EP0009954B1 - Reinigungsmittelzusammensetzungen - Google Patents

Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0009954B1
EP0009954B1 EP79302059A EP79302059A EP0009954B1 EP 0009954 B1 EP0009954 B1 EP 0009954B1 EP 79302059 A EP79302059 A EP 79302059A EP 79302059 A EP79302059 A EP 79302059A EP 0009954 B1 EP0009954 B1 EP 0009954B1
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EP
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Prior art keywords
alkali metal
weight
composition according
detergent composition
orthophosphate
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Expired
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EP79302059A
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English (en)
French (fr)
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EP0009954A1 (de
Inventor
Hermann Rabitsch
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to AT79302059T priority Critical patent/ATE79T1/de
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates

Definitions

  • the present invention relates to powdered detergent compositions which are adapted for fabric washing, and which contain synthetic detergent active compounds together with mixed phosphate detergency builders.
  • the invention concerns in particular the production of detergent compositions which contain levels of the mixed phosphate detergency builders which can be lower than conventional phosphate builder levels, but which still retain good detergency properties.
  • a particulate detergent composition based on mixed phosphate detergency builders comprises a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereof, an alkali metal orthophosphate, an alkali metal or ammonium polymer phosphate and an antideposition agent as defined below.
  • any such alkali metal pyrophosphate contributes particularly to inorganic deposits on the washing machines.
  • a major step forward is taken to control inorganic deposition on fabrics and washing machine surfaces better than hitherto, and yet still achieve good detergency building at relatively low phosphate levels.
  • an antideposition agent makes possible a further reduction in the level of inorganic deposition, especially on washed fabrics. It appears that the antideposition agents stabilise the suspended insoluble calcium orthophosphate particles, and hence-inhibit their deposition on ihe fabrics. Thus, in accordance with the invention steps are taken to control the inorganic deposition caused by both precipitated calcium pyrophosphate and orthophosphate, giving substantial technical and hence commercial benefit.
  • the alkali metal polymer phosphate used in the compositions of the invention is preferably sodium polymer phosphate, but if desired the potassium or ammonium salts can be used.
  • alkali metal polymer phosphate is used hereinafter and in the claims to include the sodium, potassium and ammonium salts.
  • the alkali metal polymer phosphates are generally represented as having the formula M Z (MP0 3 ) " , where M is sodium, potassium or ammonium and n is an integer which is at least 4 and up to about 100 or more, preferably from about 6 to about 50.
  • these figures correspond to a P z O 5 content of at least about 60.4% by weight up to a theoretical maximum of about 69.6%, preferably about 63% to about 69% P Z 0 5 by weight of the polymer phosphate.
  • the polymer phosphates must of course be water-soluble. It should be appreciated that the chemical structures of the polymer phosphates are not precisely defined, and some degree of ring formation or branching may be present in the otherwise normally linear polymer structure, especially with the shorter polymer chain lengths.
  • the polymer phosphates are sometimes also known as glassy phosphates or Graham's salt.
  • alkali metal polymer phosphate should be admixed with a detergent base powder, i.e. postdosed, to obtain the most benefit of lower alkali metal pyrophosphate content in the product.
  • a detergent base powder i.e. postdosed
  • some or all of the alkali metal polymer phosphate can be included in the base powder if desired, and this can help to improve the powder properties, particularly when relatively low alkali metal orthophosphate levels are used.
  • Any alkali metal polymer phosphate which is postdosed should, of course, have a suitable particulate form for postdosing, that is to say it should have an appropriate particle size range and powder density for uniform mixing with the base powder, so as to avoid undue segregation in the finished product.
  • Detergent compositions which are based on mixed phosphate builders and incorporate an alkali metal orthophosphate and discrete particles of alkali metal polymer phosphate, which can be made by postdosing the latter ingredient, are described in our co-pending U.K. Patent Application 39073/78 of even date.
