WO1997020021A1 - Composition detergente contenant des polymeres facilitant l'elimination des salissures - Google Patents

Composition detergente contenant des polymeres facilitant l'elimination des salissures Download PDF

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Publication number
WO1997020021A1
WO1997020021A1 PCT/EP1996/004994 EP9604994W WO9720021A1 WO 1997020021 A1 WO1997020021 A1 WO 1997020021A1 EP 9604994 W EP9604994 W EP 9604994W WO 9720021 A1 WO9720021 A1 WO 9720021A1
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WO
WIPO (PCT)
Prior art keywords
detergent composition
sodium
polymer
soil release
polyester
Prior art date
Application number
PCT/EP1996/004994
Other languages
English (en)
Inventor
Wilfried Blokzijl
Andrew Martin Creeth
Mohamad Sami Falou
Andrew David Green
Michael Hull
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Unilever Plc
Unilever N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Plc, Unilever N.V. filed Critical Unilever Plc
Priority to AU75714/96A priority Critical patent/AU698202B2/en
Priority to HU9903487A priority patent/HUP9903487A3/hu
Priority to SK714-98A priority patent/SK71498A3/sk
Priority to EP96938202A priority patent/EP0977827A1/fr
Priority to BR9611677A priority patent/BR9611677A/pt
Priority to PL96327008A priority patent/PL184578B1/pl
Publication of WO1997020021A1 publication Critical patent/WO1997020021A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the present invention relates to laundry detergent compositions containing certain water-soluble or water- dispersible polyesters exhibiting improved soil release properties.
  • Polyesters of terephthalic and other aromatic dicarboxylic acids having soil release properties are widely disclosed in the art, in particular, the so-called PET/POET (polyethylene terephthalate/polyoxyethylene terephthalate) and PET/PEG (polyethylene terephthalate/polyethylene glycol) polyesters which are disclosed, for example, in US 3 557 039 (ICI), GB 1 467 098 and EP 1305A (Procter & Gamble) .
  • Polymers of this type are available commercially, for example, as Permalose, Aquaperle and Milease (Trade Marks) (ICI) and Repel-O-Tex (Trade Mark) SRP3 (Rhone-Poulenc) .
  • EP 357 280A discloses sulphonated end-capped linear terephthalate oligomers which are condensation products of a low molecular weight diol, preferably propylene glycol or ethylene glycol, with terephthalic acid.
  • the present invention is based on the use of a class of non-end-capped sulphonated polyesters based on dicarboxylic acids and polyols which provide especially effective soil release, especially from polyester fabrics, and which are also effective in reducing soil redeposition in the wash.
  • the present invention accordingly provides a detergent composition for washing fabrics, comprising:
  • HA hydroxylated aromatic or aliphatic diacidic monomer
  • SA a polyol selected from ethylene glycol, propylene glycol, isopropylene glycol, glycerol, 1, 2,4-butanetriol and 1,2,3-butanetriol, and oligomers of these having from 1 to 8 monomer units,
  • the polyester having a sulphur content within the range of from 0.5 to 10 wt%;
  • polyesters with which the invention is concerned are defined above.
  • the polyesters and their preparation are disclosed and claimed in WO 95 32997A (Rhone-Poulenc) .
  • Preferred polyesters have the following features:
  • the unsulphonated diacidic monomer (A) is an aromatic dicarboxylic acid or an anhydride of a lower (C ⁇ C.,) alkyl diester thereof, selected from terephthalic acid, isophthalic acid, 2, 6-naphthalene dicarboxylic acid, anhydrides and lower (Ci-C alkyl diesters thereof;
  • SA sulphonated diacidic monomer
  • the mole ratio (A) : [ (A) + (SA) ] is within the range of from 60:100 to 95:100, preferably from 65:100 to 93:100; the mole ratio (SA) : [ (A) + (SA) ] is within the range of from 5:100 to 40:100, preferably from 7:100 to 35:100;
  • hydroxylated monomer (HA) if present, is a hydroxylated aromatic dicarboxylic acid, or anhydride or lower (Ci-C dialkyl ester thereof;
  • HA hydroxylated monomer
  • the quantity of (P) is such that the ratio of OH functional groups of (P) to COOH functional groups (or equivalents) of (A) + (SA) + any (HA) is within the range of from 1.05:1 to 4:1, preferably from 1.1:1 to 3.5:1, and more preferably from 1.8:1 to 3:1;
  • the polyester has a number average molecular weight of less than 20 000
  • the sulphur content is within the range of from 1.2 to 8 wt%;
  • the hydroxyl group content is at least 0.2 OH equivalent per kg of polyester.
  • the monomer (A) preferably consists of at least one dicarboxylic acid or anhydride chosen from terephthalic, isophthalic and 2,6 naphthalenedicarboxylic acids or anhydrides or their diesters.
