JP5225545B2 - Granular detergent composition - Google Patents

Description

  The present invention relates to a granular detergent composition.

Mud stains attached to clothing are difficult to remove with normal laundry, as we feel everyday. For this reason, for example, a liquid detergent composition or a soap bar is applied in advance to a mud-stained part of clothing, and the mud-stain is removed by hand-washing with a hand.
However, washing hands is very time-consuming and many people are dissatisfied.

In general, a liquid heavy detergent is used as a liquid detergent composition for such mud soil, and the liquid heavy detergent is usually directly put into water stored in a washing tub and is used for washing. Provided.
In some cases, the liquid heavy detergent or the application detergent is applied to the mud-stained portion of the garment in advance and then subjected to normal washing.
In these liquid detergent compositions such as liquid heavy detergents and application detergents, energetic research has been conducted conventionally.

For example, a laundry detergent composition comprising a cationic surfactant (see Patent Document 1) and the like are provided.
In addition, as an additive other than a surfactant, a detergent composition using an enzyme (cellulase) (see Patent Documents 2 and 3) and the like are provided.
In addition, a detergent composition containing an enzyme having a high adsorption rate to mud (see Patent Document 4) has been proposed.

Furthermore, as a pretreatment agent composition for mud soil, an acidic composition containing a phosphonic acid group-containing compound (see Patent Document 5), an acidic composition containing oxalic acid (see Patent Document 6), and the like have been proposed.
JP 54-39411 A JP-A-60-212896 JP-A-60-212497 JP 2004-210812 A JP-A-3-26797 JP 2003-105390 A

However, the detergent compositions described in Patent Documents 1 to 4 are still not sufficient for removing mud stains.
Moreover, in the pretreatment agent composition of patent documents 5-6, it is necessary to apply a pretreatment agent composition to the mud stain site | part of clothing beforehand, and it is inferior to simplicity. In addition, there is a method of removing mud stains using a commercially available reducing bleach, but it cannot be used for colored clothing, and this method requires time and labor for separating laundry.
In view of the above circumstances, an object of the present invention is to provide a granular cleaning composition having a high effect of removing mud stains even in normal washing.

As a result of intensive studies to solve the above problems, the present inventors have obtained a surfactant, a compound having a structure having both a hydroxy group and a carboxylic acid or sulfonic acid group as a substituent of the benzene ring, an enzyme, The present inventors have found that the above-mentioned problems can be achieved by combining the above, and have completed the present invention.
That is, this invention is a granular detergent composition characterized by containing the following (A) component, (B) component, and (C) component, and having a bulk density of 0.5 g / mL or more.
(A) Surfactant: 10 to 30% by mass,
(B) Compound represented by the following formula (I): 0.1 to 10% by mass,
(C) One or more enzymes selected from protease, lipase, amylase and cellulase.

（式中、ＸはＣＯＯＭまたはＳＯ_３Ｍであり、Ｍは塩形成カチオンを示す。）

(In the formula, X represents COOM or SO ₃ M, and M represents a salt-forming cation.)

Moreover, in this invention, it is preferable to contain the following (D) component and / or (E) component further.
(D) an inorganic peroxide that releases hydrogen peroxide in water;
(E) Organic peracid precursor represented by the following formula (II): 0.1 to 10% by mass.

（式中、Ｒは炭素数７〜１１のアルキル基またはアルケニル基であり、ＸはＣＯＯＭまたはＳＯ_３Ｍであり、Ｍは塩形成カチオンを示す。）

(In the formula, R is an alkyl or alkenyl group having 7 to 11 carbon atoms, X is COOM or SO ₃ M, and M represents a salt-forming cation.)

Moreover, in this invention, it is preferable that mass ratio (B) / (E) of the (B) component with respect to the said (E) component is 95 / 5-15 / 85.
In the present invention, the nonionic surfactant contained in the component (A) is preferably a nonionic surfactant having an HLB value of 9.0 to 16.5.
In the present invention, it is preferable to further contain (F) a compound having a carboxy group having a molecular weight of 1000 or less and / or a salt thereof.

  ADVANTAGE OF THE INVENTION According to this invention, the granular detergent composition with a high mud dirt removal effect can be provided also in normal washing.

The granular detergent composition of the present invention contains the following components (A), (B) and (C), and has a bulk density of 0.5 g / mL or more.
(A) Surfactant: 10 to 30% by mass,
(B) Compound represented by the formula (I): 0.1 to 10% by mass,
(C) One or more enzymes selected from protease, lipase, amylase and cellulase.
Preferably, it further contains the following component (D) and / or component (E).
(D) an inorganic peroxide that releases hydrogen peroxide in water;
(E) Organic peracid precursor represented by the formula (II): 0.1 to 10% by mass.
In addition, it preferably further contains (F) a compound having a carboxy group having a molecular weight of 1000 or less and / or a salt thereof.
Hereinafter, each component will be described in detail.

(A) component As surfactant used as (A) component of this invention, anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant, semipolar surfactant, etc. are mentioned.
The anionic surfactant is not particularly limited as long as it is conventionally used in detergents, and various anionic surfactants can be used. For example, the following can be mentioned.
(1) Alkylbenzenesulfonate (LAS) having a linear or branched alkyl group having 8 to 18 carbon atoms.
(2) Alkyl sulfate (AS) or alkenyl sulfate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkane sulfonate having 10 to 20 carbon atoms.
(5) Alkyl having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average addition mole number of 10 moles or less, ethylene oxide, propylene oxide, butylene oxide, or a mixture thereof Ether sulfate (AES) or alkenyl ether sulfate.
(6) Alkyl having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average addition mole number of 10 moles or less, ethylene oxide, propylene oxide, butylene oxide or a mixture thereof Ether carboxylate or alkenyl ether carboxylate.
(7) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(8) A higher fatty acid salt having 10 to 20 carbon atoms.
(9) C8-20 saturated or unsaturated α-sulfo fatty acid (α-SF) salts or methyl, ethyl or propyl esters thereof.

Among the above anionic surfactants, alkali metal salts of linear alkylbenzene sulfonic acid (LAS) (for example, sodium or potassium salt), AOS, α-SF, alkali metal salts of AES (for example, sodium or potassium salt, etc.) ), Alkali metal salts of higher fatty acids (for example, sodium or potassium salts).
These anionic surfactants can be used singly or in appropriate combination of two or more.

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 and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) Fatty acid alkyl ester alkoxylates represented by, for example, the following general formula (III), in which alkylene oxide is added between the ester bonds of the long-chain fatty acid alkyl ester.

