JPH11236593A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent compsn. improved in power of cleaning muddy dirt by incorporating a specific polymer into the same. SOLUTION: This compsn. contains 0.1-30 wt.%, pref. 0.5-20 wt.%, polymer of the formula: (A)m (B)n (A is a repeating unit having at least one carboxyl group and having no other anionic group; B is a repeating unit having a sulfo or sulfate group; repeating units A and B are arranged randomly or in block; and m and n are such numbers that the ratio of m/n is (100/1)-(1/1) and that the wt. average mol.wt. of the polymer is 4,000-200,000), optionally 0.1-20 wt.%, pref. 0.5-15 wt.%, hydrogen peroxide or 0.5-99 wt.%, pref. 1-95 wt.%, inorg. peroxide which generates hydrogen peroxide in an aq. soln., 0.5-50 wt.% anoionic surfactant, and 1-40 wt.% crystalline alkali silicate of the formula: M2 O.X '(SiO2 ).y' (H2 O) M is an alkali metal; x' is 1.5-2.6; and y' is 0-20).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition having a high detergency against mud stains.

[0002]

2. Description of the Related Art Mud dirt such as socks is difficult to remove because mud particles adhere firmly to fibers. Conventionally, a carboxylic acid-based polymer such as carboxymethyl cellulose,
It has been proposed to incorporate an enzyme, cellulase. In JP-A-3-26797, a specific phosphonic acid compound is used, which is disclosed in JP-A-1-30179.
No. 8 discloses a method of impregnating a water-soluble inorganic powder with a nonionic surfactant to increase the mud washing power.

Attempts have also been made to add a polymer having mud dispersing ability in order to obtain detergency against mud stains. For example, in Japanese Patent Application Laid-Open No. 7-11295, US Pat.
Japanese Patent No. 90271 discloses a method disclosed in Japanese Patent Application Laid-Open No.
No. 10730 discloses that a suitable mud stain cleaning power can be obtained by blending a specific polycarboxylate. However, even if these techniques are used, the detergency against mud dirt cannot be said to be sufficient.

[0004] An object of the present invention is to obtain a detergent composition having excellent detergency against mud stains.

[0005]

SUMMARY OF THE INVENTION The present invention provides a cleaning composition containing a polymer represented by the following general formula (1). (A) _m (B) _n (1) wherein A represents a repeating unit having at least one carboxyl group in the molecule but not having another anionic group, and B represents a sulfonic acid in the molecule. A repeating unit having a group or a sulfate group, wherein the repeating units A and B are randomly polymerized or block polymerized, and m and n are represented by m: n = 1
00: 1 to 1: 1 and the polymer has a weight average molecular weight of 4,
The numbers indicate 000 to 200,000. ]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The repeating units A and B constituting the polymer represented by the general formula (1) used in the present invention may be the same unit or two or more different units. Is also good. Further, the polymer is preferably composed of only repeating units A and B,
Other structural units can be included as long as the object of the present invention is not impaired.

The repeating unit A includes, for example, the following general formulas (I) to (VIII), and among these, (I) to (IV), among which (I) is particularly easy to polymerize. It is preferable in terms of economy. -CH ₂ CH (CO ₂ M)-(I) -CH ₂ C (CH ₃ ) (CO ₂ M)-(II) -CH ₂ C (OH) (CO ₂ M)-(III) -CH (CO ₂ M) -CH (CO ₂ M)-(IV) -CH (CH ₃ ) -CH (CO ₂ M)-(V) -CH (CO ₂ M) -C (CO ₂ M) -CH ₂ (CO _{2 M) - (VI) -CH} 2 -C (CO 2 M) -CH 2 (CO 2 M) - (VII) -C (CH 3) (CO 2 M) -CH (CO 2 M) - (VIII Wherein M is hydrogen, an alkali metal, an alkaline earth metal,
Ammonium or alkanolamine].

