JP2012131836A - Granular detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a granular detergent composition that has a high sterilizing power and good rinsability, and suppresses adhesion of colored matter to clothes.SOLUTION: The granular detergent composition includes: (A) 10-45 mass% of one or more kinds selected from a non-soap anionic surfactant and a nonionic surfactant; (B) soap; (C) 0.04-0.8 mass% of a copper compound, calculated as copper; (D) one or more kinds selected from ascorbic acid, an ascorbate, and a derivative of ascorbic acid; and (E) an inorganic peroxide, and the molar ratio expressed by copper in the (C) component/the (D) component is less than 1.

Description

  The present invention relates to a granular detergent composition.

  The presence and growth of bacteria often cause various problems such as infectious diseases, and countermeasures are required. In particular, bacteria attached to clothing may cause bad odors in the process of drying the laundry or may become a source of infection. For this reason, in washing, sterilization or removal of bacteria adhering to clothing is required.

On the other hand, a method for obtaining a bleaching effect and a bactericidal effect by utilizing a change in the oxidation state of a central metal in a metal complex at the time of washing is disclosed. The metal complex changes its oxidation state of the central metal with hydrogen peroxide in the cleaning solution to become a metal complex exhibiting a high oxidizing power, acts on stains to exert a bleaching effect, and acts on bacteria to exert a bactericidal effect. The metal complex in which the oxidation state of the central metal has returned to its original state by acting on dirt or bacteria has a function of reacting with hydrogen peroxide again. For this reason, high bleaching power and bactericidal power can be obtained with a small amount of metal complex.
A metal complex that has such a catalytic mechanism and has the feature of efficiently activating hydrogen peroxide, also called a bleach activation catalyst, exhibits a bleaching effect and a bactericidal effect at a low concentration. In addition, it is a component that is also environmentally useful.

  Conventionally, as a technique for performing sterilization by applying this metal complex in laundry, for example, an oxidation catalyst particle containing a specific chelating agent, a copper compound and a binder, an inorganic peroxide, and a surfactant-containing particle The granular detergent composition containing is proposed (refer patent documents 1-3).

JP 2009-148682 A JP 2009-148683 A JP 2009-155292 A

In recent years, washing has been performed in washing machines with a small amount of water used, for example, drum-type washing machines, due to changes in washing circumstances and increased awareness of environmental burdens.
A method of blending a higher fatty acid salt (soap) is known as a method for improving the rinsing property by suppressing the foaming of the cleaning liquid in response to such washing conditions with a small amount of water used.
However, when a higher fatty acid salt (soap) is simply blended with a detergent that uses a metal complex such as the techniques of Patent Documents 1 to 3, the problem is that green to blue-green colored substances adhere to clothes after washing. There is.
This invention is made | formed in view of the said situation, and makes it a subject to provide the granular detergent composition which has high sterilization power, is excellent in a rinse property, and the coloring matter adhesion to clothing was suppressed. .

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the granular detergent composition of the present invention comprises (A) 10 to 45% by mass of one or more selected from non-soap anionic surfactants and nonionic surfactants, (B) soap, and (C ) 0.04-0.8% by mass of copper compound in terms of copper, (D) one or more selected from ascorbic acid, ascorbate and ascorbic acid derivatives, and (E) inorganic peroxide The molar ratio represented by the copper / (D) component in the component (C) is less than 1.

The granular detergent composition of the present invention preferably further contains one or more (F) alkali agents selected from (F1) alkali metal carbonates and (F2) alkali metal hydrogen carbonates.
Moreover, in the granular detergent composition of this invention, the said (F2) component is contained, and the mass ratio represented by (F2) / [(E) + (F)] is 0.1-0.5. It is preferable.
Moreover, in the granular detergent composition of this invention, the said (F2) component is contained, and the mass ratio represented by [(A) + (B)] / [(E) + (F)] is 0.5. It is preferably ~ 3.

  According to the present invention, it is possible to provide a granular detergent composition that has high bactericidal power and good rinsing properties, and that suppresses the adhesion of colored substances to clothing.

  The granular detergent composition of the present invention comprises (A) one or more selected from a non-soap anionic surfactant and a non-ionic surfactant, (B) soap, (C) a copper compound, (D) One or more types selected from ascorbic acid, ascorbate and a derivative of ascorbic acid, and (E) an inorganic peroxide are contained.

<(A) One or more selected from non-soap anionic surfactants and nonionic surfactants>
In the present invention, the “non-soap anionic surfactant” refers to an anionic surfactant other than soap.
In the granular detergent composition of the present invention, the cleaning performance is mainly imparted by containing the component (A).

(Non-soap anionic surfactant)
Non-soap anionic surfactants include linear alkylbenzene sulfonate (LAS), alkyl sulfate (AS), α-olefin sulfonate (AOS), polyoxyethylene alkyl ether sulfate (AES), α -Alkali salts such as sulfo-fatty acid ester salt (α-SF) and α-sulfo fatty acid alkyl ester salt (MES).
Specifically, the following (1) to (8) are preferable.

(1) α-sulfo fatty acid alkyl ester salt (MES)
The α-sulfo fatty acid alkyl ester salt is preferably a compound represented by the following general formula (A-1).

［式中、Ｒ^１１は炭素数８〜２０のアルキル基又はアルケニル基を表し、Ｒ^１２は炭素数１〜６のアルキル基を表し、Ｍ^＋は対イオンを表す。］

[Wherein, R ¹¹ represents an alkyl group or alkenyl group having 8 to 20 carbon atoms, R ¹² represents an alkyl group having 1 to 6 carbon atoms, and M ⁺ represents a counter ion. ]

In the formula (A-1), the alkyl group or alkenyl group of R ¹¹ may be linear or branched. R ¹¹ has 8 to 20 carbon atoms, preferably 12 to 18 carbon atoms, and particularly preferably has 14 to 16 carbon atoms when R ¹¹ is an alkyl group.
R ¹² has 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. Among them, a methyl group, an ethyl group, and a propyl group are preferable, and a methyl group is particularly preferable because the detergency is further improved.
M ⁺ represents a counter ion. Examples of M include alkali metal atoms such as sodium and potassium; amines such as monoethanolamine, diethanolamine and triethanolamine; ammonium and the like, among which alkali metal atoms are preferable.

(2) Linear or branched alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 18 carbon atoms.
(3) C10-20 alkyl sulfate (AS) or alkenyl sulfate.
(4) C-C20 α-olefin sulfonate (AOS).
(5) Alkane sulfonate (SAS) having 10 to 20 carbon atoms.
(6) An ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 mol or less was added. Alkyl ether sulfate (AES) or alkenyl ether sulfate.
(7) An ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 moles or less was added. Alkyl ether carboxylates or alkenyl ether carboxylates.
(8) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.

