WO1999031213A1

WO1999031213A1 - Detergent composition

Info

Publication number: WO1999031213A1
Application number: PCT/JP1998/005718
Authority: WO
Inventors: Nobuyuki Ogura; Nobuyoshi Yamaguchi; Muneo Aoyagi
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 1997-12-17
Filing date: 1998-12-17
Publication date: 1999-06-24
Anticipated expiration: 2000-06-17
Also published as: JPH11236593A

Abstract

The present invention provides a detergent composition exhibiting excellent detergency against mud stains. Specifically, a detergent composition comprising a polymer having the following general formula: (A)m(B)n in which A is a unit having at least one carboxylic group in the molecule, but no other anionic group; B is a unit having a sulfonic acid group or a sulfuric acid group in the molecule; (A)m and (B)n may form either a random or block polymer; and m and n are such numbers that the m/n ranges from 100:1 to 1:1 and that the weight-average molecular weight of the polymer ranges from 4,000 to 200,000.

Description

DESCRIPTION

DETERGENT COMPOSITION

Technical Field

The present invention relates to a detergent composition exhibiting high detergency against mud stains .

Background Art

Mud stains on socks or the like are difficult to wash off, because they are resulting from the firm adhesion of mud particles to the fibers. In order to remove such mud stains , there have been made proposals to add carboxylic acid polymers such as carboxy- methylcellulose or cellulase which is an enzyme. Furthermore, a process for enhancing the detergency against mud stains by using a specific phosphoric acid compound is disclosed in JP-A 3-26797, and another process therefor by impregnating a water-soluble inorganic powder with a nonionic surfactant is disclosed in JP-A 1-301798.

For the purpose of attaining satisfactory detergency against mud stains , there have been also made attempts to add polymers having a mud-dispersing power. For example, it is disclosed that fair detergency against mud stains can be attained by adding polyaspartic acid (JP-A 7-11295), a polyethylene glycol/polyacrylate mixture (US 4490271) or a specific polycarboxylic acid salt (JP-A 1-310730). However, the detergent compositions according to these techniques were still ones which could not be recognized as being satisfactory in detergency against mud stains.

Disclosure of Invention

The present invention aims at attaining a detergent composition having excellent detergency against mud stains. The present invention provides a detergent composition comprising a polymer having the general formula ( 1 ) :

(A)_B(B)_n (1) in which A is a unit having at least one carboxylic group in the molecule, but no other anionic group; B is a unit having a sulfonic acid group or a sulfuric acid group in the molecule; (A)_m and (B)_n may form either a random or block polymer; and m and n are such numbers that the m/n ranges from 100 : 1 to 1 : 1 and that the weight-average molecular weight of the polymer ranges from 4,000 to 200,000.

Further, the polymer may be a co-polymerization product having been obtained or being obtainable by co-polymerizing a mixture of co-monomers corresponding units A and B, respectively. It may have a block structure, a random structure or an alternating structure. A and B may include plural monomers.

Mode for Carrying Out the Invention

The units A and B constituting the polymer of the formula (1) to be used in the present invention may be respectively of the same kind or of two or more different kinds. Although it is preferable that the above polymer be composed only of the units A and B, the polymer may contain other constituent units as far as the objects of the present invention are not impaire .

Examples of the unit A include those represented by the following formulae (I) to (VIII), among which those represented by the formulae (I) to (IV) are preferable. In particular, those represented by the general formula (I) are still preferable in respects of polymerizability and economic efficiency: -CH₂CH(C0₂M) - (I)

-CH₂C(CH₃) (C0₂M)- (II)

-CH₂C(OH) (C0₂M)- (III)

-CH(C0₂M) -CH(C0₂M)- (IV) -CH(CH₃) -CH(C0₂M) - (V)

-CH(C0₂M) -C(C0₂M) -CH₂(C0₂M) - (VI)

-CH₂-C(C0₂M) -CH₂(C0₂M) - (VII)

-C(CH₃) (C0₂M) -CH(C0₂M)- (VIII) wherein M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or an alkanolamine .

It is preferable that the unit A be one derived from acrylic acid, methacrylic acid, a - hydroxyacrylic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, aconitic acid, itaconic acid, citraconic acid or a salt thereof. It is particularly preferable that the unit A be one derived from acrylic acid, methacrylic acid, maleic acid or a salt thereof.

The above polymer may comprise as the unit A one or more members selected from among those described above .