The repeating unit A is composed of acrylic acid, methacrylic acid, α-hydroxyacrylic acid, maleic acid,
Those derived from fumaric acid, crotonic acid, isocrotonic acid, aconitic acid, itaconic acid, citraconic acid or salts thereof are preferred, and those derived from acrylic acid, methacrylic acid, maleic acid or salts thereof are particularly preferred. The repeating unit A may be one or more selected from the above.

The repeating unit B is desirably represented by the following general formula (2) from the viewpoint of cleaning properties against mud stains.

[0010]

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Wherein X represents hydrogen, R ¹ or —COOM;
Represents -SO ₃ M, -CO-Z or -R ² -T, wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a hydroxyalkylene group having 1 to 5 carbon atoms; Represents -NR ⁴ -R ³ -T (where R ⁴ represents hydrogen, an alkyl group having 1 to 5 carbon atoms or a hydroxyalkylene group, and R ³ has 1 to 5 carbon atoms which may be branched. R ² represents an alkylene group having 1 to 5 carbon atoms, T represents —SO ₃ M, —OSO ₃ M, and M represents hydrogen, an alkali metal, an alkaline earth metal, ammonium or alkanolamine. ｝].

More specific examples of the repeating unit B include the following general formulas (IX) to (XIV). -CH ₂ -CH (CH ₂ SO ₃ M)-(IX) -CH ₂ -CH (CH ₂ OSO ₃ M)-(X) -CH ₂ -CH (CONHCH ₂ SO ₃ M)-(XI) -CH _2- CH [CONHC (CH ₃ ) ₂ CH ₂ SO ₃ M]-(XII) -CH ₂ -C (SO ₃ M) (COOM)-(XIII) -CQ ₁ (CO ₂ M) -CQ ₂ (CO ₂ M)-(XIV) [wherein M is hydrogen, alkali metal, alkaline earth metal,
Represents ammonium or alkanolamine, and Q ₁ and Q ₂ represent hydrogen or SO ₃ M, but are not hydrogen at the same time].

The repeating unit B is represented by (IX), (XII), (X
III) is preferred. The repeating unit B includes methacrylsulfonic acid, styrenesulfonic acid, α-methylsulfonic acid,
Styrene sulfonic acid such as chlorostyrene sulfonic acid, 2
-Acrylamide-2-methylpropanesulfonic acid,
2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamidobutane-2-sulfonic acid, 3-acrylamide-2,3-dimethylbutane-2-sulfonic acid , 2
-Acrylamide-2,4,4-trimethylpentasulfonic acid, 2-acrylamide-cyclohexanesulfonic acid, 2-acrylamide-2-phenylethanesulfonic acid, 2-acrylamide-2-phenylpropanesulfonic acid Those derived from 2-acrylamide-2-tolylethanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid or salts thereof, particularly, allylsulfonic acid, 2-methacrylamide-2 Those derived from -methylpropanesulfonic acid or salts thereof are preferred. The repeating unit B may be one or more kinds selected from the above.

The most preferred combination of the repeating units A and B of the polymer represented by the general formula (1) is acrylic acid / styrene sulfonic acid, acrylic acid / allyl sulfonic acid, if the monomers are derived as A / B. , Acrylic acid /
Mention may be made of 2-acrylamidobutanesulfonic acid, maleic acid / allylsulfonic acid and salts thereof.

The polymer represented by the general formula (1) preferably forms a salt not only in an acid form but also partially or entirely, and when a salt is formed, an alkali metal such as potassium or sodium, Examples thereof include salts of alkaline earth metals such as calcium, and salts of alkanolamines such as ammonium and monoethanolamine, and those further neutralized with sodium, potassium and ammonium are preferable.

