EP0070190B1 - Detergenszusätze und diese enthaltende Detergenszusammensetzungen - Google Patents

Detergenszusätze und diese enthaltende Detergenszusammensetzungen Download PDF

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EP0070190B1
EP0070190B1 EP82303674A EP82303674A EP0070190B1 EP 0070190 B1 EP0070190 B1 EP 0070190B1 EP 82303674 A EP82303674 A EP 82303674A EP 82303674 A EP82303674 A EP 82303674A EP 0070190 B1 EP0070190 B1 EP 0070190B1
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Prior art keywords
builder
organic
weight
detergent additive
detergent
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French (fr)
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EP0070190A1 (de
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Reginald Vear Scowen
Thomas Stirling
Gordon Joseph Welch
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D3/12—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
    • 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

Definitions

  • the present invention relates to additives for detergent compositions, and to detergent compositions containing them. These compositions are particularly, but not essentially, adapted for fabric washing.
  • the invention relates more particularly to substantially phosphate-free detergent compositions.
  • Fabric washing compositions conventionally contain phosphate detergency builders such as sodium tripolyphosphate.
  • phosphate detergency builders such as sodium tripolyphosphate.
  • the use of phosphates in detergent compositions can lead to environmental problems in waste waters. There is therefore a desire to reduce the level of phosphorus, or to eliminate it altogether, in detergent compositions.
  • Water-insoluble aluminosilicate ion exchange materials have been suggested as alternative builders to phosphates; see, for example, GB-1,473,201 and GB-1,473,202 (Henkel). It has been found in practice, however, that these aluminosilicate materials, even in large amounts, tend to be undesirably slow in their exchange of cations, especially at low temperature, resulting in inferior detergency. It has accordingly been suggested that supplementary water-soluble builders should be used in combination with these aluminosilicates to raise the detergency to an acceptable level.
  • GB-1 429143 and GB-1 501 498 disclose the use of supplementary builders, including organic sequestrants and sodium carbonate and mixtures thereof, to enhance the building performance of aluminosilicates.
  • the supplementary organic sequestrant builders are generally materials that are efficient builders in their own right, for example, alkali metal tripolyphosphates, nitrilotriacetates and poly-a-hydroxyacrylates. High levels of these materials are, however, not generally desirable in detergent compositions for cost or environmental reasons.
  • detergency results are obtained by using, in combination with an aluminosilicate builder, relatively small amounts of both an organic sequestrant builder and a specified organic precipitant builder.
  • the detergency results obtained using ternary systems of this type have surprisingly been found to be better than would have been expected from consideration of the results obtained using the corresponding binary aluminosilicate/sequestrant and aluminosilicate/ precipitant systems, so that decreased amounts of the supplementary builders can be used, giving cost savings and environmental advantages.
  • aluminosilicates are enhanced by the addition of water-soluble complexing agents such as sodium tripolyphosphate.
  • water-soluble complexing agents such as sodium tripolyphosphate.
  • the complexing agent is able to take up polyvalent water hardness ions (notably Ca2+) from solid surfaces (such as the surface of a textile fibre) and pass them on to the aluminosilicate ion-exchanger after transport through the aqueous medium.
  • the complexing agent forms a chelate complex with the hardness ion which on arrival at the surface of the aluminosilicate dissociates.
  • the present invention accordingly provides, in a first aspect, a detergent additive consisting essentially of:
  • the aluminosilicate cation exchange material is preferably a crystalline or amorphous material having the general formula: wheren Cat is a cation having valency n that is exchangeable with calcium (e.g. Na + or K + ); x is a number from 0.7-1.5; y is a number from 1.3-4; and z is such that the bound water content is from 10% to 28% by weight.
  • a crystalline material which can be described by the unit cell content: wherein x and y are integers of at least 6, the ratio of ⁇ to y being in the range of 1:1 to 1:2; and z is such that the bound water content is from 10% to 28% by weight.
  • the aluminosilicate preferably has a particle size of from 0.1 to 100 micrometres, ideally between 0.1 and 10 micrometres, and an ion exchange capacity of at least 200 mg CaCO 3 per gram of aluminosilicate (anhydrous basis).
  • the water-insoluble aluminosilicate is a crystalline material having the formula described by the unit cell content: wherein z is from 20 to 30, preferably about 27.