  • the alkali metal orthophosphate used is either potassium or preferably sodium orthophosphate, as the latter is cheaper and more readily available. Normally the tri-alkali metal salts are used, but orthophosphoric acid or the di- or mono-alkali metal salts, e.g. disodium hydrogen orthophosphate or monosodium dihydrogen orthophosphate could be used if desired in the production of the compositions. In the latter event other more alkaline salts should also be present to maintain a high pH in the end product, i.e. with full neutralisation to the trialkaii meta.1 orthophosphate salts.
  • a mixture of the monosodium dihydrogen and disodium hydrogen orthophosphates in the ratio of 1:3 to 2:3, especially about 1:2, is particularly advantageous, as such a mixture (known as kiln-feed) is made in the production of sodium tripolyphosphate and is readily available. It is preferred to have all the alkali metal orthophosphate present in the detergent base powder, e.g. by inclusion in an aqueous detergent slurry and then spray dried, but part of the orthophosphate can be postdosed if desired, either separate or together with the alkali metal polymer phosphate.
  • the alkali metal orthophosphate can be used in the form of the anhydrous or hydrated salts, but in the former case it is preferred to promote hydration during processing, e.g. by adding the anhydrous orthophosphate to a detergent slurry and spray drying to form the base powder.
  • the alkali metal polymer phosphates do not form hydrated salts as such, and are normally used in anhydrous form, but they are hygroscopic and tend to absorb atmospheric moisture. The amounts of the salts used are expressed in anhydrous form.
  • the total amounts of the essential alkali metal polymer phosphate and alkali metal orthophosphate, and any other phosphates which may be present in the detergent compositions are chosen according to the overall detergency builder level which is desired in the detergent compositions or according to the maximum permitted phosphorus content.
  • the total phosphate builder level which is preferably derived solely from alkali metal polymer phosphate and alkali metal orthophosphate, is between about 10% and about 40%, by weight of the composition, preferably with an amount of at least about 5% and at least about 2% up to about 20% each of the alkali metal polymer phosphate and orthophosphate, respectively.
  • the amounts of the alkali metal polymer phosphate and alkali metal orthophosphate are each from about 5% to about 15%, especially about 5% to 10%, by weight of the composition.
  • the total amount of alkali metal polymer phosphate and alkali metal orthophosphate is preferably from about 10% to about 25%, especially about 15% to about 20%, by weight of the composition.
  • alkali metal polymer phosphate and the alkali metal orthophosphate generally within the ratio of from about 3:1 to about 1:3, especially about 2:1 to about 1:2, parts by weight, respectively.
  • ratios of polymer phosphate to orthophosphate are particularly suitable for detergent compositions used at relatively high product concentrations, i.e. 0.3% to 0.8% by weight, as is common practice in Europe; especially in front-loading automatic washing machines, and where moderate levels of phosphates are allowed in the products, i.e. equivalent to 3% to 7% P.
  • the only phosphate detergency builders used to make the compositions of the invention should be the alkali metal polymer phosphate and alkali metal orthophosphate.
  • some alkali metal tripolyphosphate may be present if desired, either in the base powder or postdosed thereto, for example because of its beneficial effect on the base powder properties or because of its relative cheapness. But for optimum detergency in relation to total phosphate content, it is preferred to have not more than about 10% by weight of other alkali metal phosphate builders, and especially not more than about 5% of tripolyphosphate present in the detergent composition.
  • tripolyphosphate and pyrophosphate are also generally found as impurities at low levels in other commercial alkali metal phosphates, and some tripolyphosphate and pyrophosphate may be formed by any hydrolysis of the polymer phosphate during processing, especially if some of it is present in the slurry rather than being all postdosed. Hence, total absence of alkali metal tripolyphosphate and pyrophosphate.is generally unattainable in the detergent compositions. It is particularly preferred to have not more than about 2.5% of alkali metal pyrophosphate present in the compositions, as at higher levels the amounts of inorganic deposits on the washing machine parts become significantly more noticeable.
  • the detergent compositions of the invention essentially contain one or more antideposition agents to decrease the tendency to form inorganic deposits on washed fabrics.