In the general formula (1), m and n are:
When n = 100: 1 to 1: 1, the number is such that the weight average molecular weight of the polymer becomes 4,000 to 200,000. m: n
Is preferably 100: 1 to 2: 1, more preferably 100: 1 to 5: 1, and still more preferably 50: 1 to 1.
5: 1, particularly preferably 50: 1 to 8: 1, most preferably 30: 1 to 10: 1. The weight average molecular weight is preferably 4,000 to 100,000, more preferably 5,000 to 100,000, and particularly preferably 5,000 to 100,000.
0-70,000, most preferably 5,000-50,
000. The weight average molecular weight is a value measured by a gel permeation chromatography (GPC) using a polyethylene oxide standard substance (manufactured by Tosoh Corporation) as a standard sample.

The content of the polymer represented by the general formula (1) is preferably 0.1 to 30% by weight in the detergent composition,
More preferably, it is 0.5 to 20% by weight.

The cleaning composition of the present invention preferably further contains hydrogen peroxide or an inorganic peroxide that releases hydrogen peroxide in an aqueous solution.

In the case of a liquid detergent composition, it is preferable to use hydrogen peroxide, the content of which is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, especially Preferably it is 0.5 to 10% by weight. The content of hydrogen peroxide is preferably 0.1% by weight or more from the viewpoint of obtaining sufficient bleaching power, and is preferably 20% by weight or less from the viewpoint of stability of hydrogen peroxide.

In the case of a powdery detergent composition, it is preferable to contain an inorganic peroxide that generates hydrogen peroxide in an aqueous solution. As the inorganic peroxide, sodium percarbonate or sodium perborate is particularly preferred. Its content is preferably 0.5 to 99% by weight, more preferably 1 to 95% by weight.
% By weight.

In the case of a general detergent composition for clothing containing a surfactant in an amount of 10% by weight or more, it is preferable that the inorganic peroxide is incorporated in an amount of 0.5 to 40% by weight. When sodium carbonate is added, 0.1 to 10 parts by weight of sodium borate and / or sodium silicate is added to 100 parts by weight of sodium percarbonate for stabilization.
It is preferable to use those coated at a ratio of 0.1 part by weight / 0.1 part by weight.

The detergent composition of the present invention preferably contains a surfactant. As the surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be used, but an anionic surfactant and a nonionic surfactant are preferable. Preferred are anionic surfactants.

As the anionic surfactants, those having 8 to 8 carbon atoms are used.
An alkylbenzene sulfonate having an alkyl chain of 20; a sulfate salt of a linear or branched primary or secondary alcohol having 8 to 20 carbon atoms; a sulfate salt of an ethoxylated product of an alcohol having 8 to 20 carbon atoms; In each case, a paraffin sulfonate, an α-olefin sulfonate, an α-sulfofatty acid salt, an α-sulfofatty acid alkyl ester salt or a fatty acid salt having 8 to 20 carbon atoms is preferable. In the present invention, in particular, a linear alkylbenzene sulfonate having an alkyl chain having an average carbon number of 12 to 14, an average carbon number of 12 to 18
Is preferred, and the counter ion is preferably an alkali metal, particularly preferably sodium or potassium.

As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, and polyoxyethylene polyoxypropylene block polymer are preferable. In the present invention, a polyoxyalkylene alkyl ether obtained by adding 4 to 20 mol of an alkylene oxide such as ethylene oxide or propylene oxide to a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms is particularly preferable.

As the surfactant, it is preferable to use an anionic surfactant as a main surfactant. In particular, the amount of the anionic surfactant other than the fatty acid salt is not less than 50% by weight of the total surfactant. By occupying, more excellent mud dirt cleaning power can be obtained. The amount of the surfactant is preferably 0.1.
5 to 50% by weight. 10 to 45% by weight is preferred for a powdery detergent composition for general clothing, 20 to 50% by weight is preferred for a liquid detergent composition, and a detergent containing 40% by weight or more of a bleaching agent. In this case, the content is preferably 1 to 10% by weight.

