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EP0056723B1 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

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Publication number
EP0056723B1
EP0056723B1 EP82300259A EP82300259A EP0056723B1 EP 0056723 B1 EP0056723 B1 EP 0056723B1 EP 82300259 A EP82300259 A EP 82300259A EP 82300259 A EP82300259 A EP 82300259A EP 0056723 B1 EP0056723 B1 EP 0056723B1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
activator
peroxybleach
detergent active
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
EP82300259A
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German (de)
English (en)
Other versions
EP0056723A1 (fr
Inventor
Peter Mccowan Duggleby
Francis Geoffrey Foster
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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.)
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Publication date
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to AT82300259T priority Critical patent/ATE10648T1/de
Publication of EP0056723A1 publication Critical patent/EP0056723A1/fr
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • 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
    • C11D3/02—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

Definitions

  • This invention relates to detergent compositions which are particularly, but not essentially, adapted for fabric washing, and more particularly to phosphate built detergent compositions including a bleach system.
  • peracid bleaches such as sodium perborate
  • peracid bleach precursors or peroxy bleach activator in detergent compositions.
  • Such detergent compositions conventionally include, in addition to a detergent active material, a phosphate detergency builder such as sodium tripolyphosphate.
  • a phosphate detergency builder such as sodium tripolyphosphate.
  • alumino-silicate ion exchange materials have been suggested as alternative builders to phosphates. (See for example GB 1 429 143-Procter Et Gamble Co.). However, it has been found that in alumino-silicate built compositions the performance of this bleach system is significantly reduced.
  • a particulate alkaline detergent composition comprising:
  • the percentage quantity of alkali metal tripolyphosphate (T) and the percentage quantity of the aluminosilicate material (A) are related to each other in such a manner that the sum lies between about 25 and about 37, preferably between about 28 and about 34.
  • the detergent compositions of the invention necessarily include from about 5% to about 40%, preferably 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 and Berch.
  • fabric washing detergent compositions also contain fluorescent agents for improving the brightening activity of the compositions towards fabrics washed therewith.
  • the fluorescent agents commonly used are derivatives of 4,4'-di(sym-triazinylamino)-stilbene-2,2'-disulphonic acid or salts thereof.
  • Other fluorescent agents that have also been used for example are derivatives of diphenyl- distyryl compounds, such as 4,4'-di(3-sulphostyryl)diphenyl; derivatives of 4,4'-di(triazolyl)stilbene-2,2'-disulphonic acid and derivatives of diphenyl-A2-pyrazoline.
  • Such fluorescent agents when incorporated in bleaching detergent compositions are liable to decompose with consequent loss of fluorescent activity, possibly owing to interaction with the bleaching system therein.
  • the fluorescer stability can be substantially maintained if a major part of the detergent active material is constituted by an anionic material.
  • the detergent active material selected from anionic synthetic detergent active materials and mixtures thereof with a lesser amount of one or more non-anionic synthetic detergent active materials.
  • the synthetic anionic detergent compounds 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 aryl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 ⁇ C 18 ) 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 acid monoglyceride 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
  • nonionic detergent compounds which may be used, preferably together with the anionic detergent compounds include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6 ⁇ C 22 ) phenols, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxides per molecule; the condensation products of aliphatic (C 8 ⁇ C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, 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.
  • a preferred anionic to nonionic ratio is at least about 2:1, most preferably from about 3:1 to about 10:1.
  • 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 it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic detergent compounds.
  • Some soaps may also be used in the compositions of the invention, but not as the sole detergent compounds. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures together with nonionic or mixed synthetic anionic and nonionic detergent compounds, which have low sudsing properties.
  • the soaps which are used are preferably the sodium, or less desirably potassium, salts of C, 6- 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 soap having a carbon chain length of 16 or over.
  • soaps from natural 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%, are preferably used to give a beneficial effect on detergency. This is particularly valuable in compositions used in hard water when the soap acts as a supplementary builder.
  • soap helps to decrease the tendency of the compositions to form inorganic deposits in the wash, for which purpose it is preferred to use about 2% to about 15%, especially about 2.5% to about 10% by weight of soap in the composition.
  • the total level of detergent actives, including the soap lies between about 5% and about 40% by weight, most preferably between about 10% and about 25% by weight.
  • the weight ratio of the synthetic anionic material and soap to the nonionic material is at least about 2:1, most preferably about 3:1 to about 10:1.
