more, and 60 mass% or more is preferable. When it is 50% by mass or more, a good cleaning effect against sebum dirt can be obtained. The upper limit of the content of the component (A) is 90% by mass or less, preferably 85% by mass or less in terms of balance with other components.

<Alkali metal carbonate>
Alkali metal carbonate plays a role of obtaining good detergency. Examples of the alkali metal include sodium, potassium, and lithium, and sodium and potassium are preferable because they are easily available.
Specific examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, and lithium carbonate, and sodium carbonate and potassium carbonate are preferable.
10-40 mass% is preferable and, as for content of the alkali metal carbonate in a granular detergent composition, 20-30 mass% is more preferable.

<Surfactant>
Surfactant can be used individually by 1 type or in combination of 2 or more types as appropriate.
[Anionic surfactant]
Examples of the anionic surfactant include the following (1) to (12).
(1) α-sulfo fatty acid alkyl ester salt.
The kind of α-sulfo fatty acid alkyl ester salt is not particularly limited, and any α-sulfo fatty acid alkyl ester salt used in a general granular detergent composition can be suitably used. Suitable examples are given below.

In the formula (A-1), R ¹¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, preferably 14 to 16 carbon atoms, or linear or branched chain having 8 to 20 carbon atoms. Of the alkenyl group. R ¹² is an alkyl group having 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group, an ethyl group, and a propyl group are preferable because the detergency is further improved, and a methyl group is particularly preferable.
M represents a counter ion, and examples thereof include alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts and the like. Of these, alkali metal salts are preferred.
As the α-sulfo fatty acid alkyl ester salt, for example, α-sulfo fatty acid methyl ester sodium salt (MES) is preferable.
When the α-sulfo fatty acid alkyl ester salt is contained in the granular detergent composition of the present invention, the content is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on 100% by mass of the entire composition. More preferably, it is 5 to 15% by mass. Within the above range, good detergency and recontamination preventing effect can be easily obtained.

(2) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(3) Alkane sulfonate having 10 to 20 carbon atoms.
(4) C-C20 α-olefin sulfonate (AOS).
(5) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(6) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms to which an average of 0.5 to 10 mol is added.
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(8) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(9) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(10) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(12) Soap. The kind of soap in particular is not restrict | limited, The soap used for a general granular detergent composition can be used conveniently. A higher fatty acid salt having 10 to 20 carbon atoms is preferable, and a higher fatty acid salt having 11 to 17 carbon atoms is more preferable.

  These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. These anionic surfactants may be used as a mixture.

[Nonionic surfactant]
Examples of nonionic surfactants include the following.
(1) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms ether.
Among these, polyoxyethylene alkyl (or alkenyl) ether (AE) and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. In addition, the alkyl group or alkenyl group may be linear or branched.
(2) Polyoxyethylene alkyl phenyl ether or polyoxyethylene alkenyl phenyl ether.
(3) A fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (II) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
R ²¹ CO (OA) _m OR ²² (II)
(In the formula, R ²¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA is an alkylene having 2 to 4 carbon atoms such as ethylene oxide or propylene oxide, preferably 2 to 3 carbon atoms. An oxide addition unit, and m represents the average number of moles of alkylene oxide added, generally 3 to 30, preferably 5 to 20. R ²² may have a substituent of 1 to 3 carbon atoms. A good lower (C1-C4) alkyl group is shown.)
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

Among the nonionic surfactants described above, the nonionic surfactant of the above (1) is preferable, and in particular, a polysiloxane obtained by adding an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 12 to 16 carbon atoms. Oxyalkylene alkyl (or alkenyl) ether is preferred.
Further, polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and 9 to 16 HLB, fatty acid methyl ester in which ethylene oxide is added to fatty acid methyl ester An ethoxylate, a fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester, and the like are preferably used.
These nonionic surfactants can be used singly or in appropriate combination of two or more.
In addition, HLB of nonionic surfactant in this specification is a value calculated | required by the method of Griffin (Yoshida, Shindo, Ogaki, Yamanaka co-edit, "New edition surfactant handbook", Kogyoshosho, 1991). Year, page 234).
Further, the melting point in the present specification is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical product”.

[Cationic surfactant]
Examples of the cationic surfactant include the following.
(1) Dilong chain alkyl dishort chain alkyl type quaternary ammonium salt.
(2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt.
(3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt.
However, the above “long chain alkyl” represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.
The “short chain alkyl” includes a substituent such as a phenyl group, a benzyl group, a hydroxy group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; a benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; a polyalkyl having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. Oxyalkylene groups are preferred.

[Amphoteric surfactant]
Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and lauric acid amidopropyl betaine are preferable.

<Other detergency builders>
[Zeolite]
Zeolites are preferably used as other detergency builders that are neither alkali metal carbonates nor sodium bicarbonate. Zeolite contributes to the improvement of detergency. Zeolite is a general term for aluminosilicates, and both a crystalline and amorphous (amorphous) can be used as the aluminosilicate. From the viewpoint of cation exchange ability, crystalline aluminosilicate is preferred.
As the crystalline aluminosilicate, A-type, X-type, Y-type, P-type zeolite and the like are suitable, and the average primary particle diameter is preferably 0.1 to 10 μm.
When the component (A) contains zeolite, the content is preferably 5% by mass or more, and 15% by mass or more in order to obtain an effect of adding sufficient detergency, etc., assuming that the whole component (A) is 100% by mass. Is more preferable. The upper limit is preferably 40% by mass or less and more preferably 30% by mass or less from the viewpoint of the storage stability of the component (C).