（式中、Ｒ^１ＣＯは、炭素数６〜２２、好ましくは８〜１８の脂肪酸残基を示し；ＯＡは、エチレンオキサイド、プロピレンオキサイド等の炭素数２〜４、好ましくは２〜３のアルキレンオキサイドの付加単位を示し；ｎはアルキレンオキサイドの平均付加モル数を示し、一般に３〜３０、好ましくは５〜２０の整数である。Ｒ^２は炭素数１〜３の置換基を有してもよい低級（炭素数１〜４）アルキル基を示す。）

(In the formula, R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms; OA is an alkylene having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide). N represents an average addition mole number of alkylene oxide, and is generally an integer of 3 to 30, preferably 5 to 20. R ² may have a substituent having 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, nonionic surfactants having an HLB value of 9.0 to 16.5 are preferable because the cleaning effect for removing mud dirt is improved. Among these, a nonionic surfactant having a melting point of 50 ° C. or lower and an HLB value of 10.0 to 16.3 is more preferable.
Specifically, polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to fatty acid methyl ester, fatty acid methyl ester and ethylene oxide A fatty acid methyl ester ethoxypropoxylate to which propylene oxide is added is preferably used.
These nonionic surfactants can be used singly or in appropriate combination of two or more.

In the present invention, the “HLB value of the nonionic surfactant” is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd.) 1991, page 234).
In the present invention, the “melting point” is a value measured by the melting point measurement method described in JIS K0064-1992 “Method for measuring the melting point and melting range of chemical products”.

In this invention, (A) component can be used individually by 1 type or in combination of 2 or more types as appropriate.
(A) As for the compounding quantity of surfactant which is a component, a lower limit is normally 10 mass% or more with respect to the whole composition, Preferably it is 12 mass% or more, More preferably, it is 15 mass% or more, Most preferably, it is 18 mass. The upper limit is preferably 30% by mass or less, preferably 28% by mass or less, more preferably 27% by mass or less, and particularly preferably 25% by mass or less. The effect of this invention is acquired because this compounding quantity is more than a lower limit. On the other hand, in the present invention, the upper limit is 30% by mass or less, preferably 28% by mass or less, and particularly preferably 25% by mass or less. It is done.

  Of the component (A), the amount of the anionic surfactant is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, based on the whole composition. It is particularly preferably 8% by mass or more, and the upper limit is preferably 30% by mass or less, preferably 28% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

  Of the above component (A), the amount of the nonionic surfactant is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more with respect to the entire composition. The upper limit is preferably 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less.

  The content ratio of the anionic surfactant to the nonionic surfactant is such that the anionic surfactant / nonionic surfactant has a mass ratio of 0.1 to 10 (0.1 ≦ (anionic surfactant / nonionic). Surfactant) ≦ 10) is preferable, preferably 0.3 or more and 5 or less, more preferably 0.5 or more and 3 or less. If the ratio of the anionic surfactant to the nonionic surfactant is too small or too large, the effect of further improving the mud dirt cleaning performance intended by the present invention may not be obtained.

(B) component As a compound used as (B) component of this invention, it is a compound represented by said Formula (I).
In the formula (I), X is COOM or SO ₃ M, that is, the component (B) is a compound represented by the following general formula (IV) or (V).

In the above formula, M is a salt-forming cation, preferably a hydrogen atom; an alkali metal atom such as sodium or potassium; a salt-forming cation that gives water solubility such as amines such as ammonium or alkanolamine, among which a hydrogen atom or an alkali metal Atoms are particularly preferred.
In the above formula, the SO ₃ M group and the COOM group can each be in the ortho, meta, or para position, with the para position being preferred.

In this invention, (B) component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The blending amount of the component (B) is usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, particularly preferably 2 with respect to the whole composition. The upper limit value is 10% by mass or less, preferably 8% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less. The effect of this invention is acquired because this compounding quantity is 0.1 mass% or more. On the other hand, even if the upper limit value is 10% by mass or less, a sufficient mud dirt removing effect can be obtained, which is economically advantageous.

(C) component The enzyme used as (C) component of this invention is 1 type, or 2 or more types chosen from protease, lipase, amylase, and a cellulase.

The protease that can be used in the present invention is not particularly limited as long as it is usually used in detergents. Specific examples of protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin BPN ', papain, promeline, carboxypeptidase A and B, aminopeptidase, aspergillopeptidase A and B, etc. .
Examples of the protease used in the present invention include JP-A-51-8401, JP-A-46-43551, JP-A-46-42956, JP-A-59-59189, and JP-A-54. -62386, JP-A-48-2794, JP-A-50-16435, JP-A-53-18594, JP-A-55-46711, JP-A-57-42310, JP-A-58-16200, JP-A-56-24512, JP-A-47-1832, JP-A-52-35758, JP-A-50-34633, JP-B-46-41596 JP, 58-134990, 55-14086, 51-81783, 51-125407, 55-39794 JP-A 46-1840, JP-A 46-23989, JP-A 58-15282, JP-A 61-280278, JP-A 4-197182, JP 3-79987. Those described in Japanese Patent Laid-Open No. 5-25492 and the like can also be used.
Of course, these purified fractions can of course also use crude enzymes and granulated products thereof. Available commercially available enzymes include savinase, alcalase, evalase, cannase, esperase (manufactured by Novozymes), API21 (showa Denko), maxatase ( Maxaze), Maxacal, Purafect, Maxapem (Genencore), KAP (Kao), Protease K-14 and K-16 described in JP-A-5-25492 (above) , All trade names). Among these, it can also be used combining 1 type or 2 or more types.
As the protease in the present invention, sabinase and everase (above, trade name: manufactured by Novozymes) are preferable, and sabinase is particularly preferable.

The lipase in the present invention is defined by Enzyme Classification No. E.E. according to the recommendation (1992) of International Union of Biochemistry and Molecular Biology (IUBMB). C. Shows enzymes classified under 3.1.1 (carboxylic ester hydrolase).
In other words, lipase is a type of ester bond present in at least one of lipids such as mono-, di- and triglycerides, phospholipids (all types), thioesters, cholesterol esters, wax-esters, cutins, suberins, synthetic esters. It is an enzyme which shows a hydrolysis activity with respect to at least 1 of these. In other words, lipases include those conventionally referred to as lipases, phospholipases, esterases or cutinases, etc., and naturally occurring enzymes and one or more amino acid residues are denatured compared to naturally occurring enzymes. Including the mutants.
Specific examples of the lipase include commercially available lipases such as lipolase, lipolase ultra, lipex (trade name; manufactured by Novozymes) and liposome (trade name, manufactured by Showa Denko KK).
As the lipase in the present invention, lipolase ultra and lipex (above, trade name: manufactured by Novozymes) are preferable, and lipex is particularly preferable.