Among the non-soap anionic surfactants described above, (E) LAS having an effect of improving the bactericidal effect of the inorganic peroxide and MES having excellent detergency are preferable.
Examples of the salt form include alkali metal salts such as sodium salt and potassium salt; alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt; ammonium salt and the like. Of these, alkali metal salts are preferred.

(Nonionic surfactant)
Examples of the nonionic surfactant include (11) to (18) shown below.
(11) A polyoxyalkylene alkyl ether or poly, wherein an average of 3 to 30 mol, preferably 3 to 20 mol, of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Oxyalkylene alkenyl ether.
Among these, preferred examples include polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols, and primary alcohols are preferred. Moreover, the alkyl group or alkenyl group may be linear or branched.
(12) Polyoxyethylene alkyl phenyl ether or polyoxyethylene alkenyl phenyl ether.

(13) A fatty acid alkyl ester alkoxylate represented by the following general formula (I), wherein an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
R ¹³ CO (OA) _n OR ¹⁴ (I)
In the formula (I), R ¹³ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents an oxyalkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. n shows the average repeating number of an oxyalkylene group, and is 3-30, Preferably it is the number of 5-20. R ¹⁴ represents an alkyl group having 1 to 3 carbon atoms.

(14) Polyoxyethylene sorbitan fatty acid ester.
(15) Polyoxyethylene sorbite fatty acid ester.
(16) Polyoxyethylene fatty acid ester.
(17) Polyoxyethylene hydrogenated castor oil.
(18) Glycerin fatty acid ester.

Among the above nonionic surfactants, the nonionic surfactant of (11) is preferable, and among these, an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms in an aliphatic alcohol having 12 to 16 carbon atoms. The added polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether is particularly preferred.
Polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyoxyethylene polyoxypropylene alkenyl ether, fatty acid methyl ester having a melting point of 50 ° C. or lower and HLB of 9 to 16 Also suitable are fatty acid methyl ester ethoxylates to which ethylene oxide has been added, fatty acid methyl ester ethoxypropoxylates to which ethylene oxide and propylene oxide have been added to fatty acid methyl esters.
The “melting point” here means a value measured by a melting point measurement method described in JIS K 0064-1992 “Measuring method of melting point and melting range of chemical product”.
“HLB” means a value obtained by the GRIFFIN method (see Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991, page 234). .

As the component (A), one or more selected from non-soap anionic surfactants and nonionic surfactants can be used. Especially, since a detergency improves, it is preferable to use a non-soap anionic surfactant and a nonionic surfactant together.
In the case where a non-soap anionic surfactant and a non-ionic surfactant are used in combination, the content ratio of both is a non-soap anionic surfactant / non-ionic surfactant = 0.1 to 20 by mass ratio. It is preferable that it is, and it is more preferable that it is 1.5-9.5. When the mass ratio is not less than the lower limit, the detergency is particularly excellent when water having high hardness is used, and when the mass ratio is not more than the upper limit, the powder preparation is hardly solidified.

In the granular detergent composition, the content of the component (A) (based on the whole composition) is 10 to 45% by mass in total of the non-soap anionic surfactant and the non-ionic surfactant, It is preferable that it is 15-30 mass%.
When the content of the component (A) is at least the lower limit value, a good cleaning effect is exhibited. On the other hand, when the upper limit is exceeded, it is difficult to formulate and it is difficult to obtain the effect of improving the detergency due to the increase in content.

<(B) soap>
In the granular detergent composition of the present invention, by containing the component (B), the rinsing properties (foam suppression effect of the granular detergent composition) are mainly improved, and the cleaning performance is also improved.
As the component (B), any soap used in a general detergent composition can be used. Among them, 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.
In the granular detergent composition, the content of the component (B) (based on the whole composition) is preferably 0.1 to 20% by mass, more preferably 3 to 10% by mass. More preferably, it is -7 mass%.
When the content of the component (B) is equal to or higher than the lower limit value, it is easy to obtain a foam suppression effect and a good cleaning effect is easily exhibited. On the other hand, when the upper limit is exceeded, formulation is likely to be difficult.

<(C) Copper compound>
In the granular detergent composition of the present invention, the bactericidal effect is mainly improved by containing the component (C).
(C) As a component, what is necessary is just a compound containing a copper atom, and inorganic compounds, such as copper sulfate, copper chloride, copper carbonate, copper bromide, copper iodide, copper hydroxide, copper nitrate, or these hydrates An organic compound such as copper acetate, copper acetylacetonate, copper gluconate, copper oxalate, and copper tartrate. Of these, copper sulfate, copper chloride or a hydrate thereof is preferable, and since the solubility in water is particularly good, a copper sulfate hydrate and a copper chloride hydrate are more preferable.
(C) A component may be used individually by 1 type or in combination of 2 or more types as appropriate.
In the granular detergent composition, the content of component (C) (based on the whole composition) is 0.04 to 0.8% by mass in terms of copper content (in terms of copper) in the copper compound, and is 0.04. It is preferable that it is -0.3 mass%, and it is further more preferable that it is 0.1-0.3 mass%.
When the content of the component (C) is equal to or higher than the lower limit value, a bactericidal effect is easily obtained. On the other hand, even if the upper limit is exceeded, no improvement in the bactericidal effect due to the increased content is observed. Moreover, there exists a possibility that a colored material may adhere easily to clothing.

The copper content (in terms of copper) in the copper compound can be calculated as follows when, for example, the granular detergent composition contains 1% by mass of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O). it can.
Copper content (% by mass) in copper compounds
= Content of copper sulfate pentahydrate (mass%) × (Cu molecular weight / CuSO ₄ .5H ₂ O molecular weight)
= 1 x (64/250)
= 0.26 (mass%)

<(D) One or more selected from ascorbic acid, ascorbate and derivatives of ascorbic acid>
In the granular detergent composition of the present invention, by containing the component (D), the adhesion of colored substances to clothing is mainly suppressed.
Examples of the ascorbate include sodium ascorbate, potassium ascorbate, calcium ascorbate, and magnesium ascorbate.
Ascorbic acid derivatives include ascorbyl 6-stearate, ascorbyl 6-palmitate, ascorbyl 2,6-dipalmitate, ascorbyl 2,3,5,6-tetrahexyldecanoate, (ascorbyl / tocopheryl) potassium phosphate, Examples include ascorbic acid-2-sulfate disodium, ascorbic acid-2-magnesium phosphate, ascorbyl-2-sodium phosphate, ascorbyl-2-glucoside and the like.
Among these, as the component (D), ascorbic acid, sodium ascorbate, and ascorbyl 6-stearate are preferable, and ascorbic acid is most preferable.
(D) A component may be used individually by 1 type or in combination of 2 or more types as appropriate.
In the granular detergent composition, the content of the component (D) (based on the whole composition) is determined according to the content of the component (C), and is preferably 0.1 to 5% by mass, More preferably, it is 0.2-3 mass%.
When the content of the component (D) is equal to or higher than the lower limit value, coloring matter adhesion to clothing is further suppressed. In addition, the bactericidal effect is further enhanced. On the other hand, when the content of the component (D) exceeds 3% by mass, it is difficult to obtain the sterilizing effect of the increase in content, and when it exceeds 5% by mass, the content of other components is reduced to reduce washing. The power may be reduced.