[Organic Builder]
An organic builder may be included as another detergency builder that is neither alkali metal carbonate nor sodium bicarbonate.
Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates, cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; Salt of acrylic acid-allyl alcohol copolymer, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid such as polyglyoxylic acid; hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Salt of acrylic acid polymer or copolymer such as polymer; salt of polymer or copolymer such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid; starch, And polysaccharide derivatives such as polysaccharide oxides such as cellulose, amylose and pectin.
Among the organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, polyacrylate, polyglyoxyl having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) Polyacetal carboxylates such as acids (for example, those described in JP-A-54-52196) are preferred.
As for content of an organic builder, 1-20 mass% is preferable in a granular detergent composition, More preferably, it is 1-10 mass%, Most preferably, it is 2-5 mass%.
The other detergency builders can be used singly or in appropriate combination of two or more.

  Among the other detergency builders, the detergency and soil dispersibility in the washing liquid are improved, so that methylglycine such as citrate and aminocarboxylate (for example, trisodium methylglycine diacetate (MGDA)) is improved. Syndiacetate), hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid and the like and inorganic builder such as zeolite are preferably used in combination. .

  The total content of alkali metal carbonate, sodium hydrogen carbonate, and other detergency builders in the granular detergent composition is preferably 15 to 80% by mass from the viewpoint of imparting sufficient detergency. The mass% is more preferable.

<Component (B)>
Component (B) is sodium hydrogen carbonate particles. Ingredient (B) contributes to the improvement of the cleaning effect by suppressing the coloring of the pigment due to the contact with the cleaning liquid in the cleaning of stain stains containing phenolic pigments such as black tea and red wine.
The higher the purity of the sodium hydrogen carbonate particles as the component (B), the higher the effect of the present invention. For example, the purity is preferably 98% by mass or more, and more preferably 100% by mass. Such component (B) is available from commercial products.

Although the particle diameter of a component (B) is not specifically limited, For example, 10-1000 micrometers of average particle diameters are preferable, and 150-350 micrometers is more preferable. If it is 10 micrometers or more, the powdering in the manufacturing process of a granular detergent composition will be suppressed, and if it is 1000 micrometers or less, the solubility to water at the time of use is favorable. In addition, the average particle diameter of a component (B) is a value obtained by said measuring method similarly to the average particle diameter of a component (A).
The particle size distribution of the component (B) is not particularly limited, but it is preferable that particles having a particle diameter of 600 μm or more are not substantially contained. The absence of such particles improves the solubility and improves the effects of the present invention.
Moreover, as for a component (B), it is preferable that the particle | grains whose particle diameter is 150 micrometers or more are less than 20 mass% in a component (B), and it is more preferable that it is less than 10 mass%. When the particles having a particle diameter of less than 150 μm are less than 20% by mass, solidification of particles in the granular detergent composition can be easily suppressed.
In addition, the average particle diameter and particle size distribution of a component (B) can be adjusted by sieving.

<Ingredient (C)>
Component (C) is sodium percarbonate particles, and the surface may be coated with a known coating agent. Component (C) is a bleaching component that contributes to the effect of improving bleaching, sterilization, and detergency, and particularly contributes to the effect of improving the detergency of stain stains containing phenolic dyes when used in combination with component (B).
Further, the component (C) preferably has a slower dissolution rate in water than the component (B). When the component (C) has a slower dissolution rate, it is easy to obtain a good cleaning effect for stain stains containing phenolic pigments.

Examples of the coating agent for component (C) include silicate and magnesium sulfate. The coating method is not particularly limited, but carbonate (sodium carbonate, potassium carbonate), sulfate (sodium sulfate, potassium sulfate, magnesium sulfate), silicate (sodium silicate), surfactant, etc. are mixed. The slurry is applied by spraying the surface of sodium percarbonate to coat the surface.
Thus, the sodium percarbonate particle | grains by which the surface was coat | covered have the effect of delaying a dissolution rate with the suppression of decomposition | disassembly of sodium percarbonate itself. For coating the surface, a fluid bed granulator, a rolling granulator or the like is preferably used.

200-1000 micrometers is preferable and, as for the average particle diameter of a component (C), 500-1000 micrometers is more preferable. Further, from the viewpoint of delaying the dissolution rate, the particles having a particle size of less than 600 μm are preferably less than 10% by mass, and the particles having a particle size of less than 700 μm are more preferably less than 10% by mass.
Component (C) is available from commercial products. As a commercially available product of sodium percarbonate particles, SPCC (Zhejiang Jin Chemicals Co., Ltd.); Sodium Percarbonate (Zhejiang DC Chemical Co., Ltd.) can be cited as a preferred product. The content (as P ₂ O ₅ ) is 0.10 to 0.50%.

[Contents of Component (B) and Component (C)]
The total content of component (B) and component (C) in the granular detergent composition is 10% by mass or more, preferably 15% by mass or more , and more preferably 20% by mass or more. An upper limit is 50 mass% or less, and 40 mass% or less is preferable. Moreover, mass ratio (C) / (B) of a component (B) and a component (C) is 0.15-1.00, and 0.2-0.9 are preferable.
When the component (B) and component (C) content and mass ratio are in the above ranges, the washing liquid is weakly alkaline to suppress the deterioration of the phenolic dye, and the stain containing the phenolic dye can be washed well. it can.
5-35 mass% is preferable and, as for content of the component (B) in a granular detergent composition, 10-30 mass% is more preferable. When the amount is not less than the lower limit of the range, the effect of suppressing the color development of a stain containing a phenolic dye can be sufficiently obtained, and when the amount is not more than the upper limit, the detergency is hardly reduced, and the granular detergent composition is solidified. Is easily suppressed.
1-30 mass% is preferable, as for content of the component (C) in a granular detergent composition, 2-20 mass% is more preferable, and 2 mass% or more and 10 mass% are more preferable. When it is at least the lower limit of the range, a sufficient bleaching effect by the component (C) can be easily obtained, and a sufficient detergency against stain stains can be easily obtained. When the amount is not more than the upper limit, the content of the component (A) and the component (B) is secured, and a good cleaning effect is easily obtained.

