AU620140B2 - Detergent compositions - Google Patents

Description

I I I l4' 620140

AUSTRALIA

PATENTS ACT 1952 COMPLETE SPECIFICATION Form

(ORIGINAL)

FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: o 0 0 0*BI 0 *40 TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: 04 04 0 0 08 a oo UNILEVER PLC UNILEVER HOUSE

BLACKFRIARS

LONDON EC4

ENGLAND

Actual Inventor: Address for Service: GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.

0 *608 Complete Specification for the invention entitled: DETERGENT COMPOSITIONS The following statement is a full description of this invention including the best method of performing it known to me:-

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q Y IA- C.3267 o e 4 e a o 0 005 DETERGENT COMPOSITIONS TECHNICAL FIELD The present invention relates to fabric washing detergent compositions built with zeolite and having improved antiredeposition properties.

BACKGROUND AND PRIOR ART Redeposition of soil removed from washed articles t a o 00 0-0- 0 o back onto the articles themselves is a well-known problem which is of particular significance with textile fabrics, 15 and many solutions to this problem have been suggested.

Classically, sodium carboxymethyl cellulose was incorporated into fabric washing compositions, and that compound is still used today. More recently, copolymers of ethylene or vinyl methyl ether and maleic anhydride, copolymers of acrylic acid and maleic anhydride, and homopolymers of acrylic acid have been suggested in the patent literature; see, for example, GB 1 269 848 (Procter Gamble) and GB 1 460 893 (Unilever).

j 2 C.3267 EP 219 048A (BASF) discloses the use of graft copolymers of polyalkylene oxide with vinyl acetate as greying inhibitors in the washing and post-wash treatment of synthetic textile fabrics.

We have now discovered that detergent compositions built predominantly or wholly with zeolite and containing a graft copolymer of this type in conjunction with an acrylic and/or maleic polymer exhibit surprisingly enhanced soil suspension (antiredeposition) properties on polyester and polyester/cotton fabrics. A corresponding improvement is not observed with phosphate-built compositions.

10 50 *000 c DEFINITION OF THE INVENTION te 00*000t 005400C The present invention provides a detergent composition comprising: from 2 to 50% by weight of a detergent active system comprising one or more anionic, nonionic, cationic, zwitterionic or amphoteric surfactants; from 10 to 60% by weight of crystalline or amorphous alkali metal aluminosilicate; 00W 0 OIUI 25 0* 0 P 0 O 00 from 0.5 to 5% by weight of a polycarboxylate polymer comprising (meth)acrylate units and/or maleate units in acid or salt form; and from 0.1 to 3% by weight of a graft copolymer of polyethylene oxide, polypropylene oxide or polybutylene oxide with (ii) vinyl acetate (optionally partially saponified) in a weight ratio of to (ii) of from 1:0.2 to 1:10.

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3 C.3267 DETAILED DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions containing four specified ingredients a surfactant system, an aluminosilicate builder, a polycarboxylate polymer, and a graft copolymer which may additionally contain any other conventional detergent ingredients, for example, other builders, bleach systems, antifoam systems, fluorescers, inorganic salts, and other materials well known to those skilled in formulating detergents. The compositions of the invention may take any suitable foriil, for example, powders, liquids or bars.

t 0 Ott 15 The surfactant system The total amount of detergent-active material (surfactant) in the compositions of the invention is from 2 to 50% by weight, and is preferably from 5 to 40% by weight.

o The compositions of the invention may contain one or more soap or non-soap anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, or combinations o* 25 of these. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", tit' Volumes I and II, by Schwartz, Perry and Berch.

The preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic surfactants and nonionic surfactants.

I I -i 4 C.3267 Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8

-C

15 primary and secondary alkyl sulphates, particularly sodium C 12

-C

15 primary alcohol sulphates; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.

Suitable nonionic detergent compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.

o° Specific nonionic detergent compounds are alkyl (C6- 22 phenol-ethylene oxide condensates, the condensation °oO products of linear or branched aliphatic C 8 20 primary or secondary alcohols with ethylene oxide, and products made 0 0 20 by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long-chain tertiary amine oxides, tertiary phosphine oxides, and -go, dialkyl sulphoxides.

Especially preferred are the primary and secondary alcohol ethoxylates, especially the C 1 2 -5 primary and secondary alcohols ethoxylated with an average of from to 20 moles of ethylene oxide per mole of alcohol.

