Classifications

• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
  • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
• • 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
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
• • 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
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/361—Phosphonates, phosphinates or phosphonites
• • 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
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

• the present invention relates to a laundry detergent composition
• a laundry detergent composition comprising a tenside component, a builder component and optionally one or more adjuvants and additives.
• DE Publication No. 39 05 423 (Henkel) relates to a zeolite-based particulate to pulverulent water softener comprising a bleach and a nonionic tenside for use together with conventional detergent compositions.
• the water softener is used together with a conventional detergent composition comprising both anionic and nonionic tensides, the proportion of anionic tensides being higher than the proportion of nonionic tensides.
• the detergent further comprises zeolite, silicate, polycarboxylate and cellulose ether but not citrate.
• EP Publication No. 289.767 discloses a zeolite-based particulate adsorbent with high adsorptivity for liquid and pasty substances in washing or cleaning compositions, especially nonionic tensides, said adsorbent being a suitable particulate carrier in phosphate-free washing and cleaning compositions or washing and cleaning compositions having a low phosphate content.
• Table 1 of the publication reveals a washing composition formulation including said adsorbent.
• the formulation comprises both anionic and nonionic tensides, the percentage of anionic tensides being higher than the one of nonionic tensides.
• the washing composition further comprises zeolite, silicate, polycarboxylate and cellulose ether, but not citrate. Experiments with the washing composition prepared according to said formulation result in incrustations in the range of 3.5-4.4% after 25 wash cycles with swatches of terry cloth, cf. Table 5.
• DE Publication No. 38 38 086 (Henkel) pertains to a special preparation of polycarboxylate and zeolite-containing granulates for use during the manufacture of phosphate-free detergent compositions. It is disclosed that said granulates are suitable carriers for liquid to wax-like detersive substances including nonionic tensides.
• the publication does, however, not disclose formulations for specific detergent compositions and makes no mention of a connection between the formulation of detergent compositions and incrustations/lime depositions.
• EP Publication No. 291.869 discloses a detergent composition comprising phosphonates, said composition having a reduced tendency to form incrustations.
• the detergent composition further comprises tensides selected from the group consisting of anionic and nonionic tensides, zeolite, optionally polycarboxylate as well as other conventional ingredients of detergent compositions.
• DK Printed Accepted Publication No. 154.827 (corresponding to GB-PS No. 2.005.715) (Colgate-Palmolive) relates to a phosphate-free detergent composition comprising a water-soluble nonionic detergent and zeolite as phosphate replacer, the nonionic detergent being absorbed into spray-dried beads comprising a mixture of zeolite and either sodium carbonate or a mixture of sodium carbonate and sodium bicarbonate.
• the detergent composition formulations of the publication are characterized by comprising neither complex-binders (sequestrants), such as phosphonates, EDTA nor polymeric substances or citrates. No mention is made as regards reduced incrustations/depositions.
• DK Printed Accepted Publication No. 151.231 (Henkel) (corresponding to GB-PS No. 1.473.201) discloses a washing composition comprising water-insoluble, finely-divided aluminium silicate (zeolite) as well as at least one substance selected from the group consisting of tensides, builders and bleaches, said washing composition comprising crystalline or X-ray amorphous aluminium silicate (zeolite) as phosphate replacer.
• Example 9 of the publication is a formulation of a zeolite-based washing composition, where the tenside is exclusively a nonionic tenside.
• the bleach-containing washing composition further comprises sodium citrate, silicate as well as a soil-dispersing agent.
• the product does not contain polymeric compounds. It should be noted that specific results for the use of said washing composition are not mentioned. Neither is it mentioned that there is a connection between the choice of tensides and the formulation on the one hand, and incrustations and depositions on heating elements on the other.
• DK Printed Accepted Publication No. 156.173 (Henkel) (corresponding to GB-PS No. 1.473.202) is an additional to the above-mentioned DK Printed Accepted Publication No. 151.231 (Henkel). It relates to a zeolite-based washing composition as disclosed in DK Printed Accepted Publication No. 151.231, where the tenside component comprises 1 part by weight of nonionic tenside and 0-3 parts by weight of anionic tenside.
• Example 7 suggests a formulation for a zeolite-based washing composition without anionic tensides, i.e. the tenside is solely nonionic tenside. Specific washing results obtained with said formulation are not mentioned. Neither does the publication mention a connection between the choice of tenside and the formulation on the one hand, and the incrustations and depositions on heating elements on the other.
• EP Publiction No. 243,908 discloses a phosphate-free granular water softener comprising 50-60 % by weight of fine crystalline zeolite, 3.5 to 5 % by weight of sodium salt of polyacrylic acid or polymethacrylic acid or a copolymer of these acids with maleic acid, 4 to 15% by weight of sodium citrate, 4 to 12 % by weight of sodium carbonate, 0 to 2% by weight of sodium carboxymethylcellulose and 12 to 25% by weight of water.