<Component (D)>
The granular detergent composition of the present invention preferably contains carboxymethyl cellulose (hereinafter sometimes abbreviated as CMC) as component (D) in addition to components (A) to (C). Carboxymethylcellulose in the present specification is a concept including salts thereof. Examples of the salt of carboxymethyl cellulose include alkali metal salts such as sodium and potassium, ammonium salts, and the like, and a mixture of these salts may be used. Of the above-mentioned salts, sodium salts are preferably used. CMC contributes to the effect of improving the detergency of stains containing phenolic pigments.

Examples of CMC include anionic water-soluble cellulose ether or water-insoluble cellulose ether obtained by reacting monochloroacetic acid after treating pulp with caustic soda as a raw material.
Specifically, a polymer compound having a repeating unit represented by the following formula (I) is exemplified.

[In formula (I), n represents the number of repeating units, and R ^{1 to} R ³ each independently represent a hydroxyl group or a carboxymethyl group (—CH ₂ COO-Z +; Z + is a counter ion). . ]

  The weight average molecular weight of CMC is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 800,000 or more. As an upper limit, 1.2 million or less is preferable, for example, 1 million or less is more preferable. When the weight average molecular weight of CMC is within the above range, the stain resistance of the phenolic dye can be improved. Further, when the weight average molecular weight of CMC is 1,200,000 or less, the solubility becomes good.

The degree of etherification of CMC is preferably 0.2 to 1.3, more preferably 0.2 to 1.0, and still more preferably 0.2 to 0.7.
In the present specification, the degree of etherification of CMC means the average number of hydroxyl groups substituted with a carboxymethyl group or a salt thereof per glucose ring unit (of the three hydroxyl groups of the glucose ring, how many are carboxymethyl groups or their It indicates whether or not it has been replaced by a salt, and is a maximum of 3). For example, in the above formula (I), the average number of ethers in which R ^{1 to} R ³ are substituted with a carboxymethyl group or a salt thereof among —OR ¹ , —OR ² , and —OR ³ is the degree of etherification. .

CMC can use a commercial item suitably. For example, 1110, 1120, 1130, 1140, 1160, 1170, 1180, 1190, 1220, 1240, 1260, 1280, 1290, 1380, 2200 sold under the trade name “CMC Daicel” from Daicel Chemical Industries, Ltd. 2260, 2280, 2450, 2340, etc .; Sunrose F series such as F10LC, F600LC, F1400LC, F10MC, F150MC, F350HC, F1400MC, F1400MG sold under the trade name “Sunrose” from Nippon Paper Chemical Co., Ltd. ; Sunrose A series such as A02SH, A20SH, A200SH; SLD-F1 (named above). Among the above, CMC Daicel 1130, 1170, 1180, 1190, Sunrose F1400LC, F1400MC, and Sunrose SLD-F1 are particularly preferable.
CMC can be used alone or in combination of two or more. When using CMC, the content is preferably 0.6 to 5% by mass, more preferably 1 to 5% by mass, and even more preferably 3 to 5% by mass when the entire granular detergent composition is 100% by mass. If it is within the above range, the effect of improving the detergency of stain stains containing phenolic pigments can be easily obtained.

<(E) Bleach activator>
The granular detergent composition of the present invention preferably contains a bleach activator as component (E) in addition to components (A) to (D).
Component (E) has a function of improving the bleaching power of component (C). In particular, the component (A), the component (B) and the component (C) which are components of the present invention are contained, and the component (C) / component (B) is set to 0.15 to 1.00, and the component ( C) makes the dissolution rate with respect to water slower than that of component (B), so that the blending effect of component (E) is increased, and the effect of improving the cleaning power of stain stains containing phenolic pigments is improved.
As component (E), sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, octanoyl Examples thereof include organic peracid precursors such as oxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, and dodecanoyloxybenzoic acid.
Of these, sodium nonanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, and decanoyloxybenzoic acid are preferred.
A component (E) can be used individually by 1 type or in combination of 2 or more types as appropriate.
The component (E) is preferably blended as a granulated product or molded product, and more preferably blended as a granulated product, from the viewpoint of storage stability during storage.

The content of the component (E) is preferably 0.1% by mass or more and 3% by mass or less, and more preferably 0.1% by mass or more and 2% by mass or less in the granular detergent composition. When the component (E) is at least the lower limit of the above range, the bleaching effect of the component (C) becomes prominent, and the effect of improving the detergency of stain stains containing phenolic dyes is easily obtained. Even if it exceeds the upper limit, the effects may not be enhanced, and at the same time, damage to clothing may occur.
In addition, although the improvement of the bleaching effect of (C) by the inclusion of the component (E) is known, in the present invention, the coexistence of the component (B) has an effect of improving the detergency of a stain stain containing a phenolic dye. can get. It is presumed that the pH buffering ability of component (B) further enhances the effect of component (E).

<Other optional components>
In addition to the above-mentioned particles, the granular detergent composition of the present invention may contain a bleach-activating catalyst such as zinc sulfate, an enzyme, an antifoaming agent, a fragrance, and a pigment as necessary.

<Method for producing granular detergent composition>
In the granular detergent composition of the present invention, for example, the first step of obtaining the component (A), the obtained component (A), the component (B), and the component (C) are mixed while flowing. Obtained by the second step.