The cleaning composition of the present invention contains at least one selected from a crystalline aluminosilicate, an alkali agent, a carboxylic acid polymer other than the polymer represented by the general formula (1), and an alkaline crystalline silicate. Is preferred.

The crystalline aluminosilicate has been conventionally known as a synthetic zeolite, and prevents calcium ions and the like in water from being trapped by ion exchange to prevent the influence of hardness on washing. . The crystal structure is represented by A-type, X-type and P-type zeolites, and A-type is particularly preferred. The average primary particle size of the synthetic zeolite is preferably 0.1 to 10 μm, particularly preferably 0.1 to 5 μm. The compounding amount of the crystalline aluminosilicate is preferably 1 to 60% by weight, more preferably 5 to 50% by weight.

Examples of the alkaline agent include alkali metal carbonates such as sodium carbonate, sodium sesquicarbonate, and sodium hydrogencarbonate, which are collectively referred to as dense ash and light ash;
In addition to amorphous alkali metal silicates such as No. 2 and 3, phosphates such as tripolyphosphate generally known as a sequestering agent can also be used as the alkali agent. These inorganic alkali agents are effective in forming the skeleton of particles during the production of detergent particles, and can provide a detergent having excellent fluidity. In addition, organic alkaline agents such as alkanolamines can also be used. The amount of the alkali agent is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. When the bleaching agent component is mixed in powder or granules in an amount of 40% by weight or more, 1% of sodium carbonate (as dense ash) as an alkali agent is added.
It is preferable to mix 0 to 50% by weight.

The alkaline crystalline silicate has a maximum pH of 11 or more when dispersed in ion-exchanged water at 20 ° C. at 0.1% by weight, and adjusts the pH to 10 with respect to 1 L of the dispersion. For this reason, those which have an excellent alkaline buffering capacity and require 5 ml or more of 0.1N HCl aqueous solution are distinguished from crystalline aluminosilicates having a pH of less than 11.

Preferred as alkaline crystalline silicates are those having the following composition: _{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (3) [ wherein, M is Group Ia elements of the periodic table (preferably K and /
Or Na), and Me is one or a combination (preferably Mg, C) selected from the group IIa element, group IIb element, group IIIa element, group IVa element or group VIII element of the periodic table.
a), y / x = 0.5 to 2.6, z / x = 0.0
1 to 0.9, w = 0 to 20, n / m = 0.5 to 2.0. ] The alkaline crystalline silicate represented by the composition (3) is
It can be produced by the method described in JP-A-7-89712.

Further, an alkaline crystalline silicate having the following composition can also be preferably used. M ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (4) wherein M is an alkali metal (preferably K and / or N
a), where x ′ = 1.5 to 2.6 and y ′ = 0 to 20 (preferably y ′ = 0). ] The alkaline crystalline silicate of the formula (4) is disclosed in
27895 and Phys. Chem. Glasses. 7, 127-138 (19
66), Z. Kristallogr., 129, p396-p404 (1969). In addition, the product name "Na-SKS"
-6 "As _{(δ-Na 2 Si 2 O} 5), powdered, those granular available. These crystalline silicates not only have the above-mentioned alkali buffering ability, but also have an excellent ion exchange ability.

The amount of the alkaline crystalline silicate is preferably 1 to 40% by weight from the viewpoint of obtaining excellent detergency.
More preferably, the content is 3 to 30% by weight.

The carboxylic acid-based polymer other than the general formula (1) has a function of sequestering metal ions, an effect of dispersing solid particle dirt from clothing into a washing bath, and an effect of reattaching the particles to clothing. Has the effect of preventing. Examples of the carboxylic acid-based polymer include homopolymers or copolymers of acrylic acid, methacrylic acid, and itaconic acid, and the copolymer is preferably a copolymer of the above monomer and maleic acid, and has a molecular weight of several thousand. ~ 100,000 is preferred. In addition, polymers such as polyglycidylates, cellulose derivatives such as carboxymethylcellulose, and aminocarboxylic acid-based polymers such as polyaspartates can also be mentioned, and these have a sequestering ability, a dispersing ability and a re-contamination preventing ability. Have.