It is desirable in respect of detergency against mud stains that the unit B be one represented by the following formula (2): /

CH₂— c: (2)

wherein X is a hydrogen atom, R¹ or -COOM; and Y is -S0₃M, -CO-Z or -R²-T, wherein R¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group or a hydroxyalkylene group having 1 to 5 carbon atoms; Z is -NR -R³-T, wherein R⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyalkylene group having 1 to 5 carbon atoms; and R³ is an alkylene group having 1 to 5 carbon atoms which may be branched ; R² is an alkylene group having 1 to 5 carbon atoms; T is -S0₃M or -OS0₃M; and M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or an alkanolamine .

More specific examples of the unit B include those represented by the formulae (IX) to (XIV):

-CH₂-CH(CH₂S0₃M) - (IX) -CH₂-CH(CH₂OS0₃M) - (X) -CH₂-CH(CONHCH₂S0₃M) - (XI) -CH₂-CH[CONHC(CH₃)₂CH₂S0₃M] (XII) -CH₂-C(S0₃M) (COOM) - (XIII) -CQ₁(C0₂M)-CQ₂(C0₂M)- (xiv) wherein M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or an alkanolamine; and Q_λ and Q₂ are each a hydrogen atom or S0₃M, provided both of Qi and Q₂ must not be hydrogen simultaneously.

It is preferable that the unit B be selected from among those represented by the formulae ( IX) , (XII ) and (XIII) .

Specifically, it is preferable that the unit B be one derived from methacrylsulfonic acid, a styrenesulfonic acid such as styrenesulfonic acid, a -methylstyrenesulfonic acid or chlorostyrenesulfonic acid, 2 -acrylamido- 2-methylpropanesulfonic acid, 2- methacrylamido-2-methylpropanesulfonic acid, 2- acrylamidobutanesulfonic acid, 3-acrylamidobutane- 2-sulfonic acid, 3 -acrylamido- 2 , 3 - dimethylbutane- 2 - sulfonic acid, 2 -acrylamido- 2 , 4 , 4 - trimethylpentane- sulfonic acid, 2 -acrylamidocyclohexanesulfonic acid, 2 -acrylamido- 2-phenylethanesulfonic acid, 2- acrylamido-2-phenylpropanesulfonic acid, 2- acrylamido- 2 - tolylethanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid or a salt thereof. It is particularly preferable that the unit B be one derived from allylsulfonic acid. 2 -methacrylamido-2-methylpropanesulfonic acid or a salt thereof.

The above polymer may also comprise as the unit B one or more members selected from among those described above.

Most desirable examples of the combination of the units A and B as expressed in terms of corresponding monomers in the style of A/B include acrylic acid/ styrenesulf onic acid, acrylic acid/ allylsulfonic acid, acrylic acid/2- acrylamidobut anesulf onic acid, maleic acid/ allylsulfonic acid and salts thereof.

Although the polymer represented by the general formula (1) may take an acid form, it is preferable that part or the whole of the polymer take the form of a salt. Such a salt includes salts with alkali metals such as potassium and sodium, alkaline earth metals such as calcium, ammonium, and alkanolamines such as monoethanolamine . It is still preferable that the polymer be one neutralized with sodium, potassium or ammonium .

In the formula (1) , m and n are such numbers that the m/n ranges from 100 : 1 to 1 : 1 and that the weight - average molecular weight of the polymer ranges f rom 4 , 0 0 0 t o 2 0 0 , 0 0 0 .

It is desirable that the m/n ranges from 100 : 1 to 2 : 1, more desirably 100 : 1 to 5 : 1, still more desirably 50 : 1 to 5 : 1, particularly desirably 50 : 1 to 8 : 1, and most desirably 30 : 1 to 10 : 1.

It is desirable that the weight-average molecular weight ranges from 4,000 to 100,000, more desirably 5,000 to 100,000, particularly desirably 5,000 to 70,000, most desirably 5,000 to 50,000. The term "weight-average molecular weight" used in this specification refers to a value determined according to gel permeation chromatography (GPC) by the use of a polyethylene oxide reference (a product of Tosoh Corp.) as the standard sample. It is preferable that the detergent composition of the present invention comprise a polymer represented by the formula ( 1 ) in an amount of 0.1 to 30 % by weight , still preferably 0.5 to 20 % by weight.

It is preferable that the detergent composition of the present invention further comprise hydrogen peroxide or an inorganic peroxide to generate hydrogen peroxide in an aqueous solution thereof.