• the above water softener is adapted for use in combination with a traditional laundry detergent composition in case of hard laundry water.
• EP 243,908 gives no directions as to the requirements made to the tenside component of a laundry detergent composition to be used together with the water softener to avoid depositions on the heating elements of the washing machine or incrustations in the textiles when used in a low dosage, such as a typical dosage for a so-called compact type detergent composition.
• DK patent application No. 834/86 discloses a detergent composition containing 5-50% by weight of zeolite, and 0.1-20% by weight of polycarboxylate polymer.
• this detergent composition also includes nitrilotriacetic acid but in these Examples the tenside component contains an essential amount of anionic tensides, about 42 to 90 % by weight of the total tenside component combined with only a moderate amount of nonionic tenside, from about 10-49 % by weight.
• Anionic tensides are known to provide phosphate-free laundry detergent compositions with an excellent detergency, but gives problems in case of low dosage use in compact type compositions.
• calcium and magnesium ions in hard supply water cause a significant reduction in detergency.
• calcium and magnesium ions can cause depositions both in the form of lime depositions on the heating elements of the washing machine and in the form of so-called incrustations, i.e. depositions in the laundry, said incrustations remaining in the textiles, where they accumulate when the textiles are washed several times.
• the prescribed dosage for the laundry detergent compositions according to the present invention is, however, even lower than the recommended dosage of a compact-type detergent composition.
• the object of the invention is accomplished by a detergent composition comprising a tenside component, a builder component and optionally one or more adjuvants and additives characterized by the tenside component comprising at least 50% by weight of nonionic tensides and by the builder component comprising a builder A including one or more ion-exchangers, a builder B including one or more ion-transferring agents, a builder C including one or more precipitation inhibitors, a builder D including one or more soil-suspending agents, as well as optionally further builders.
• a detergent composition comprising a tenside component, a builder component and optionally one or more adjuvants and additives characterized by the tenside component comprising at least 50% by weight of nonionic tensides and by the builder component comprising a builder A including one or more ion-exchangers, a builder B including one or more ion-transferring agents, a builder C including one or more precipitation inhibitors,
• the tenside component of said detergent composition may advantageously be at least 55% by weight, such as at least 60% by weight of nonionic tenside, preferably at least 70% by weight, especially preferred at least 80% by weight, for instance at least 90% by weight.
• the weight ratio between the builders of the builder component in the laundry detergent composition according to the invention is preferably as stated below, based on 100 parts by weight of builder A.
• the amount of builder B is advantageously at least 3.7, preferably at least 6.2 and particularly preferred at least 6.9 parts by weight of builder B per 100 parts by weight of builder A, and advantageously at most 55, especially preferred at most 50 and most preferred at most 47 parts by weight of builder B per 100 parts by weight of builder A.
• the amount of builder C is advantageously at least 5.7, preferably at least 8.6 and most preferred at least 9 parts by weight of builder C per 100 parts by weight of builder A, and advantageously at most 21, especially preferred at most 16 and most preferred at most 12 parts by weight of builder C per 100 parts by weight of builder A.
• the amount of builder D is advantageously at least 1.7, particularly preferred at least 2.8 and especially at least 3.9 parts by weight of builder D per 100 parts by weight of builder A, and advantageously at most 5.3, especially preferred at most 4.2 and most preferred at most 3.9 parts by weight of builder D.
• weight parts are calculated on the basis of anhydrous products without hydration water.
• the amount of builder component in the laundry detergent composition according to the invention is advantageously at least 0.9, preferably at least 1.2, particularly preferred 1.4, and especially at least 1.7 parts by weight per part by weight of tenside component and at most 3.6, preferably at most 3.4, particularly preferred at most 3.2, and such as at most 3.0 parts by weight per part by weight of tenside component.
• additional builders which do not fall into the categories of said builders A, B, C or D are included in the builder component.
• Builder A of the laundry detergent composition according to the invention may advantageously comprise one or more ion-exchangers selected from the group consisting of zeolite and clay, optionally combined with alkali metal silicate.
• builder B may comprise ion-transferring agents selected from the group consisting of citrate, citric acid, nitrilotriacetic acid and chelatinizing tensides.
• Builder C may advantageously comprise dispersing agents and/or precipitation inhibitors selected from the group consisting of phosphonates and homopolymeric and/or copolymeric carboxylic acids including polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid, citraconic acid as well as copolymers of such carboxylic acids with each other or with other ethylenically unsaturated compounds including ethylene, propylene, isobutylene, vinyl alcohol, vinylmethyl ether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid and crotonic acid.
• dispersing agents and/or precipitation inhibitors selected from the group consisting of phosphonates and homopolymeric and/or copolymeric carboxylic acids including polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconi
• builder D may include soil-suspending agents selected from the group consisting of cellulose derivatives comprising ether cellulose derivatives including carboxyethyl celluloses, carboxymethyl celluloses, hydroxyethyl celluloses and methylhydroxyethyl celluloses.