The amount of the carboxylic acid polymer other than the general formula (1) is preferably 1 to 20% by weight, more preferably 2 to 10% by weight.

When hydrogen peroxide or an inorganic peroxide releasing hydrogen peroxide in an aqueous solution is used in the washing system, one or more bleach activators represented by the following general formula (5) may be used. it can. The compounding amount of these compounds is preferably 0.1 to 20% by weight, more preferably 0.5 to 30% by weight.

[0036]

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Wherein n is a number from 7 to 11, and Y is -SO
₃ M or -COOM (where M represents a hydrogen, an alkali metal, an alkaline earth metal or an ammonium group). Examples of such bleach activators include sodium lauroyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium octanoyloxybenzenesulfonate, lauroyloxybenzoic acid, decanoyloxybenzoic acid, octanoyloxy Benzoic acid and the like can be mentioned.

[0038] The cleaning composition of the present invention comprises, as other components, JP-A-8-218093, p.
The components described in the 4th line to the 7th line on the 7th page can be blended. Further, organic sequestering agents such as citric acid, bulking agents such as sodium sulfate, dispersing agents such as polyethylene glycol and polyvinyl alcohol, color transfer inhibitors such as polyvinyl pyrrolidone, enzymes such as proteases, cellulases, amylase and lipase, and boron. It is preferable to add a compound and an enzyme stabilizer such as sodium sulfite, biphenyl-type and stilbene-type fluorescent dyes, silicone and silica-based antifoaming agents, antioxidants, coloring agents, and fragrances as necessary.

When hydrogen peroxide or an inorganic peroxide releasing hydrogen peroxide in an aqueous solution is contained, see JP-A-9-21.
It is preferable to mix the sequestering agents listed in column 8, line 44 to column 9, line 35 of JP 7090. Further, in the case of a liquid bleaching detergent composition containing hydrogen peroxide, it is preferable to mix the components described in JP-A-9-217090, column 9, line 41 to column 11, line 9, Alternatively, in the case of a powdery bleaching detergent composition, JP-A-8-74170, columns 7, 47
It is preferable to mix the components described in rows to columns 8 and 9.

Regarding the form of the cleaning composition of the present invention,
In the case of a granular material having a high bulk density, the average particle size is preferably 200 to 1000 μm in order to obtain desirable powder properties,
Further, it is preferably from 200 to 600 μm, and particularly preferably does not contain particles of 100 μm or less and 1300 μm or more. The bulk density is preferably 0.5 to 1.2 g / cm ³ , more preferably 0.6 to 1.0 g / cm ³ .

[0041]

[Example] <Synthesis of polymer>-Synthesis of polymer A

[0042]

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(Weight average molecular weight = 8200, n / m = 20/1) 50 g (0.53%) of sodium acrylate (manufactured by Aldrich) was placed in a 1 L four-necked flask equipped with a thermometer, a mechanical stirrer, a condenser, and a nitrogen inlet tube. Mol), 3.8 g of sodium allyl sulfonate (manufactured by Wako Pure Chemical Industries, Ltd.)
(0.027 mol), potassium persulfate 5 g, ethanol 5
g, sodium hypophosphite 0.05 g, ion-exchanged water 50
After charging 0 g, the mixture was reacted at 90 to 100 ° C. for 8 hours while bubbling nitrogen through a nitrogen introducing tube. Thereafter, the solution was concentrated by an evaporator to obtain a 35% aqueous solution. As a result of GPC analysis, the molecular weight was 8,200.