When the detergent composition is liquid, the use of hydrogen peroxide is preferable and the content thereof in the composition is preferably 0.1 to 20 % by weight, still preferably 0.5 to 15 % by weight, particularly preferably 0.5 to 10 % by weight. The limitation of the hydrogen peroxide content to 0.1 % by weight or above is desirable from the standpoint of attaining a satisfactory bleaching effect, while that of the content to 20 % by weight or below is desirable in respect of the stability of hydrogen peroxide.

When the detergent composition is powdery, it is preferable to use an inorganic peroxide to generate hydrogen peroxide in an aqueous solution thereof. The inorganic peroxide is particularly preferably sodium percarbonate or sodium perborate . The content thereof in the composition is preferably 0.5 to 99 % by weight, still preferably 1 to 95 % by weight.

With respect to general detergent compositions for clothes containing surfactants in amounts of 10 % by weight or above, it is preferable to add such an inorganic peroxide in an amount of 0.5 to 40 % by weight . When sodium percarbonate is added to a detergent containing zeolite, it is preferable in respect of stability that the sodium percarbonate be one coated with sodium borate and/or sodium silicate each in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the sodium percarbonate.

It is preferable that the detergent composition of the present invention comprise a surfactant. Although anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants can be used in the present invention, the use of an anionic or nonionic surfactant is desirable, and the use of an anionic surfactant is more desirable.

Preferable examples of the anionic surfactant include alkyl ( C₈-C₂₀ ) benzenesulfonates , sulfates of C₈-C₂₀ primary and secondary alcohols, sulfates of C₈-C₂₀ alcohol ethoxylates , paraffinsulfonates having 8 to 20 carbon atoms, a -olefinsulfonates having 8 to 20 carbon atoms, a -sulfofatty acid salts having C₈-C₂₀ alkyl chain, salts of alkyl esters of a -sulfofatty acids wherein the alkyl chain has 8 to 20 carbon atoms, and fatty acid salts having C₈-C₂₀ alkyl chain. In the present invention, it is still preferable to use a linear alkylbenzenesulfonate wherein the alkyl chain has 12 to 18 carbon atoms on the average or an alkylsulfate having 12 to 18 carbon atoms on the average. The counter ion is preferably an alkali metal, with sodium or potassium being particularly preferable. Preferable examples of the nonionic surfactant include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene glycol fatty acid esters and polyoxyethylene/polyoxypropylene block polymers . In the present invention, it is particularly preferable to use a polyoxyalkylene alkyl ether prepared by the addition reaction of a C₁₀-C₁₈ primary or secondary alcohol with 4 to 20 molecules of an alkylene oxide such as ethylene oxide and propylene oxide. In the present invention, it is preferable to use an anionic surfactant as the main surfactant. In particular, more excellent detergency against mud stains can be attained, when the content of anionic surfactants other than fatty acid salts accounts for at least 50 % by weight of the total surfactant content . It is preferable that the detergent composition of the present invention contain surfactants in an amount of 0.5 to 50 % by weight. Precisely, when the detergent composition is a general powdered one for clothes, it is preferable that surfactants be contained in an amount of 10 to 45 % by weight. When the detergent composition is a liquid one, it is preferable that they be contained in an amount of 20 to 50 % by weight. Further, when it is one containing a bleaching agent in an amount of 40 % by weight or above, it is preferable that they be contained in an amount of 1 to 10 % by weight .

It is preferable that the detergent composition of the present invention comprise one or more builders selected from among crystalline aluminosilicates, alkali agents , carboxylic acid polymers other than the polymers represented by the formula (1) and alkaline crystalline silicates. Crystalline aluminosilicates have been known as synthetic zeolites and have the ability to capture calcium ions or the like in water through ion exchange to thereby inhibit the adverse effects of hardness of water on detergency. The most of crystalline aluminosilicates may be zeolite A, X or P, zeolite A being particularly preferable. It is suitable to use a synthetic zeolite having a mean primary particle diameter of 0.1 to 10 Mm, particularly 0.1 to 5 m. It is preferable that the detergent composition comprise such a crystalline aluminosilicate in an amount of 1 to 60 % by weight, still preferably 5 to 50 % by weight . Examples of the alkali agent to be used in the present invention include not only alkali metal carbonates such as sodium carbonate known generically as "dense ash" and "light ash", sodium sesquicarbonate and sodium hydrogencarbonate; and JIS No. 1, 2 and 3 amorphous alkali metal silicates, but also phosphate salts (such as tripolyphosphoric acid salts) generally known as sequestering agents. These inorganic alkali agents are effective in forming the skeletons of particles in the preparation of detergent particles, thus permitting the production of a detergent excellent in fluidity. Further, organic alkali agents such as alkanolamines may be also used in the present invention .