• the tenside component of the laundry detergent composition according to the invention comprises a nonionic tenside.
• said nonionic tenside is a major part of the tenside component, such as at least 50% by weight.
• the nonionic tensides used can in principle be selected from the group consisting of all conventional nonionic tensides usually manufactured by condensation of a hydrophilic alkylene oxide and a hydrophobic compound.
• a survey over the classes and types of nonionic tensides suitable for laundry detergent compositions according to the invention is given in US-PS Nos. 3.664.961, 4.222.905 and 4.239.659, incorporated herein by reference.
• suitable nonionic tensides are alkoxylated non-ionic surface-active compounds having an alkoxy moiety of ethylene oxide (EO), propylene oxide and/or butylene oxide as well as mixtures thereof.
• a suitable hydrophobic compound may be an alcohol, thioalcohol, diol, fatty acid, fatty acid amide, alkane sulphonamide, alkyl amine as well as alkyl phenol.
• nonionic tensides ethoxylated compounds of primary and secondary fatty alcohols are preferred.
• condensation products based on linear fatty alcohols such as C12 ⁇ 18 coco alcohols, C16 ⁇ 18 tallow alcohols, oleyl alcohol or other natural alcohols as well as mixtures thereof having 3-16 mole EO per mole fatty alcohol.
• DOBANOLTM 26-7 available from Shell Chemical Corp., said product being a C12 ⁇ 15 fatty alcohol with 7 mole EO.
• Another commercial product is SYNPERONICTM, available from ICI, the C13 ⁇ 15 fatty alcohol with 7 mole EO being particularly preferred.
• LUTENSOLTM A07 is of the same type as the latter and available from BASF AG, Ludwigshafen, Germany.
• DEHYDOLTM LT 7 linear-based fatty alcohol ethoxylates
• DEHYDOLTM 2144 available from Henkel.
• DEHYDOLTM LT 7 is manufactured from vegetable C12 ⁇ 18 fatty alcohols with 7 mole EO and DEHYDOLTM 2144 is a mixture of natural fatty alcohol ethoxylates.
• nonionic tensides suitable for the laundry detergent composition according to the invention the following types of sugar-based tensides may further be mentioned, such as sugar esters, sugar ethers, acetylated sugar ethers etc. disclosed in e.g. US-PS No. 4.800.038 incorporated herein by reference.
• sugar esters include mono- and dilauric acid of sucrose as well as mono- and dipalmitic acid/stearic acid esters of sucrose, commercially available under the trade names of GRILLOTEN LSE 87 and GRILLOTEN PSE 141G, respectively, from Grillo Werke AG, Duisburg, Germany.
• the nonionic tenside may comprise all known types of fully biologically degradable alkyl polyglycosides manufactured on the basis of natural oils and carbohydrates.
• Such examples include a short-chained natural C8 ⁇ 10 fatty alcohol glycoside as well as a natural C12 ⁇ 14 fatty alcohol glycoside available under the trade names of PLANTAREN APG 600 and PLANTAREN APG 225, respectively, from Henkel KGaA, Düsseldorf, Germany.
• alkyl polyglycosides as well as of the oxyalkylated alkyl polyglycosides, which are just as suitable to be incorporated in the present laundry detergent composition, are disclosed in WO Publication No. 86/05199 (Malik, A. E. Staley Manufacturing Company) as well as WO Publication No. 88/01639 (Roth et al., A.E. Staley Manufacturing Company) incorporated herein by reference.
• the major part of the tenside component is a nonionic tenside. It is just as essential that said composition does not comprise interfering amounts of anionic tensides, as such tensides form insoluble compounds when subjected to high water hardness, resulting in a reduction of the washing performance. Accordingly the amount of anionic tensides should be kept low, preferably below 25% by weight of the total tenside component, more preferred below 10% by weight, even more preferred below 5% by weight and most preferred about 0% by weight.
• the tenside component may comprise other tensides of non-anionic type, such as all known types of cationic, amphoteric, ampholytic and zwitterionic surface-active compounds in amounts of usually not more than 50% of the total amount of tenside. Examples of said tensides are extensively discussed in US-PS No. 4.111.855, US-PS No. 3.995.669 and GB publication No. 2.075.043A incorporated herein by reference.
• a particularly preferred tenside is an amphoteric tenside in the form of a powder of cocoamidopropyl betaine available under the trade name TEGOBETAIN L-7 from Goldschmidt AG, Essen, Germany, the amount of active component in said product being 80%.
• Builder A comprises zeolite and/or clays, in Germany known as "Schichtsilikate", and optionally also alkali metal silicate, such as sodium silicate.