In the present invention, “the molar ratio represented by the copper in the component (C) / (D) component” means the ratio of the number of moles of copper in the component (C) to the number of moles in the component (D) ).
In the granular detergent composition of the present invention, the molar ratio represented by the copper / (D) component in the component (C) is less than 1, preferably 0.05 to less than 1, and preferably 0.2 to More preferably, it is 0.5.
When the molar ratio represented by the copper / (D) component in the component (C) is less than 1, coloring matter adhesion to clothing is suppressed.

In this invention, the molar ratio represented by the copper / (D) component in (C) component can be calculated | required from the following Formula.
Copper in component (C) / (D) component = [Copper (mass%) in component (C) / Molecular weight of copper 64 in component] / [Included in granular detergent composition (D) Component (mass%) / (D) component molecular weight]
For example, when the component (C) contains 1% by mass of copper sulfate pentahydrate (molecular weight 250) and 1% by mass of ascorbic acid (molecular weight 176),
Copper in component (C) / (D) component = [(1 × 64/250) / 64] / [1/176] = 0.70.

<(E) Inorganic peroxide>
In the granular detergent composition of the present invention, the bactericidal effect is mainly exhibited by containing the component (E).
(E) As a component, what generate | occur | produces hydrogen peroxide when it melt | dissolves in water is used, and sodium percarbonate and sodium perborate are preferable. Of these, sodium percarbonate is particularly preferred because of its better stability over time.
(E) A component may be used individually by 1 type or in combination of 2 or more types as appropriate.
In the granular detergent composition, the content of the component (E) (based on the whole composition) is preferably 0.1 to 50% by mass, and more preferably 5 to 20% by mass.
When the content of the component (E) is at least the lower limit value, the bactericidal effect is easily exhibited. On the other hand, when the content of the component (E) exceeds the upper limit value, the detergency may decrease due to a decrease in the content of other components, for example, the component (A) or the component (B).

When moisture or other components come into contact with the inorganic peroxide, the inorganic peroxide may be decomposed. In order to prevent this, the component (E) that has been subjected to a treatment such as coating may be used.
As the particles of the component (E) that have been coated, oxygen-based bleaching particles that have already been disclosed can be used (see Japanese Patent No. 2918991). The bleaching particle is a granulated product obtained by spraying an aqueous boric acid solution and an alkali metal silicate aqueous solution separately onto sodium percarbonate particles maintained in a fluid state, and then drying.
In addition, particles of the component (E) coated with a conventionally known stabilizer (such as a chelating agent) in combination with a coating agent can also be used. Examples of the chelating agent include iminodisuccinic acid, 3-hydroxy-2,2′-iminodisuccinic acid, nitrilotriacetic acid, methylglycinediacetic acid, dicarboxymethylglutamic acid, L-aspartic acid-N, N-diacetic acid, serinediacetic acid, Or salts thereof (alkali metal salts such as sodium salt and potassium salt; alkanolamine salts such as monoethanolamine salt and diethanolamine salt). Examples of the coating agent include water-insoluble organic compounds such as paraffin and wax.

<(F) Alkaline agent>
The granular detergent composition of the present invention preferably further contains one or more (F) alkali agents selected from (F1) alkali metal carbonates and (F2) alkali metal hydrogen carbonates. (F) By further containing an alkali agent, the detergency is further increased.
However, the component (F) does not include a component (such as an alkali metal percarbonate) corresponding to the component (E).

-(F1) Alkali metal carbonate As (F1) component, the well-known alkali metal carbonate normally used for a detergent can be used, Sodium carbonate, potassium carbonate, etc. are mentioned suitably.

-(F2) Alkali metal hydrogencarbonate As (F2) component, the well-known alkali metal hydrogencarbonate normally used for a detergent can be used, Sodium bicarbonate, potassium bicarbonate, etc. are mentioned suitably.

The component (F) is preferably one or more selected from the component (F1) and the component (F2). Particularly, since the bactericidal effect is enhanced, it is particularly preferable to use the component (F1) and the component (F2) in combination. .
When the (F1) component and the (F2) component are used in combination, the content ratio of both is preferably (F1) / (F2) = 0.1-10 in terms of mass ratio, and is 0.2-5. More preferably. When it is at least the lower limit of the mass ratio, the detergency will be better, while when it is below the upper limit, the bactericidal effect will be better.

In the granular detergent composition, the content of the component (F) (based on the whole composition) is preferably 5 to 50% by mass in total of the component (F1) and the component (F2). More preferably, it is 40 mass%.
When the content of the component (F) is equal to or higher than the lower limit, the detergency tends to increase. On the other hand, when the content of the component (F) is not more than the upper limit value, it becomes easy to achieve a blending balance with other components.

In the present invention, “mass ratio represented by (F2) / [(E) + (F)]” is the content of the component (F2) relative to the total content of the component (E) and the component (F). It represents the ratio (mass ratio) of the quantity.
In the granular detergent composition of the present invention, when the component (F2) is contained, a good bactericidal effect is easily obtained, so that the mass ratio represented by (F2) / [(E) + (F)] is It is preferable that it is 0.1-0.5. Furthermore, since it is excellent in the bactericidal effect, it is more preferable that the mass ratio represented by (F2) / [(E) + (F)] is 0.2 to 0.4.

In the present invention, the “mass ratio represented by [(A) + (B)] / [(E) + (F)]” refers to the total content of the (E) component and the (F) component, The ratio (mass ratio) of the total content of (A) component and (B) component is represented.
In the granular detergent composition of this invention, when it contains (F2) component, the mass ratio represented by [(A) + (B)] / [(E) + (F)] is 0.5-3. It is preferable that it is, and it is more preferable that it is 0.5-2.
If it is at least the lower limit of the mass ratio, adhesion of colored substances to clothing is likely to be suppressed. On the other hand, if it is less than or equal to the upper limit value, it is possible to obtain excellent bactericidal effects in addition to easy adhesion of colored substances to clothing.