  • the alkali tripolyphosphate is preferably sodium tripolyphosphate, advantageously present in an amount of from more than about 15% to about 22% by weight. While it is desirable that the only phosphate material present is the tripolyphosphate, up to about 5% by weight of the composition of other phosphate materials may also be added, such as orthophosphate or pyrophosphate. Low levels of these other phosphate materials, even over 5% by weight of the composition, may in any case be present in compositions which have been prepared by spray drying, as a consequence of the hydrolysis of sodium tripolyphosphate. Thus, for example, a spray dried product nominally containing 25% sodium tripolyphosphate (STP) may in fact contain up to. about 10% by weight of other phosphates derived from the breakdown of the tripolyphosphates. The resulting sodium orthophosphate and sodium pyrophosphate both contribute to fabric ashing and should be kept to a minimum.
  • STP sodium tripolyphosphate
  • the aluminosilicate builder material is preferably crystalline or amorphous material having the general formula: wherein Z and Y are integers of at least 6, the molar ratio of Z to Y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264 such that the moisture content is from 10% to 28% by weight.
  • the preferred range of aluminosilicate is from about 12% to about 30% on an anhydrous basis.
  • the alumino-silicate preferably has a particle size of from 0.1 to 100 ,um, ideally between 0.1 and 10 ⁇ m and a calcium ion exchange capacity of at least 200 mg calcium carbonate/g.
  • the water-insoluble aluminosilicate ion exchange material has the formula wherein x is an integer of from 20 to 30, preferably about 27. This material is available commercially as Zeolite A.
  • the bleach system used essentially comprises a peroxy bleach compound which is an inorganic persalt, and an activator therefor.
  • the activator makes the bleaching more effective at lower temperatures, i.e. in the range from ambient temperature to about 60°C, so that such bleach systems are commonly known as low-temperature bleach systems and are well known in the art.
  • the inorganic persalt such as sodium perborate, both the monohydrate and the tetrahydrate, acts to release active oxygen in solution, and the activator therefor is usually an organic compound having one or more reactive acyl residues, which cause the formation of peracids, the latter providing for a more effective bleaching action at lower temperatures than the peroxybleach compound.
  • the ratio by weight of the peroxy bleach compound to the activator is about 15:1 to about 2:1, preferably about 10:1 to about 3.5:1. Whilst the amount of the bleach system, i.e. peroxy bleach compound and activator may be varied between about 5% and about 35% by weight of the detergent compositions, it is preferred to use about 6% to about 30% of the ingredients forming the bleach system. thus, the preferred level of the peroxy bleach compound in the composition is between about 5.5% and about 27% by weight, while the preferred level of the activator is between about 0.5% and about 10%, most preferably between about 0.5% and about 3.2% by weight.
  • Suitable peroxybleach compounds are alkalimetal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred.
  • the peroxybleach compound is normally added in separately to the detergent base powder, and it is desirable to avoid segregation by having the particles of both of generally the same order.
  • Activators for peroxybleach compounds have been amply described in the literature, including British patents 836,988, 855,735, 907,356, 907,358, 970,950, 1,003,310 and 1,246,339, US patents 3,332,882 and 4,128,494, Canadian patent 844,481 and South African patent 68/6,344.
  • Specific suitable activators include:
  • N-diacylated and N,N'-polyacylatedamines mentioned under (a) are of special interest, particularly, N,N,N',N'-tetra-acetyl-ethylenediamine (TAED).
  • TAED N,N,N',N'-tetra-acetyl-ethylenediamine
  • the activator in granular form, preferably wherein the activator is finely divided as described in our UK patent application No. 8021979 (GB-A-2053998). Specifically, it is preferred to have an activator of an average particle size of less than 150 micrometers, which gives significant improvement in bleach efficiency. The sedimentation losses, when using an activator with an average particle size of less than 150 ⁇ m, are substantially decreased. Even better bleach performance is obtained if the average particle size of the activator is less than 100 ⁇ m.
  • the activator should not have more than 20% by weight of particles with a size of less than 50 ⁇ m.
  • the activator may have a certain amount of particles of a size greater than 150 ⁇ m, but it should not contain more than 5% by weight of particles greater than 300 pm, and not more than 20% by weight of particles greater than 200 ⁇ m, preferably greater than 150,um. It is to be understood that these particle sizes refer to the activator present in the granules, and not to the granules themselves.
  • the latter have a particle size, the major part of it ranging from 100 to 2000 ⁇ m, preferably 250 to 1000 ⁇ m. Up to 5% by weight of granules with a particle size of greater than 1700 ⁇ m and up to 10% by weight of granules less than 250 ⁇ m is tolerable.
  • the granules incorporating the activator preferably in this finely-divided form, may be obtained by granulating a suitable carrier material, such as sodium tripolyphosphate and/or potassium tripolyphosphate with activator particles of the required size. Other granulation methods, e.g. using organic and/or inorganic granulation aids, can also be usefully applied. The granules can be subsequently dried, if required.
  • any granulation process is applicable, as long as the granule contains the activator, and as long as the other materials present in the granule do not negatively affect the activator.