Examples of amylases that can be used in the present invention include α-amylase, β-amylase, α-glucosidase, and glucoamylase that hydrolyze α-1,4 bonds such as starch and glycogen, and α-1,6 such as starch and glycogen. Examples include glucoamylase, pullulanase, isoamylase, amylo-1,6 glucosidase / 4-alpha glucanotransferase, oligo-1,6-glucosidase, etc. that hydrolyze the bond.
Such an amylase is not particularly limited as long as it is an enzyme that hydrolyzes starch, and can be used alone or in combination of two or more.
Examples of amylases that can be used in the present invention are given below. However, the following examples do not limit the present invention. Examples of commercially available enzymes include the following. Termamyl, Duramil, Stainzyme, Promozyme 200L (trade name; manufactured by Novozymes), Maxamyl (tradename, manufactured by Genencor), Amano Pharmaceutical Pullanose derived from Amano, DB-250, Aerobacter aerogenes ATCC 9621 (trade name; crude or crystallized product released from Seikagaku Corporation).
As the amylase in the present invention, duramil and stainzyme (trade name; manufactured by Novozymes) are preferable, and stainzyme is particularly preferable.

  Specific examples of cellulases that can be used in the present invention include cellzyme, carezyme (trade name; manufactured by Novozymes), KAC500 (trade name, manufactured by Kao Corporation), and claim 4 of JP-A 63-264699. The cellulase described can be mentioned.

In the present invention, the above-mentioned enzymes can be used alone or in combination of two or more.
The enzyme is a granulated product of a stabilizer, filler, extender, whitening agent, binder, coating agent, etc., based on a normal granulation method, in a dry blended state with detergent dough (particles). It is suitable for use in. Moreover, when granulating two or more kinds of enzymes, they may be granulated separately, or the enzymes may be mixed to form the same granulated product. Usually, the amount of the enzyme in the enzyme granulated product is about 0.1 to 10% by mass, preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass as the amount of enzyme protein. .

As methods for granulating enzyme-containing particles, JP-A No. 53-6484, JP-A No. 60-262900, JP-A No. 62-257990, JP-A No. 1-112983, JP-A No. 3-129, No. 503775, JP-A-4-503369, JP-A-2000-178593, and the like.
The average particle size of the enzyme-containing particles is preferably 200 to 1,000 μm, more preferably 300 to 700 μm, from the viewpoints of solubility and storage stability.

Component (C), the amount of the enzyme as component, is usually 0.001% by mass or more, more preferably 0.002% by mass or more, and particularly preferably the lower limit of the amount of enzyme protein relative to the whole composition. The upper limit is preferably 0.05% by mass or less, more preferably 0.03% by mass or less, and particularly preferably 0.02% by mass or less. preferable. The effect of this invention improves because this compounding quantity is 0.001 mass% or more. On the other hand, even if the upper limit value is 0.05% by mass or less, a mud dirt removing effect can be sufficiently obtained, which is economically advantageous.
In addition, the amount of enzyme protein in the granular detergent composition can be determined by obtaining a crude enzyme by separation means such as salting-out method, precipitation method, ultrafiltration method, etc. Alternatively, the band formed by sodium dodecyl sulfate (SDS) -polyacrylamide gel electrophoresis is stained by a known staining method, and the degree of staining is compared with a known enzyme purified product.

The granular detergent composition of the present invention preferably further contains a bleaching system (a component having a bleaching effect) in terms of the mud dirt cleaning effect.
In the present invention, as a component constituting such a bleaching system (component having a bleaching effect), (D) an inorganic peroxide that releases hydrogen peroxide in water and / or a percarboxylic acid by reaction with the inorganic peroxide. It is preferable that (E) which produces | generates an acid contains the organic peracid precursor (bleaching activator) represented by said Formula (II).

(D) Component The compound used as the (D) component of the present invention is an inorganic peroxide that releases hydrogen peroxide in water.
The component (D) is not particularly limited, and among them, a percarbonate or a perborate is preferable.
Moreover, when using for the granular cleaning composition containing a zeolite, it is preferable to use the sodium percarbonate coat | covered with the inorganic or organic compound for stabilization. Examples of the coating agent include boric acid or borate, amorphous silicate, magnesium salt, or water-insoluble organic compounds such as paraffin and wax. The coated sodium percarbonate can be produced by a known method. For example, in addition to JP-A-59-196399 and USP4526698 (both sodium percarbonate is coated with borate), Examples thereof include the methods described in JP-A-4-31498, JP-A-6-40709, and JP-A-7-11803.
The average particle diameter of the inorganic peroxide has a lower limit of 200 μm or more, preferably 250 μm or more, more preferably 300 μm or more, and an upper limit of 1000 μm or less, preferably 900 μm or less, more preferably 800 μm or less. .
In order to satisfy both the solubility and the stability, it is preferable that the particles having an average particle diameter of 125 μm or less and the particles of 1200 μm or more are 10% by mass or less of the entire inorganic peroxide particles.

In this invention, (D) component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The blending amount of the component (D) is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more with respect to the entire composition. The upper limit is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less. The effect of this invention improves because this compounding quantity is 0.5 mass% or more. On the other hand, even if the upper limit value is 10% by mass or less, a sufficient mud dirt removing effect can be obtained, which is economically advantageous.

(E) Component The compound used as the (E) component of the present invention is an organic peracid precursor represented by the formula (II).
In the formula (II), X is COOM or SO ₃ M. That is, the component (E) is a compound represented by the following general formula (VI) or (VII).

（式中、Ｒ^３、Ｒ^４はそれぞれ独立して炭素数７〜１１のアルキル基またはアルケニル基であり、Ｍは塩形成カチオンを示す。）

(In the formula, R ³ and R ⁴ are each independently an alkyl group or alkenyl group having 7 to 11 carbon atoms, and M represents a salt-forming cation.)

In the above formula, as the alkyl group and the alkenyl group, either a straight chain or a branched chain can be used, but a straight chain is preferable.
R ³ is preferably an alkyl group having 9 to 11 carbon atoms. R ⁴ is preferably an alkyl group having 9 to 11 carbon atoms.
M is a salt-forming cation and is the same as M in the formula (1), and among them, a hydrogen atom or an alkali metal atom is preferable.
In the above formula, the SO ₃ M group and the COOM group can each be in the ortho, meta, or para position, with the para position being preferred.