It may also be desirable to include one or more soaps of fatty acids. These are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rape seed oil.

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1 I 5 C.3267 A preferred type of detergent composition suitable for use in most automatic fabric washing machines contains anionic and nonionic surfactant together in a weight ratio of at least 0.67:1, preferably at least 1:1, and more preferably within the range of from 1:1 to 10:1.

Soap may also be present if desired.

The aluminosilicate builder 0 The detergent compositions of the invention contain from 10 to 60% by weight, preferably from 15 to 50% by weight, of crystalline or amorphous alkali metal aluminosilicate builder.

0 0 0 o 0 00 *0* 0 r o oo oo O a o ooo0 The alkali metal (preferably sodium) aluminosilicates used in the compositions of the invention may be either crystalline or amorphous or mixtures thereof, and they have the general formula: 0.8-1.5 Na20. A1 2 0 3 0.8-6 SiO 2 These materials contain some bound water and are required to have a calcium ion exchange capacity of at least about 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.

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i 1 a i:: 6 C.3267 Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 473 201 (Henkel) and GB 1 429 143 (Procter Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites,. particularly zeolites A and X, and mixtures thereof. Especially preferred is zeolite 4A.

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o *006 15 o a; 20 Other builders may also be included in the compositions of the invention if necessary or desired: suitable organic or inorganic water-soluble or water-insoluble builders will readily suggest themselves to the skilled detergent formulator. Inorganic builders that may be present include alkali metal (generally sodium) ortho-, pyro- and tripolyphosphate, and carbonate; while organic builders include nitrilotriacetates, citrates and carboxymethyloxysuccinates. This list is not intended to be exhaustive. The total level of detergency builder is generally within the range of from 20 to 80% by weight.

According to a preferred embodiment of the invention, the compositions contain less than 10% by weight of inorganic phosphate builders, and are more preferably substantially free of inorganic phosphate.

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7 C.3267 The polycarboxylate polymer The compositions of the invention also contain from to 5% by weight, preferably from 1 to 3% by weight, of a polycarboxylate polymer containing (meth)acrylate and/or maleate units. These anionic polymers may be in acid form or in wholly or partially neutralised salt form. Preferred polymers are homopolymers and copolymers of acrylic acid. Of especial interest are polyacrylates, acrylic/maleic acid copolymers, and acrylic phosphinates.

*4 0e 0 004 09 B* 09$ 0 0$ $0 000* Suitable polymers, which may be used alone or in combination, include the following: Polymer type Trade name Supplier Polyacrylate *o o 00oo 00 0 @0 0 Polyacrylate Polyacrylate Versicol* Versicol* E7 Versicol* E9 Narlex* LD 30 Narlex* LD 34 Allied Colloids Allied Colloids Allied Colloids National Adhesives National Adhesives Average m.wt.

3500 27 000 70 000 @o 0 oor Polyacrylate Polyacrylate 5000 25 000 8 C. 3267 Polymer type Trade name Supplier Average M.Wt.

Polyacrylate Polyacrylate a 09 0 0 00 0 000 0 0 00 Polyacrylate Polyacrylate Polyacrylate Acrysol* LMW- 10 Acrysol* LMW- 2 0 Acrysol* LMW-45 Ac rysol1* Al1- 1\ Sokalan* Sokalan* Sokalan* Sokalan* PA-110 R8hxn Haas R~5hx Haas R~5hm Haas R~hm H-aas

BASF

1000 4500 2000 60 000 2500 0 0 0 0 0600 Polyacrylate Polyacrylate

BASF

BASF

BAS F 15 000 70 000 Polyacrylate 250 000 I, I

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A ,i 9 C.3267 Polymer type Trade name Supplier Ethylene/ maleic acid EMA* Monsanto Methyl vinyl ether/maleic acid Acrylate/ maleate Gantrez* AN 119 Sokalan* CP5, CP7

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Belsperse*

GAF

Corporation

BASF

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Acrylic phosphinate Acrylic phosphinate National Adhesives Ciba-Geigy *denotes Trade Mark 000 06a O 0 a 00 0e 06 o The graft copolymer The graft copolymers used in the compositions of the present invention are described and claimed in EP 219 048A (BASF). They are obtainable by grafting a polyalkylene oxide of molecular weight (number average) 2000 100 000 with vinyl acetate, which may be partially saponified, in a weight ratio of polyalkylene oxide to vinyl acetate of 1:0.2 to 1:10. The vinyl acetate may, for example, be saponified to an extent of up to 15%. The polyalkylene oxide may contain units of ethylene oxide, propylene oxide and/or butylene oxide; polyethylene oxide is preferred.