Synthesis of polymer B

[0045]

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(Weight average molecular weight = 21000, n / m = 5/1) In the same four-necked flask as above, 50 g (0.53 mol) of sodium acrylate (manufactured by Aldrich), 2-acrylamide-2-methylpropanesulfone Sodium acid (manufactured by Wako Pure Chemical Industries, Ltd., neutralized with NaOH) 3.8 g (0.11
Mol), azo-based polymerization initiator (V-50, manufactured by Wako Pure Chemical Industries, Ltd.)
g, ethanol 5 g, sodium hypophosphite 0.05 g,
500 g of ion-exchanged water was charged and reacted at 70 to 80 ° C. for 8 hours while bubbling nitrogen through a nitrogen inlet tube.
Thereafter, the solution was concentrated by an evaporator to obtain a 37% aqueous solution. As a result of GPC analysis, the molecular weight was 21,000.

Synthesis of polymer C

[0048]

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(Weight average molecular weight = 36000, n / m = 30/1) In the same four-necked flask as above, sodium acrylate
(Aldrich) 50 g (0.53 mol), α-sulfo
Disodium acrylate (methyl acrylate and SO _ThreeAnti
The reaction is sulfonated, hydrolyzed, recrystallized and synthesized.
Was. ) 3.47 g (0.0177 mol), azo polymerization initiator
(V-50, manufactured by Wako Pure Chemical Industries, Ltd.) 1 g, ethanol 5 g,
Prepare 0.05 g of sodium phosphate and 500 g of ion-exchanged water.
, While bubbling nitrogen through the nitrogen inlet tube.
The reaction was performed at 80 ° C. for 8 hours. After that, the evaporator
And concentrated to a 37% aqueous solution. As a result of GPC analysis,
The molecular weight was 36,000.

Synthesis of polymer D (weight average molecular weight = 10000, n / m = 50/1) According to the method of synthesizing polymer A, the synthesis was performed by changing the monomer ratio to be blended.

Synthesis of Polymer E (Weight Average Molecular Weight = 10000, n / m = 2/1) According to the method of synthesizing Polymer A, it was synthesized by changing the monomer ratio to be blended.

Synthesis of Polymer E (Weight average molecular weight = 2000, n / m = 2/1) According to the synthesis method of Polymer A, the synthesis was performed by changing the monomer ratio to be blended.

The details of each component described in Tables 2 to 4 below are as follows:
It is as follows. LAS-1: 48% of Nippon Oil Detergent Co., Ltd. alkylbenzene sulfonic acid "alkene L (alkyl chain having 10 to 14 carbon atoms)"
LAS-2: 50% of alkyl benzene sulfonic acid “alkene L (carbon number of alkyl chain is 10 to 14)” manufactured by Nisseki Detergent Co., Ltd.
Neutralized with KOH AS: Sodium salt of dovanol 25 sulfate (C12-C15 sulfate) manufactured by Mitsubishi Chemical Corporation SAS: Hostapur SAS manufactured by Hoechst Japan K.K.
93, C13-18 sodium alkane sulfonate AOS: sodium α-olefin sulfonate (C12
-14)-Fatty acid salt: sodium palmitate-AES: sodium polyoxyethylene alkyl (C12-15) ether sulfate (average number of moles of ethylene oxide (EO) added: 2)-AE-1: Nonided R-7 (of C12-C15) AE-2: Sophthanol 70 (C12-C15 secondary alcohol with an average of 7 moles of EO, manufactured by Nippon Shokubai) Zeolite A: crystalline aluminosilicate, 4A type zeolite, average particle size 2.7 μm, manufactured by Tosoh Corporation ・ Oil-absorbing carrier: TIXOLEX 25 (amorphous sodium aluminosilicate, manufactured by Kofran Chemical Co., oil absorption capacity 235)
ml / 100g ・ Crystalline silicate: alkali crystalline silicate, SKS-6
(Δ-Na ₂ Si ₂ O ₅ , crystalline layered silicate, average particle diameter 20 μm, Clariant Japan Co., Ltd. ・ Amorphous silicate: JIS No. 1 sodium silicate ・ Sodium carbonate: dense grain ash ・ PAA: sodium polyacrylate, average Molecular weight 12
000 AA-MA: socaran CP5, acrylic acid-maleic acid copolymer, average molecular weight 70000 PEG: polyethylene glycol, average molecular weight 600
0 ・ Fluorescent dye: Tinopearl CBS (Ciba-Geigy)
And Whitetex SA (manufactured by Sumitomo Chemical Co., Ltd.) in the same amount by weight.-Fragrance: Use the fragrance composition described in Examples of JP-A-8-239700.-Enzyme: Sabinase 12.0T type-W (protease ), Lipolase 100T (lipase), Termamyl 60T (amylase) (the above enzymes, manufactured by Novo Nordisk) and KAC
500 (alkaline cellulase, manufactured by Kao) in a weight ratio of 3:
PC: sodium percarbonate (average particle diameter 700 μm, sodium metaborate / JIS No. 1 sodium silicate = 2 parts by weight / 3 parts by weight with respect to 100 parts by weight of sodium percarbonate) AC-1: Granulated bleach activator [TAED (tetraacetylelenediamine)] AC-2: Granulated bleach activator [C12 to C14]
(Average 12.5) Sodium salt of esterified product of linear fatty acid and phenolsulfonic acid] (Both AC-1 and AC-2 have a bleaching activator / alkyl (C12) sulfate sodium salt having an average particle size of 600 μm. / Polyethylene glycol / succinic acid = 70/25/4
/ 1 (weight ratio).