  • monomer (A) is present in a quantity corresponding to a molar ratio (A) / [ (A) + (SA) ] within the range of from 95:100 to 60:100, preferably from 93:100 to 65:100.
  • the unsulphonated diacidic monomer (A) preferably consists of 50 to 100 mole%, more preferably 70 to 90 mole%, of terephthalic acid or anhydride or lower alkyl (methyl, ethyl, propyl, isopropyl, butyl) diester, and of 0 to 50 mole%, more preferably from 10 to 30 mole%, of isophthalic acid or anhydride and/or of 2,6- naphthalenedicarboxylic acid or anhydride or lower alkyl (methyl, ethyl, propyl, isopropyl, butyl) diester; the preferred diesters are methyl diesters.
  • aromatic diacids other than those mentioned above, such as ortho- phthalic acid, anthracene, 1,8-naphthalene, 1,4-naphthalene and biphenyl dicarboxylic acids or aliphatic diacids such as adipic, glutaric, succinic, trimethyladipic, pimelic, azelaic, sebacic, suberic, itaconic and maleic acids, etc. in the form of acid, anhydride or lower (methyl, ethyl, propyl, isopropyl, butyl) diesters.
  • aromatic diacids other than those mentioned above, such as ortho- phthalic acid, anthracene, 1,8-naphthalene, 1,4-naphthalene and biphenyl dicarboxylic acids or aliphatic diacids such as adipic, glutaric, succinic, trimethyladipic, pimelic, azelaic, sebacic, suberic
  • SA sulphonated diacidic monomer
  • the sulphonated diacidic monomer (SA) consists of at least one sulphonated aromatic or sulphonated aliphatic dicarboxylic acid or anhydride or lower (C 1 -C 4 ) alkyl diester.
  • Aromatic dicarboxylic acids and their derivatives are preferred.
  • monomer (SA) is present in a quantity corresponding to a molar ratio (SA)/[(A) + (SA) ] within the range of from 5:100 to 40:100, more preferably from 7:100 to 35:100.
  • the sulphonated diacidic monomer (SA) has at least one sulphonic acid group, preferably in the form of an alkali metal (preferably sodium) sulphonate, and two acidic functional groups or acidic functional group equivalents (that is to say an anhydride functional group or two ester functional groups) attached to one or a number of aromatic rings, when aromatic dicarboxylic acids or anhydrides or their diesters are involved, or to the aliphatic chain when aliphatic dicarboxylic acids or anhydrides or their diesters are involved.
  • an alkali metal preferably sodium
  • two acidic functional groups or acidic functional group equivalents that is to say an anhydride functional group or two ester functional groups
  • Suitable aromatic sulphonated diacidic monomers include sulphoisophthalic, sulphoterephthalic, sulpho- ortho-phthalic acids or anhydrides, 4-sulpho-2,7- naphthalenedicarboxylic acids or anhydrides, sulpho 4,4'- bis (hydroxycarbonyl) diphenyl sulphones, sulphodiphenyldicarboxylic acids or anhydrides, sulpho 4,4' -bis (hydroxycarbonyl) diphenylmethanes, sulpho-5- phenoxyisophthalic acids or anhydrides or their lower (methyl, ethyl, propyl, isopropyl, butyl) diesters.
  • Suitable aliphatic sulphonated diacidic monomers include sulphosuccinic acids or anhydrides or their lower alkyl (methyl, ethyl, propyl, isopropyl, butyl) diesters.
  • SA sulphonated diacidic monomer
  • diester preferably dimethyl ester
  • HA hydroxylated diacidic monomer
  • the hydroxylated diacidic monomer (HA) which is optionally present and can replace up to 50 mole%, preferably up to 30 mole%, of (A) and/or (SA) , consists of least one hydroxylated aromatic or aliphatic dicarboxylic acid or anhydride or a lower (C1-C4) alkyl diester thereof.
  • the hydroxylated diacidic monomer (HA) has at least one hydroxyl group attached to one or a number of aromatic rings when it is an aromatic monomer or to the aliphatic chain when it is an aliphatic monomer. Aromatic monomers are preferred.
  • Suitable hydroxylated diacidic monomers include 5-hydroxyisophthalic, 4-hydroxyisophthalic, 4-hydroxyphthalic, 2-hydroxymethylsuccinic, hydroxymethylglutaric and hydroxyglutaric acids, in acid, anhydride or lower alkyl diester form.
  • the polyol (P) may be a oligomer comprising up to 8 monomer units, preferably up to 6 and more preferably up to 4 monomer units, but is most preferably a monomer.
  • the polyol is selected from ethylene glycol, propylene glycol, glycerol, 1,2,4-butanetriol, 1,2,3-butanetriol and combinations of these, and their lower (2 to 8, preferably 2 to 6, more preferably 2 to 4) oligomers.
  • the polyol (P) is present in a quantity corresponding to a ratio of the number of OH functional groups of the polyol (P) to the number of COOH functional groups or functional group equivalents of the total diacidic monomer (A) + (SA) + (HA) within the range of from 1.05:1 to 4:1, preferably from 1.1:1 to 3.5:1 and more preferably from 1.8:1 to 3:1.