  • Zeolite type A is the commercially available product known as Zeolite type A, which is typically: and is also described by the unit cell content:
  • the organic precipitant builder is a water-soluble material of the formula I given above, which forms an insoluble calcium salt and which has a divalent anion.
  • Materials having a divalent anion are substantially more weight-effective as builders than are soaps; only one mole is consumed by each gram ion of Ca2+ or Mg 2+ hardness ions, as compared with two moles of soap.
  • the solubility product of the calcium salt of the organic precipitant builder is preferably less than 10- 8 .
  • the organic precipitant builder is a compound of the formula II. wherein R 1' Y and Z have the meanings given above, and p is 0 or 1.
  • Compounds of the formula V are described, for example, in GB-1,368,736 and GB-1,380,390 (Unilever).
  • a typical example is disodium a-sulphostearate (C 18 -SFAS).
  • Blends of compounds of different chain lengths for example the a-sulpho salt of coconut fatty acids (coco-SFAS), or of tallow fatty acids (tallow-SFAS), or of blended coconut and tallow fatty acids, may also advantageously be used.
  • the organic precipitant builder is a compound of the formula VI: or of the formula VII: wherein R 1 and Y have the meanings given above and v and w are each 1 to 4, preferably 1 or 2.
  • GB-761,384 (California Research Corporation) discloses detergent compositions containing 10 to 50% by weight of alkylbenzene sulphonate and 5 to 20% by weight of a water-soluble salt of an N-(C 8 ⁇ C 18 alkyl)-iminodiacetic acid, the latter component acting as a foam promoter.
  • GB-761,383 (California Research Corporation) discloses combinations of alkyl sulphates and N-(C 8 ⁇ C 18 alkyl)-iminodicarboxylic acids.
  • Other specifications relating to the use of compounds of the formula VI in detergent compositions are GB-446,737 and GB-446,813 (I. G. Maschinen).
  • the organic sequestrant builder is a water-soluble material which forms soluble complexes with calcium, preferably with pK ca greater than 3.0, preferably greater than 4.0 and more preferably greater than 4.5.
  • the sequestrant builder also forms complexes with magnesium, preferably with pK Mg greater than 4.0.
  • suitable materials include alkali metal (especially sodium) salts of the following acids: nitrilotriacetic acid, ethylenediamine tetracetic acid, polyacrylic acid, poly(a-hydroxyacrylic) acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, oxydiacetic acid, oxydisuccinic acid, citric acid, dipicolinic acid and many more.
  • alkali metal (especially sodium) salts of the following acids nitrilotriacetic acid, ethylenediamine tetracetic acid, polyacrylic acid, poly(a-hydroxyacrylic) acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, oxydiacetic acid, oxydisuccinic acid, citric acid, dipicolinic acid and many more.
  • NTA nitrilotriacetic acid
  • the use of NTA salts in combination with precipitant builders having a divalent anion is especially preferred.
  • nitrilotriacetic acid compounds preferably used according to the present invention are known sequestering agents and may be represented by the following structural formula wherein X, as before is hydrogen or a solubilizing cation. These compounds further contain C-bonded substituents of an inert and innoxious nature such as alkyl, eg methyl or ethyl, or haloalkyl, eg chloromethyl.
  • substituents be devoid of any tendency to deleteriously affect the desirable properties of the nitrilotriacetic acid compound.
  • Preferred compounds falling within the ambit of the above-described definition and formula are nitrilotriacetic acid, trisodium nitrilotriacetate monohydrate, tripotassium nitrilotriacetate, disodium nitrilotriacetate and dipotassium nitrilotriacetate.
  • the organic precipitant builder and the organic sequestrant builder together constitute from 3% to 75% by weight of the builder mix (detergent additive) of the invention, preferably from 10% to 60% and especially from 20% to 50%.
  • the ratio of precipitant to sequestrant is from 10:1 to 1:10, preferably from 3:1 to 1:3 and desirably from 3:1 to 1:1.
  • the detergent additive of the present invention is an efficient builder system yielding good detergency results when incorporated, with detergent-active materials, in a detergent composition.
  • the present invention provides a detergent composition comprising from 3 to 90% by weight of at least one synthetic detergent-active material, and from 10 to 97% by weight of a detergent additive as previously defined.