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a p i n r I i 10 C.3267 Preferably the polyalkylene oxide has a number-average molecular weight of from 4000 to 50 000, and the weight ratio of polyalkylene oxide to vinyl acetate is from 1:0.5 to 1:6. Especially preferred are polymers derived from polyethylene oxide of molecular weight 2000-50 000 and having a weight ratio of polyethylene oxide to vinyl acetate of from 1:0.5 to 1:6.

A material within this definition, based on polyethylene oxide of molecular weight 6000 (equivalent to 136 ethylene oxide units), containing approximately oO*, 3 parts by weight of vinyl acetate units per 1 part by 0. weight of polyethylene oxide, and having itself a o omolecular weight of 24 000, is commercially available 15 from BASF as Sokalan (Trade Mark) HP22.

0 000 The polymers are present in the compositions of the invention in amounts of from 0.1 to 3% by weight, preferably from 0.3 to 1% by weight.

o 00 o0 0 Optional ingredients As well as the four ingredients surfactant system, detergency builder, polycarboxylate polymer and graft copolymer already specified, the compositions ,C of the invention may contain any other non-interfering ingredients known to be suitable for incorporation into detergent compositions.

For example, the detergent compositions according to the invention may suitably contain a bleach system.

Preferred are peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve ;i j 1 11 C.3267 bleaching action at low wash temperatures. The skilled detergent worker will have no difficulty in applying the normal principles to choose a suitable bleach system.

Other materials that may be present in the detergent compositions of the invention include sodium silicate, fluorescers, inorganic salts such as sodium sulphate, enzymes, lather control agents or lather boosters as appropriate, pigments, and perfumes. Again, this list is not intended to be exhaustive.

00 Preparation of detergent compositions 15 Detergent compositions of the invention may be 0 prepared by any suitable method. Deterqent powders are suitably prepared by spray-drying a slurry of compatible heat-insensitive components, and then spraying on or postdosing those ingredients unsuitable for processing via the slurry. The skilled detergent formulator will 0 o generally have no difficulty in deciding which components o°o should be included in the slurry and which should be postdosed or sprayed on.

0 00 *0 0 The graft copolymer is available as a solution having a solids content of 20% which is stable at slurry processing temperatures and can be incorporated in the slurry without problems, provided that the pH is maintained below 12.

Similarly, the polycarboxylate polymer can normally j be included in the slurry.

The invention is further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated.

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EXAMPLES

Examples 1 to 3 Detergent compositions were prepared to the following formulation by conventional slurry-making, spray-drying and postdosing techniques: o s 00 4 0 40 00 00 00 0 Sodium linear alkylbenzene sulphonate Nonionic surfactant 7EO Zeolite 4A (hydrated basis) 15 Sodium alkaline silicate Sodium sulphate Sodium carbonate Sodium carboxymethylcellulose Fluorescer 20 Sodium perborate monohydrate Tetraacetylethylenediamine (76% granules) Enzyme granules Sodium polyacrylate (see below) Graft copolymer (Sokalan HP22) Water and minor ingredients 24.0 19.3 0.7 0 or 2., 0 or to 100.0 040 0 0 0 io 's 0 0 5 04 S C 4' t The sodium polyacrylate polymers used were Sokalan PA 20, PA 40 and PA 110 (see previously). The polymers present in the various compositions prepared are shown in Table 1 below.

ii LLj~ I -ilL _V- LIII iI i I 13 C.3267 The soil suspension (antiredeposition) properties of the compositions were compared by means of the following procedure. Two new, clean, unwashed polyester test cloths were washed together with five soiled cloths in a tergotometer at 60 C in 500 (French) hard water (Ca:Mg ratio 4:1) at a liquor to cloth ratio of about 50:1, the wash liquor containing 4 g/l of the detergent composition under test. The soiled cloths carried a range of different soils such as clay, oil, fat, proteinaceous, and ink. The wash cycle was repeated a further nine times, the soiled cloths being replaced by new soiled cloths (with the same range of soils) for each wash 0 0 0 cycle.