  • the preferred polyols (P) are ethylene glycol and glycerol, ethylene glycol being especially preferred.
  • the sulphonated diacidic monomer (SA) consists of at least one sulphonated aromatic dicarboxylic acid or anhydride or of a mixture of sulphonated aromatic acids or anhydrides and of sulphonated aliphatic acids or anhydrides or their diesters when the polyol (P) does not contain any polyol other than a glycol or when the hydroxylated diacidic monomer (HA) is absent.
  • the polyester used in accordance with the invention has a number average molecular weight not exceeding 20 000, and preferably not exceeding 15 000.
  • the molecular weight may be much lower than these limits. Polyesters having molecular weights below 1000, for example, 500-1000, have proved highly effective.
  • Number average molecular weight may be measured by gel permeation chromatography, for example, in dimethylacetamide containing 10 "2 N of LiBr, at 25°C, or in tetrahydrofuran. The results are expressed as polystyrene equivalents. Hydroxyl functional group content
  • the hydroxyl functional group content of the polyester is at least 0.2.
  • the hydroxyl functional group content may be estimated from proton NMR, the measurement being carried out in dimethyl sulphoxide.
  • the elementary unit considered in the definition of the mole of monomer (A) , (SA) or (HA) is the COOH functional group in the case of the diacids or the COOH functional group equivalent in the case of the anhydrides or of the diesters.
  • An especially preferred polyester is obtainable from the following monomers:
  • HA hydroxylated terephthalic or isophthalic acid
  • polyesters in accordance with the invention based on terephthalic acid, isophthalic acid, sulphoisophthalic acid and monoethylene glycol, may be described as having backbone units of the following formula:
  • n 1, 2, 3 or 4
  • a minority being of the formulae
  • R is a lower alkyl group, preferably methyl.
  • polyesters unlike many disclosed in the prior art, are not end-capped with hydrocarbon or sulphonated capping groups.
  • the polyesters may be prepared by the usual esterification and/or transesterification and polycondensation processes, for example, by esterification and/or transesterification in the presence of a catalyst of the polyol P with the various diacidic monomers (in acid, anhydride or diester form) , and polycondensation of the polyol esters at reduced pressure in the presence of a polycondensation catalyst.
  • the polyesters are suitably incorporated into detergent compositions in amounts of from 0.01 to 10 wt%, preferably from 0.1 to 5 wt% and more preferably from 0.25 to 3 wt%.
  • the detergent compositions of the invention also contain, as essential ingredients, one or more detergent- active compounds (surfactants) , and a detergency builder system including sodium tripolyphosphate; they may also optionally contain bleaching components and other active ingredients to enhance performance and properties.
  • the surfactant svstem The surfactant svstem
  • the detergent-active compounds may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
  • suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", 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 and nonionic compounds.
  • the total amount of surfactant present ranges from 2 to 50 wt%, preferably from 5 to 40 wt%.
  • Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkylsulphates, particularly C 8 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • polyesters of the present invention are especially suitable for use in compositions containing anionic sulphonate and sulphate type surfactants, for example, primary alkyl sulphates, alkyl ether sulphates, alkylbenzene sulphonates, and mixtures of these.
  • anionic sulphonate and sulphate type surfactants for example, primary alkyl sulphates, alkyl ether sulphates, alkylbenzene sulphonates, and mixtures of these.
  • compositions of the invention contain a surfactant system which consists of anionic surfactant only, or of anionic and nonionic surfactants in a weight ratio of at least 0.9:1, preferably at least 1:1.
  • the anionic surfactant is preferably present in an amount of from 5 to 45 wt%, more preferably from 10 to 40 wt%.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide) .
  • ethoxylated nonionic surfactants Especially preferred are ethoxylated nonionic surfactants, alkylpolyglycosides, and mixtures of these.
  • detergent compositions of the invention may also advantageously contain fatty acid soap.
  • the detergent compositions of the invention also contain a detergency builder system.