  • the detergent composition of the invention contains from 10% to 97% by weight of the detergent additive of the invention, preferably from 10% to 80%, more preferably from 25% to 70%, and especially from 28% to 67%.
  • the aluminosilicate content of the detergent composition can range from 2.5% to 94%.
  • the content of organic builders can range from 0.3% to 73%, a range of from 5% to 40%, especially from 7% to 27%, being preferred.
  • the preferred range for the content of the precipitant builder is from 3% to 20%, especially from 5% to 10%; for the sequestrant builder the preferred range is from 1% to 15%, especially from 2% to 10%.
  • the detergent compositions of the present invention are preferably substantially free of inorganic phosphate.
  • compositions according to the invention containing no inorganic phosphate have been found to exhibit detergency properties comparable to those of sodium tripolyphosphate-built products.
  • compositions may contain inorganic phosphate, but preferably at a level not exceeding 10% based on the whole product; a level below 5% is advantageous, and a level below 3% is especially preferred.
  • Any phosphate present may, for example, be in the form of alkali metal (preferably sodium) tripolyphosphate, orthophosphate, pyrophosphate or polymeric phosphate.
  • the detergent composition of the invention necessarily includes from 3% to 90% by weight, preferably from 5% to 40% by weight, more preferably from 10% to 25% by weight, of detergent active material, which may include synthetic anionic, nonionic, amphoteric or zwitterionic detergent compounds or mixtures thereof.
  • detergent active material which may include synthetic anionic, nonionic, amphoteric or zwitterionic detergent compounds or mixtures thereof.
  • suitable detergent-active compounds 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.
  • 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 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 1s ) 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 methyl
  • nonionic detergent compounds examples include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-CZZ) phenols, generally 5 to 25 EO, ie 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 6 to 30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • alkylene oxides usually ethylene oxide
  • alkyl (C6-CZZ) phenols generally 5 to 25 EO, ie 5 to 25 units of ethylene oxide per molecule
  • condensation products of aliphatic (C 8 ⁇ C 18 ) primary or secondary linear or branched alcohols with ethylene oxide generally 6 to 30 EO
  • 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.
  • Anionic and nonionic detergent compounds are advantageously used together in ratios of from 3:1 to 1.5:1.
  • 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/or nonionic detergent compounds.
  • the composition of the invention may also include soap.
  • soap which may be used are especially the sodium or less desirably the potassium, salts of C10--C14 fatty acids. Soaps based mainly on the longer-chain fatty acids within this range, that is to say, with at least half of the soap having a chain length of C 16 or more, are especially preferred. This preferred chain length distribution may be conveniently obtained by using soaps from natural sources such as tallow, palm oil or rapeseed oil, which may 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 detergent composition also contains a bleach system.
  • the bleach system preferably comprises a peroxy bleach compound which is an inorganic persalt, which is preferably used in conjunction with an activator therefor.
  • the persalt may be, for example, sodium perborate (either the monohydrate or the tetrahydrate) or sodium percarbonate.
  • the activator makes the bleaching more effective at lower temperatures, ie 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 acts to release active oxygen in solution
  • the activator 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 can be obtained by use of the peroxy bleach compound alone.
  • the ratio by weight of the peroxy bleach compound to the activator is generally from about 20:1 to about 1:1, preferably about 15:1 to about 2:1.
  • the detergent composition of the invention preferably contains from about 5% to about 30% by weight of the peroxy bleach compound, and about 0.1 to about 15% by weight of the activator.
  • the total amount of the bleach system ingredients preferably lies within the range of from 5% to 35% by weight, especially from about 6% to about 30% by weight.
  • Suitable peroxy bleach compounds are alkali metal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred.
  • 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' - polyacylated amines mentioned under (a) are of special interest, particularly N,N,N',N' - tetra - acetyl - ethylenediamine (TAED).
  • the activator in granularform, preferably wherein the activator is finely divided as described in GB-2053998 B (Unilever) Specifically, it is preferred to have an activator of an average particle size of less than 150 micrometres, which gives significant improvement in bleach efficiency.
  • Even better bleach performance is obtained if the average particle size of the activator is less than 100 11 m.