It is preferable that the detergent composition comprise such an alkali agent in an amount of 5 to 50 % by weight, still preferably 10 to 40 % by weight. When a powdery or granular bleaching agent is added in an amount of 40 % by weight or above, it is preferable to add sodium carbonate as the alkali agent in an amount of 10 to 50 % by weight in terms of dense ash.

The term "alkaline crystalline silicate" used in this specification refers to one which exhibits a maximum pH of 11 or above in the form of a 0.1 % by weight

dispersion in ion-exchanged water at 20 °C and has such a high alkali buffer capacity that at least 5 ml of 0.1 N aqueous hydrochloric acid is consumed to lower the pH of one liter of the above dispersion to 10. Thus, alkaline crystalline silicates can be distinguished from crystalline aluminosilicates having pH values of lower than 11.

Examples of the alkaline crystalline silicate to be favorably used in the present invention include those having the following compositions: x(M₂0) ^• y(Si0₂) ^• z(Me_mO_n) *w(H₂0) (3) wherein M is a Group la element of the periodic table (preferably K and/or Na) ; Me is one member selected from among Group Ila, lib. Ilia, IVa and VIII elements of the periodic table or a combination of two or more members selected from among them (preferably Mg or Ca) ; y/x is 0.5 to 2.6; z/x is 0.01 to 0.9; w is 0 to 20; and n/m is 0.5 to 2.0.

The alkaline crystalline silicates having the above compositions (3) can be prepared by the process described in JP-A 7-89712.

Further, alkaline crystalline silicates having the following compositions can be also used favorably in the present invention:

M₂0 ^• x' (Si0₂) ^• y ' (H₂0) (4) wherein M is an alkali metal (preferably K and/or Na) ; x' is 1.5 to 2.6; and y' is 0 to 20 (preferably 0). The alkaline crystalline silicates represented by the formula (4) are described in JP-A 60-227895, Phys . Chem. Glasses.1, 127-138 (1966), Z. Kristallogr . , 129. 396-404 (1969) and so on. Further, they are commercially available under the trade name of "Na- SKS-6" ( δ -Na₂Si₂0₅) supplied by Clariant as a powdery or granular product. These crystalline silicates exhibit not only such high alkali buffer capacities as described above but also high ion exchange capacities.

It is preferable from the standpoint of attaining excellent detergency that the detergent composition comprise such an alkaline crystalline silicate in an amount of 1 to 40 % by weight, still preferably 3 to 30 % by weight.

Carboxylic acid polymers other than the polymers represented by the formula (1) not only exhibit a sequestering activity but also the activity of dispersing solid-particle stains on clothes into a washing solution and the activity of inhibiting the solid particles thus dispersed from redepositing on the clothes . Such carboxylic acid polymers include homopolymers and copolymers of acrylic acid, meth- acrylic acid and itaconic acid. Preferable examples of the copolymers include those prepared by copolymerizing the above monomer with maleic acid, among which those having molecular weights of thousands to a hundred thousand are still preferable. The carboxylic acid polymer to be used in the present invention also includes polyglycidic acid salts; cellulose derivatives such as carboxylmethylcellulose ; and polymers of amino carboxylic acids such as polyaspartic acid salts.

These polymers exhibit sequestering, dispersing and antiredeposition activities.

It is preferable that the detergent composition comprise a carboxylic acid polymer other than the polymers of the formula (1) in an amount of 1 to 20 % by weight, still preferably 2 to 10 % by weight.