• Builder A may, for instance, be composed of zeolite and sodium silicate or builder A may solely comprise a clay. It is furthermore possible to use a combination of zeolite, alkali metal silicate and clay or of zeolite and clay. Zeolite and clay possess ion-exchanging properties, while alkali metal silicates, such as sodium silicate, support the ion-exchanging effect. In case the ion exchanger is zeolite, an alkali metal silicate is usually requisite.
• the amount of sodium silicate is preferably 13-29 parts by weight per 100 parts by weight of zeolite, particularly preferred 15-27 parts by weight, more particularly preferred 17-25 parts by weight and especially 19-23 parts by weight of sodium silicate per 100 parts by weight of zeolite. It is also possible to combine zeolite with another alkaline builder.
• zeolite includes in principle all known types of aluminosilicates. Corresponding examples are mentioned in DK Printed Accepted Publication No. 151.231, DK Printed Accepted Publication No. 154.827 and EP Publication No. 289.767.
• the zeolite type may be selected with respect to a composition, grain size, bulk density, solubility, absorbtivity etc. suitable for the manufacturing method.
• the laundry detergent composition according to the invention is preferably manufactured by means of a single spray-mix process, and comprises preferably a highly absorbing zeolite granulate, such as the product sold under the trade name WESSALITHTM CD available from Degussa AG, Frankfurt am Main, Germany.
• the product comprises 71% zeolite A as well as polycarboxylate and nonionic tenside.
• builder A may completely or in part comprise a so-called clay having the stoicheiometric composition Na2SiO5, each stratum comprising SiO4-tetrahedrons.
• clays are able to also bind magnesium ions, the latter playing an important role in connection with lime depositions on heating elements.
• a preferred clay of the laundry detergent composition according to the invention is a granulate, such as the one sold under the trade name "SKS-6" by Hoechst AG, Frankfurt am Main, Germany.
• builder A is utilized together with builder B acting as ion-transferring agent (carrier), builder C acting as a precipitation inhibitor (thresholder) and builder D acting as a soil-suspending agent.
• the ion-transferring agent (builder B) binds the ions responsible for the water hardness and transfers them to the ion-exchanger, e.g. zeolite, where they are deposited and bound by ion exchange.
• the ion-exchanger e.g. zeolite
• hard water is softened faster than before, as the softening effect of zeolite alone is comparatively slow and based on the ion exchange of substantially calcium ions.
• builder A comprises a large amount of clay instead of zeolite, the necessary amount of ion-transferring agent (builder B) may presumably be reduced or possibly left out altogether.
• the citrate usually comprises citrate.
• the citrate may be in the form of trisodium citrate dihydrate, anhydrous trisodium citrate as well as anhydrous monosodium citrate, the latter being preferred and available from i.a. Citrique Belge Ltd., Tienen, Belgium.
• Citric acid, nitrilotriacetic acid (NTA) or so-called chelatinizing tensides may also be used, the latter having the advantage of being soluble in fatty soil (as regards chelatinizing tensides reference is made to Novak et al., Seifen ⁇ le Fette Wachse 111 (1985), 1.35-87).
• the percentage of citric acid, and thus builder B may be in the upper range, i.e. up to 55 parts by weight of builder B per 100 parts by weight of builder A.
• the amount of builder B is usually less, for instance 3.7-12, preferably 6.2-9.2 and especially 6.9-8.5 parts by weight of builder B per 100 parts by weight of builder A.
• builder C i.e. the above-mentioned precipitation inhibitor
• Builder C may especially be in the form of a polymeric carboxylic acid.
• a corresponding effect is achieved by certain complex-binders, for instance phosphonate and phytate, however by means of a different reaction mechanism.
• builder C is preferably a polycarboxylate, it is thus conceivable that a greater or smaller part thereof may be such a complex-binder.
• Suitable polymeric precipitation inhibitors for the laundry detergent composition according to the invention include all know polyanionic polymers, such as those disclosed in US-PS Nos. 3.308.067, 3.723.322, 4.144.226 and 4.146.495 as well as GB Publication No. 1.596.756.
• Non-limiting examples include polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid, citraconic acid etc. as well as copolymers of the above-mentioned carboxylic acids with each other or with other ethylenically unsaturated compounds, such as ethylene, propylene, isobutylene, vinyl alcohol, vinylmethyl ether, furan, acrolein, vinyl acetate, acrylamide, acrylonitril, methacrylic acid, crotonic acid etc.
• the molecular weight of homopolymers and copolymers is in the range of approx. 1,000-1,000,000, preferably 2,000-250,000 and most preferred 5,000-100,000.
• the preferred polycarboxylate is especially the sodium salt of the acrylic/maleic acid copolymer having a molecular weight of approx. 70,000.
• SOKALANTM CP 5 is one example of a commercial product having such a composition, said product being available from BASF AG, Ludwigshafen, Germany.