  • too small a particle size gives increased decomposition, dust-formation and handling problems, and although particle sizes below 100 ⁇ m can provide for an improved bleaching efficiency, it is desirable that the activator should not have more than 20% by weight of particles with a size of less than 50 pm.
  • the activator may have a certain amount of particles of a size greater than 150 pm, but it should not contain more than 5% by weight of particles >300 ⁇ m,and not more than 20% by weight of particles >200 pm, preferably >150 pm. 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 pm, preferably 250 to 1000 pm. Up to 5% by weight of granules with a particle size of >1700 ⁇ m and up to 10% by weight of granules ⁇ 250 ⁇ m is tolerable.
  • the granules incorporating the activator may be obtained by granulating a suitable carrier material, such as sodium tripolyphosphate and/or potassium tripolyphosphate with activator particles of the required size.
  • a suitable carrier material such as sodium tripolyphosphate and/or potassium tripolyphosphate
  • 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. Basically, 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 stabilisers can be used in acid or salt form, especially in calcium, magnesium, zinc or aluminium salt form, as described in GB-2 048 930B (Unilever).
  • 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, silicones, or alkyl phosphonic acids incorporated in petroleum jelly, wax or mineral oil; anti-redeposition agents such as sodium carboxymethylcellulose and cellulose ethers; 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.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • lather depressants such as alkyl phosphates, silicones, or alkyl phosphonic acids incorporated in petroleum jelly, wax or mineral
  • 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 composition, 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.
  • the composition of the invention is preferably alkaline, but not too strongly alkaline as this could result in fabric damage and also be hazardous for domestic usage.
  • the composition should desirably 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 pH's 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°H (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.
  • up to 10% by weight of alkali metal carbonate, preferably sodium carbonate may be included in order to raise the pH and to maintain adequate buffer capacity in the presence of acidic soils.
  • any antideposition agent is normally from about 0.1 % to about 5% by weight, preferably from about 0.2% to about 1.5% by weight of the composition.
  • the preferred antideposition agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.
  • the detergent compositions of the invention should desirably be in free-flowing particulate, for exampte, powdered or granular form, and can be produced by any of the techniques commonly employed in the manufacture of such washing compositions, for example, by slurry-making and spray-drying processes. 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.
  • the detergent compositions of the invention may also be in the form of bars or tablets, or in liquid form.
  • a wash liquor was prepared using the ingredients stated below in the concentrations stated below, in 40°FH (Ca) or 20°FH (Ca) water.
  • the wash liquor was allowed to equilibrate for 15 minutes.
  • Test cloth pieces four pieces per litre, each measuring 76.2 mmx76.2 mm) were then added and a 20-minute wash at 80°C, pH 10.0 and 55 rpm agitation was carried out, followed by a rinse in water of the same hardness as that of the water used to prepare the wash liquor.
  • the detergent additive according to the invention was used at concentration of from 1.00 to 5.00 g/litre, and the other components of the composition were used at a constant total concentration of 2.495 g/litre, so that the total concentration ranged from 3.495 to 7.495 g/litre.
  • the percentage of the total composition constituted by the detergent additive of the invention at each concentration of the latter was as follows: All percentages given in the Examples are by weight and are based on the anhydrous materials.
  • compositions containing a ternary builder system were compared at two different concentrations and water hardnesses, with those of control compositions containing single or binary builder systems.
  • the aluminosilicate used was zeolite A
  • the organic precipitant was disodium dodecylmalonate (C 12 AKM)
  • the organic sequestrant was trisodium nitrilotriacetate (NTA).
  • Example 2 A similar procedure to that of Example 1 was carried out using the organic sequestrant poly (a-hydroxy acrylate) (PHAC) instead of NTA.
  • Example 2 A similar procedure to that of Example 1 was carried out using as organic sequestrant a polyacrylate (Versicol (Trade Mark) E7) instead of NTA. The tests were carried out at 3.0 g/I and in 40°FH (Ca2) water, and the results were as follows:
  • Example 2 A similar procedure to that of Example 1 was carried out using as organic sequestrant tetrasodium ethylenediamine-tetraacetate (EDTA) instead of NTA, at 3.0 g/I and in 40°FH (Ca 2+ ) water.