  • the total amount of detergency builder in the compositions will suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.
  • the builder system contains, as an essential ingredient, sodium tripolyphosphate (STP) in an amount of at least 5 wt%, preferably at least 10 wt%, based on the whole composition.
  • STP sodium tripolyphosphate
  • the STP may be the sole builder present, in which case it is preferably present in an amount of at least 15 wt%, and preferably at least 20 wt%, suitably from 20 to 50 wt%.
  • the STP may be used in combination with one or more other builders, which may be inorganic or organic.
  • inorganic builders that may be present include other phosphate builders, for example, sodium orthophosphate and/or sodium pyrophosphate; sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201
  • An especially preferred builder system comprises at least 5 wt% of STP in combination with at least 10 wt% of zeolite A.
  • the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
  • Other zeolites that may be used include zeolites X and Y.
  • it may be maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070B (Unilever) .
  • Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33. Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
  • Supplementary organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates
  • Detergent compositions according to the invention may also suitably contain a bleach system, which may contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as ethylenediamine tetramethylene phosphonate (EDTMP) and its salts, and diethylenetriamine pentamethylene phosphonate (DETPMP) and its salts.
  • EDTA ethylenediamine tetraacetate
  • ETMP ethylenediamine tetramethylene phosphonate
  • DETPMP diethylenetriamine pentamethylene phosphonate
  • compositions suitable for washing delicate fabrics may, for example, have one or more of the following characteristics:
  • a polycarboxylate polymer for example, an acrylic/ aleic copolymer such as Sokalan (Trade Mark) CP5 ex BASF;
  • a polymer effective to inhibit dye transfer for example, polyvinyl pyrrolidone
  • compositions of the invention may also contain one or more enzymes. Suitable enzymes include the proteases, amylases, cellulases and lipases usable for incorporation in detergent compositions.
  • Preferred proteolytic enzymes are normally solid, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
  • proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention.
  • suitable proteolytic enzymes are the subtilisins, which are obtained from particular strains of B. subtilis and B. licheniformis, such as the commercially available subtilisins Maxatase (Trade Mark) , as supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase (Trade Mark) , as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade Mark) .
  • Esperase Trade Mark
  • Savinase Trade Mark
  • Other commercial proteases are Kazusase (Trade Mark) (obtainable from Showa-Denko of Japan), Optimase (Trade Mark) (from Miles Kali-Chemie, Hannover, West Germany) , and Superase (Trade Mark) (obtainable from Pfizer of U.S.A.).
  • Proteases having isoelectric points below 10 include
  • Proteases having isoelectric points of 10 or above include Savinase, Maxacal, Purafect, Opticlean and Esperase (all Trade Marks) .
  • Detergency enzymes are commonly employed in granular form in amounts of from 0.01 to 5.0 wt%.
  • detergent compositions of the invention include inorganic salts such as sodium carbonate, sodium sulphate or sodium silicate; antiredeposition agents such as cellulosic polymers; fluorescers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; dyes; coloured speckles; perfumes; foam controllers; and fabric softening compounds. This list is not intended to be exhaustive.
  • Detergent compositions of the invention may be of any suitable physical form, for example, powders or granules, liquids, gels and solid bars.
  • Detergent compositions of the invention may be prepared by any suitable method.
  • Particulate detergent compositions are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and then spraying on or postdosing those ingredients unsuitable for processing via the slurry.
  • the skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
  • Particulate detergent compositions of the invention preferably have a bulk density of at least 400 g/1, more preferably at least 500 g/1. Especially preferred compositions have bulk densities of at least 650 g/litre, more preferably at least 700 g/litre.
  • Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever) .