[First step]
The first step is a step of obtaining component (A), and a conventionally known method for producing surfactant-containing particles can be used. For example, a surfactant, alkali metal carbonate, and optionally added components are dispersed and dissolved in water to prepare a slurry for spray drying (slurry preparation operation), and the slurry for spray drying is dried by a spray dryer. To obtain spray-dried particles (spraying operation). Furthermore, the spray-dried particles obtained by the spraying operation can be granulated (granulating operation) together with the surfactant and optional components to obtain the component (A).
If necessary, the obtained component (A) may be sieved and adjusted to the desired average particle size and particle size distribution. For example, multiple types of sieves are prepared, stacked in the order of small sieves and sieves with large meshes to form a sieve unit, and component (A) is added to the upper part of the sieve unit, and the sieve unit is vibrated. And sieve. The component (A) remaining on the sieve is recovered for each sieve, and the recovered component (A) is mixed to obtain the component (A) having a desired average particle diameter or particle size distribution.

In the spraying operation, a high temperature gas is supplied into the spray drying tower at the time of spray drying of the slurry for spray drying. This hot gas is supplied from, for example, the lower part of the spray drying tower and discharged from the top of the spray drying tower. The temperature of the high-temperature gas is preferably 170 to 300 ° C, and more preferably 200 to 280 ° C. If it is this range, the slurry for spray-drying can fully be dried, and the spray-drying particle | grains of the desired water content can be obtained easily.
Moreover, it is preferable that the temperature of the gas discharged | emitted from a spray-drying tower is 70-125 degreeC normally, and it is more preferable that it is 70-115 degreeC.

  In addition, when high temperature gas is supplied from the lower part of a spray-drying tower and discharged | emitted from the tower top of a spray-drying tower (countercurrent type), in order to suppress that the temperature of the spray-dried particle obtained becomes too high, it sprays. Cold air can be supplied from the bottom of the drying tower. At the same time, for example, inorganic fine particles (zeolite, etc.) are introduced from the lower part of the spray drying tower and brought into contact with the spray drying particles, thereby preventing the spray drying particles from adhering to the inner walls of the spray drying tower. The fluidity of spray-dried particles can be improved. The spray drying tower may be a countercurrent type or a cocurrent type, and among them, the countercurrent type is preferable because thermal efficiency and dry powder (spray-dried particles) can be sufficiently dried. Examples of the atomizer for the slurry for spray drying include a pressure spray nozzle, a two-fluid spray nozzle, and a rotary disk type. Among them, it is preferable to use a pressure spray nozzle that can easily obtain a desired average particle size. Here, the “pressure spray nozzle” includes all nozzles used when spraying and atomizing the slurry for spray-drying from the spray port of the nozzle by applying pressure. Among these, a nozzle having a structure in which the slurry for spray drying is guided from one or a plurality of inlets of the nozzle to the spiral chamber in the nozzle and sprayed from the spray port as a swirling flow in the spiral chamber is particularly preferable. The pressure during spraying is preferably 2 to 4 MPa (gauge pressure), more preferably 2.5 to 3 MPa (gauge pressure).

  For the granulation operation, a conventionally known method can be used, for example, pulverization granulation in which spray-dried particles and other optional components are kneaded and then pulverized, stirring granulation, rolling granulation, fluidized bed For example, granulation.

[Second step]
A 2nd process is a process of mixing a component (A), a component (B), a component (C), and arbitrary components, and a conventionally well-known method can be used. For example, the method of mixing these components, making it flow with a stirring granulator, a rolling granulator, and a fluid bed granulator is mentioned.

  Examples of the mixing operation include a method in which components (A), (B), and (C) are added and mixed using a container-rotating cylindrical mixer equipped with a stirring blade in a bottomed cylindrical container. . In the mixing operation using the container rotating cylindrical mixer, the Froude number (Fr) represented by the following formula (2) is preferably set to 0.01 to 0.8. By setting Fr in the above range, components (A), (B), and (C) can be mixed well.

Fr = V2 / (R × g) (2)
[However, in the formula (2), V represents the peripheral speed (m / s) of the outermost periphery of the stirring blade of the container-rotating cylindrical mixer. R represents a radius (m) from the rotation center of the outermost periphery in the container rotating cylindrical mixer. g represents a gravitational acceleration (m / s ² ). ]

Since the granular detergent composition of the present invention contains particles (component (A)) containing a surfactant and an alkali metal carbonate, it has a good detergency against sebum dirt and the like, and is a percarbonate that is a bleaching component. Since it contains sodium (component (C)), the stain stain can be bleached and washed by contact with the stain stain for a relatively long time.
In addition, by containing the component (B) in the same amount or more as the component (C), it is possible to satisfactorily suppress the color development of the phenolic dye when the cleaning time is short (initial stage of cleaning). When the color development of the phenolic dye at the initial stage of washing is suppressed, the time necessary for bleaching the stain stain with the component (C) is shortened, and the cleaning power against the stain stain is improved.
The reason why such an effect can be obtained is considered as follows. That is, it is considered that the phenolic pigment contained in black tea or red wine is altered by the alkaline component derived from the component (A) and the component (C) to generate strong color development. Although the component (C) exhibits strong alkalinity, in the present invention, it is considered that the cleaning liquid can be kept weakly alkaline by containing the component (B) in the same amount or more as the component (C), and the coloring of the phenolic dye can be suppressed. It is done.

In the present invention, when the dissolution rate of the component (B) in water is faster than both the component (A) and the component (C), the color development of the phenolic dye at the initial stage of washing is satisfactorily suppressed.
This is because the component (B) is dissolved before the component (A) and the component (C), so that the pH buffering ability by the component (B) can be effectively obtained, and the cleaning liquid can generate strong color of the phenolic dye. It is thought that it is difficult to reach the generated high pH range.
For example, when the dissolution rate of each component is represented by T90 described later, assuming that the T90 value of the component (A) is 100%, the T90 value of the component (B) is preferably 60% or less, more preferably 50% or less. preferable. When the value of T90 of component (C) is 100%, the value of T90 of component (B) is preferably 50% or less, more preferably 40% or less. The dissolution rate of component (B) can be increased by reducing the particle size, for example.