In this invention, (E) component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The amount of component (E) is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and particularly preferably 0% with respect to the entire composition. The upper limit is preferably 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 3% by mass or less. The effect of this invention improves because this compounding quantity is 0.1 mass% or more. On the other hand, even if the upper limit value is 10% by mass or less, a sufficient mud dirt removing effect can be obtained, which is economically advantageous.

In the present invention, the organic peracid precursor (bleach activator) as the component (E) is preferably blended as a granulated product from the viewpoint of storage stability.
The bleach activator is prepared by heating and melting a solid binder material such as polyethylene glycol having an average molecular weight of 1000 to 20000, preferably 4000 to 8000 at room temperature. A surfactant powder such as a salt or alkyl sulfate ester salt is dispersed and then extruded to produce a bleached activator granulated product having a diameter of about 0.6 to 1 mm, and then a length of 0.5 to 3 mm. It is preferable to blend by lightly grinding to the extent. As the surfactant powder, an α-olefin sulfonate having an alkyl chain length of 14 is preferred.
The blending amount of the bleach activator in the granulated product is preferably 30 to 90% by mass, more preferably 50 to 80% by mass. When the blending amount is within this range, the effect of granulation can be obtained more.
The compounding quantity of the said binder substance is 0.5-30 mass% in a granulated material, Preferably it is 1-25 mass%, More preferably, it is 5-20 mass%.
The blending amount of the surfactant powder is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 30% by mass in the granulated product.
The average particle size of the bleach activator particles is preferably 200 to 1,500 μm, more preferably 300 to 1,000 μm, from the viewpoint of solubility and storage stability.
The blending amount of the bleach activator granulated product is 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, and further preferably 0.3 to 5% by mass with respect to the total amount of the composition.
In addition, the average molecular weight of the polyethylene glycol in this invention shows the average molecular weight of cosmetic raw material reference | standard (2nd edition comment) description.

In the present invention, the mass ratio (B) / (E) of the component (B) to the component (E) is preferably 95/5 to 15/85.
The lower limit of (B) / (E) is preferably 15/85 or more, more preferably 20/80 or more, and particularly preferably 30/70 or more. On the other hand, the upper limit is preferably 95/5 or less, more preferably 90/10 or less, and particularly preferably 85/15 or less. The effect of this invention improves more by being more than a lower limit. On the other hand, since it is less than an upper limit and the cleaning effect with respect to mud dirt removal is acquired effectively, it is economically advantageous.

(F) Component In the present invention, it is preferable to further contain (F) a compound having a carboxy group having a molecular weight of 1000 or less and / or a salt thereof (hereinafter sometimes referred to as (F) component). By including the component (F), the effect of the present invention is further improved.
The molecular weight of the component (F) is 1000 or less, and from the viewpoint of cleaning performance, the upper limit value of the molecular weight is preferably 800 or less, more preferably 600 or less, particularly preferably 400 or less, while the lower limit value is preferably 200. Above, more preferably 240 or more, particularly preferably 270 or more.
In addition, when (F) component is a polymer, this molecular weight represents a weight average molecular weight. In the present invention, “weight average molecular weight” is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance.

  The component (F) may be a monomer or a polymer. For example, nitrilotriacetate (NTA), ethylenediaminetetraacetate (EDTA), ethylenediamine disuccinate (EDDS), Aminocarboxylates such as β-alanine diacetate (β-ADAA), aspartate diacetate (ASDA), methylglycine diacetate (MGDA), ethylglycine diacetate (EGDA), and iminodisuccinate (IDS) ; Hydroxyaminocarboxylates such as serine diacetate, hydroxyiminodisuccinate (HIDS), hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; hydroxyacetate, tartrate, citrate, gluconate, etc. Hydroxycarboxylate; pyromellitic acid salt, benzopolycarboxylate, Cyclocarboxylates such as cyclopentanetetracarboxylate; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, monotartaric acid or disuccinate; weight average molecular weight of 1000 or less, poly Acrylic acid (salt), acrylic acid-allyl alcohol copolymer (salt), water-soluble acrylic acid-maleic acid copolymer (salt), hydroxyacrylic acid polymer (salt), polysaccharide-acrylic acid copolymer, etc. Acrylic acid polymers and copolymers thereof, or salts thereof; polymers or copolymers of maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid, or the like Salts: polysaccharide oxides such as starch, cellulose, amylose, pectin, and calcium Polysaccharides such as carboxymethyl cellulose and the like.

These components (F) are blended in the form of an acid and then neutralized with potassium hydroxide, sodium hydroxide, ammonium hydroxide, potassium carbonate, sodium carbonate, monoethanolamine, diethanolamine or the like to at least partially salt. It is good. Moreover, you may mix | blend after making at least one part of a carboxyl group into a salt previously.
Among these, from the viewpoint of cleaning performance, it is particularly preferable that at least a part of the carboxy groups are sodium salt, potassium salt or ammonium salt. In terms of cleaning performance, a compound having at least one nitrogen atom and 2 to 5 COOM ′ groups (M ′ represents a hydrogen atom, Na, K, or NH ₄ ) in the molecule is preferable. Of these, aminocarboxylates and hydroxyaminocarboxylates are preferred, ethylenediamine disuccinate (EDDS), β-alanine diacetate (β-ADAA), aspartate diacetate (ASDA), methylglycine diacetate (MGDA), serine diacetate, and hydroxyiminodisuccinate (HIDS) are more preferable, and methylglycine diacetate (MGDA) and hydroxyiminodisuccinate (HIDS) are most preferable.

In this invention, (F) component can be used individually by 1 type or in combination of 2 or more types as appropriate.
The blending amount of the component (F) is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more with respect to the entire composition. The upper limit is preferably 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less. The effect of this invention improves because this compounding quantity is 1 mass% or more. On the other hand, even if the upper limit is 30% by mass or less, a mud dirt removing effect is sufficiently obtained, which is economically advantageous.

The component (F) has a calcium ion stability constant pKca of preferably 4 or more, more preferably 5 or more, and particularly preferably 6 or more from the viewpoint of cleaning performance. The upper limit value of pKca is preferably 15 or less, more preferably 13 or less, and particularly preferably 12 or less.
The calcium ion stability constant pKca in the present invention can be determined by the following method.