  • Polymer 1 was a water-soluble sulphonated polyester of terephthalic acid, isophthalic acid, sulphoisophthalic acid and ethylene glycol having the following approximate composition :
  • diacidic monomer comprising approximately 77 mole% terephthalate, 3.7 mole% isophthalate, 18.2 mole% sulphoisophthalate;
  • Polymer A Sokalan (Trade Mark) HP22 ex BASF, a graft copolymer of polyethylene glycol and polyvinyl acetate.
  • Polymer B Repel-O-Tex (Trade Mark) ex Rhone-Poulenc, a PET/POET polymer, used in the form of a granule (50% wt% polymer, 50 wt% sodium sulphate) .
  • Polymer C Aquaperle (Trade Mark) 3991 ex ICI, a PET/POET polymer.
  • Phosphate-built particulate detergent compositions were prepared to the following general formulation, using spray-drying and postdosing techniques:
  • Soil release polymer (see below) 0 or 0.40 Antifoam granule, enzymes, sodium carbonate, perfume, water to 100.00
  • Soil release and detergency were measured using radio( 3 H) -labelled triolein as a soil.
  • the wash regime was as follows: polyester cloths were washed for 20 minutes in Tergotometers in the test formulations (with or without soil release polymer at 0.4 wt%) , at the product dosages stated, at 40°C in 24°FH (calcium only) water. Single wash: soiled cloths were washed as described above.
  • Prewash as single wash but no soil present; after prewash the fabrics were rinsed in a beaker with 1 litre of water at 20°C and dried overnight.
  • Main wash as for single wash but using pretreated fabrics.
  • Phosphate-built particulate detergent compositions were prepared to the following general formulation, using spray-drying and postdosing techniques:
  • Amylase (Termamyl* 60T) 0.08
  • the formulations had a bulk density of 420-440 g/litre and a 1 wt% aqueous solution pH in demineralised water at 25°C of 9.7-9.8.
  • Soil release and detergency on knitted polyester test cloths stained with Oilsol Blue dye/olive oil were assessed in the tergotometer at two different product dosages, using the following wash regimes: 3.8 g/1 1.3 g/1
  • Stain removal was also assessed visually by an experienced panel of five people. The results, expressed on a scale of 1 (heavy staining, initial stain) to 10 (complete removal), were as follows:
  • Lipase (Lipolase* 100T) 0.253 Antifoam (silicone oil/silica) 0.04
  • the formulations had a bulk density of 370-430 g/litre and a 1 wt% aqueous solution pH in demineralised water at 25°C of 9.7-9.8.
  • Soil release properties were also assessed at a product dosage of 1.3 g/1, by measuring relectance after a first wash and again after a second wash.
  • the wash regime in the tergotometer was as follows:
  • zeolites used were zeolite 4A (Wessalith* P de Degussa) and zeolite P having a Si:Al ratio less than 1.33 (zeolite MAP) (Doucil* A24 ex Crosfield Chemicals) .
  • Polymer 1 caused a significant detergency increase.
  • Polymer B caused smaller detergency increases in the two zeolite formulations, but in the STP formulation the presence of Polymer B actually brought about a substantial fall in detergency, while the presence of Polymer 1 caused a comparable rise in detergency.
  • phosphate-built non-bleaching high bulk density particulate detergent compositions containing soil release polymers of the invention are as follows:
  • Lipase (Lipolase* 100T) 0.08 0.10 0.26
  • Amylase (Termamyl* 60T) 0.14 - -
  • Example 5 The composition of Example 5 is of low solution pH (9.7-9.8) and is especially suitable for washing delicate fabrics.
  • a further example of a high bulk density non- bleaching phosphate-built powder of low solution pH in accordance with the invention, suitable for washing delicate fabrics, is as follows:
  • Citric acid 2 Citric acid 2, .25
  • Lipase (Lipolase* 100T) 0 .05
  • Amylase (Termamyl* 60T) 0 .25
  • Cellulase (Celluzyme* 0.7T) 0 .40
  • Lipase (Lipolase* 100T) )
  • phosphate-built spray-dried non-bleaching particulate detergent compositions in accordance with the invention containing high levels of anionic surfactant are as follows:
  • phosphate-built high bulk density non- bleaching particulate detergent compositions in accordance with the invention containing high levels of anionic surfactant are as follows:
  • Zeolite A (as hydrated) 3.00 3.00 Enzymes: Savinase*/Lipolase* 0.50 0.50
  • Zeolite A (as hydrated) 3.576
  • phosphate-built non-bleaching particulate detergent compositions in accordance with the invention one spray-dried and the other of high bulk density, are as follows:
  • An example of a phosphate- and carbonate-built spray- dried particulate detergent composition in accordance with the invention containing a high level of anionic surfactant, a bleach system and a photobleach, is as follows:
  • Zeolite A (anhydrous basis) 8.00 12.00