  • a stabiliser for the bleach system for example ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate.
  • These activators can be used in acid or salts form, especially in calcium, magnesium, zinc or aluminium salt form, as described in our UK patent application 7,912,141 (GB-. A-2048930).
  • the stabiliser may be present at a level of up to about 1% by weight, preferably between about 0.1% and about 0.5% by weight.
  • 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 and silicates, antiredeposition agents such as sodium carboxymethylcellulose and alkyl or substituted alkyl cellulose ethers other stabilisers such as ethylenediamine tetraacetic acid, fabric softening agents, inorganic salts such as sodium sulphate and sodium carbonate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides and colourants.
  • compositions according to the invention may include the salt of an alkyl phosphoric acid as suds-suppressant and a wax as hydrophobic material as disclosed in DE-A-2 701 664.
  • the fluorescent agents which can be used in the bleaching detergent compositions of the invention are well known and many such fluorescent agents are available commercially. Specific fluorescent agents which may be mentioned by way of example are:
  • fluorescer X The salt of the acid defined in (a) above, is referred to below as "fluorescer X”.
  • the detergent composition of the invention may contain other types of fluorescent agents as desired.
  • the total amount of the fluorescent agent or agents used in a detergent composition is generally from 0.02-2% by weight.
  • antideposition agents in the detergent compositions of the invention, to decrease a tendency to form inorganic deposits on washed fabrics.
  • the amount of any such antideposition agent is normally from about 0.1 % to about 5% by weight, preferably from about 0.2% to about 2.5% by weight of the composition.
  • the preferred antideposition agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.
  • an amount of an alkali metal silicate particularly sodium ortho-, meta- or preferably neutral or alkaline silicate.
  • alkali metal 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 about 8.5 to about 11 in use in aqueous wash solution. It is preferred in particular for domestic products to have a pH of from about 9.0 to about 10.5 as lower pHs tend to be less effective for optimum detergency building, and 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° FH (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 detergent compositions of the invention should be in free-flowing particulate, e.g. powdered or granular form, and can be produced by any. of the technique commonly employed in the manufacture of such washing compositions, but preferably by slurry making and spray drying processes to form a detergent base powder to which the ingredients of the bleach system, and optionally also the alkali metal tripolyphosphate are added. It is preferred that the process used to form the compositions should result in a product having a moisture content of not more than about 12%, more preferably from about 4% to about 10% by weight as the lower moisture levels have been found to be beneficial for stability of the bleach systems employed.
  • Example 1 The experiments of Example 1 were repeated with powders made up according to the following formulations:
  • Example - 1 The procedure of Example - 1 was modified in that the experiment was carried out in a Tergotometer with a heat-up from 16°C to 60°C in 34 minutes. A product dosage of 5 g/I was used. The water hardness was 40° FH.
  • Detergent powders were prepared according to the following approximate formulations and were found to give excellent results when compared with similar formulations in which sodium tripolyphosphate (STP) was the only builder material.
  • STP sodium tripolyphosphate
  • the suds-suppressant material used was a 1:3 mixture of a C 16 alkyl phosphoric acid ester and petroleum jelly with a drop melting point of 54°C.
  • Example 1 The experiments of Example 1 were repeated with powders made up according to the following formulations (parts by weight):
  • Example 1 The procedure of Example 1 was modified in that the experiment was carried out in a Tergotometer with a heat-up from 16°C to 55°C in 30 minutes. With a further 30 minutes at 55°C a product dosage of 5 g/I was used. Water hardnesses of 35° FH and 60° FH were used.
  • Example 7 demonstrates that the bleaching performance of the composition according to the invention (Example 7) is improved with increased water hardness, while the bleaching performance of the compositions based on STP only and zeolite only (Comparative Examples E and F) is reduced with increased water hardness.
  • Example 1 The experiments of Example 1 were repeated with powders made up according to the following formulations (parts by weight):
  • Example 1 The procedure of Example 1 was modified in that the experiment was carried out in a Tergotometer with a heat-up from 16°C to 55°C in 60 minutes. A product dosage of 5 g/I was used. Water hardnesses of 35°FH and 60°FH were used.
  • Example 8 demonstrates that the bleaching performance of the composition according to the invention (Example 8) is improved with increased water hardness, while the bleaching performance of the composition containing perborate without TAED is reduced with increased water hardness.
  • the following formulation represents a further exemplary detergent composition according to the invention.
  • the anionic detergent active used was the sodium salt of alkyl (approx. C 12 ) benzene sulphonate and the nonionic used was a mixture of Dobanol 45-18 and Lutensol 12EO.
  • the soap used was a mixture of hardened tallow soap and hardened rapeseed soap.
  • the zeolite used was zeolite A (ex Degussa).
  • o FH with respect to water hardness is the molar concentration of frce water hardness ionsx 10 -4 and "°FH (Ca)" indicates that the water hardness ions are calcium ions only.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (4)