  • the antideposition agents appear to be effective by stabilising insoluble calcium orthophosphate particles by stabilising insoluble calcium orthophosphate particles in suspension.
  • the best test for determining whether or not an antideposition agent is effective in a detergent composition according to the invention is to determine the level of inorganic deposits on fabric washed with and without the antideposition agent present.
  • the most effective antideposition agents are generally anionic polyelectrolytes, especially polymeric aliphatic carboxylates.
  • the amount of any such antideposition agent can be from about 0.0196 to about 10% of the compositions, but is normally from about 0.1% to about 5% by weight, preferably from about 0.2% to about 2% by weight of the compositions.
  • Specific preferred antideposition agents are the alkali metal or ammonium, preferably the sodium, salts of homo- and co-polymers of acrylic acid or substituted acrylic acids, such as sodium polyacrylate, the sodium salt of copolymethacrylamide/acrylic acid and sodium poly-alpha-hydroxyacrylate, salts of copolymers of maleic anhydride with ethylene, acrylic acid, vinylmethylether or styrene, especially 1:1 copolymers, and optionally with partial esterification of the carboxyl groups.
  • Such copolymers preferably have relatively low molecular weights, e.g. in the range of about 1,000 to 50,000.
  • antideposition agents include the sodium salts of polymaleic acid, polyitaconic acid and polyaspartic acid, phosphate esters of ethoxylated aliphatic alcohols, polyethylene glycol phosphate esters, and certain organic phosphonic acids or salts thereof such as sodium ethane-1-hydroxy-1,1 -diphosphonate. sodium ethylenediamine tetramethyiene phosphonate, and sodium 2-phosphonobutane tricarboxylate. Mixtures of organic phosphonic acids or substituted acrylic acids or their salts with protective colloids such as gelatin may also be used.
  • the most preferred anti-deposition agents are sodium polyacrylates having a MW of about 10,000 to 50,000, for example about 20,000 to 30,000.
  • the detergent compositions of the invention necessarily include from about 2.5% to about 50%, preferably about 5% to about 30%, and especially about 10% to about 25%, by weight of a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereof.
  • a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereof are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry & Berch.
  • the preferred detergent compounds which can be used are synthetic anionic and nonionic compounds.
  • the former are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C S -C 1s ) alcohols produced for example from tallow or coconut oil; sodium and potassium alkyl (C 9 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 ⁇ C 15 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monogiyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 9 ⁇ C 18 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of
  • 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.
  • Specific nonionic detergent compounds are alkyl (C 6 ⁇ C 22 ) phenol- ethylene oxide condensates, generally 5 to 25 EO, i.e.
  • ethylene oxide per molecule 5 to 25 units of ethylene oxide per molecule, the condensation products of aliphatic (C 8 ⁇ C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally a to 30 EO, or with both ethylene oxide and propylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • detergent compounds for example mixed anionic or mixed anionic and nonionic compounds may be used in the detergent compositions, particularly in the latter case to provide controlled low sudsing properties. This is beneficial for compositions intended for use in suds-intolerant automatic washing machines.
  • some nonionic detergent compounds in the compositions decreases the tendency of insoluble phosphate salts to deposit on the washed fabrics, especially when used in admixture with some soaps as described below.
  • Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used if is generally in small amounts in compositions based on the much. more commonly used synthetic anionic and/or nonionic detergent compounds. For example, mixtures of amine oxides and ethoxylated nonionic detergent compounds can be used.
  • Soaps may also be present in the detergent compositions of the invention, but not as the sole detergent compounds.
  • the soaps are particularly useful at low levels in binary and ternary mixtures, together with nonionic or mixed synthetic anionic and nonionic detergent compounds, which have low sudsing properties.
  • the soaps which are used are the sodium, or less desirably potassium, salts of C 10 ⁇ C 24 fatty acids. It is particularly preferred that the soaps should be based mainly on the longer chain fatty acids within this range, that is with at least half of the soaps having a carbon chain length of 16 or over.