(Measurement method of calcium stability constant “pKca”)
For measurement of the Ca ²⁺ concentration, an ion meter equipped with a calcium ion electrode (for example, manufactured by Horiba, Ltd.) is used.
First, a 1% by mass NH ₄ Cl—NH ₄ OH (pH 10) aqueous solution is prepared as a buffer solution, the relationship between the calcium chloride concentration and the electrode potential is obtained, and a calibration curve between the calcium ion concentration and the electrode potential is prepared. .
Next, an aqueous solution of 7.13 × 10 ⁻² mol / L calcium chloride aqueous solution and 7.13 × 10 ⁻⁴ mol / L component (F) are prepared. Then, 1 mL of a calcium chloride aqueous solution is added to 100 mL of the aqueous solution of the component (F), and the mixture is stirred for 10 minutes, and the remaining calcium ion (Ca ²⁺ ) concentration is measured using a calcium ion electrode.
Assuming that the component (F) forms a chelate complex with Ca ²⁺ at 1: 1, the calcium stability constant pKca is obtained from the following formula.

（式中、［Ｃａ］は遊離のカルシウムイオン濃度、［Ｃａ_０］は仕込みのカルシウムイオン濃度、［Ｌ_０］はキレートされたカルシウムイオン濃度をそれぞれ表す。）

(In the formula, [Ca] represents the free calcium ion concentration, [Ca ₀ ] represents the charged calcium ion concentration, and [L ₀ ] represents the chelated calcium ion concentration.)

The granular detergent composition of the present invention contains the following optional components (1) to (10), which are usually blended in the detergent composition, as necessary, in addition to the above essential components, as long as the effects of the present invention are not hindered. Can be blended.
(1) Builders Examples of builders include inorganic builders and organic builders.
Examples of organic builders other than those included in the component (F) include hydroxycarboxylates such as hydroxyacetate, tartrate, citrate and gluconate; pyromellitic acid salt and benzopolycarboxylate Cyclocarboxylates such as cyclopentanetetracarboxylate; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, monotartaric acid or disuccinate; Acrylic acid (salt), acrylic acid-allyl alcohol copolymer (salt), water-soluble acrylic acid-maleic acid copolymer (salt), hydroxyacrylic acid polymer (salt), polysaccharide-acrylic acid copolymer, etc. Acrylic acid polymers and copolymers thereof, or salts thereof; maleic acid, itako Polymers or copolymers of acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid, etc., or salts thereof; polysaccharide oxides such as starch, cellulose, amylose, pectin, carboxymethyl cellulose, etc. Non-dissociative polymer compounds such as polyethylene glycol, polyvinyl alcohol, and polyvinyl pyrrolidone. Among them, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate having a weight average molecular weight exceeding 1000, and water-soluble acrylic acid-maleic acid copolymer salt are preferable.

Examples of the inorganic builder include alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, and amorphous layered sodium silicate; sodium sulfate, potassium sulfate, Neutral salts such as sodium chloride and potassium chloride; phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate; general formula x ¹ (M ₂ O). Al ₂ O ₂ · y ¹ (SiO ₂ ) · w ¹ (H ₂ O) (wherein M is an alkali metal atom such as sodium or potassium, x ¹ , y ¹ and w ¹ are the number of moles of each component) In general, x ¹ is a number of 0.7 to 1.5, y ¹ is a number of 0.8 to 6.0, and w ¹ is an arbitrary positive number. Salts; formula _{^{x 2 (M 2 O) ·}} Al 2 O 3 · y 2 (SiO 2) · w 2 (H 2 O) ( wherein, M is sodium, an alkali metal atom such as ^{potassium, x} 2, y ² and w ² represent the number of moles of each component, generally x ² is a number from 0.7 to 1.2, y ² is a number from 1.6 to 2.8, and w ² is 0 or arbitrary Amorphous aluminosilicate represented by general formula x ³ (N ₂ O) · Al ₂ O ₃ · y ³ (SiO ₂ ) · z ³ (P ₂ O ₅ ) · w ³ (H ₂ O) (wherein M is an alkali metal atom such as sodium or potassium, x ³ , y ³ , z ³ and w ³ represent the number of moles of each component, and generally x ³ is 0.2 the number of to 1.1, ^{y 3} is the number of 0.2 to 4.0, ^{z 3} is 0.001 to 0.8, ^{amorphous w 3} is expressed by.) indicating 0 or any positive number Aluminum Silicic acid salts, and the like. Of these, sodium carbonate, potassium carbonate, sodium silicate, and sodium aluminosilicate are preferable.
Moreover, when mix | blending what shows low-temperature solubility improvement effects, such as potassium carbonate, sodium chloride, potassium chloride, among the said inorganic builders, 2-15 mass% in the granular cleaning composition of this invention, From Preferably, 4 to 10% by mass is blended.

The said builder can be used individually by 1 type or in combination of 2 or more types as appropriate.
The blending amount of the builder is preferably 10 to 70% by mass, particularly preferably 20 to 50% by mass, based on the entire composition. If it is this range, cleaning power will improve more.

(2) As a fluorescent brightening agent, bis (triazinylaminostilbene) disulfonic acid derivative [trade name: Tinopal AMS-GX], bis (sulfostyryl) biphenyl salt [trade name: Tinopal CBS-X] and the like.
(3) As a surface modifier, fine powdered calcium carbonate, fine powdered zeolite, granular zeolite, polyethylene glycol and the like.
(4) Cellulose derivatives such as carboxymethylcellulose, polyvinylpyrrolidone and derivatives thereof as anti-staining agents.
(5) As a porous oil absorbent, amorphous anhydrous silicic acid, calcium silicate, etc.
(6) As a flexibility imparting agent, cationic surfactants such as dialkyl quaternary ammonium salts, clay minerals such as smectite, and the like.
(7) Silicone oil or the like as an antifoaming agent.
(8) Fragrance.
(9) Coloring agents such as water-soluble dyes and pigments.
(10) Enzymes other than component (C).

The method for preparing the granular detergent composition of the present invention is not particularly limited, and the above components (A) to (C), preferably (D) to (F), and optional components as necessary. The granular detergent composition to be contained can be prepared according to a conventional method.
In the present invention, the bulk density of the granular detergent composition is 0.5 g / mL or more, preferably 0.6 g / mL or more, more preferably 0.7 g / mL or more, particularly preferably 0.8 g / mL. That's it. The upper limit is 1.3 g / mL or less, preferably 1.2 g / mL or less, more preferably 1.1 g / mL or less, and particularly preferably 1.0 g / mL.
When the bulk density is 0.5 g / mL or more, the bulk of the granular detergent composition is suppressed, and when the granular detergent composition is filled in a container or the like, the packaging form can be reduced, which is economical. Is also advantageous. On the other hand, the solubility to the water of a granular cleaning composition improves by being 1.3 g / mL or less.