Further, in the present invention, in addition to the components (A), (B), and (C), the component (D) is further added, so that the stain stain containing the phenolic dye can be colored when the cleaning time is short. The cleaning power against stains and stains when the cleaning time is extended is improved, and the cleaning power against sebum stains is also improved. It is considered that the effect of suppressing recontamination by component (D) contributes to this effect.
Furthermore, by containing a component (E), the bleaching effect of a component (C) can be improved and the cleaning effect of the stain stain containing a phenol-type pigment | dye especially when cleaning time is long increases.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Unless otherwise specified, the compounding amounts of the components used in each example are pure conversion values.

The raw materials used in each example are shown below.
<Component (A)>
MES: Sodium salt of fatty acid methyl ester sulfonate having 16 carbon atoms: 18 carbon atoms = 80: 20 (mass ratio) (manufactured by Lion Corporation, AI = 70%, the balance being unreacted fatty acid methyl ester, sodium sulfate, Methyl sulfate, hydrogen peroxide, water, etc.).
LAS salt: LAS-H (linear alkyl (carbon number 10 to 14) benzenesulfonic acid (manufactured by Lion Co., Ltd., product name: Lipon LH-200 (pure content: 96% by mass)) with a concentration of 48% by mass hydroxide Neutralized with an aqueous potassium solution (the amount in the table indicates mass% as LAS-K (potassium)).
-Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure; 67% by mass, titer; 40 to 45 ° C., fatty acid composition; C12 = 11.7% by mass, C14 = 0.4% by mass, C16 = 29.2 mass%, C18F0 (stearic acid) = 0.7 mass%, C18F1 (oleic acid) = 56.8 mass%, C18F2 (linoleic acid) = 1.2 mass%, molecular weight; 289).

Sodium carbonate: granular ash, average particle size 320 μm, bulk density 1.07 g / cm ³ , manufactured by Asahi Glass Co., Ltd.
Potassium carbonate: potassium carbonate (powder), average particle size 490 μm, bulk density 1.30 g / cm ³ , manufactured by Asahi Glass Co., Ltd.
Sodium sulfate: neutral anhydrous sodium sulfate A0, manufactured by Shikoku Kasei Kogyo Co., Ltd.
Nonionic surfactant: LMAO-90 (trade name, manufactured by Nippon Shokubai) [polyoxyethylene (EO15 ^* ) alkyl (C12-14 ^* ) ether]. * “EO15” indicates that the average added mole number of ethylene oxide is 15, and (C12-14) indicates that the alkyl group has 12 to 14 carbon atoms.
MA agent: acrylic acid-maleic anhydride copolymer sodium salt, trade name: AQUALIC TL-400, pure 40% by weight aqueous solution, manufactured by Nippon Shokubai Co., Ltd.
Zeolite: A-type zeolite, product name: Shilton B, pure content 80% by mass, manufactured by Mizusawa Chemical Co., Ltd.
ZnSO ₄ : zinc sulfate (II) (manufactured by Kanto Chemical Co., Inc.)
MGDA: trisodium methyl glycine diacetate (manufactured by BASF)

<Component (B)>
-(B) -1: Sodium bicarbonate particles, manufactured by Asahi Glass Co., Ltd., trade name: sodium bicarbonate (for general industrial use), engineering weight KG, average particle size 250 μm, content of particles with particle size less than 150 μm; 15% by mass In addition, particles having a particle diameter of 600 μm or more are not included.
(B) -2: Sodium hydrogen carbonate particles, manufactured by Penrice, Inc., trade name; SODIUM BICARBONATE FOOD GRADE COARSE GRANULAR, average particle size of 300 μm, particle content of particle size less than 150 μm; 3% by mass, particle size of 600 μm or more Does not contain particles.

<Ingredient (C)>
-(C) -1: Sodium percarbonate particles (trade name: SPCC, manufactured by Zhejiang Jin Chemicals Co., Ltd., effective oxygen amount: 13.8% by mass, average particle size: 870 μm).
-(C) -2: Sodium percarbonate particles (trade name; PC-W, manufactured by Nippon Peroxide Co., Ltd., effective oxygen amount 12.5%, average particle diameter 850 μm).
<Component (D)>
-(D) -1: Carboxymethylcellulose particles (manufactured by Daicel Chemical Industries, trade name; CMC Daicel 1170).
<Ingredient (E)>
(E) -1: OBS, sodium 4-dodecanoyloxybenzenesulfonate-containing particles produced by the method of Production Example 2 (the amount shown in the table is the amount as a granulated product).

<Production Example 1: Production of component (A)>
According to the composition (unit: mass%) shown in Table 1, surfactant-containing particles (A) -1 to (A) -4 were produced by the following production method. In this example, by changing the rotation speed of the kneader in the kneading kneading step, the surfactant-containing particles (A) -1 to (A) -1 ( A) -3 was produced. Further, the surfactant-containing particles (A) -4 were produced by changing the composition.
[Spray drying process]
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. To this, a surfactant excluding MES and nonionic surfactant was added and stirred for 10 minutes. Subsequently, the MA agent was added. After further stirring for 10 minutes, a part of the zeolite A (1.0% by mass for addition during kneading, 5.0% by mass for grinding aid, 1.5% by mass from the addition amount shown in the table) (Amount excluding A-type zeolite for surface modification), sodium carbonate, potassium carbonate, and sodium sulfate. After further stirring for 20 minutes to prepare a slurry for spray drying having a moisture content of 38% by mass, the slurry is spray-dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain an average particle size (mass 50%) of 320 μm, Spray-dried particles having a bulk density of 0.30 g / cm ³ and a water content of 5% were obtained.