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Abstract

L'invention concerne une composition détergente pour le linge, contenant un tensioactif, du tripolyphosphate de sodium comme adjuvant de détergence à raison d'au moins 5 % et un polymère facilitant l'élimination des salissures, qui est un polyester sulfoné soluble ou dispersible dans l'eau, à groupes terminaux libres. Ce polyester peut être constitué, par exemple, d'acide téréphtalique, isophtalique, sulfoisophtalique et d'éthylène glycol.
PCT/EP1996/004994 1995-11-30 1996-11-11 Composition detergente contenant des polymeres facilitant l'elimination des salissures WO1997020021A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU75714/96A AU698202B2 (en) 1995-11-30 1996-11-11 Detergent compositions containing soil release polymers
HU9903487A HUP9903487A3 (en) 1995-11-30 1996-11-11 Detergent compositions containing soil release polymers
SK714-98A SK71498A3 (en) 1995-11-30 1996-11-11 Detergent compositions containing soil release polymers
EP96938202A EP0977827A1 (fr) 1995-11-30 1996-11-11 Composition detergente contenant des polymeres facilitant l'elimination des salissures
BR9611677A BR9611677A (pt) 1995-11-30 1996-11-11 Composição detergente para lavagem de tecidos
PL96327008A PL184578B1 (pl) 1995-11-30 1996-11-11 Kompozycja detergentowa do prania tkanin zawierająca polimery usuwające brud

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9524493.5A GB9524493D0 (en) 1995-11-30 1995-11-30 Detergent compositions containing soil release polymers
GB9524493.5 1995-11-30

Publications (1)

Publication Number Publication Date
WO1997020021A1 true WO1997020021A1 (fr) 1997-06-05

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/004994 WO1997020021A1 (fr) 1995-11-30 1996-11-11 Composition detergente contenant des polymeres facilitant l'elimination des salissures

Country Status (15)

Country Link
EP (1) EP0977827A1 (fr)
CN (1) CN1113087C (fr)
AR (1) AR004811A1 (fr)
AU (1) AU698202B2 (fr)
BR (1) BR9611677A (fr)
CA (1) CA2238479A1 (fr)
CZ (1) CZ166898A3 (fr)
GB (1) GB9524493D0 (fr)
HU (1) HUP9903487A3 (fr)
IN (1) IN187473B (fr)
PL (1) PL184578B1 (fr)
SK (1) SK71498A3 (fr)
TR (1) TR199800963T2 (fr)
WO (1) WO1997020021A1 (fr)
ZA (1) ZA969727B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0989183A2 (fr) † 1998-08-19 2000-03-29 Henkel KGaA Fixage de perfumes aux surfaces dures et douces
US7160848B2 (en) 2002-12-13 2007-01-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Polymers and laundry detergent compositions containing them
US7160947B2 (en) 2002-12-13 2007-01-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Polymers and laundry detergent compositions containing them

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024032573A1 (fr) * 2022-08-08 2024-02-15 Specialty Operations France Polymère de polyester antisalissures biodégradable et composition de nettoyage le comprenant