  When the granular detergent composition according to the present invention is, for example, a bleaching detergent composition, the average particle diameter of the particles of the composition is 200 μm or more, preferably 250 μm or more, from the viewpoint of solubility and stability. More preferably, it is 300 μm or more, and the upper limit value is 1000 μm or less, preferably 700 μm or less, and more preferably 600 μm or less. When the average particle size is 200 μm or more, powdering is suppressed during use, and when it is 1000 μm or less, the solubility in water is improved.

  The granular detergent composition of the present invention is particularly suitably used as a detergent for clothing, and its usage is not particularly limited and can be used in a conventional manner.

ADVANTAGE OF THE INVENTION According to this invention, the granular detergent composition with a high mud dirt removal effect can be provided also in normal washing.
In addition, the granular detergent composition of the present invention has a reduced environmental load, a reduced amount of surfactant as compared with the conventional one, and has a high detergency.
In addition, according to the granular detergent composition of the present invention, preferably, the liquid detergent composition or the soap bar is applied in advance to the mud soil portion of the clothes (pretreatment), by ordinary washing, You can easily remove mud dirt.

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

<< Preparation method of granular detergent composition >>
(I) Method for preparing granular detergent composition (part 1)
Among the detergent compositions shown in Table 1, Examples 1 to 5, 10 and Comparative Examples 11 to 12 were prepared by the following procedure.
Nonionic surfactant, part of zeolite, layered silicate, enzyme, fragrance, pigment, percarbonate, surface treatment water-soluble inorganic compound particles, each component excluding bleach activator granulated material, solid content A 40% by weight slurry for spray drying was prepared. The temperature of the resulting slurry for spray drying was 60 ° C. This slurry is spray-dried with a counter-current spray dryer equipped with a pressure spray nozzle, the volatile matter (105 ° C., reduced for 2 hours) is 3% by mass, the bulk density is 0.35 g / mL, and the average particle size Obtained spray-dried particles of 300 μm. Note that fine powder A-type zeolite (trade name: Shilton B, manufactured by Mizusawa Chemical) was used as the zeolite of the slurry for spray drying.
The obtained spray-dried particles were added to a biaxial continuous kneader (trade name: KRC Kneader # 2 type, manufactured by Kurimoto Steel Works) kept at 40 ° C. together with a part of nonionic surfactant and water for adjusting water content. I put it and obtained a koji. Thereafter, this kneaded product was extruded, chopped into 1 to 2 cm square dice, and crushed and granulated together with 3% by mass of granule A-type zeolite (average particle size 200 μm, manufactured by Cosmo). Under the present circumstances, the crusher (The Okada Seiko make, brand name: Speed mill ND-10 type | mold; a rotation speed of 1500 rpm and an opening diameter 2mm screen) was used.
The obtained crushed granulated material was coated with 2% by mass of finely divided A-type zeolite (trade name: Shilton B, manufactured by Mizusawa Chemical) with a rolling drum, and a part of nonionic surfactant (1% by mass) was sprayed. Thereafter, a detergent composition having an average particle size of 500 μm and a bulk density of 0.85 g / mL was obtained.
Further, percarbonate, surface-treated water-soluble inorganic compound particles, bleach activator granulated product, enzyme, and layered silicate are mixed with a tumbling drum, and further, a 20% by weight pigment aqueous dispersion and a fragrance are sprayed. Addition to obtain a granular detergent composition.
Table 1 also shows the results of evaluating the cleaning performance against mud soil and the average particle diameter and bulk density of the obtained granular detergent composition for the obtained granular detergent composition according to the following evaluation method.

(Ii) Preparation method of granular detergent composition (part 2)
Among the detergent compositions shown in Table 1, Examples 6 to 9 and Comparative Examples 13 and 14 were prepared by the following procedure.
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 50 ° C. To this, sodium sulfate and fluorescent brightening agent were added respectively, and after stirring for 10 minutes, sodium carbonate was added, and then the acrylic acid polymer, the component (B) and the component (F) were added, and further 10 minutes. After stirring, sodium chloride and a part of the powdered zeolite were added. Furthermore, it stirred for 30 minutes and prepared the slurry for spray drying. The temperature of the resulting slurry for spray drying was 60 ° C. This slurry is spray-dried in a counter-current spray dryer equipped with a pressure spray nozzle, the volatile content (105 ° C., reduced for 2 hours) is 3% by mass, the bulk density is 0.50 g / mL, and the average particle size Yielded spray-dried particles of 250 μm.
Next, a nonionic surfactant and an anionic surfactant were added at 80 ° C. under mixing to prepare a surfactant composition having a water content of 10% by mass.
Next, spray-dried particles were put into a Redige mixer M20 type (manufactured by Matsuzaka Giken Co., Ltd.), and stirring of the main shaft (150 rpm) and chopper (4000 rpm) was started. Warm water at 80 ° C. was passed through the jacket at a flow rate of 10 L / min. The surfactant composition was added to the mixture for 2 minutes, and then stirred for 5 minutes. Then, a layered silicate and a part (10% by mass) of the powdered zeolite were added to perform a surface coating treatment for 2 minutes. A detergent composition having an average particle diameter of 300 μm and a bulk density of 0.75 g / mL was obtained.
To this detergent composition, a part (2% by mass) of the above powdered zeolite was mixed with a V blender, and then the enzyme, percarbonate, surface-treated water-soluble inorganic compound particles, and bleach activator granulated product were mixed with V. The mixture was blended with a blender, and a 20% by weight pigment aqueous dispersion and a fragrance were added by spraying to obtain a granular detergent composition.
Table 1 also shows the results of evaluating the cleaning performance against mud soil and the average particle diameter and bulk density of the obtained granular detergent composition for the obtained granular detergent composition according to the following evaluation method.

<< Preparation method of bleach activator granulated product >>
(I) Preparation method of bleach activator granulated product A First, synthesis of bleach activator 4-decanoyloxybenzene sulfonate sodium was used as a raw material, sodium 4-hydroxybenzenesulfonate (manufactured by Kanto Chemical Co., Ltd., Reagent), N, N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd., reagent), decanoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent), acetone (manufactured by Kanto Chemical Co., Ltd., reagent) The following method was used.
3,000 g (15.3 mol) of sodium 4-hydroxybenzenesulfonate dehydrated in advance was dispersed in 9000 g of N, N-dimethylformamide, and 2918 g (15.3 mol) of decanoic acid chloride was stirred at 50 ° C. for 30 minutes. It was dripped over.
Reaction was performed after completion | finish of dripping for 3 hours, and N, N- dimethylformamide was distilled off at 100 degreeC under pressure reduction (0.5-1 mmHg). After washing with acetone, purification was performed by recrystallization in a water / acetone (= 1/1 mol) solvent to obtain crystals of sodium 4-decanoyloxybenzenesulfonate. The yield was 91% by mass.