When hydrogen peroxide or an inorganic peroxide which generates hydrogen peroxide in an aqueous solution thereof is added to the detergent system, at least one bleaching activator represented by the following formula (5) can be used preferably in an amount of 0.1 to 20 % by weight, still preferably 0.5 to 30 % by weight:

wherein n is a number of 7 to 11; and Y is -S0₃M or -COOM, wherein M is a hydrogen atom, an alkali metal, an alkaline earth metal or ammonium. Examples of such a bleaching activator include sodium lauroyloxybenzenesulfonate , sodium decanoyl- oxybenzenesulfonate , sodium octanoyloxybenzene- sulfonate, lauroyloxybenzoic acid , decanoyloxybenzoic acid and octanoyloxybenzoic acid. The detergent composition of the present invention may additionally contain one or more of the components described in JP-A 8-218093 from line 44 of column 8 on page 5 to line 17 of column 11 on page 7. Further, it is preferable that the detergent composition contain various additives at need, and such additives include organic sequestering agents such as citric acid; fillers such as sodium sulfate; dispersing agents such as polyethylene glycol and polyvinyl alcohol; color migration inhibitors such as polyvinylpyrrolidone ; enzymes such as protease, cellulase, amylase and lipase; enzyme stabilizers such as boron compounds and sodium sulfite; fluorescent dyes such as biphenyl and stilbene dyes; antifoamers such as silicone and silica; antioxidants ; coloring agents and perfumes . When the detergent composition of the present invention comprises hydrogen peroxide or an inorganic peroxide which generates hydrogen peroxide in an aqueous solution thereof, it is preferable to add a sequestering agent as listed in JP-A 9-217090 from line 44 of column 8 to line 35 of column 9. When the detergent composition is a liquid bleaching detergent composition containing hydrogen peroxide, it is preferable to add the components described in JP-A 9-217090 from line 41 of column 9 to line 9 of column 11, while when the detergent composition is a granular or powdery bleaching detergent composition, it is preferable to add the components described in JP-A 8-74170 from line 47 of column 7 to line 9 of column 8. When the detergent composition of the present invention takes a granular form having a high bulk density, it is preferable from the standpoint of attaining desirable powder characteristics that the

mean particle diameter be 200 to 1000 Mm, still preferably 200 to 600 U rn . In particular, it is desirable that the composition is free from particles whose diameters are 100 μ m or below or 1300 μ m or above . The bulk density is preferably 0.5 to 1.2 g/cm³, still preferably 0.6 to 1.0 g/cm³.

Example <Synthesis of polymers) ^• Synthesis of Polymer A

(weight-average molecular weight: 8200, n/m: 20/1) Fifty grams (0.53 mol) of sodium acrylate (a product of Aldrich Chemical Co., Inc.), 3.8 g (0.027 mol) of sodium allylsulfonate (a product of Wako Pure Chemical Industries, Ltd. ) , 5 gof potassium persulfate, 5 g of ethanol, 0.05 g of sodium hypophosphite and 500 g of ion-exchanged water were charged into a 1-1 four-necked flask equipped with a thermometer, a mechanical stirrer, a condenser and a nitrogen inlet tube. The contents were reacted at 90 to 100 C for 8 hours , while nitrogen from the nitrogen inlet tube was bubbled into the contents. Then, the contents were concentrated into a 35 % aqueous solution by the use of an evaporator. The GPC analysis of the solution revealed that the polymer thus formed had a molecular weight of 8200. ^• Synthesis of Polymer B

—(CHr-CH*,—(CHr-CH)*—

COONa CONHC(CH₃)₂CH₂Sθ3Na

(weight-average molecular weight: 21000, n/m: 5/1)

Fifty grams (0.53 mol) of sodium acrylate (a product of Aldrich Chemical Co., Inc.), 3.8g (0.11 mol) of sodium 2-acrylamido- 2 -methylpropanesulfonate (a product of Wako Pure Chemical Industries, Ltd., a product of neutralization with NaOH) , 1 g of an azo polymerization initiator (a product of Wako Pure Chemical Industries, Ltd., V-50), 5 g of ethanol, 0.05 g of sodium hypophosphite and 500 g of ion-exchanged water were charged into the same four-necked flask as used above. The contents were reacted at 70 to 80 ^*C for 8 hours, while nitrogen from the nitrogen inlet tube was bubbled into the contents. Then, the contents were concentrated into a 37 % aqueous solution by the use of an evaporator. The GPC analysis of the solution revealed that the polymer thus formed had a molecular weight of 21000. ^• Synthesis of Polymer C

(weight-average molecular weight: 36000, n/m: 30/1) Fifty grams (0.53 mol) of sodium acrylate (a product of Aldrich Chemical Co., Inc.), 3.47 g (0.0177

mol) of disodium salt of a -sulfoacrylic acid (prepared by sulfonating methyl acrylate with S0₃ , hydrolyzing the obtained product and recrystallizing the hydrolyzate ) , 1 g of an azo polymerization initiator (a product of Wako Pure Chemical Industries, Ltd. , V-50) , 5 g of ethanol, 0.05 g of sodium hypophosphite and 500 g of ion-exchanged water were charged into the same four-necked flask as used above. The contents were reacted at 70 to 80 °C for 8 hours, while nitrogen from the nitrogen inlet tube was bubbled into the contents . Then, the contents were concentrated into a 37 % aqueous solution by the use of an evaporator. The GPC analysis of the solution revealed that the polymer thus formed had a molecular weight of 36000.