0e oo I 15 The reflectance of the two new cloths was measured S before washing, and after the tenth wash cycle. The reduction in reflectance of the washed fabrics after ten washes is shown in Table 1; the lower the reduction in reflectance, the less redeposition had occurred.

It will be seen that Compositions 1 to 3 illustrates the invention while Compositions A to E are comparative.

O06 °o The graft copolymer Sokalan HP22 had little effect on its 0 ocwn on redeposition. The polyacrylates became 25 increasingly effective with increasing molecular weight at reducing redeposition, but for each of them the effect was considerably enhanced by the presence of the graft 4"l copolymer.

4i iui mm 1 1i I i 14 C.3267 Table 1 Example Polymers Reflectance change (delta R 460 no polymers Sokalan HP22 o 00 o o a0000 Sokalan HP22 0.5% Sokalan HP22 0.5% Sokalan HP22 2.0% 2.0% 2.0% 2.0% 2.0% Sokalan PA 20 Sokalan PA 20 Sokalan PA 40 Sokalan PA 40 Sokalan PA 110 Sokalan PA 110 -7.1 -4.3 -2.3 -2.3 -1.6 9044 o o o0 0o* o 0 0 00 o o0 o orl 0 0 4 0004 0 00 C00 0 0 00 00 0 f Examples 4 and The procedure of Examples 1 to 3 was repeated using 25 acrylic/maleic copolymers instead of the sodium polyacrylates. These were Sokalan CP5 and Sokalan CP7, which differ in the proportions of acrylic units and maleic units they contain: Sokalan CP5 contains about by weight of acrylic units and 30% by weight of maleic units, while Sokalan CP7 contains about 50% by weight of each.

1': ii: :1 if i A i~~ 15 C.3267 The compositions prepared, and the results obtained, are shown in Table 2 below, the controls A and B being shown again for comparison. Again, numbered compositions illustrate the invention while those represented by letters are comparative. The two acrylate/maleate copolymers were both quite effective at reducing redeposition, but for each of them the effect was considerably enhanced by the presence of the graft copolymer.

Table 2 00 9 o og 0r 09 .99*'Uq 15 09 0 0 0 t) 9, Example Polymers Reflectance change (delta RiG,)

A

B

no polymers 0.5% Sokalan HP22 -7.1 09 o o 0 049 9 0 no 0 9 @6 r0 0 o 0 a (99 0.5% Sokalan 0.5% Sokalan 2.0% Sokalan CP 5 HP22 2.0% Sokalan CP 5 Sokalan CP 7 HP22 2.0% Sokalan CP 7 -3.4 -2.6 -4.0 -3.2 i i r ;ii i a i: I ;i 0 0 d 'L rC C ij 1

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16 C.3267 Comparative Examples H to V The procedure of Examples 1 to 5 Vas repeated using a phosphate-built detergent composition having the following formulation: Parts 9 00 0 0 0 *Dag*

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0 0 .00 Sodium linear alkylbenzene sulphonate Nonionic surfactant 7EO Soap Sodium tripolyphosphate Sodium alkaline silicate Sodium sulphate 15 Sodium carbonate Sodium carboxymethylcellulose Fluorescer Sodium perborate tetrahydrate Enzyme granules Lather control granules Polycarboxylate polymer (see below) Graft copolymer (Sokalan HP22) Water and minor ingredients 1.1 30.0 12.9 0.6 0.3 18.0 1.3 0 or 0 or to 100.0 a 00 o oi r The compositions prepared, and the reflectance reduction results obtained, are shown in Table 3 below.

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f 17 C. 3267 Table 3 Example Polymers Reflectance change (delta R 460 H no polymers j 0.5% Sokalan HP22 0* 9 *4

C

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4616 0*0* 0.5% Sokalan HP22 0.5% Sokalan HP22 0.5% Sokalan HP22 0.5% Sokalan HP22 0.5% Sokalan HP22 Sokalan PA 40 2.0% Sokalan PA 40 2.0% Sokalan PA 70 2.0% Sokalan PA 70 2.0% Sokalan PA 110 2.0% Sokalan PA 110 2.0% Sokalan CP 5 2.0% Sokalan CP 5 2.0% Sokalan CP 7 2.0% Sokalan CP 7 -2.6 8 -1.8 -2.7 -1.8 -2.2 -1 .8 *4000 0 0 U

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25 V In all cases, the combination of polymers was inferior to the graft copolymer alone, showing that the benefit that characterises the present invention is not observed in detergent compositions built with sodium tripolyphosphate.