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57143400A (en) * 1981-02-27 1982-09-04 Nippon Synthetic Chem Ind Detergent composition
EP0182600A2 (fr) * 1984-11-16 1986-05-28 Ciba Specialty Chemicals Water Treatments Limited Usage de polymères solubles dans l'eau dans des fluides de forage et packer aqueux et comme adjuvants de lavage
EP0311342A2 (fr) * 1987-10-05 1989-04-12 The Procter & Gamble Company Esters oligomères à groupes terminaux sulfoaroyle utilisables comme agents anti-redéposition dans des compositions détergentes et dans des produits pour le conditionnement du linge
EP0357280A2 (fr) * 1988-08-26 1990-03-07 The Procter & Gamble Company Agents antisalissures ayant des groupes terminaux sulfonés dérivés de groupes allyliques
JPH0321698A (ja) * 1989-06-20 1991-01-30 Sanyo Chem Ind Ltd 高分子電解質ビルダー及び洗剤組成物
WO1995002029A1 (fr) * 1993-07-08 1995-01-19 The Procter & Gamble Company Compositions detersives a agents antisalissure
WO1995032997A1 (fr) * 1994-05-30 1995-12-07 Rhone-Poulenc Chimie Nouveaux polyesters sulfones et leur utilisation comme agents anti-salissure dans les compositions detergentes, de rinçage, d'adoucissage et de traitement des textiles

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57143400A (en) * 1981-02-27 1982-09-04 Nippon Synthetic Chem Ind Detergent composition
EP0182600A2 (fr) * 1984-11-16 1986-05-28 Ciba Specialty Chemicals Water Treatments Limited Usage de polymères solubles dans l'eau dans des fluides de forage et packer aqueux et comme adjuvants de lavage
EP0311342A2 (fr) * 1987-10-05 1989-04-12 The Procter & Gamble Company Esters oligomères à groupes terminaux sulfoaroyle utilisables comme agents anti-redéposition dans des compositions détergentes et dans des produits pour le conditionnement du linge
EP0357280A2 (fr) * 1988-08-26 1990-03-07 The Procter & Gamble Company Agents antisalissures ayant des groupes terminaux sulfonés dérivés de groupes allyliques
JPH0321698A (ja) * 1989-06-20 1991-01-30 Sanyo Chem Ind Ltd 高分子電解質ビルダー及び洗剤組成物
WO1995002029A1 (fr) * 1993-07-08 1995-01-19 The Procter & Gamble Company Compositions detersives a agents antisalissure
WO1995032997A1 (fr) * 1994-05-30 1995-12-07 Rhone-Poulenc Chimie Nouveaux polyesters sulfones et leur utilisation comme agents anti-salissure dans les compositions detergentes, de rinçage, d'adoucissage et de traitement des textiles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8241, Derwent World Patents Index; Class A97, AN 82-86831E, XP002028457 *
DATABASE WPI Section Ch Week 9111, Derwent World Patents Index; Class A97, AN 91-076199, XP002028456 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0989183A2 (fr) † 1998-08-19 2000-03-29 Henkel KGaA Fixage de perfumes aux surfaces dures et douces
US7160848B2 (en) 2002-12-13 2007-01-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Polymers and laundry detergent compositions containing them
US7160947B2 (en) 2002-12-13 2007-01-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Polymers and laundry detergent compositions containing them

Also Published As

Publication number Publication date
CA2238479A1 (fr) 1997-06-05
GB9524493D0 (en) 1996-01-31
CN1207764A (zh) 1999-02-10
CN1113087C (zh) 2003-07-02
AR004811A1 (es) 1999-03-10
IN187473B (fr) 2002-05-04
CZ166898A3 (cs) 1998-10-14
HUP9903487A2 (hu) 2000-03-28
PL184578B1 (pl) 2002-11-29
ZA969727B (en) 1998-05-20
SK71498A3 (en) 1998-12-02
BR9611677A (pt) 1999-03-02
EP0977827A1 (fr) 2000-02-09
AU7571496A (en) 1997-06-19
HUP9903487A3 (en) 2002-04-29
PL327008A1 (en) 1998-11-09
TR199800963T2 (xx) 1998-12-21
AU698202B2 (en) 1998-10-29

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