<Examples 1 to 6, Comparative Examples 1 and 2> Cleaning agents shown in Table 1 using sodium percarbonate, polymers A to C, soda ash, and bleaching activators b-1 and b-2 described below. A composition was prepared and its mud washing performance was evaluated. Table 1 shows the results. As a comparative example, sodium polyacrylate (oligomer D manufactured by Kao Corporation, weight average molecular weight 10,000) was used.

[0055]

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<Examples 7 to 19 and Comparative Examples 3 to 5> The compositions of Examples 7 to 19 and Comparative Examples 3 to 5 were produced by the following methods. Among the components shown in Tables 2 to 4, AE-1 and AE
-2% by weight of zeolite A and 12% by weight of zeolite A, and the remaining components except for the total amount of crystalline silicate, fragrance, enzyme, PC, AC-1 and AC-2 were mixed with water, A detergent slurry having a solid content of 50% by weight (added water content of 50% by weight) was prepared. This was kept at a temperature of 65 ° C. and spray-dried with a countercurrent spray-drying apparatus to obtain low-density spray-dried particles. The resulting spray-dried particles were converted to zeolite A previously removed.
Was mixed in a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.) in an amount corresponding to 4% by weight in the table with the remaining AE-1 or AE-2 (Table 2). 3 in
(Corresponding to% by weight) while spraying and granulating while crushing, and performing a densification treatment. 30 seconds before the end of the granulation, zeolite A (corresponding to 4% by weight in the table) was added to the spray-dried particles to coat the surface of the detergent cloth and spray a fragrance at the same time. Next, the granulated product was sieved with a 1.3 mm opening sieve, and coarse particles on the sieve were pulverized with a Fitzmill (manufactured by Hosokawa Micron Corporation), and then mixed with the material passed through the sieve. After this sieving, the remaining zeolite A, enzyme, PC, AC-1 and AC-2 were mixed in a V blender, and then fine powder was removed to obtain a final granular detergent. The resulting detergent particles are 100
Almost no particles below 1 μm and above 1300 μm,
The bulk density of the high-density granular detergent was 750 ± 50 g / cm ³ , and the average particle size was 500 ± 30 μm.