B I 18 C.3267 Examples 6 and 7 The procedure of Examples 1 and 5, with the same zeolite-built detergent composition and the same polymers, was repeated using polyester/cotton test cloths. The results were as shown in Table 4 below.

Table 4 Example Polymers 0 00 *I 4 00 0 0 00V0 O 0r 0 04 *00 Reflectance change (delta

R

4 6 0 no polymers 0.5% Sokalan HP22 00 4 4 44 4 0 00

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6

Z

7 0.5% Sokalan HP22 0.5% Sokalan HP22 2.0% Sokalan PA 20 2.0% Sokalan PA 20 2.0% Sokalan CP 7 2.0% Sokalan CP 7 -5.6 -5.1 -2.4 -3.9 It will be seen that combinations of these two representative polycarboxylate polymers with the graft copolymer gave antiredeposition benefits on polyester/cotton fabric.

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Claims (6)

1. A detergent composition comprising: from 2 to 50% by weight of a detergent active system comprising one or more anionic, nonionic, cationic, zwitterionic or amphoteric surfactants; S(b) from 10 to 60% by weight of crystalline or amorphous alkali metal aluminosilicate builder; from 0.5 to 5% by weight of a polycarboxylate S.,o 15 polymer comprising (meth)acrylate units and/or maleate units in acid or salt form; and from 0.1 to 3% by weight of a graft copolymer of polyethylene oxide, polypropylene oxide or polybutylene S 20 oxide with (ii) vinyl acetate (optionally partially Ssaponified) in a weight ratio of to (ii) of from 1:0.2 0 2. A detergent composition as claimed in claim 1, which 25 contains less than 10% by weight of inorganic phosphate Sbuilder.

3. A detergent composition as claimed in claim 2, which is free of inorganic phosphate builders.

4. A detergent composition as claimed in any preceding claim, wherein the polycarboxylate polymer is a homopolymer or copolymer of acrylic acid. /I j. T CDGNNL W i 1 I ;t 20 C.3267 A detergent composition as claimed in claim 4, wherein the polycarboxylate polymer is a polyacrylate, an acrylate/maleate copolymer, or an acrylic phosphinate.

6. A detergent composition as claimed in any preceding claim, wherein the polycarboxylate polymer is present in an amount of from 1 to 3% by weight. to 7. A detergent composition as claimed in any preceding claim, wherein the graft copolymer is obtained by grafting a polyalkylene oxide of molecular weight (number average) 2000 100 000 with vinyl acetate (optionally partially saponified) in a weight ratio of polyalkylene oxide to vinyl acetate of 1:0.2 to 1:10. 20 8. A detergent composition as claimed in any preceding claim, wherein the graft copolymer is obtained by grafting a polyalkylene oxide of molecular weight (number average) 4000 50 000 with vinyl acetate (optionally partially saponified) in a weight ratio of polyalkylene 0 0 °25 oxide to vinyl acetate of 1:0.5 to 1:6. 0 0

9. A detergent composition as claimed in any one of claims 1 to 7, wherein the graft copolymer is 30 obtained by grafting a polyethylene oxide of molecular weight (number average) 2000 50 000 with vinyl acetate (optionally partially saponified) in a weight ratio of polyethylene oxide to vinyl acetate of 1:0.5 to 1:6. K 0F. t 0 Q :i ;I r- l i: 1 iI, W BM C.3267AU A detergent composition as claimed in any preceding claim, wherein the graft copolymer is present in an amount of from 0.3 to 1.0% by weight.

11. A detergent composition as claimed in any preceding claim, wherein the aluminosilicate builder is zeolite 4A. 10 12. A detergent composition as claimed in any preceding claim, wherein the aluminosilicate builder is present in an amount of from 15 to 50% by weight. o 94 9 O r 94 9 4 099 B 9 o 8 0 4 0006 0 a a9 4 e b6aol)e OO O o Sro 0 4 4« 4 9 4 9 4 DATED THIS 20TH DAY OF NOVEMBER 1991 UNILEVER PLC By its Patent Attorneys: GRIFFITH HACK CO Fellows Institute of Patent Attorneys of Australia. YL' i 'ir. i 1 ,,rJrP; i:iII-i 1 1 7 tL: .1