  • soaps from naturat sources such as tallow, palm oil or rapeseed oil, which can be hardened if desired, with lesser amounts of other shorter chain soaps, prepared from nut oils such as coconut oil or palm kernel oil.
  • the amount of such soaps can be varied between about 0.5% and about 25% by weight, with lower amounts of about 0.5% to about 5% being generally sufficient for lather control.
  • Amounts of soap between about 2% and about 20%, especially between about 5% and about 15%, can advantageously be used to give a beneficial effect on detergency.
  • the detergent compositions of the invention can contain any of the conventional additives in the amounts in which such materials are normally employed in fabric washing detergent compositions.
  • these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants such as alkyl phosphates, waxes and silicones, antiredeposition agents such as sodium carboxymethylcellulose and polyvinyl pyrrolidone optionally copolymerised with vinyl acetate, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, per-acid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid and alkali metal salts of dichloroisocyanuric acid, fabric softening agents, inorganic salts such as sodium sulphate, sodium carbonate and magnesium silicate, and; usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as protea
  • an amount of sodium perborate preferably between about 10% and about 40%, for example about 1 5% to about 30%, by weight. It has been found that the bleaching action of sodium perborate is boosted under the highly alkaline conditions which also give optimum detergency building action for the alkali metal orthophosphate. Thus, it becomes possible to achieve improve bleaching properties by using the same levels of sodium perborate as normal; or decreased levels of sodium perborate can be used to give equal bleaching properties to those of conventional products with higher levels of perborate and sodium tripolyphosphate as the sold detergency builder. The latter option can also be used to further decrease the raw materials costs of the compositions, if a cheap filler is used in place of part of the sodium perborate.
  • non-phosphate detergency builders which may be either so-called precipitant builders, ion exchange or sequestrant builders.
  • precipitant builders ion exchange or sequestrant builders.
  • detergency builders examples include amine carboxylates such as sodium nitrilotriacetate, sodium carbonate, sodium aluminosilicate ionexchange materials such as zeolites A and X, sodium citrate and soap, which can function as a detergency builder, as discussed above.
  • amine carboxylates such as sodium nitrilotriacetate, sodium carbonate, sodium aluminosilicate ionexchange materials such as zeolites A and X, sodium citrate and soap, which can function as a detergency builder, as discussed above.
  • such other builder materials are not essential and it is a particular benefit of using the mixed alkali metal polymer phosphate and orthophosphate that. satisfactory detergency properties can be achieved at lower total phosphate levels than hitherto considered necessary without other detergency builders.
  • an amount of an alkali metal silicate particularly sodium ortho- meta- or preferably neutral or alkaline silicate.
  • an alkali metal silicate particularly sodium ortho- meta- or preferably neutral or alkaline silicate.
  • the presence of such alkalimetal silicates at levels of at least about 1%, and preferably from about 5% to about 15%, by weight of the compositions, is advantageous in decreasing the corrosion of metal parts in washing machines, besides giving processing benefits and generally improved powder properties.
  • the more highly alkaline ortho- and meta-silicates would normally only be used at lower amounts within this range, in admixture with the neutral or alkaline silicates.
  • compositions of the invention are required to be alkaline, but not too strongly alkaline as this could result in fabric damage and also be hazardous for domestic usage.
  • the compositions should give a pH of from 9 to 11 in use in aqueous wash solution. It is preferred in particular for domestic products to have a minimum pH of at least 9.25 and especially a pH of 9.5 or over, as lower pHs tend to be less effective for optimum detergency building, and a maximum pH of 10.5, as more highly alkaline products can be hazardous if misused.
  • the pH is measured at the lowest normal usage concentration of 0.1 % w/v of the product in water of 12°l ⁇ i (Ca), (French permanent hardness, calcium only) at 50°C so that a satisfactory degree of alkalinity can be assured in use at all normal product concentrations.
  • the pH of the detergent compositions in use is controlled by the amount of alkali metal orthophosphate and any other alkaline salts such as alkali metal silicate, sodium perborate and sodium carbonate present.