1. Procédé de preparation d'une composition détergente alcaline particulaire comprenant au moins une matière active détergente de synthèse choisie entre les composes détergents anioniques, non ioniques, amphotères ou hermaphrodites de synthèse ou leurs mélanges, un tripolyphosphate de métal alcalin, un auxiliaire de détergence aluminosilicate insoluble dans l'eau, un agent de blanchiment peroxy qui est un persel inorganique, et un activateur pour ledit agent de blanchiment peroxy, ledit procédé impliquant de sécher par pulvérisation une bouillie contenant la matière active détergente, la matière aluminosilicate et le tripolyphosphate pour former une poudre de base détergente et d'y ajouter l'agent de blanchiment peroxy et l'activateur, caractérisé en ce que la composition contient:
d'environ 5% à environ 40% en poids de ladite matière active détergente de synthèse;
d'environ 12,5% à environ 25% en poids dudit tripolyphosphate de métal alcalin calculé sur une base anhydre;
d'environ 7,0% à environ 36% en poids dudit auxiliaire de détergence aluminosilicate insoluble dans l'eau calculé sur une base anhydre;
d'environ 5% à environ 30% en poids dudit agent de blanchiment peroxy; et
jusqu'à environ 15% en poids dudit activateur pour ledit agent de blanchiment, le rapport pondéral dudit agent de blanchiment peroxy audit activateur étant compris entre environ 2:1 et environ 15:1.
2. Procédé de preparation d'une composition détergente alcaline particulaire comprenant au moins une matière active détergente de synthèse choisie dans les composes détergents anioniques, non ioniques, amphotères ou hermaphrodites de synthèse ou leurs mélanges, un tripolyphosphate de métal alcalin, un auxiliaire de détergence aluminosilicate insoluble dans l'eau, un agent de blanchiment peroxy qui est un persel inorganique, et un activateur pour ledit agent de blanchiment peroxy, ledit procédé impliquant de sécher par pulvérisation une bouillie contenant la matière active détergente et la matière aluminosilicate pour former une poudre de base détergente et d'y ajouter l'agent de blanchiment peroxy, l'activateur et le tripolyphosphate, caractérisé en ce que la composition contient:
d'environ 5% à environ 40% en poids de ladite matière active détergente de synthèse;
d'environ 12,5% à environ 25% en poids dudit tripolyphosphate de métal alcalin calculé sur une base anhydre;
d'environ 7,0% à environ 36% en poids dudit auxiliaire de détergence aluminosilicate insoluble dans l'eau calculé sur une base anhydre;
d'environ 5% à environ 30% en poids dudit agent de blanchiment peroxy; et
jusqu'à environ 15% en poids dudit activateur pour ledit agent de blanchiment, le rapport pondéral dudit agent de blanchiment peroxy audit activatèur étant compris entre environ 2:1 et environ 15:1.
3. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que ladite matière active détergente de synthèse au moins présente est choisie entre les matière actives détergentes de synthèse anioniques et leurs mélanges avec une moindre quantité d'une ou plusieurs matières actives détergentes de synthèse non-anioniques.
4. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que la matière active détergente de synthèse au moins presente comprend une matière active détergente anionique et une matière active détergente non ionique dans un rapport pondéral relatif d'au moins 2:1.
EP82300259A 1981-01-21 1982-01-19 Compositions détergentes Expired EP0056723B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82300259T ATE10648T1 (de) 1981-01-21 1982-01-19 Detergenszusammensetzungen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8101791 1981-01-21
GB8101791 1981-01-21
GB8118805 1981-06-18
GB8118805 1981-06-18