<Other ingredients>
A granular detergent composition may contain other components other than the said (A)-(F) component as needed.
As other components, those commonly used in detergent compositions for clothing and the like can be used, and surfactants (cationic surfactants, amphoteric surfactants) other than component (A), cleaning Examples include sex builders, bleaches, fluorescent brighteners, enzymes, enzyme stabilizers, polymers, anti-caking agents, antifoaming agents, metal ion scavengers, perfumes, and dyes.

(Cationic surfactant)
Examples of the cationic surfactant include (21) to (23) shown below.
(21) Dilong chain alkyldishort chain alkyl type quaternary ammonium salt.
(22) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt.
(23) 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.
“Short-chain alkyl” refers to an alkyl group having 1 to 4 carbon atoms which may have a substituent such as a phenyl group or a hydroxy group, or may have an ether bond between carbon atoms. Specifically, 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; 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. The group having a polyoxyalkylene group is preferable.

(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.

(Detergency builder)
Examples of detergency builders include inorganic builders and organic builders (except for those corresponding to component (F)).
Examples of inorganic builders include alkali metal sulfites such as sodium sulfite and potassium sulfite; sulfates such as sodium sulfate and potassium sulfate; alkali metal chlorides such as sodium chloride and potassium chloride; orthophosphate, pyrophosphate, and tripolyphosphate And phosphates such as metaphosphate, hexametaphosphate and phytate; crystalline aluminosilicate and amorphous aluminosilicate.
Among the inorganic builders, aluminosilicates and sulfates or alkali metal chlorides are preferred as having the effect of improving solubility.
As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, and crystalline aluminosilicate is preferred from the viewpoint of cation exchange ability.
As the crystalline aluminosilicate, A-type, X-type, Y-type and P-type zeolite are preferable, and the average primary particle diameter is preferably 0.1 to 10 μm. The content of the crystalline aluminosilicate in the granular detergent composition (based on the whole composition) is preferably 1 to 40% by mass, and 2 to 30 in terms of powder properties such as cleaning performance and fluidity. The mass% is more preferable.

Examples of organic builders include nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodisucci Acid salts, hydroxyaminocarboxylates such as hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzopoly Cyclocarboxylates such as carboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; Acid salt, 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 Acrylic acid polymer or copolymer salt such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid, etc .; salt of starch, cellulose And polysaccharide oxides such as 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.
In the granular detergent composition, the content of the organic builder (based on the whole composition) is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and further preferably 2 to 5% by mass.

The said detergency builder can be used individually by 1 type or in combination of 2 or more types as appropriate.
Among the above detergency builders, the detergency and dirt dispersibility in the washing liquid are improved, so that citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid It is preferable to use an organic builder such as a copolymer salt or a polyacetal carboxylic acid salt in combination with an inorganic builder such as zeolite.
In the granular detergent composition, the total content of the detergency builder (based on the whole composition) is preferably 3 to 50% by mass, more preferably 5 to 30% by mass from the viewpoint of imparting sufficient cleaning performance. .

(bleach)
Examples of the bleaching agent include a bleaching activator and a bleaching activation catalyst (except for those corresponding to the component (E)).
As the bleach activator, a known one can be used, and among them, an organic peracid precursor is preferably used. It is also preferred to use in the form of particles containing a bleach activator.
Examples of the organic peracid precursor include tetraacetylethylenediamine, alkanoyloxybenzenesulfonic acid having 8 to 12 carbon atoms, alkanoyloxybenzoic acid having 8 to 12 carbon atoms, and salts thereof. Of these, 4-decanoyloxybenzoic acid, sodium 4-dodecanoyloxybenzenesulfonate, and sodium 4-nonanoyloxybenzenesulfonate are preferable. These organic peracid precursors can be used singly or in appropriate combination of two or more.
Particles containing the bleach activator can be produced by a known production method. For example, it can be produced by an extrusion granulation method or a granulation method by a tablet shape using a briquetting machine. Specifically, the organic peracid precursor particles are obtained by heating and melting a solid binder material at room temperature such as polyethylene glycol of PEG # 3000 to # 20000, preferably PEG # 4000 to # 6000. And a powder of a surfactant such as olefin sulfonate, alkylbenzene sulfonate, alkyl sulfate ester salt, and the like, and extruded to produce a noodle-shaped organic peracid precursor granule having a diameter of about 1 mm, Then, what is mix | blended by lightly grind | pulverizing to about 0.5-3 mm in length is preferable. The surfactant powder is preferably an α-olefin sulfonate having an alkyl chain having 14 carbon atoms.

As the bleach activation catalyst, a known catalyst can be used. Specifically, it is coordinated with a transition metal atom such as iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, and molybdenum. What formed a complex with a ligand through a nitrogen atom, an oxygen atom, etc. is preferable. It is also preferred to use in the form of particles containing a bleach activating catalyst.
Particles containing the bleach activating catalyst can be produced by a known granulation method. For example, it can be produced by an extrusion granulation method or a granulation method by a tablet shape using a briquetting machine.

(Fluorescent brightener)
Examples of optical brighteners include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) ) Naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, bis- (triazinylaminostilbene) disulfonic acid derivatives, and the like.
The said fluorescent brightening agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
In the granular detergent composition, the content of the optical brightener (based on the whole composition) is preferably 0.001 to 1% by mass.
Specific examples of commercially available products include Whiteex SA, Whitex SKC (trade name; manufactured by Sumitomo Chemical Co., Ltd.); Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS-X (above, trade name; Ciba). -Specialty Chemicals); Lemonite CBUS-3B (trade name, manufactured by Khyati Chemicals) and the like are preferable. Of these, Tinopearl CBS-X and Tinopearl AMS-GX are more preferable.

(enzyme)
As the enzyme, protease, cellulase, esterase, lipase, nuclease, amylase, pectinase and the like can be added.
Specific examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promeline, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like.
Commercially available products include sabinase, alcalase, everase, cannase, everase, deozyme, and porozyme (above, trade name: manufactured by Novozymes); API21 (trade name, manufactured by Showa Denko KK); maxatase, maxacal, purefect, maxapem ( As mentioned above, protease K-14 and K-16 described in JP-A-5-25492 and the like can be mentioned, Genencor Corp.), KAP (manufactured by Kao Corporation).
As cellulases, commercially available cellzymes, carezymes, cellcleans (trade names, manufactured by Novozymes); KAC500 (manufactured by Kao Corporation), alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K -539, alkaline cellulase K-577, alkaline cellulase K-425, alkaline cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline cellulase K-522, CMCase I, CMC Examples include ase II, alkaline cellulase E-II, and alkaline cellulase E-III (the cellulase described in JP-A-63-264699).
Specific examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.
Specific examples of the lipase include lipolase, lipolase ultra, lipex (trade name; manufactured by Novozymes), liposome (trade name, manufactured by Showa Denko KK) and the like.
Specific examples of amylase include commercially available stainzymes, termamyls, duramils (above, trade names; manufactured by Novozymes) and the like.
The said enzyme can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).