^• Synthesis of Polymer D

(weight-average molecular weight: 10000, n/m: 50/1) Prepared according to the above process for the preparation of Polymer A except that the proportions of the monomers were changed.

^• Synthesis of Polymer E

(weight-average molecular weight: 10000, n/m: 2/1) Prepared according to the above process for the preparation of Polymer A except that the proportions of the monomers were changed.

^• Synthesis of Polymer F

(weight-average molecular weight: 2000, n/m: 2/1) Prepared according to the above process for the preparation of Polymer A except that the proportions of the monomers were changed.

The components listed in Tables 2 to 4 will now be described in detail.

^• LAS-1 : sodium alkylbenzenesulfonate wherein the alkyl chain has 10 to 14 carbon atoms

^• LAS-2: potassium alkylbenzenesulfonate wherein the alkyl chain has 10 to 14 carbon atoms ^• AS: sodium salt of sulfate of "Dobanol 25" (C₁₂-C₁₅ alcohol mfd. by Mitsubishi Chemical Corp.)

^• SAS : a product of Hoechst Japan Ltd., "Hostapur SAS 93", sodium C₁₃-C₁₈ alkanesulfonate ^• AOS: sodium a - olefinsulfonate (C₁₂-C₁₄)

^• fatty acid salt: sodium palmitate

^• AES: sodium salt of sulfate of polyoxyethylene alkyl ( C₁₂-C₁₅ ) ether (the average number of ethylene oxide (EO) molecules added: 2) ^• AE-1: "Nonidet R-7" (a product of Mitsubishi Chemical Corp., an adduct of C₁₂-C₁₅ alcohol with an average of 7.2 EO molecules)

^• AE-2: "Softanol 70" (a product of Nippon Shokubai Co . , Ltd., an adduct of C₁₂-C₁₅ secondary alcohol with an average of 7 EO molecules)

^• zeolite A: crystalline aluminosilicate, type A zeolite, mean particle diameter: 2.7 p. m , a product of Tosoh Corp.

^• oil absorbing carrier : "TIXOLEX25" ( amorphous sodium aluminosilicate, a product of Kofran Chemical, oil absorption: 235 ml/100 g)

^• crystalline silicate : alkaline crystalline silicate , "SKS-6" ( δ -Na₂Si₂0₅) , crystalline layered silicate. mean particle diameter: 20 Mm, a product of Clariant Japan

^• amorphous silicate: JIS No .1 sodium silicate

^• sodium carbonate: dense granular ash ^• PAA: polysodium acrylate, average molecular weight: 12000

^• AA-MA: "Sokalan CP5", acrylic acid/maleic acid copolymer, average molecular weight: 70000

^• PEG: polyethylene glycol, average molecular weight: 6000

^• fluorescent dye: a 1 : 1 (by weight ) mixture of "Tinopal CBS" (a product of Ciba Geigy) with "Whitex SA" (a product of Sumitomo Chemical Co., Ltd.)

^• perfume: the same perfume composition as described in Example of JP-A 8-239700

^• enzyme: a mixture comprising "Sabinase 12.0T type W" (protease), "Lipolase 100T" (lipase), "Termamyl 60T" (amylase) (these three enzymes are products of Novo Nordisk) and "KAC500" (alkali cellulase, a product of Kao Corporation) at a weight ratio of 3 : 2 : 1 : 0.5.

^• PC: sodium percarbonate (a product having a mean particle diameter of 700 Mm, obtained by coating 100 parts by weight of sodium percarbonate with 2 parts by weight of sodium metaborate and 3 parts by weight of JIS No .1 sodium silicate)

^• AC-1: granulated bleaching activator [TAED ( tetra-acetylethylenediamine ) ]

^• AC-2: granulated bleaching activator [sodium salt of ester of linear fatty acid having 12 to 14 carbon atoms (12.5 carbon atoms on the average) with phenolsulfonic acid]