  • alkali metal silicates especially the alkali metal silicates
  • the presence of such other alkaline salts, especially the alkali metal silicates, is particularly beneficial, because the alkalinity of the alkali metal orthophosphate is diminished in hard water due to precipitation of the calcium salt.
  • the alkali metal polymer phosphate is more stable and resistant to hydrolysis under highly alkaline conditions.
  • the other ingredients in the alkaline detergent compositions of the invention should of course be chosen for alkaline stability, especially the pH sensitive materials such as enzymes.
  • the detergent compositions of the invention are normally made in particulate form, for example by slurry making and spray drying, preferably with admixture of the alkali metal polymer phosphate to a spray dried base powder.
  • the detergent compositions may be compressed or compacted into tablets or blocks, or otherwise treated for example by granulation, prior to packaging and sale. Because of the hygroscopic nature of the alkali metal polymer phosphates, it may be desirable. to use moisture impermeable packaging for the detergent compositions, for example in plastic or fabric sachets containing pre-measured doses for washing machine usage.
  • a series of detergent powders were prepared by firstly spray drying a detergent base powder to the following formulation:
  • detergent compositions were evaluated for washing performance, including especially inorganic deposition on fabrics.
  • the tests were accomplished in laundrometer machines using a product concentration of 8 g/I in water of 40° French hardness at 95°C.
  • the levels of deposition on the fabrics were determined after 10 repeat wash cycles using standard fabrics as indicated.
  • a series of detergent compositions were prepared by mixing the ingredients to the following formulation:
  • the sodium polymer phosphate used had a chain length (n) of about 18 and the sodium polyacrylates used had molecular weights as follows:
  • compositions were then tested for detergency and inorganic deposition on washed fabrics (ash). Considering the low phosphate builder level the detergency properties were good, and the ash levels were particularly low, being between 0.5% and 0.9% on cotton poplin fabric and between 1.5% and 2.0% on Krefeld cotton after 10 wash cycles. The tests were conducted at a product concentration of 8 g/1 in an Atlas Launderometer at 95°C in 23°CH water. By way of comparison, the ash levels for a similar sodium tripolyphosphate-sodium orthophosphate built formulation were 2.0% and 5.7% respectively, under the same conditions.
  • compositions were evaluated for detergency and inorganic fabric deposition, and found'to be good in both respects.
  • the average figures for the latter on different cotton types after 10 wash cycles were only 0.3%, 0.65%, 0.75% and 1.3%, respectively, under the same conditions as for Examples 10 tor 14.

Claims (16)

1. Teilchenförmiges alkalisches Waschmittel mit etwa 2,5 bis etwa 50 Gew.-% einer synthetischen anionischen, nichtionischen, amphoteren oder zwitterionischen Detergensverbindung oder deren Gemisch und gemischten PhosphatWaschmitteibuiidern und anderen bekannten Bestandteilen, gekennzeichnet durch einen Gehalt von wenigstens etwa 5 Gew.-% eines wasserlöslichen Alkalimetallpolymerphosphats der Formel M2O―(MPO3)n, worin M Alkalimetall und n eine ganze Zahl von wenigstens 4 ist, und wenigstens etwa 2 Gew.-% eines Alkalimetallorthophosphats, wobei das Verhältnis von Polymerphosphat zu Orthophosphat etwa 10:1 bis etwa 1:5 Gewichsteile ist, wobei die Gesamtmenge des Alkalimetallpolymerphosphats und des Alkalimetallorihophosphats etwa .10 bis etwai 40 Gew.-% des Mittels ausmacht und nicht mehr als etwa 10% anderer Alkalimetallphosphat-Builder im Mittel vorliegen, und etwa 0,01 bis etwa 10 Gew.-% eines anionischen Poiyeiektroiyten als der Abscheidung entgegenwirkendem Mittel.
2. Waschmittel nach Anspruch 1, dadurch gekennzeichnet, daß das Aikalimetallpolymerphosphat in Form des Natriumsalzes vorliegt.
3. Waschmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß in der Formel des Alkalimetallpolymerphosphats n etwa 6 bis etwa 50 ist.
4. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Menge an Alkalimetallpoiymerphosphat etwa 5 bis 15 Gew.-% des Mittels beträgt.
5. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Alkalimetallorthophosphat Trinatriumorthophosphat, Dinatriummonohydrogenorthophosphat, Mononatriumdihydrogenorthophosphat oder ein Gemisch hiervon ist.
6. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Menge an Alkalimetallorthophosphat etwa 5 bis etwa 15 Gew.-% des Mittels beträgt.
7. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Gesamtmenge des Alkalimetallpolymerphosphats und des Alkalimetailorthophosphats etwa 10 bis etwa 25 Gew.-% des Mittels beträgt.
8. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Gewichtsverhältnis von Alkalimetallpolymerphosphat zu Alkalimetallorthophosphat etwa 3:1 bis etwa 1:3 ist.
9. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß nicht mehr als etwa 5 Gew.-% Alkalimetalltripolyphosphat eingebracht sind.
10. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß nicht mehr als etwa 2,5 Gew.-%. Alkalimetallpyrophosphat eingearbeitet sind.
11. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das der Abscneidung entgegenwirkende Mittel ein polymeres aliphatisches Carboxylat ist.
12. Waschmittel nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das der Abscheidung entgegenwirkende Mittel eine organische Phosphonsäure oder deren Salz ist.
13. Waschmittel nach Anspruch 11, dadurch gekennzeichnet, daß das polymere aliphatische Carboxylat Natriumpolyacrylat ist.
14. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Menge des der Ascheidung entgegenwirkenden Mittels etwa 0,1 bis etwa 5 Gew.-% des Mittels ist.
15. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß etwa 0,5 bis etwa 25 Gew.-% Seife enthalten sind.
16. Waschmittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß etwa 10 bis etwa 40 Gew.-% Natriumperborat oder -percarbonat enthalten sind.
EP79302059A 1978-10-03 1979-10-01 Reinigungsmittelzusammensetzungen Expired EP0009954B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79302059T ATE79T1 (de) 1978-10-03 1979-10-01 Reinigungsmittelzusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7839071 1978-10-03
GB3907178 1978-10-03

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EP0009954A1 EP0009954A1 (de) 1980-04-16
EP0009954B1 true EP0009954B1 (de) 1981-06-10

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EP (1) EP0009954B1 (de)
JP (1) JPS5550095A (de)
AT (1) ATE79T1 (de)
AU (1) AU533316B2 (de)
BR (1) BR7906346A (de)
CA (1) CA1121690A (de)
DE (1) DE2960405D1 (de)
ZA (1) ZA795232B (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3035805A1 (de) * 1980-09-23 1982-05-06 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von granulaten kondensierter phosphate
GR76045B (de) * 1981-04-08 1984-08-03 Procter & Gamble
JPS5821498A (ja) * 1981-07-30 1983-02-08 ダスキンフランチヤイズ株式会社 漂白剤組成物及びその製造方法
GB2233338A (en) * 1989-06-23 1991-01-09 Unilever Plc Detergent composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116852A (en) * 1975-02-14 1978-09-26 The Procter & Gamble Company Builders and built detergent compositions
MX143145A (es) * 1975-02-20 1981-03-25 Procter & Gamble Composicion detergente granular mejorada
GB1530799A (en) * 1975-08-28 1978-11-01 Unilever Ltd Detergent compositions
DE2816770C2 (de) * 1977-04-22 1984-10-18 The Procter & Gamble Co., Cincinnati, Ohio Gerüststoffhaltiges Textilwaschmittel

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AU5136079A (en) 1980-04-17
JPS5550095A (en) 1980-04-11
EP0009954A1 (de) 1980-04-16
DE2960405D1 (en) 1981-09-17
ATE79T1 (de) 1981-06-15
BR7906346A (pt) 1980-05-27
AU533316B2 (en) 1983-11-17
CA1121690A (en) 1982-04-13
ZA795232B (en) 1981-05-27

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