(Enzyme stabilizer)
As the enzyme stabilizer, calcium salt, magnesium salt, polyol, formic acid, boron compound and the like can be blended. Of these, sodium tetraborate, calcium chloride and the like are preferable.
An enzyme stabilizer can be used individually by 1 type or in combination of 2 or more types as appropriate.
In the granular detergent composition, the content of the enzyme stabilizer (based on the whole composition) is preferably 0.05 to 2% by mass.

(Polymers)
In the granular detergent composition of the present invention, as a binder or a powder property modifier used when densifying the granular detergent composition particles, or to impart a recontamination preventing effect on hydrophobic fine particles (dirt). Polyethylene glycol having an average molecular weight of 200 to 200,000, salt of acrylic acid and / or maleic acid polymer having a weight average molecular weight of 1,000 to 100,000, polyvinyl alcohol; carboxymethylcellulose (CMC), hydroxypropylmethylcellulose (HPMC), hydroxyethylmethylcellulose (HEMC) ), Cellulose derivatives such as methylcellulose (MC) and cationized cellulose, and celluloses such as powdered cellulose.
Moreover, a copolymer or terpolymer of a repeating unit derived from terephthalic acid and a repeating unit derived from ethylene glycol and / or propylene glycol can be blended as a soil release agent.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer.
Such polymers can be used singly or in appropriate combination of two or more.
In the granular detergent composition, the content of the above polymers (based on the whole composition) is preferably 0.05 to 5% by mass.

(Anti-caking agent)
As the anti-caking agent, paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like can be blended.

(Defoamer)
Examples of the antifoaming agent include conventionally known silicone / silica-based ones. Moreover, you may use this antifoamer as an antifoamer granulated material obtained by the following manufacturing method.
First, 100 g of maltodextrin (trade name, manufactured by Nissho Chemical Co., Ltd .; enzyme-modified dextrin) is added with 20 g of silicone (compound type, product name: PS Antifoam, manufactured by Dow Corning) as an antifoam component. To obtain a homogeneous mixture. Next, 50% by mass of the obtained homogeneous mixture, 25% by mass of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25% by mass of neutral anhydrous sodium sulfate at 70 to 80 ° C. were mixed with an extrusion granulator ( Granulate by model EXKS-1, manufactured by Fuji Paudal Co., Ltd. to obtain a defoamer granulated product (see JP-A-3-186307).

(Metal ion scavenger)
The metal ion scavenger captures trace metal ions and the like in tap water and has an effect of suppressing adsorption of metal ions to clothing.
As metal ion scavengers, in addition to those included in the detergency builder, aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, glycol ethylenediamine hexaacetic acid or salts thereof; 1-hydroxyethane-1,1- Diphosphonic acid (HEDP-H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1 , 2-diphosphonic acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (Methylene phosphonic acid) etc. Machine phosphonic acid derivative or salts thereof; diglycolic acid, tartaric acid, oxalic acid, organic acids or their salts, such as gluconic acid and the like.
The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
In the granular detergent composition, the content of the metal ion scavenger (based on the whole composition) is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass. If it is 0.1 mass% or more, the effect which capture | acquires the metal ion in tap water will improve. On the other hand, even if it exceeds 5% by mass, it is difficult to obtain the effect of capturing the metal ions corresponding to the increased content.

(Fragrance)
The fragrance is not particularly limited, and may be one generally used in detergents, and examples thereof include a fragrance component, a solvent, a fragrance stabilizer and the like.
As such a fragrance, those described in JP-A Nos. 2002-146399 and 2003-89800 can be used.
In the granular detergent composition, the content of the fragrance (based on the whole composition) is preferably 0.001 to 2% by mass, more preferably 0.01 to 1% by mass.

(Dye)
In the present invention, various dyes such as dyes and pigments can be used to improve the appearance of the granular detergent composition. Of these, pigments are preferable from the viewpoint of storage stability, and those having oxidation resistance are particularly preferable.
Examples of such dyes include oxides, and among them, titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine blue, bitumen, cyanine blue, cyanine green and the like are preferable.

The method for producing the granular detergent composition of the present invention is not particularly limited, and can be produced by a known production method.
For example, after preparing a slurry by dispersing and dissolving a detergent raw material such as a surfactant, an inorganic builder, an organic builder, or an alkali agent in water, the slurry is spray-dried to obtain spray-dried particles. Next, the spray-dried particles and other detergent materials are subjected to kneading / extrusion, agitation granulation, rolling granulation, etc., and subjected to kneading, granulation, compression molding, etc., and if necessary A granular detergent composition can be produced by grinding or the like.

The form of the granular detergent composition of the present invention is granular and includes powders, granules and the like.
The average particle diameter of a granular detergent composition is not specifically limited, 100-1000 micrometers is preferable and 300-500 micrometers is more preferable. Generation | occurrence | production of dust is suppressed as an average particle diameter is more than a lower limit, on the other hand, the solubility to water improves that it is below an upper limit.
In the present invention, the “average particle diameter” is a value obtained by performing a classification operation using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm.
In the classification operation, the 9-stage sieve is stacked on a tray in the order of a sieve having a small mesh size and a sieve having a large mesh size, and a measurement sample of 100 g / time is put on the top sieve having a mesh size of 1680 μm. , Attached to a low-tap type sieve shaker (made by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute), vibrated for 10 minutes, and then remained on each sieve and tray The collected sample is collected for each mesh and the mass of the sample is measured.
When the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle diameter (50 mass% particle diameter) can be obtained from the following equation, where c is the total mass frequency from the sieve to a μm sieve and d is the mass frequency on the a μm sieve.

The bulk density of the granular detergent composition can be determined in consideration of the bulk density of the detergent raw material blended in the detergent composition, preferably 0.3 g / mL or more, 0.5 to 1.3 g / mL. Is more preferable, and 0.6 to 1.2 g / mL is more preferable. If it is this range, classification of detergent raw materials can be prevented.
In the present invention, the bulk density is a value measured by a method according to JIS K3362-1998.