• the laundry detergent composition according to the invention preferably comprises sodium disilicate having an Na2O:SiO2 ratio of 1:2, such a product being, for instance, available from Crossfield Chemie B.V., Eijsden, The Netherlands.
• Examples of builder substances apart from the builders A, B, C and D advantageously incorporated in the laundry detergent composition according to the invention include alkaline builders, such as alkali metal carbonates, alkali metal dicarbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, alkali metal borates, alkali metal sulphates as well as mixtures thereof.
• alkaline builders such as alkali metal carbonates, alkali metal dicarbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, alkali metal borates, alkali metal sulphates as well as mixtures thereof.
• Sodium carbonate is particularly preferred.
• the suspending agent is usually a cellulose derivative.
• cellulose derivatives include in principle all water-soluble cellulose derivatives such as those disclosed in EP Publication No. 291.869 and GB-PS No. 1.596.756.
• Particularly preferred are ether cellulose derivatives, such as carboxyethyl celluloses, carboxymethyl celluloses, hydroxyethyl celluloses and methylhydroxyethyl celluloses.
• Most preferred is a mixture of sodium carboxymethyl cellulose and methylhydroxyethyl cellulose at a ratio of between 10:1 to 1:5, preferably 5:1 to 1:2 and most preferred 2:1 to 1:2.
• builder substances optionally incorporated in the laundry detergent composition according to the invention include complex-binders preventing precipitation due to their ability to bind polyvalent cations and counteracting undesired reactions, thus stabilizing the entire washing process including especially the bleaching step.
• complex-binders are usually part of builder C.
• Some complex-binders have, however, ion-transferring powers and are therefore included in builder B.
• Complex-binders and thus precipitation inhibitors of builder C can include phosphonates, i.e. phosphonic acids or salts thereof, such as alkali metal, ammonium or substituted ammonium phosphonic acids alkali metal, ammonium or substituted ammonium polyphosphonic acids, alkali metal, ammonium or substituted ammonium alkane polyphosphonic acids, alkali metal, ammonium or substituted ammonium aminohydroxyalkane polyphosphonic acids, and alkali metal, ammonium or substituted ammonium hydroxyalkane polyphosphonic acids, alkali metal, ammonium or substituted ammonium phosphonic carboxylic acids etc. as well as mixtures thereof.
• phosphonates i.e. phosphonic acids or salts thereof, such as alkali metal, ammonium or substituted ammonium phosphonic acids alkali metal, ammonium or substituted ammonium polyphosphonic acids, alkali metal, ammonium or substituted ammonium alkane polyphosphonic
• Examples of phosphonates and phosphonic acids include in particular ethane-1-hydroxy-1,1-diphosphonic acid (HEDP), ethylene diamine tetra(methylenephosphonic acid) (EDTMP), diethylene triamine penta(methylenephosphonic acid) (DETPMP), aminotrismethylene phosphonic acid (ATMP) as well as salts thereof.
• HEDP ethane-1-hydroxy-1,1-diphosphonic acid
• ETMP ethylene diamine tetra(methylenephosphonic acid)
• DETPMP diethylene triamine penta(methylenephosphonic acid)
• ATMP aminotrismethylene phosphonic acid
• disodium and tetrasodium salt of ethane-1-hydroxy-1,1-diphosphonic acid in the form of a free-flowing powder.
• Complex-binders presumably also having ion-transferring properties include water-soluble polycarboxylic acids and alkali metal, ammonium or substituted ammonium polycarboxylic acids including dicarboxylic acids, non-cyclic polycarboxylic acids, cyclic di- or polycarboxylic acids, hydroxymonocarboxylic acids, aminopolycarboxylic acids as well as higher homologues thereof and salts thereof.
• suitable complex-binders include tartaric acid, glutaric acid, lactic acid, malic acid, gluconic acid, tartronic acid, ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), hydroxyethylethylene diamine triacetic acid (HEEDTA), isoserine diacetic acid (ISDA) and salts thereof.
• EDTA ethylene diamine tetraacetic acid
• DETPA diethylene triamine pentaacetic acid
• HEEDTA hydroxyethylethylene diamine triacetic acid
• ISDA isoserine diacetic acid
• Phytic acid and its derivatives including salts thereof should also be mentioned.
• complex-binders are not as biologically degradable in nature as will be required in the future.
• a biologically degradable complex-binder such as isoserine-N,N-diacetic acid (ISDA) (HOOCCH2)2N-CH2-CHOH-COOH as well as salts thereof.
• the laundry detergent composition according to the invention usually also includes one or more conventional adjuvants or additives.
• conventional adjuvants or additives include agents preventing the running of colour, tabletting adjuvants, antiagglutinants, known rinsing substances, such as of the bentonite type, colours, deodorants, antioxidants, aerosol propellants, solvents, such as lower alcohols, glycols or glycol ethers, foam inhibitors, perfume, enzymes, bleaches, bleach activators, bleach stabilizers, such as magnesium silicate, optical brighteners, antistatics, bactericides, fungicides, hydrotropics, wetting agents and fillers.