(AC-1 and AC-2 are products having a mean particle diameter of 600 Mm, obtained by the extruding granulation of a mixture comprising the bleaching activator, sodium salt of C₁₂ alkyl sulfate, polyethylene glycol and succinic acid at a weight ratio of 70/25/4/1) <Examples 1 to 6 and Comparative Examples 1 and 2>

Detergent compositions were prepared according to the formulations specified in Table 1 by using sodium percarbonate. Polymers A to C, soda ash and Bleaching Activators b-1 and b-2 which will be described below, and examined for detergency against mud stains. The results are given in Table 1. In Comparative Examples was used polysodium acrylate (weight-average molecular weight: 10000, a product of Kao Corporation, "Oligomer D" ) .

a polymer mfd. by Sumitomo Chemical Co. Ltd a copolymer of

with acrylic acid

Compositions of Examples 7 to 19 and Comparative Examples 3 to 5 were prepared by the following process. Excepting a portion (corresponding to 3 % by weight) of AE-1 and AE-2, a portion (corresponding to 12 % by weight) of zeolite A and the whole amounts of crystalline silicate, perfume, enzyme, PC, AC-1 and AC-2, all of the components listed in Table 2, 3 or 4 were mixed with water to prepare a detergent slurry having a solid content of 50 % by weight (i.e., the content of water added was 50 % by weight ) . This slurry was kept at 65 °C and spray-dried by the use of a counter-flow spray dryer to obtain low-density spray-dried particles.

In a high-speed mixer (mfd. by Fukae Kogyo K.K) , the spray-dried particles were mixed with a portion (corresponding to 4 % by weight) of the zeolite previously put aside and the crystalline silicate put aside, and the mixture was granulated through crushing, while the rest (corresponding to 3 % by weight) of AE-1 or AE-2 was sprayed thereon. Thus, the density of the particles was enhanced. Thirty seconds before the completion of the granulation, a portion (corresponding to 4 % by weight) of zeolite A was added to the resulting spray-dried particles to coat the detergent particles therewith, simultaneously with the spraying of the perfume thereon. Then, the resulting particles were passed through a screen having an opening of 1.3 mm. The oversize coarse particles were pulverized by the use of a Fits mill (mfd. by Hosokawa Micron Corp.) and then mixed with the undersize particles. The resulting particles were mixed with the rest of zeolite A and the enzyme, PC, AC-1 and AC-2 put aside in a type V blender. The obtained mixture was freed from dust-size particles to give a final powdered detergent . This detergent little contained particles whose sizes were 100 M m or below or 1300 M m or above, and had a bulk density of 750 ± 50 g/cm³ and a mean particle diameter of 500 ± 30 Mm. <Examples 20 and 21> Compositions of Examples 20 and 21 were prepared by the following process.

Excepting a portion (corresponding to 5 % by weight) of zeolite A, and the whole amounts of AE-1, AE-2, oil-absorbing carrier, crystalline silicate, perfume, enzyme, PC and AC-2, all of the components listed in Table 3 were mixed with water to prepare a detergent slurry having a solid content of 50 % by weight (i.e. , the content of water added was 50 % by weight) . This slurry was kept at 65 °C and spray-dried by the use of a counter-flow spray dryer to obtain low-density spray-dried particles.

In a Lδdige mixer (mfd. by Matsuzaka Giken K.K) , the spray-dried particles were mixed with a portion (corresponding to the amount specified in Table 3 minus 5 % by weight, i.e. , 15 % by weight in Examples 20, and 5 % by weight in Example 21 ) of the oil-absorbing carrier and the crystalline silicate put aside, and the mixture was granulated, while the AE-1 and AE-2 put aside were sprayed thereon. Thus, the density of the spray-dried particles was enhanced. Thirty seconds before the completion of the granulation, the rest (corresponding to 5 % by weight) of the oil-absorbing carrier was added to the resulting spray-dried particles to thereby coat the detergent particles therewith, simultaneously with the spraying of the perfume thereon. Then, the resulting particles were passed through a screen having an opening of 1.3 mm. The resulting particles were mixed with the rest (corresponding to 15 % by weight ) of zeolite A and the enzyme, PC and AC-2 put aside in a type V blender. The obtained mixture was freed from dust-size particles to give a final powdered detergent. This detergent little contained particles whose sizes were 100 Mm or below or 1300 Mm or above, and had a bulk density of 820 ± 50 g/cm³ and a mean particle diameter of 500 ± 30 Mm. <Cleansing test on mud> ^• Preparation of stained cloth