<Embodiments 20 and 21> Embodiments 20 and 2
The composition of No. 1 was produced by the following method. In Table 3, zeolite A was used in an amount corresponding to 5% by weight in the table, AE-1, AE-2, an oil-absorbing carrier, a crystalline silicate, a fragrance, an enzyme, PC and AC-.
The remaining components except for the total amount of No. 2 were mixed with water to obtain a solid content of 50%.
A detergent slurry of 50% by weight (50% by weight of added water) was prepared. This was kept at a temperature of 65 ° C. and spray-dried with a countercurrent spray-drying apparatus to obtain low-density spray-dried particles. The amount of the obtained spray-dried particles except for the amount corresponding to 5% by weight in the table of the oil-absorbing carrier (Example 20: 15% by weight, Example 21: 5% by weight) Are mixed together in a Loedige mixer (Matsuzaka Giken), and AE-1 and AE-
The mixture was granulated while spraying No. 2 to increase the density. Thirty seconds before the end of the granulation, 5% by weight of an oil-absorbing carrier was added to coat the surface of the detergent cloth and simultaneously spray a fragrance. Next, the granulated product was sieved with a 1.3 mm mesh sieve, and the remaining amount of zeolite A corresponding to 15% by weight, enzyme,
After mixing PC and AC-2 with a V blender, fine powder was removed to obtain a final granular detergent. The resulting detergent particles are 100
Almost no particles below 1 μm and above 1300 μm,
Bulk density is 820 ± 50 g / cm ³ , average particle diameter 500 ± 3
It was 0 μm.

<Mud washing test> Preparation of contaminated cloth Knitted cloth (manufactured by Tanigato) was cut into 1m x 10cm strips, and gently poured into a mud solution (Kanuma mud 30μmpass product, 100g / L chloroform uniform dispersion). Soaked. This operation was repeated three times and air-dried. Then, excess mud attached to the surface was removed using a brush, cut into 10 cm × 10 cm, and used for the experiment.

Evaluation of mud washing power 1 (in the case of Examples 1 to 6 and Comparative Examples 1 and 2) In the case of Examples 1 to 6 and Comparative Examples 1 and 2, 2.5 g of the detergent composition was added to 500 ml of tap water. , And 5 sheets of the above-mentioned mud-contaminated cloth were dipped and left for 2 hours. Thereafter, the product was washed with a commercial detergent using a tergotometer, rinsed and dried, and the washing rate was determined by the following method. In addition, a detergent concentration of 0.067% by weight, a washing time of 10 minutes, 100 rpm
Was performed under the following conditions.

Evaluation of mud washing power 2 (in the case of Examples 7 to 21 and Comparative Examples 3 to 5) Examples 7 to 21 and Comparative Examples 3 to 5 were produced by the above-mentioned production method in 1 L of an aqueous detergent solution for evaluation. The high-density granular detergent composition was added so as to have the following concentration, and at the same time, five contaminated cloths were put in and washed with a tergotometer (set value: 100 rpm). Detailed washing conditions are as follows.・ Cleaning conditions Cleaning time: 10 minutes Cleaning agent concentration: 0.067% Water hardness: 71.2 mg CaCO ₃ / L (4 ° DH) Water temperature: 20 ° C. Rinse: 5 minutes with tap water ・ Measurement of cleaning rate Before contamination The reflectance at 550 nm of the original cloth and the contaminated cloth before and after cleaning were measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate was calculated by the following equation.

[0061]

(Equation 1)

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

Claims (2)

[Claims] 1. A cleaning composition containing a polymer represented by the following general formula (1). (A) _m (B) _n (1) wherein A represents a repeating unit having at least one carboxyl group in the molecule but not having another anionic group, and B represents a sulfonic acid in the molecule. A repeating unit having a group or a sulfate group, wherein the repeating units A and B are randomly polymerized or block polymerized, and m and n are represented by m: n = 1
00: 1 to 1: 1 and the polymer has a weight average molecular weight of 4,
The numbers indicate 000 to 200,000. ] 2. The cleaning composition according to claim 1, further comprising hydrogen peroxide or an inorganic peroxide that releases hydrogen peroxide in an aqueous solution.