The granular detergent composition of the present invention has a high bactericidal power and good rinsing properties, and the adhesion of colored substances to clothing is suppressed.
In the granular detergent composition, by using an inorganic peroxide, a chelating agent, and copper in combination, a metal complex exhibiting high oxidizing power in the cleaning liquid is formed, and a bleaching effect and a bactericidal effect can be obtained. Moreover, by adding soap, foaming at the time of rinsing can be suppressed, and rinsing properties can be improved.
However, in the granular detergent composition containing soap and utilizing the metal complex, there is a problem that green to blue-green coloring matters easily adhere to clothes after washing. This is thought to be because a compound of soap and copper (a green to blue-green colored product) is generated in the cleaning liquid, and the colored product adheres to the clothes after washing.
The granular detergent composition of the present invention contains the components (A) to (E) described above, and the molar ratio represented by the copper / (D) component in the component (C) is less than 1. Thus, since the copper in (C) component and (D) component are mix | blended by specific ratio, since the coupling | bonding of the copper ion derived from (C) component and (B) component (soap) is suppressed. It is considered that a colored product is hardly formed.

Moreover, the granular detergent composition of the present invention has a content ratio of the component (E) to the component (F) and a mass ratio represented by (F2) / [(E) + (F)] of 0.1 to 0. .5, the sterilizing effect is particularly excellent. This is because the potential of the copper atom changes when the component (C) is combined with the component (D) (reducing agent) to form a complex in the cleaning solution, and hydrogen peroxide generated from the component (E) And the presence of a specific amount of the (F2) component is considered to be because an oxidizing power effective for sterilization can be obtained.
In addition, it contains the component (F2), the content ratio of the component (A), the component (B), the component (E), and the component (F), [(A) + (B)] / [(E) + By setting the mass ratio represented by (F)] to 0.5 to 3, in addition to obtaining an excellent sterilizing effect, it is easy to suppress coloring matter adhesion to clothing. The reason why such an effect is obtained is not clear, but is presumed as follows. Also in the component coexisting system (F), precipitation and aggregation of the component (C) are suppressed by the components (A) and (B) which are surfactants. Thereby, the contact efficiency with a microbial cell and (C) component increases, and it is excellent in a bactericidal effect. Furthermore, by specifying the amounts of the component (A) and the component (B) which are surfactants, the copper ions derived from the component (C) and the component (B) (soap) are combined to form a colored product. Even if it is formed, the colored product is considered to be difficult to adhere to clothing by being easily drained together with the surfactant.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

<Measurement method of average particle diameter>
In this example, the average particle size was determined as described above, and the average particle size (50% by mass particle size) was determined from the above formula.

<Method for measuring bulk density>
In this example, the bulk density was measured by a method according to JIS K3362-1998.

<Method for measuring water content>
In this example, the moisture content was measured using an infrared moisture meter (manufactured by Kett Scientific Laboratory) under the conditions of a sample 5 g, a sample surface temperature of 130 ° C., and a measurement time of 20 minutes.

The composition of the granular detergent composition of each example is shown in Tables 1-3.
The raw materials used in this example are as follows.
<(A) component>.
-MES mixed concentrate: First, methyl palmitate (product name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (product name: Pastel M-180, manufactured by Lion Corporation) are 80: It mixed so that it might become 20 (mass ratio), and also by hydrogenating by a conventional method, the iodine value was reduced to 0.2 and it refine | purified and the refined fatty acid methyl ester was obtained. Using this falling fatty acid methyl ester, the reaction molar ratio (SO ₃ / saturated fatty acid ester) = 1.18 with a SO ₃ gas prepared to 7% by volume with dehumidified air using a falling-type thin film reactor, reaction temperature 80 Sulfonation was performed under the condition of ° C to obtain a sulfonated product. The resulting sulfonated product was then introduced into a loop ripening tube with a double tube jacket having an average residence time of 20 minutes. Three loop-type ripening tubes were continuously connected, and the average residence time was 60 minutes. In order to maintain sufficient stirring and a constant temperature, the sulfonation product is flowed through the loop aging tube at a linear speed of 0.16 m / s, and the aging reaction is performed at 78 to 82 ° C. to complete the sulfonation. , Α-sulfo fatty acid methyl ester was obtained. Then, after introducing 20 parts by mass of methanol (manufactured by Sumitomo Chemical Co., Ltd., industrial grade, moisture 500 ppm or less) to 100 parts by mass of the α-sulfo fatty acid methyl ester obtained, this mixture and 35% by mass hydrogen peroxide (Mitsubishi Gas Chemical Co., Ltd. 35% industrial hydrogen peroxide, industrial grade) 5.7 parts by mass were introduced into a continuous loop reactor equipped with a mixing mixer and a heat exchanger, and bleached. A sulfo fatty acid methyl ester bleached product was obtained. Next, with respect to 125 parts by mass of the obtained α-sulfo fatty acid methyl ester bleached product, 28 parts by mass of 48% by mass NaOH aqueous solution (caustic soda manufactured by Daiso Corporation, industrial grade), nonionic surfactant (POE alkyl ether) ) 25 parts by mass, 69 parts by mass of water, 24 parts by mass of methanol (Methanol manufactured by Sumitomo Chemical Co., Ltd., industrial grade), and 5 parts by mass of linear alkylbenzene sulfonic acid (LAS-H) were continuously added to the neutralization line. Supplied. The neutralization method employs the neutralization method described in JP-A-2001-64248, and a 48% by mass aqueous solution of sodium hydroxide is quantitatively fed between the premixer and the neutralization mixer. I was able to neutralize. And after neutralizing the neutralized product of the α-sulfo fatty acid methyl ester bleached product previously neutralized and the α-sulfo fatty acid methyl ester bleached product with a premixer, an aqueous sodium hydroxide solution and A neutralized product was obtained by mixing. Further, using the neutralized product as a raw material surfactant aqueous solution, recycling flash evaporation described in JP-A-2004-210807 is performed, lower alcohol is removed and concentrated, and MES having a water content of 10.8% by mass is obtained. A concentrated mixture (62% by mass of MES, 3.5% by mass of LAS-Na, 16.8% by mass of nonionic surfactant (1)) was obtained.

LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (LAS-H, manufactured by Lion Corporation, Lipon LH-200, AV value (potassium hydroxide required to neutralize 1 g of LAS-H) Mg number) = 180.0) neutralized with a 48% by mass aqueous sodium hydroxide solution.
AOS-Na: a mixture of alkene sulfonic acid Na having 14 to 18 carbon atoms and hydroxyalkane sulfonic acid Na, Liporan LB-840 manufactured by Lion Corporation (pure content 38% by mass).
-SAS-Na: Hostapur SAS93 having an alkyl group having 14 to 17 carbon atoms, manufactured by Clariant.

-Nonionic surfactant (1): An average of 15 moles of ethylene oxide adduct of ECOROL26 (ECOGRENE, alcohol having an alkyl group having 12 to 16 carbon atoms).
Nonionic surfactant (2): Ethanol oxide average 7 mol adduct of ECOROL26 (produced by ECOGREEN, alcohol having 12 to 16 carbon atoms) (pure content 90% by mass, water 10% by mass).