[Kazuwa kneading process]
On the other hand, an aqueous slurry of MES-Na (prepared to a water concentration of 25% by mass) obtained by sulfonating and neutralizing the fatty acid ester of the raw material, a part of the nonionic surfactant (based on MES-Na). 25% by mass) and concentrated under reduced pressure with a thin-film dryer until the water content was 11% by mass to obtain a mixed concentrate of MES-Na and nonionic surfactant.
The spray-dried particles obtained in the above [spray-drying step], the above-mentioned mixed concentrate, 1.0% by mass of A-type zeolite, 0.3% by weight of nonionic surfactant for spray addition, and the above-mentioned mixed concentrate The remaining nonionic surfactant excluding the nonionic surfactant, fluorescent brightener, zinc sulfate, MGDA and water were put into a continuous kneader (KRC-S4 type, manufactured by Kurimoto Steel Corporation), and the kneaders shown in the table were used. The mixture was kneaded under the conditions of the number of revolutions (160 rpm, 135 rpm, or 90 rpm) and the temperature of 60 ° C. to obtain a surfactant-containing kneaded material containing 7% by weight of the surfactant. The surfactant-containing kneaded product is cut with a cutter while extruding it with a pelleter double (Fuji Powder Co., Ltd., EXDFJS-100 type) equipped with a die having a hole diameter of 10 mm (cutter peripheral speed is 5 m / s) to obtain a pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm.

[Crushing process]
Next, an amount corresponding to 5.0% by mass of particulate A-type zeolite (average particle diameter 180 μm) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and cold air (10 ° C., 15 m / s) was added. ) In the coexistence, pulverization was performed using Fitzmill (Doka-3, manufactured by Hosokawa Micron Co., Ltd.) arranged in three stages in series to obtain a pulverized product (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: 1st stage / 2nd stage / 3rd stage is 4700 rpm).
Table 1 shows the bulk density, average particle diameter, and water content of the obtained surfactant-containing particles. Further, T90 was measured by the method described later as an index of the dissolution rate of the obtained surfactant-containing particles. The results are shown in Table 1.

<Production Example 2: Production of component (E)>
First, sodium 4-dodecanoyloxybenzenesulfonate was synthesized as a bleach activator.
Sodium p-phenolsulfonate (manufactured by Kanto Chemical Co., Ltd., reagent), N, N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd., reagent), and lauric acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) Reagents) and acetone (manufactured by Kanto Chemical Co., Ltd., reagent) were used for synthesis by the following method.
100 g (0.51 mol) of sodium p-phenolsulfonate dehydrated in advance was dispersed in 300 g of N, N-dimethylformamide, and 111 g (0.51 mol) of lauric acid chloride was stirred at 50 ° C. while stirring with a magnetic stirrer. It was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was carried out for 3 hours, and N, N-dimethylformamide was distilled off at 100 ° C. under reduced pressure (0.5 to 1 mmHg), washed with acetone, and then in a water / acetone (= 1/1 mol) solvent. To obtain sodium 4-dodecanoyloxybenzenesulfonate. The yield was 90%.
70 parts by mass of sodium 4-dodecanoyloxybenzenesulfonate thus obtained, 20 parts by mass of PEG [trade name: polyethylene glycol # 6000M, manufactured by Lion Corporation], sodium alkyl sulfate having 14 to 18 carbon atoms [product] Name: Sandet LNM, Sanyo Kasei Kogyo Co., Ltd.] A mixed powder was obtained by mixing with a continuous pro-shear mixer (WA type Taiheiyo Kiko Co., Ltd.) so as to have a ratio of 5 parts by mass. The mixed powder was put into a continuous kneader (KRS-S1 type, manufactured by Kurimoto Iron Works Co., Ltd.), kneaded at 60 ° C., and then extruded through a 0.8 mm porous screen to obtain a noodle-like mixture. The resulting mixture was pulverized using a pulverizer (NEW SPEED MILL, manufactured by Okada Seiko Co., Ltd.) while mixing the mixture so that the amount of A-type zeolite was 5 parts by mass as a pulverization aid. The pulverized product was sieved to obtain granules (particles having a pure content of OBS of 70% by mass) having a particle size of 300 to 700 μm.

<Examples 1 to 14 and Comparative Examples 1 to 6: Production of granular detergent composition>
Component (A) obtained in Production Example 1 above, Component (B), Component (C), and Component (D) as necessary, and Component (E) obtained in Production Example 2 were rotated in a container. It mixed using the type | formula cylindrical mixer. The mixing ratio (unit: parts by mass) of these components is shown in Tables 2 to 4. In the table, the results of measuring T90 as an index of dissolution rate by the method described later for the component (B) and the component (C) are also described.
The container rotating cylindrical mixer has a diameter of 0.7 m, a length of 1.4 m, an inclination angle of 3.0 °, an outlet weir height of 0.15 m, an internal mixing blade of 0.1 m in height, and a length of 1 .4 m flat blade is attached every 90 °. Moreover, the rotation speed of the internal mixing blade was adjusted so that the Froude number was Fr = 0.2.

First, components (A) to (E) were simultaneously charged at a predetermined mixing ratio into the container rotating cylindrical mixer at a rate of 15 kg / min.
1.5 mass% A-type zeolite for surface modification is added to the particle group fluidized by rotating the container and sprayed with 0.3 mass% nonionic surfactant adjusted to 75 ° C in advance. And rolled for 1 minute to obtain a granular detergent composition.
The composition of the granular detergent composition thus obtained is shown in Tables 2-4. Moreover, about the obtained granular detergent composition, the tea stain | pollution | contamination washing | cleaning power, sebum dirt washing | cleaning power, solubility, and solidification property were evaluated by the below-mentioned method. The results are shown in Tables 2-4.