• agents preventing the running of colour tabletting adjuvants, antiagglutinants, known rinsing substances, such as of the bentonite type, colours, deodorants, antioxidants, aerosol propellants, solvents, such as lower alcohols, glycols or glycol ethers, foam inhibitors, perfume, enzymes, bleaches,
• enzymes advantageously used in the laundry detergent composition according to the invention include mixtures of specific types, such as proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases disclosed in US-PS Nos. 3.519.570 and 3.533.139.
• Non-dusting granulates such as T-granulates available from NOVO NORDISK A/S, Bagsv ⁇ rd, Denmark, are particularly preferred for incorporation in the laundry detergent composition according to the invention.
• T-granulates are proteolytic enzymes available under the trade names ESPERASETM, SAVINASETM and ALCALASETM, amylolytic enzymes available under the trade name TERMAMYLTM, lipolytic enzymes available under the trade name LIPOLASETM, and cellulytic enzymes available under the trade name CELLUZYMETM, as well as mixtures thereof.
• proteolytic mixture ESPERASETM/SAVINASETM 2.0/2.0 T or ESPERASETM 6.0 T having 2 x 2.0 Kilo Novo Protease Units (KNPU/g) and 6.0 KNPU/g, respectively.
• optical brighteners to be incorporated in the laundry detergent composition according to the invention include diaminostilbene disulphonic acid derivatives as well as those types disclosed in EP Publication No. 291.869 and DK Printed Accepted Publication No. 156.173 (corresponding to GB-PS No. 1.473.202).
• Foam inhibitors in the laundry detergent composition according to the invention include both silicone-free and silicone-based compounds.
• Preferred compounds of the latter type are organopolysiloxan compounds, for instance present in the mixture with special silicon compounds, paraffins, waxes, microcrystallinic waxes etc., respectively.
• ANTIFOAM VP 1166 a pulverulent product available from Wacker Chemie GmbH, Germany, is one example of a silicone-based product to be incorporated in the laundry detergent composition according to the invention.
• the laundry detergent composition according to the invention may be a mixed with polyvinyl pyrrolidone (PVP), such as in the form of the product SOKALANTM HP 50 (powder) available from BASF AG, Germany.
• PVP polyvinyl pyrrolidone
• Tabletting adjuvants to be incorporated in the tabletted laundry detergent composition according to the invention are added to optimize granulation, breaking strength, dissolving time, agglutinating tendencies etc.
• Said adjuvants include amongst others granulation adjuvants, such as those described in DE Publication No. 3.827.895 and Ritschel, "Die Tablette", ed. Cantor, 1966, starch derivatives, sodium sulphate, sodium acetate, urea, polyvinyl (poly)pyrrolidone compounds, glycerol, stearate compounds, polyethylene glycols of a molecular weight of between 100-6,000 as well as mixtures thereof.
• suitable bleaches for use in the laundry detergent composition according to the invention include all known chlorine-based bleaches, perhydrates and peroxy compounds as well as mixtures thereof.
• chlorine bleaches are alkali metal compounds of dichloro- and trichlorocyanuric acid, N-chloroimides etc.
• Perhydrates include preferably alkali metal compounds of perborates in the form of the tetra- and monohydrates, perborax, percarbonates, persilicates, citrate perhydrates as well as perhydrates of urea and melamine compounds.
• perbenzoates and peroxycarboxylic acids such as peroxyphthalate, magnesium monoperoxyphthalic acid, diperoxyphthalic acids, 2-octyl diperoxysuccinic acids, diperoxydodecane diacids, diperoxyazelaic acids, imidoperoxycarboxylic acids as well as salts and mixtures thereof are also suitable.
• Non-limiting examples of bleach activators include N-acyl compounds and O-acyl compounds, such as acylated amines, diamines, diamides, acylated glycolurils, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulphuryl amides, cyanurates and imidazolines, carboxylic acid anhydrides, acylated sugar compounds, acylated ester compounds etc.
• N-acyl compounds and O-acyl compounds such as acylated amines, diamines, diamides, acylated glycolurils, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulphuryl amides, cyanurates and imidazolines, carboxylic acid anhydrides, acylated sugar compounds, acylated ester compounds etc.
• TAED tetraacetyl methylene diamine
• TAED tetraacetyl ethylene diamine
• TAGU tetraacetyl glycoluril
• PAG pentaacetyl glucose
• NOBS sodium nonanoyloxybenzene sulphonate
• TAED such as in the form of a granulate, the active compound being present in an amount of 85-95% by weight.
• the washing effect when using the laundry detergent composition according to the invention fully compares with the best laundry detergent compositions on the market.
• the water hardness is 20°dH, 25°dH or 35°dH
• no significant amount of incrustations are found in the textiles after the 25th wash
• the incrustation percentage rises when using a conventional detergent composition and when the water hardness increases.