<(B) component>
Higher fatty acid salt: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content 67% by mass, titer 40 to 45 ° C .; fatty acid composition: C12 (lauric acid) 1% by mass, C14 (myristic acid) 10 Mass%, C16 (palmitic acid) 24 mass%, C18F0 (stearic acid) 10 mass%, C18F1 (oleic acid) 54 mass%, C18F2 (linoleic acid) 1 mass%).

<(C) component>
Copper sulfate pentahydrate: reagent grade, manufactured by Junsei Co., Ltd., molecular weight 250 (atomic weight of copper 64).

<Comparison component (C ′) of component (C)>
Manganese sulfate heptahydrate: reagent grade, manufactured by Junsei Chemical Co., Ltd., molecular weight 277 (atomic weight of manganese 55).

<(D) component>
Ascorbic acid: Special grade, manufactured by Kanto Chemical Co., Inc., molecular weight 176
-Sodium ascorbate: Special grade, manufactured by Kanto Chemical Co., Inc., molecular weight 198.
Ascorbyl 6-stearate: manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 442.

<(E) component>
-Sodium percarbonate: Trade name SPCC, manufactured by Zhejiang JINKE CHEMICALS. Effective oxygen amount 13.8%, average particle size (50% by mass particle size) 870 μm.

<(F1) component>
Sodium carbonate: granular ash (manufactured by Asahi Glass Co., Ltd., average particle size (50% by mass particle size) 320 μm, bulk density 1.07 g / mL).
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd. average particle size (50% by mass particle size) 490 μm, bulk density 1.30 g / mL).

<(F2) component>
・ Sodium bicarbonate: Sodium bicarbonate, reagent grade, manufactured by Pure Science.

<Other ingredients>
Zeolite: A-type zeolite SP # 2300 (average particle size (50% by mass particle size) 1.25 μm, manufactured by Nitto Flour Chemical Co., Ltd.)
MA agent: acrylic acid / maleic anhydride copolymer sodium salt (trade name: Aqualic TL-400, manufactured by Nippon Shokubai Co., Ltd .; pure 40% by weight aqueous solution).
PAA agent: sodium polyacrylate (trade name: Aqualic DL, manufactured by Nippon Shokubai Co., Ltd .; pure 40% by mass aqueous solution).
・ Sodium chloride: Special grade reagent, manufactured by Pure Science.
-Na-type bentonite granulated product: Brand name Landrosyl DGA Powder, manufactured by Zudchemi.
-Brightening agent: Chinopearl CBS-X (Ciba Specialty Chemicals Co., Ltd.) / Chinopearl AMS-GX (Ciba Specialty Chemicals Co., Ltd.) = 3/1 (mass ratio) mixture.
Carboxymethyl cellulose: CMC Daicel 1170 (trade name, manufactured by Daicel Chemical Industries, Ltd., average particle size (50% by mass particle size) 60 μm).
Enzyme: Protease (Sabinase 12T) / Lipase (LIPEX100T) / Amylase (Stainzyme 12GTS) / Cellulase (Cellzyme 0.7T) (Novozymes Japan Ltd.) = 4/1/4/1 (mass ratio) Mixture of.
-Fragrance | flavor: The fragrance | flavor composition A described in [Table 11]-[Table 18] of Unexamined-Japanese-Patent No. 2002-146399.
-Dye: Ultramarine, 20% by mass aqueous dispersion manufactured by Dainichi Seika Kogyo Co., Ltd.
Water / sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.).

<Production example of granular detergent composition>
Each granular detergent composition was produced by the following production method according to the composition components and contents (% by mass) of the compositions shown in Tables 1 to 3 (when there are blank composition components in the table, the composition components). Is not blended).
In the table, the content of the compounding component indicates a pure equivalent amount.
“Molar ratio: copper in component (C) / component (D)” represents the ratio (molar ratio) of the number of moles of copper in component (C) to the number of moles of component (D). In addition, the molar ratio of Comparative Example 9 represents the ratio (molar ratio) of the number of moles of manganese in the component (C ′) to the number of moles of the component (D).
“Mass ratio: (F2) / [(E) + (F)]” is the ratio (mass ratio) of the content of component (F2) to the total content of component (E) and component (F). Represents.
“Mass ratio: [(A) + (B)] / [(E) + (F)]” means that the (A) component and the (B) with respect to the total content of the (E) component and the (F) component ) Represents the ratio (mass ratio) of the total content with the component.

(Examples 1-25, Comparative Examples 1-8)
Step (i)
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. (A) component (however, except MES and nonionic surfactant (1), (2)) and (B) component were added here, and it stirred for 10 minutes. Subsequently, the MA agent was added. After further stirring for 10 minutes, a part of the powdered zeolite (from the content shown in the table, 1.0% for addition during kneading, 5.0% for grinding aid, 1.5% surface coating) (Minus each amount for use), sodium carbonate (F1), potassium carbonate (F1), sodium bicarbonate (F2), and sodium sulfate were added. 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 at a hot air temperature of 280 ° C. using a counter-current spray drying tower to obtain an average particle size (50% by mass particle size). ) Obtained spray-dried particles of 320 μm, a bulk density of 0.30 g / mL, and a moisture content of 5% by mass.

Step (ii)
Spray dried particles obtained in step (i), MES mixed concentrate, 1.0% powdery zeolite for kneading addition, nonionic surfactant for spray addition (1) or (2) 0. The remaining nonionic surfactant (1) or (2) excluding 5%, fluorescent whitening agent, and water were put into a continuous kneader (Kurimoto Steel Works, KRC-S4 type) The mixture was kneaded under conditions of a sum capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a mixture containing 6% by mass of water containing a surfactant.

Step (iii)
Cutting the mixture obtained in step (ii) with a cutter while using a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm (cutter peripheral speed is 5 m) / S) to obtain pellets having a length of about 5 to 30 mm.
Next, 5.0% powdery zeolite (average particle size (50% by mass particle size) 180 μm) for grinding aid was added to the obtained pellets, and coexisting with cold air (10 ° C., 15 m / s). (Screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, number of revolutions: Fitzmill arranged in three stages in series (manufactured by Hosokawa Micron Corporation, DKA-3) 1st stage / 2nd stage / 3rd stage are all 4700 rpm).

Step (iv)
The pulverized product obtained in step (iii), the component (C), the component (D), the component (E), and carboxymethylcellulose are mixed into a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length). 490 mm, having a baffle plate with a clearance of 20 mm and a height of 45 mm with respect to the inner wall surface of the drum of the container 131.7L, and a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. Add 5% powdery zeolite, and spray 0.5% nonionic surfactant (1) or (2), perfume, and dye (20% by weight aqueous dispersion) for 1 minute. And surface modification to obtain particles.
Obtained above in a horizontal cylindrical rolling mixer (with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a drum internal wall surface of the container 131.7 L and two baffle plates with a clearance of 20 mm from the internal wall surface and a height of 45 mm) The obtained particles and enzyme were added and mixed for 5 minutes under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. to obtain a granular detergent composition.