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Publication Number Publication Date
EP0056723A1 EP0056723A1 (fr) 1982-07-28
EP0056723B1 true EP0056723B1 (fr) 1984-12-05

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EP (1) EP0056723B1 (fr)
DE (1) DE3261394D1 (fr)
NO (1) NO820164L (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19538028A1 (de) * 1995-10-12 1997-04-17 Sued Chemie Ag Waschmittelzusatz

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DK161841C (da) * 1983-03-15 1992-01-27 Colgate Palmolive Co Blege- og vaskemiddel, der er fri for vandoploeselige silikater, og fremgangsmaade til blegning
GB9007999D0 (en) * 1990-04-09 1990-06-06 Unilever Plc Particulate bleaching detergent composition
AU3847299A (en) * 1998-05-13 1999-11-29 Oxyster S.N.C. Di Skepetaris % C. Stabilized disinfectant preparation containing peroxides

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ZA767283B (en) * 1975-12-15 1978-07-26 Colgate Palmolive Co Bleaching compositions
ZA767016B (en) * 1975-12-15 1978-06-28 Colgate Palmolive Co Non-caking bleach
ZA767017B (en) * 1975-12-15 1978-06-28 Colgate Palmolive Co Method for reconditioning detergent powders
US4064062A (en) * 1975-12-15 1977-12-20 Colgate-Palmolive Stabilized activated percompound bleaching compositions and methods for manufacture thereof
GB2040981B (en) * 1977-06-21 1982-08-25 Procter & Gamble Low-phosphate detergent composition for fabric washing
DE2733849A1 (de) * 1977-07-27 1979-02-15 Basf Ag Feste kaltbleichaktivatoren fuer aktivsauerstoff abgebende verbindungen enthaltende wasch- und reinigungsmittel
DE2902236A1 (de) * 1978-01-25 1979-07-26 Kao Corp Bleichmittelmischung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19538028A1 (de) * 1995-10-12 1997-04-17 Sued Chemie Ag Waschmittelzusatz

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Publication number Publication date
NO820164L (no) 1982-07-22
EP0056723A1 (fr) 1982-07-28
DE3261394D1 (en) 1985-01-17

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