• the detergent composition according to the invention does not display an increased tendency of forming depositions with water hardness increasing from 20°dH to 35°dH
• a conventional detergent composition displays a considerably increased tendency to lime depositions already at 20°dH, which rises drastically with increasing water hardness.
• a detergent composition according to the invention is prepared from the following ingredients, the percentages by weight being based on the anhydrous form of 100% active substances, so that the optional water-content of all substances is part of the water percentage:
• the above formulations CLT 1 and BLM 1 are advantageously compressed to tablets having a weight of 22.5 g and 25.0 g, respectively.
• the basic washing powder is manufactured by spraying the liquids of the tenside fraction on the components of the basic powder fraction.
• the ingredients are mixed in a suitable mixer being stirred continuously for approx. 12-18 minutes, whereupon the rest fraction is added under stirring for another 2-10 minutes.
• the washing powder appears as a free-flowing, lightly granulated powder having a bulk density of approx. 6-700 g/l.
• the powder mixture is compressed to tablets having a diameter of 40 mm in a tablet press (such as Korch, type EK III).
• the thickness varies depending on the desired weight of the tablets and their formulation and ranges between approx. 13-20 mm.
• the detergent composition is compressed to tablets in manners known per se and as disclosed in US-PS Nos. 4.099.912, 4.828.749 and 4.913.832 and DE Publication No. 3.827.895.
• the dosage for the comparative trial was 45 g of the above formulation CLT 1 and 25 g of BLM 1 per 18 l supply water or a dosage of 97.5 g ArielTM Ultra per 18 l supply water.
• the washing trials were performed at 60°C i 4 washing machines of the type Bauknecht WA 1200 (capacity 5.0 kg dry textiles) with 3.2 kg normally soiled laundry and a water amount of 18 l, using a regular programme without pre-wash. Standard-soiled swatches having a size of 10 x 15 cm were washed with the above dosages of Ariel Ultra and CLT 1 + BLM 1, respectively.
• the washing trials were carried out at 17, 25 and 35°dH hard water, respectively, the ratio between calcium and magnesium ions being 3:1.
• the swatches were fastened to a piece of cotton, washed, dried and ironed, whereupon they were measured reflectometrically with a colorimeter of the type MINOLTA CR 200.
• Standard swatch Type of soil Manufacturer 10 C WFK standard soil (pigment/lanolin) on cotton WFK PC 9 Pigment/oil on polyester/cotton CFT 20 D Pigment/sebum on polyester/cotton WFK 10 B Blood on cotton WFK 10 F Cocoa/lanolin on cotton WFK 20 F Cocoa/lanolin on polyester/cotton WFK 10 K Coffee on cotton WFK 10 L Red wine on cotton WFK BC 1 Tea on cotton CFT 20 G Tea on polyester/ cotton WFK
• Table 1 shows the measured reflections of the various swatches after washing at 60°C in 17, 25 and 35°dH hard water, respectively.
• the reflection was measured on the basis of the Y, x, y colour system, CIE (Commission Internationale de L'Eclairage), the maximum whiteness, or the best washing performance, being defined as 100.
• CIE Commission Internationale de L'Eclairage
• the Y, x, y colour system defines Y as the brightness factor expressed as a percentage of the perfect reflection of 100%.
• Table 2 evaluates the values of table 1 in three categories: Soil removal: The sum of reflections of swatches 10 C, PC 9 and 20 D.
• Bleaching effect The sum of reflections from the bleach-depending swatches 10 B, 10 F, 20 F, 10 K, 10 L, BC 1 and 20 G.
• This example is a comparison between Ariel Ultra and CLT 1 as regards incrustations formed after 25 washes at 60°C using a dosage of 97.5 g Ariel Ultra per 18 litres of supply water or 45.0 g of CLT 1 per 18 litres of supply water.
• the experiment was carried out using supply water having a hardness of 20, 25 and 35°dH, respectively.
• CLT 1 results only in a small quantity of incrustations, regardless of the water hardness, whereas ARIEL ULTRA shows an increasing amount of incrustations with increasing water hardness.
• the dosages of the products of the table are g per 18 l supply water.
• Amphoteric tenside (Tegobetain L 7, 80% active) 6.3
• Sodium disilicate 5.6 Monosodium citrate 3.3 SOKALAN TM CP 5 1.9 ESPERASETM/SAVINASETM 1.5
• CMC (carboxymethyl cellulose) 0.7 TYLOSETM MH 300
• DEHYDOL TM 2144 7.5
• Amphoteric tenside (Tegobetain L 7, 80% active) 25.0
• Sodium disilicate 4.5 Monosodium citrate
• PersilTM is a conventional detergent composition available from Henkel. CalgonTM is a water softener to be added when the supply water is particularly hard. CalgonTM is available from Benckiser, Germany.