(Example 26)
In step (ii), the MES mixed concentrate is not blended, in step (i), the PAA agent is added at the same blending position as the MA agent, sodium chloride is added in step (iii), and Na-type bentonite is formed in step (iv). A granular detergent composition was obtained in the same manner as in Examples 1 to 25 except that the granules were added.

(Example 27)
A granular detergent composition was obtained in the same manner as in Example 8 except that sodium bicarbonate (F2) was added in step (iv) instead of step (i).

(Comparative Example 9)
A granular detergent composition was obtained in the same manner as in Example 2 except that the comparative component (C ′) was used in place of the component (C) and the comparative component (C ′) was added in step (iv).

<Evaluation of granular detergent composition>
About the granular detergent composition of each example, evaluation of "bactericidal effect", "rinsing property", and "inhibition of colored substance adhesion to clothing" was performed by the following evaluation methods. The results are also shown in Tables 1-3.

[Evaluation of bactericidal effect]
Staphylococcus aureus NBRC12732 was inoculated into a plate medium of a nutrient agar medium (Difco) and cultured at 37 ° C. for 24 hours, the growing bacteria were collected at a platinum loop, suspended in sterile water, A suspension (bacterial solution) having a turbidity of about 2 at 550 nm was prepared.
To 10 mL of a solution prepared by dissolving 1 g of a sample (granular detergent composition in each example) in 1.5 L of 3 ° DH water, 0.1 mL of the bacterial solution was added and reacted at 25 ° C. for 10 minutes. 1 mL of the liquid was added to 9 mL of SCDLP medium (Daigo) to complete the reaction. Then, it diluted one by one 5 times with SCDLP culture medium sequentially. Add 1 mL of the diluted solution to a 90 mm petri dish, add a neutral agar medium kept at 45 ° C., mix, count the number of colonies grown at 37 ° C., and count the number of viable bacteria in the reaction solution. (N) was determined. As a control, the number of viable bacteria (M) reacted at 3 ° DH with no sample added was determined. And the following formula
Bactericidal effect (ΔLOG) = log ₁₀ M-log ₁₀ N
Thus, the difference in the number of viable bacteria was calculated, and the bactericidal effect was evaluated.
The larger the value of the bactericidal effect (ΔLOG), the higher the bactericidal effect.

[Rinse evaluation]
20 g of the granular detergent composition of each example was weighed and put into a two-tank washing machine (CW-C30A1-H manufactured by Mitsubishi Electric Corporation) containing 30 L of tap water at 25 ° C. and stirred for 1 minute. A skin shirt to which 1% by weight of artificial soil owf was attached was added so that the bath ratio was about 30, and washed for 10 minutes and dehydrated for 1 minute. Thereafter, 30 L of tap water at 25 ° C. was added, stirred for 3 minutes, and dehydrated for 1 minute. Furthermore, 30 L of tap water of 25 ° C. was added and stirred for 3 minutes, the foaming state after 1 minute was observed, and rinsing properties were evaluated according to the following evaluation criteria.
Evaluation criteria A: The height of the foam was less than 3 mm, and no white portion due to fine foam was observed.
○: The bubble height was less than 5 mm, and no white portion due to fine bubbles was observed.
(Triangle | delta): The bubble height is less than 5 mm and the white-like part by a fine bubble was recognized.
X: A place having a bubble height of 5 mm or more was observed.
Artificial dirt having the following composition was used. Myristic acid 0.5% by mass, palmitic acid 1.5% by mass, oleic acid 1.3% by mass, triolein 1.7% by mass, cholesterol stearate 0.8% by mass, squalene 0.8% by mass, solid paraffin 0.8 mass%, 0.9 mass% cholesterol, benzene residue.
“Artificial dirt 1 mass% owf” means that the concentration of artificial dirt is 1 mass% with respect to the total amount of skin shirt.
The “bath ratio” represents the mass ratio of tap water to the skin shirt to which 1% by mass of artificial dirt is attached.

[Evaluation of color sticking suppression to clothing]
Take 3 g of granular detergent composition of each example in a 1 L beaker, add 500 mL of tap water adjusted to 25 ° C. (3 ° DH), magnetic stirrer (manufactured by Mitamura Riken Kogyo Co., Ltd., CONSTANT TORQUE MAGMIX STIRERR, rotor dimensions: The mixture was stirred for 1 minute at a length of 15 mm, a diameter of 5 mm, and a rotation speed of 200 rpm.
One 10 cm ² kana cloth was put into this solution and allowed to stand at 25 ° C. for 10 minutes. Thereafter, the kana cloth was taken out, and the taken kana cloth was put into a 1 L beaker containing 500 mL of distilled water, followed by stirring for 1 minute. Thereafter, the kana cloth was taken out and dried naturally. And the kana kin cloth after natural drying and the kana kin cloth (control) treated only with tap water were compared visually with respect to the color tone, and the color material adhesion suppression to clothing was evaluated according to the following evaluation criteria. .
Evaluation Criteria A: Green to blue-green coloring was not observed as compared with the control.
○: Green to blue-green coloration was hardly recognized as compared with the control.
Δ: Slight green to blue-green coloring was observed compared to the control.
X: Compared with the control, green to blue-green coloring was clearly recognized.

  From the results of Tables 1 to 3, it can be seen that the granular detergent compositions of Examples 1 to 27 have high bactericidal power and good rinsing properties, and adhesion of colored substances to clothing is suppressed.

Claims (4)

(A) 10 to 45% by mass of one or more selected from non-soap anionic surfactants and non-ionic surfactants;
(B) soap and
(C) 0.04 to 0.8 mass% of the copper compound in terms of copper,
(D) one or more selected from ascorbic acid, ascorbate and derivatives of ascorbic acid;
(E) containing an inorganic peroxide,
(C) The granular detergent composition whose molar ratio represented by the copper / (D) component in a component is less than one.   The granular detergent composition according to claim 1, further comprising one or more (F) alkali agents selected from (F1) alkali metal carbonates and (F2) alkali metal hydrogen carbonates.   The granular detergent composition of Claim 2 which contains the said (F2) component and whose mass ratio represented by (F2) / [(E) + (F)] is 0.1-0.5.   The said (F2) component is contained, The mass ratio represented by [(A) + (B)] / [(E) + (F)] is 0.5-3, The claim 2 or Claim 3 The granular detergent composition as described.