Next, a bleaching activator granulated product A was prepared by the following method.
70 parts by mass of sodium 4-decanoyloxybenzenesulfonate synthesized by the above method as a bleaching activator, 20 parts by mass of PEG (trade name: polyethylene glycol # 6000M (manufactured by Lion Corporation)), α having 14 carbon atoms -Sodium olefin sulfonate powder product (trade name: Lipolane PJ-400 (manufactured by Lion Corporation)) Extrude Ohmics EM-6 manufactured by Hosokawa Micron Co., Ltd. (product) No. 1) and kneaded and extruded to obtain a noodle-like extruded product having a diameter of 0.8 mmφ.
This extruded product (60 ° C.) was introduced into Fitzmill DKA-3 type (trade name) manufactured by Hosokawa Micron Co., Ltd., and 5 parts by mass of A-type zeolite powder was similarly supplied as an auxiliary agent and pulverized to obtain an average particle size. About 700 μm of bleach activator granulated product A was obtained.

(Ii) Preparation method of bleach activator granulated product B First, the synthesis of bleach activator 4-dodecanoyloxybenzenesulfonate sodium was used as a raw material, sodium 4-hydroxybenzenesulfonate (manufactured by Kanto Chemical Co., Ltd., Reagent), N, N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd., reagent), lauric acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent), acetone (manufactured by Kanto Chemical Co., Ltd., reagent), The following method was used.
3000 g (15.3 mol) of sodium 4-hydroxybenzenesulfonate dehydrated in advance was dispersed in 9000 g of N, N-dimethylformamide, and 3347 g (15.3 mol) of lauric acid chloride was stirred at 50 ° C. for 30 minutes while stirring with a stirrer. It was dripped over.
Reaction was performed after completion | finish of dripping for 3 hours, and N, N- dimethylformamide was distilled off at 100 degreeC under pressure reduction (0.5-1 mmHg). After washing with acetone, purification was performed by recrystallization in a water / acetone (= 1/1 mol) solvent to obtain crystals of sodium 4-dodecanoyloxybenzenesulfonate. The yield was 90% by mass.

Next, a bleaching activator granulated product B was prepared by the following method.
In the method for preparing the bleaching activator granulated product A, sodium 4-dodecanoyloxybenzenesulfonate synthesized by the above method is used as the bleaching activator instead of sodium 4-decanoyloxybenzenesulfonate. A bleaching activator granulated product B was prepared in the same manner as the bleaching activator granulated product A except for the above.

(Iii) Method for preparing bleach activator granulated product C In the method for preparing bleach activator granulated product A, as a bleach activator, instead of sodium 4-decanoyloxybenzenesulfonate, 4-deca Bleach activator granulated product C was prepared in the same manner as the bleach activator granulated product A except that noyloxybenzoic acid (manufactured by Mitsui Chemicals, Inc.) was used.

≪Description of ingredients shown in the table≫
In addition, the component used in the following example is as follows.
A-1: linear alkyl (C10-C14) benzenesulfonic acid (Laipon LH-200 (trade name, manufactured by Raipon Co., Ltd., linear alkylbenzenesulfonic acid (LAS-H) pure 96% by mass)) This is potassium alkylbenzene sulfonate (LAS-K), which was neutralized with a 48 mass% potassium hydroxide aqueous solution at the time of preparation. The compounding quantity in a table | surface shows the mass% as LAS-K.
A-2: Sodium α-olefin sulfonate having an alkyl group having 14 to 18 carbon atoms (manufactured by Lion Corporation).
A-3: Sodium alkyl ether sulfate (manufactured by Lion Corporation) obtained by sulfate-converting an ethylene oxide 2-mol adduct of Neodol 23 (trade name, manufactured by Shell Corporation) and neutralizing with an aqueous sodium hydroxide solution.
.Alpha.-sulfo fatty acid methyl of A-4: carbon number 14: carbon number 16 = 18: 82 (mass ratio of the compound having a hydrocarbon group having 14 carbon atoms and the compound having a hydrocarbon group having 16 carbon atoms) Sodium salt of ester (manufactured by Lion Co., Ltd., pure (AI) = 70% by mass, balance is unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc.).
A-5: linear alkyl (C10-C14) benzenesulfonic acid (Lypon LH-200 (trade name, manufactured by Lion Corporation, LAS-H pure 96 mass%), 48 mass% water during preparation It is a linear sodium alkylbenzene sulfonate (LAS-Na) neutralized with an aqueous sodium oxide solution). The compounding quantity in a table | surface shows the mass% as LAS-Na.
A-6: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C .; fatty acid composition (mixing ratio of carbon number of alkyl group) is C12: 11. 7%, C14: 0.4%, C16: 29.2%, C18 (stearic acid): 0.7%, C18 (oleic acid): 56.8%, C18 (linoleic acid): 1.2% Yes, molecular weight: 289).
A-7: ECOROL26 (trade name, manufactured by ECOGREEN Co., Ltd., alcohol having an alkyl group having 12 to 16 carbon atoms) average ethylene oxide 6 mol adduct (pure content 90% by mass, HLB value 11.5).
A-8: ECOROL26 (trade name, manufactured by ECOGREEN, alcohol having an alkyl group having 12 to 16 carbon atoms) an average of 15 moles of ethylene oxide adduct (pure 90% by mass, HLB value 15.4, melting point 43 ° C. ).
-A-9: Ethylene oxide average 20 mol adduct of Diadol 13 (trade name, manufactured by Mitsubishi Chemical Corporation) (pure content: 90 mass%, HLB value: 16.3, melting point: 45 ° C).