Knitted cloth (a product of Yato Shoten) was cut into strips (1 10 cm) , and these strips were gently immersed in a mud solution (a homogeneous dispersion of 100 g of Kanuma tsuchi (a kind of tephra) passing through a 30 Mm sieve in one liter of chloroform) . This immersion was repeated thrice, and the resulting strips were spontaneously dried and brushed to remove the excess mud adhering to the surfaces. The strips were cut into pieces (10 cm X 10 cm) and these pieces were subjected to the test. ^• Evaluation 1 for detergency against mud stains (with respect to the detergent compositions of Examples 1 to 6 and Comparative Examples 1 and 2)

With respect to the detergent compositions of Examples 1 to 6 and Comparative Examples 1 and 2, 2.5 g of each detergent composition was dissolved in 500 ml of tap water, and five muddy pieces prepared above were immersed in the obtained solution for 2 hours. Then, the pieces were washed with a commercially available detergent in a Terg-O-Tometer , and rinsed and dried. The rate of cleansing was determined according to the method which will be described below. The washing in a Terg-O-Tometer was conducted under the conditions of a detergent concentration of 0.067 % by weight, a washing time of 10 minutes and 100 rpm . ^• Evaluation 2 for detergency against mud stains (with respect to the detergent compositions of Examples 7 to 21 and Comparative Examples 3 to 5)

With respect to the detergent compositions of Examples 7 to 21 and Comparative Examples 3 to 5 , each high-density powdered detergent composition prepared above was added to one liter of an aqueous detergent solution for evaluation in the following concentration. The resulting solution and five muddy pieces prepared above were put in a Terg-O-Tometer simultaneously and the muddy pieces were washed therein (at 100 rpm). Detailed washing conditions are as follows:

^• Washing conditions washing time: 10 min detergent concn.: 0.067 % hardness of water: 71.2 mg CaC0₃/L (4^° DH) temp, of water: 20 'C rinsing: with tap water for 5 min.

^• Determination of rate of cleansing The rate of cleansing of the stained cloth was determined by measuring the reflectivities at 550 nm of the unstained cloth and the stained cloth before and after the washing by the use of a self -colorimeter (mfd. by Shimadzu Corporation) and calculating the rate of cleansing according to the following formula.

Rate of cleansing (%) = (reflectivity after washing - that before washing )/( that of unstained cloth - that before washing) X 100 Table 1

Table2

Table3

Table4

Claims

CLA IMS

1. A detergent composition comprising a polymer having a weight-average polymerization degree of 4,000 to 200,000 and having the formula (1): (A)_m(B)_n (1)

in which A is a unit having at least one carboxylic group in the molecule, but no other anionic group; B is a unit having sulfonic acid group or sulfuric acid group; (A)_m and (B)_n may form either a random or block polymer; m

and n are polymerization degrees; and m/n ranges from 100: 1 to 1:1.

2. The composition as claimed in Claim 1, wherein the m/n ranges from 100:1 to 2:1.

3. The composition as claimed in Claim 1 , which further comprises hydrogen peroxide or an inorganic peroxide to generate hydrogen peroxide in an aqeuous solution thereof .

4. The composition as claimed in Claim 1, which comprises 0.1 to 30 percent by weight of the polymer and the balance of conventional additives.

5. The composition as claimed in Claim 1, in which the polymer has a weight-average polymerization degree of 5 , 000 to 100 , 000.

6. The composition as claimed in Claim 1, in which A is derived from a carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, α -hydroxyacrylic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, aconitic acid, itaconic acid and citraconic acid or a salt thereof with an alkali metal, an alkaline earth metal, ammonium or an alkanolamine.

7. The composition as claimed in Claim 1, in which B has the formula (2) -(CH₂-CXY)- (2) in which X is hydrogen atom, R^ or -COOM, R^ being an alkyl having 1 to 10 carbon atoms, an aryl or a hydroxyalkylene having 1 to 5 carbon atoms, M being hydrogen atom, an alkali metal , an alkaline earth metal , ammonium or an alkanolamine, Y is -SO3M, -COZ or -R₂- , M being defined as above, Z being -NR4-R₃-T, R₄ being

hydrogen atom, an alkyl having 1 to 5 carbon atoms, a hydroxyalkylene having 1 to 5 carbon atoms, R₃ being an alkylene having 1 to 5 carbon atoms which may be branched, R₂ being an alkylene having 1 to 5 carbon atoms , T being -SO₃M or -OSO₃M, M being defined as above.