• the detergent compositions according to the invention have a significantly lower tendency to form depositions on heating elements as compared to known detergent compositions. Is further apparent that the depositions do not increase with increasing water hardness. Moreover, it is apparent that even with a percentage of approx. 50% amphoteric tenside (CLT 3) the amount of depositions is still reduced compared to known detergent compositions.
• CLT 3 amphoteric tenside
• This example describes an all-purpose formulation for the laundry detergent composition according to the invention comprising bleach in the form of a tablet having a weight of 30 g to be used in amounts based on the use of two tablets per wash cycle, i.e. in a conventional washing machine using 18 l of supply water.
• the tablets were prepared using the following ingredients: CLT 4 % by weight WESSALITHTM CD 42.6 DEHYDOLTM LT 7 11.3 DEHYDOLTM 2144 7.5 LUTENSOLTM AT 25 2.2 Sodium percarbonate 20.0 TAED 3711 5.0 Sodium disilicate 4.5 Monosodium citrate 2.6 SOKALANTM CP 5 1.6 Enzyme (as in Example 1) 1.2 Carboxymethyl cellulose 0.6 TYLOSETM MH 300P 0.6 ANTIFOAM VP 1166 0.3 100.0 ⁇
• This example describes an all-purpose formulation for the laundry detergent composition according to the invention comprising bleach in the form of a tablet having a weight of 35 g to be used in an amount of two tablets per wash cycle, i.e. in a conventional washing machine using 18 l of supply water.
• the tablets were prepared using the following ingredients: CLT 5 % by weight WESSALITHTM CD 36.3 DEHYDOLTM LT 7 11.1 DEHYDOLTM 2144 5.5 LUTENSOLTM AT 25 1.9 TAED 3711 4.3 Sodium carbonate 14.1 Sodium disilicate 3.8 Monosodium citrate 2.2 SOKALANTM CP 5 1.3 Enzyme (as in Example 1) 1.0 Carboxymethyl cellulose 0.5 TYLOSETM MH 300 P 0.5 ANTIFOAM VP 1166 0.3 Sodium perborate - monohydrate 17.0 Perfume 0.2 100.0 ⁇
• This example illustrates the preparation of a detergent composition according to the invention in the form of a basic tablet without bleach and perfume.
• CLT 6 % by weight WESSALITHTM CD 56.7 DEHYDOLTM LT 7 15.0 DEHYDOLTM 2144 10.2 LUTENSOLTM AT 25 3.0 Sodium disilicate 6.0 Monosodium citrate 3.5 SOKALANTM CP 5 2.0 Enzyme (as in Example 1) 1.6 Carboxymethyl cellulose 0.8 TYLOSETM MH 300 P 0.8 ANTIFOAM VP 1166 0.4 100.0 ⁇
• the tablets were prepared as described in Example 1, each tablet weighing 22.5 g, two tablets being used per wash cycle in a conventional washing machine.
• This example illustrates the preparation of a detergent composition according to the invention in the form of a basic tablet of 25 g without bleach but characterized by a high amount of specific enzymes.
• the detergent composition is suitable for i.a. soaking.
• the tablets were prepared as described in Example 1, each tablet weighing 25 g, one tablet to be used for soaking in a sink and two tablets per wash cycle in a conventional washing machine.
• This example describes the preparation of a detergent composition according to the invention in the form of a basic tablet of 30 g without bleach, the composition being particularly suitable for oily and dirty textiles, such as work clothes etc.
• Proteolytic enzyme ESPERASETM 6.0 T
• CMC 0.6 TYLOSETM MH 300
• the tablets were prepared as described in Example 1, each tablet weighing 30 g, two tablets to be used per wash cycle in a conventional washing machine.
• CLT 12 being a basic detergent composition with both zeolite and clay
• CLT 13 being a basic detergent composition without zeolite, but with clay
• CLT 14 being an all-purpose detergent composition without zeolite but with clay
• CLT 15 being an all-purpose detergent composition without zeolite but with clay and soda (sodium carbonate).
• This example illustrates the formulation of the laundry detergent composition according to the invention in the form of a tablet having a weight of 30 g to be used in an amount of two tablets per wash in a conventional washing machine.
• the tablets are formulated with respect to achieving an improved dissolving time by adding a large amount of citric acid, said acid reacting with sodium carbonate and/or sodium bicarbonate to give off gas bubbles upon the addition of water.
• the p.t. preferred embodiment of the invention is in the form of two tablets having a total weight of 45 g of formulation CLT 1 according to Example 1, optionally combined with a bleach tablet having a weight of 25 g of composition BLM 1.

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Cited By (14)

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• 1991
  • 1991-04-12 DK DK66591A patent/DK167363B1/da not_active IP Right Cessation
• 1992
  • 1992-04-10 EP EP19920610026 patent/EP0508934A1/de not_active Withdrawn

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