<Evaluation method>
(1) Method of measuring T90, which is an indicator of the dissolution rate of components (A) to (C) The dissolution rate of components (A) to (C) in this specification is as follows. It can be measured based on the change over time of the conductivity of the solution when dissolved while stirring.
Specifically, first, 1 L of tap water was put in a 1 L beaker, and this was set in a constant temperature water bath of 15 ° C., and stirred at a rotation speed of 250 rotations / minute to adjust the water temperature to 15 ° C. 0.6 g (concentration 600 ppm) of the component (particles) to be measured is added here, and the conductivity of the solution is measured with a conductivity meter (product name: WM-50EG, manufactured by Toa Denpa Inc.) while stirring is continued. did. The conductivity at which no change in conductivity was observed was taken as the value of 100% dissolution, and the time when the conductivity value of 90% was reached was taken as 90% dissolution time T90 (unit: seconds). A smaller T90 value indicates a faster dissolution rate.

(2) Evaluation method of tea stain cleaning power About the tea-stained cloth (10 sheets) prepared as follows, the color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE-2000) is used to determine the reflectance before cleaning. (Measured from Hunter Whiteness Z as reflectance R = Z / 100. The same applies hereinafter).
After washing under the following washing conditions, the reflectance after washing was measured, and the washing rate was calculated by the following formula. The reflectance R ₀ of the raw fabric was 85%.
Washing rate (%) = (reflectance before cleaning R′−reflectance after cleaning R ″) / (reflectance before cleaning R′−reflectance of raw cloth R ₀ ) × 100
The larger the value of the cleaning rate obtained, the higher the cleaning power. If the color of the black tea cloth changes due to washing and the color becomes darker, the washing rate value is negative.
Tables 2 to 4 show the average washing rate of 10 black tea-contaminated cloths. Based on the average value of the cleaning rate, the cleaning power was evaluated according to the following criteria. The results are shown in Tables 2-4.

[Cleaning conditions]
Put tap water (900ml, 15 ° C) into a washing tank of Terg-O-Tometer (manufactured by U.S. Testing Company), cut 10 tea-stained cloths and charge cloths (knit cloths finely, thoroughly wash and rinse) The dried product was weighed to a predetermined bath ratio (20 times) and put into a washing tank, and 0.6 g of the granular detergent compositions of Examples and Comparative Examples were added, and immediately after rotating at 120 rpm. The cleaning was performed for a predetermined cleaning time. After the completion of washing, the film was rinsed with running water for 3 minutes in a two-tank washing machine, dehydrated for 1 minute, and the reflectance was measured after drying.
The washing time was evaluated at three levels of 10 minutes, 30 minutes, or 60 minutes.
[Tea contaminated cloth]
80 g of twining tea pack (orange peco) was boiled in 4 liters of tap water for 5 minutes, rubbed with desalted smooth cotton, 120 g of plain woven cotton cloth (# 100) was immersed in this solution, and left for 30 minutes. After standing, dehydration, natural drying, and pressing were performed to obtain a 5 cm × 5 cm test piece, which was subjected to an evaluation test.

[Criteria]
When the cleaning time is 10 minutes: A cleaning rate of −4% or more is evaluated as “◯” (accepted), and a value less than −4% is determined as “×” (failed).
When the cleaning time is 30 minutes: A cleaning rate of 20% or more is evaluated as ◯ (pass), and a cleaning rate of less than 20% is determined as x (failed).
When the cleaning time is 60 minutes: A cleaning rate of 30% or more is evaluated as ◯ (pass), and a cleaning rate of less than 30% is determined as x (failed).

(3) Evaluation method of sebum stain cleaning power Using Terg-O-Tometer (manufactured by U.S. Testing) as a cleaning tester, 10 wet artificial contamination cloths (purchased from Laundry Science Association) and charge cloth (knitted cloth) And was washed to a predetermined bath ratio (30 times) and weighed into a washing tank, and a washing liquid was added. The cleaning liquid used was that obtained by dissolving the granular detergent compositions of Examples and Comparative Examples in 900 mL of tap water at 15 ° C. to a detergent concentration of 667 ppm.
After washing at a rotation speed of 120 rpm and a temperature of 15 ° C. for 10 minutes, rinsing was performed with 900 mL of 15 ° C. tap water for 3 minutes. After rinsing, the reflectance of the contaminated cloth after washing was measured, and the washing rate was calculated by the following equation.
In the formula, R is a reflectance measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE-2000). The reflectance was measured using a 460 nm filter.
The larger the value of the cleaning rate obtained, the higher the cleaning power. Tables 2 to 4 show the average value of the washing rate of 10 artificially contaminated cloths. When the average value of the cleaning rate was 75% or more, it was evaluated as “good” (good), and when it was less than 75%, it was evaluated as “poor” (failed). The results are shown in Tables 2-4.

(4) Method for evaluating solubility of granular detergent composition Using each granular detergent composition obtained above as a sample, a two-tank washing machine CW-225 (W) type (manufactured by Mitsubishi Electric Corporation), 5 The following evaluation was performed using tap water adjusted to ° C.
The total mass of the cloth to be washed was three kinds of cloth for evaluation, including two acrylic shirts, two nylon slips, two cotton shirts, and five skin shirts for weight balance. Was 1.5 kg.
The washing cloth was charged into a two-tank washing machine so that all three kinds of washing cloths for evaluation could be seen when viewed from above. The cloth to be washed was soaked under conditions of 30 L of water and a bath ratio of 1:20, and washing was performed for 5 minutes with 30 g of the sample.