B-1: sodium 4-hydroxybenzenesulfonate.
B-2: 4-hydroxybenzoic acid.
C-1: Sabinase 12T (trade name, manufactured by Novozymes, protease).
C-2: Evalase 8T (trade name, manufactured by Novozymes, protease).
C-3: Lipex 100T (trade name, manufactured by Novozymes, lipase).
C-4: Stainzyme 12T (trade name, manufactured by Novozymes, amylase).
C-5: Cellzyme 0.7T (trade name, manufactured by Novozymes, Cellulase).
D-1: Coated sodium percarbonate (Mitsubishi Gas Chemical Co., Ltd., trade name: SPC-D).
E-1: Bleach activator granulated product obtained by the method for preparing the bleach activator granulated product A.
E-2: Bleach activator granulated product obtained by the method for preparing the bleach activator granulated product B.
E-3: Bleach activator granulated product obtained by the method for preparing the bleach activator granulated product C.
F-1: tetrasodium hydroxyiminodisuccinate (pKca 5.0) prepared according to the method disclosed in Example 1 of JP-A-10-158226.
F-2: Trisodium methylglycine diacetate (BASF, trade name: Trilon M, pKca 6.2).
F-3: Aspartate diacetic acid tetrasodium (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Clewat Bi-ADS / ASDA-4Na, pKca 6.8).

-Sodium carbonate: Heavy sodium carbonate (soda ash manufactured by Asahi Glass Co., Ltd., trade name: granular ash).
Potassium carbonate: Potassium carbonate (Asahi Glass Co., Ltd.).
Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Shikoku Chemicals Co., Ltd.)
Sodium chloride: Nissei Yaki salt C (trade name: manufactured by Nippon Salt Corporation).
Layered silicate: crystalline layered sodium silicate (manufactured by Clariant Tokuyama Co., Ltd., trade name: SKS-6).
-Sodium silicate: JIS No. 1 sodium silicate (trade name: manufactured by Nippon Chemical Co., Ltd.).
Zeolite: Type A zeolite (manufactured by Mizusawa Chemical Co., Ltd., trade name: Shilton B).
Acrylic acid polymer A: sodium salt of acrylic acid / maleic acid copolymer (manufactured by Nippon Shokubai Co., Ltd., trade name: Aqualic TL-400).
Acrylic acid polymer B: sodium polyacrylate (manufactured by BASF, trade name: Socaran PA30).
-Brightening agent: Chinopearl CBS-X (trade name: Socaran PA30 Ciba Specialty Chemicals) and Chinopearl AMS-GX (trade name: Ciba Specialty Chemicals) in a mass ratio of 8/2.
Surface-treated water-soluble inorganic compound particles: Surface-treated water-soluble inorganic compound particles a9 described in Table 1 of International Publication No. 2004/094313.
-Dye A: Ultramarine (manufactured by Dainichi Seika Kogyo, trade name: Ultramarine Blue).
-Dye B: Pigment Green 7 (trade name: manufactured by Dainichi Seika Kogyo).
Dye C: A spherical resin particle having an average particle size of 0.35 μm obtained by radical emulsion polymerization in an aqueous dispersion using acrylonitrile / styrene / acrylic acid as a constituent monomer, and about 1% by mass of C.I. I. An aqueous dispersion of a pink fluorescent pigment obtained by adding BASIC RED-1 (trade name) to a polymer resin suspension and heat-treating it.
Fragrance A: Fragrance composition A shown in Tables 11 to 18 of JP-A-2002-146399.
Fragrance B: Fragrance composition B shown in Tables 11 to 18 of JP-A No. 2002-146399.
Fragrance C: Fragrance composition C shown in Tables 11 to 18 of JP-A-2002-146399.
-Fragrance | flavor D: The fragrance | flavor composition D shown to Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.

≪Mud dirt cleaning performance evaluation≫
(I) Preparation method of mud stain evaluation cloth Take 20 g of red soil (red and yellow soil (Hikatagahara, Shizuoka Prefecture, Mikatagahara) dried at 200 ° C and ground to an average particle size of about 1 μm with a micron atomizer). And put into 500 g of tap water. The mixture was dispersed at 8000 rpm for about 10 minutes using a homogenizer (Polytron). 15 pieces of cotton knitted fabric cut to 10 cm × 25 cm were dipped in the solution, the cloth was thoroughly rubbed by hand, and the whole was uniformly squeezed with a mud dispersion, and then lightly squeezed using a roller.
Then, after air-drying for 30 minutes, it was made to dry for 1 hour in a 105 degreeC thermostat. The cloth surface was polished to remove excess mud particles and used as a mud dirt evaluation cloth.

(Ii) Evaluation of mud stain cleaning performance of granular detergent composition Using Teg-O-meter (trade name) of US Testing Company as a cleaning tester, the above five mud stain evaluation cloths, sebum cloth, and cleaning knitted cloth were used. The granular detergent composition shown in the table was added so that the detergent concentration would be 0.0667% by mass, and washed at 120 rpm and 20 ° C. for 10 minutes in accordance with the bath ratio of 30 times. The water used was 4 ° DH, the amount of the cleaning solution was 900 mL, and the rinse was washed with 900 mL of water for 3 minutes. After rinsing, the mud stain evaluation cloth was dried, and the washing rate was calculated by the following equation.
Detergency (%) = (K / S of contaminated cloth−cleaning cloth K / S) / (K / S of contaminated cloth−K / S of uncontaminated cloth) × 100
Here, K / S = (1−R / 100) ² / (2R / 100) (where R is reflectance (%)). The reflectance was measured with Σ90 (manufactured by Nippon Denshoku Industries Co., Ltd.) using a 460 nm filter.
Evaluation criteria determined that the cleaning power was good when the cleaning rate (%) calculated by the above formula was 36% or more. For the cleaning rate (%), the average value of five sheets of mud dirt evaluation cloth was used.

  As is clear from the results shown in Tables 1 and 2, it was confirmed that Examples 1 to 10 according to the present invention have a higher effect of removing mud stains even in normal washing than Comparative Examples 11 to 14. .

Claims (1)

The following (A) component, (B) component, (C) component, (D) component, (E) component, and (F) component are contained, and mass ratio (B) of said (B) component with respect to said (E) component (B) ) / (E) is 95/5 to 15/85, and the bulk density is 0.5 g / mL or more.
(A) Surfactant: 10 to 30% by mass,
(B) Compound represented by the following formula (I): 0.1 to 10% by mass,

(In the formula, X represents COOM or SO ₃ M, and M represents a salt-forming cation.)
(C) one or more enzymes selected from protease, lipase, amylase and cellulase,
(D) an inorganic peroxide that releases hydrogen peroxide in water;
(E) Organic peracid precursor represented by the following formula (II): 0.1 to 10% by mass,

(In the formula, R is an alkyl or alkenyl group having 7 to 11 carbon atoms, X is COOM or SO ₃ M, and M represents a salt-forming cation.)
(F) asparagine di acid sodium salt, methyl glycine diacetic acid sodium salt, one selected from hydroxy iminodiacetonitrile sodium succinate.