After washing, after the washing cloth is dehydrated for 1 minute, the degree of adhesion of the sample to the washing cloth is visually observed, and the solubility of the granular detergent composition is evaluated according to the following criteria. Scores 1 and 2 were accepted. If the granular detergent composition is dissolved in water and gelation / aggregation of particles occurs, deposits (undissolved) on the cloth to be washed tend to occur.
[Criteria]
Score 1 (no undissolved residue): no adhering material.
2 (very little undissolved): Very little adhering material is observed.
3 (Some remaining undissolved): Slightly adhering matter.
4 (Large undissolved): Many adhering substances are recognized.

(5) Evaluation method of solidification property of granular detergent composition Coated cardboard (basis weight: 350 g / m ² ), wax sand paper (basis weight: 30 g / m ² ), kraft pulp paper (basis weight: 70 g / m) A box having a length of 15 cm, a width of 9.3 cm, and a height of 18.5 cm was prepared using paper composed of three layers of m ² ). The granular detergent composition 1.1kg of each example was put into this box, and operation which increases the contact point of particle | grains by dropping 10 times from the height of 10 cm was performed. Thereafter, the box containing the granular detergent composition was stored for 14 days in a constant temperature and humidity chamber of 45 ° C., 85% RH, 8 hours and 25 ° C., 65% RH, 16 hours. After leaving the box taken out of the thermostatic chamber at 20 ° C. and 60% RH for 6 hours, the granular detergent composition in the box was gently transferred onto a sieve having an opening of 5 mm. After gently shaking the sieve left and right 10 times, the residue on the sieve and the mass passing through the sieve were determined, and the solidification rate was calculated from the following equation. The smaller the value of the solidification rate, the less solidification occurs and the better the solidification property. The results are shown in Tables 2-4.

As shown in the results of Tables 2 to 4, Examples 1 to 14 according to the present invention have good cleaning power against sebum stains and the like, and tea stains when the cleaning time is short (10 minutes). Dark color development is prevented, and a good cleaning effect on black tea stains can be obtained by increasing the washing time to 30 minutes or 60 minutes. Further, the solubility of the granular detergent composition is good, and solidification during storage is less likely to occur.
On the other hand, since Comparative Example 1 does not contain the components (B) and (C), black tea stains are darkly developed in a washing time of 10 minutes, and black tea stains are not easily removed even if the washing time is extended.
Although the comparative example 2 contains component (B) and (C), since there is little content of a component (A), the cleaning power of sebum dirt is insufficient.
Comparative Example 3 contains components (A) and (C), but does not contain component (B), so that black tea stains were darkly developed in a washing time of 10 minutes. Therefore, the washing of tea stains was insufficient with a washing time of 30 minutes, and a good washing effect was obtained after washing for 60 minutes.
Comparative Example 4 contains components (A) and (B) but does not contain component (C). Coloring of black tea stains after a washing time of 10 minutes was prevented, but black tea stains were not easily removed even if the washing time was extended.
Although the comparative example 5 contains component (A), (B), (C), (C) / (B) is 0.06 and there are few components (C). Coloring of black tea stains after a washing time of 10 minutes was prevented, but black tea stains were not easily removed even if the washing time was extended.
Comparative Example 6 includes components (A), (B), and (C), but (C) / (B) is 2.00, and the component (B) is less than the component (C). The tea stain was darkly colored in 10 minutes. Therefore, the washing of tea stains was insufficient with a washing time of 30 minutes, and a good washing effect was obtained after washing for 60 minutes.

In particular, when Examples 3 to 5 are compared, the smaller (C) / (B) tends to be less likely to cause blackening of tea stains after a washing time of 10 minutes. On the other hand, when (C) / (B) is large, the cleaning power for black tea stains at 30 minutes and 60 minutes is improved, and the solidification property tends to be improved.
When Example 1 and Example 11 and Example 3 and Example 6 are compared, respectively, if the content of alkali metal carbonate in component (A) is large, there is a tendency that the detergency against sebum stains is improved, When there is little content of alkali metal carbonate, there exists a tendency for the solubility of a granular detergent composition to improve.
When Examples 3, 7, and 8 are compared, the slower the dissolution rate of component (A), the less likely it is to develop black tea stains with a washing time of 10 minutes, and the better cleaning ability of black tea stains with a washing time of 30 minutes. Tend to.
Comparing Example 1 and Example 9, by containing component (D), the color development of black tea stains at a washing time of 10 minutes is further suppressed, and the washing power of black tea stains at a washing time of 30 minutes and 60 minutes, And the detergency of sebum dirt was improved.
When Example 1 and Example 10 are compared, the faster the dissolution rate of component (B), the more the color development of black tea stains with a washing time of 10 minutes is further suppressed, and the washing of black tea stains with a washing time of 30 minutes and 60 minutes. Power tends to improve. On the other hand, when the dissolution rate of the component (B) is slower, the solidification property tends to be improved.
When Example 1 and Example 13 and Example 9 and Example 14 were compared, the washing | cleaning power of black tea stains improved by component (E) in washing | cleaning time 30 minutes and 60 minutes.

Claims (3)

It is a granular detergent composition containing the following components (A) to (C), wherein the component (A) is 50 to 90% by mass of the whole granular detergent composition, and the components (B) and (C) A granular detergent composition, wherein the total is 10 to 50% by mass, and the mass ratio (C) / (B) of component (B) to component (C) is 0.15 to 1.00.
Component (A): Surfactant-containing particles containing an alkali metal carbonate.
Component (B): Sodium hydrogen carbonate particles.
Component (C): Sodium percarbonate particles. Component (B) in Oite are particles having a particle diameter of less than 150μm is less than 20 wt%, the particles a particle diameter of 600μm or contains Marezu, an average particle size of 150～350Myuemu, claim 1 The granular detergent composition as described in 2.   Furthermore, the granular detergent composition of Claim 1 or 2 which contains carboxymethylcellulose as a component (D).