  • EDTA organic sequestrant tetrasodium ethylenediamine-tetraacetate
  • Example 2 A similar procedure to that of Example 1 was carried out using as organic sequestrant tetrasodium oxydisuccinate (ODS) instead of NTA, at 3.0 g/I and in 40°FH (Ca 2+ ) water.
  • ODS organic sequestrant tetrasodium oxydisuccinate
  • Example 2 A similar procedure to that of Example 1 was carried out using as organic sequestrant instead of NTA, an oxidised starch as described in GB-1,330,121. The tests were carried out at 3.0 g/I in40°FH (Ca 2+ ) water and the results were as follows:
  • Example 2 A similar procedure to that of Example 1 was carried out using as organic precipitant, instead of C 12 AKM, disodium hexadecenyl succinate (C 16 AKS). The tests were carried out in 40°FH (Ca2+) water and the results were as follows:
  • Example 2 A similar procedure to that of Example 1 was carried out using, as organic precipitant, instead of C 12 AKM, disodium a-sulphostearate (C 18 SFAS). The tests were carried out in 40°FH (Ca 2+ ) water and the results were as follows:
  • Example 2 A similar procedure to that of Example 1 was carried out using, as organic precipitant, instead of C 12 AKM, disodium hexadecyliminodiacetate (C 16 IMA). The tests were carried out at a total builder concentration of 4 g/litre in 40°FH (Ca 2+ ) water. Tests were carried out using both a clay-soiled test cloth and a test cloth soiled with a mixture of organic and particulate soils. The results were as follows:

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Claims (16)

1. Detergenszusatz, umfassend ein kristallines oder amorphes Aluminosilicat-Kationenaustauschmaterial in Kombination mit einem organischen Builder, dadurch gekennzeichnet, daß der Zusatz im wesentlichen besteht aus
(a) 25 bis 97 Gew.-% des Aluminosilicat-Kationenaustauschmaterials und
(b) 3 bis 75 Gew.-% insgesamt
(i) eines organischen, fällenden Builders der Formel I
Figure imgb0035
worin R1 eine C10―C24-Alkyl-, -Alkenyl-, -Arylalkyl- oder -Alkylaryl-Gruppe ist, X CH, CR2, N oder CON ist, R2 C1―C3-Alkyl ist, Y Wasserstoff oder ein löslich machendes Kation ist, n und m, die gleich oder verschieden sein können, 0 oder ganze Zahlen von 1 bis 4 sind und Z COOY oder S03Y ist, und
(ii) eines organischen sequestrierenden Builders, der mit Calcium einen löslichen Komplex bildet, wobei das Gewichtsverhältnis von (i) zu (ii) 10:1 bis 1:10 ist.
2. Detergenszusatz nach Anspruch 1, dadurch gekennzeichnet, daß der organische, fällende Builder eine Verbindung der Formel II
Figure imgb0036
ist, worin R1, Y und Z die in Anspruch 1 gegebenen Bedeutungen haben und p 0 oder 1 ist.
3. Detergenszusatz nach Anspruch 2, dadurch gekennzeichnet, daß der organische, fällende Builder eine Verbindung der Formel III
Figure imgb0037
ist, worin R1 und Y die in Anspruch 1 gegebenen Bedeutungen haben.
4. Detergenszusatz nach Anspruch 2, dadurch gekennzeichnet, daß der organische, fällende Builder eine Verbindung der Formel IV
Figure imgb0038
ist, worin R1 und Y die in Anspruch 1 gegebenen Bedeutungen haben.
5. Detergenszusatz nach Anspruch 2, dadurch gekennzeichnet, daß der organische, fällende Builder eine Verbindung der Formel V
Figure imgb0039
ist, worin R1 und Y die in Anspruch 1 gegebenen Bedeutungen haben.
6. Detergenszusatz nach Anspruch 1, dadurch gekennzeichnet, daß der organische, fällende Builder eine Verbindung der Formel VI
Figure imgb0040
ist, worin R1 und Y die in Anspruch 1 gegebenen Bedeutungen haben und v und w jeweils ganze Zahlen im Bereich von 1 bis 4 sind.
7. Detergenszusatz nach Anspruch 1, dadurch gekennzeichnet, daß der organische, fällende Builder eine Verbindung der Formel VII
Figure imgb0041
ist, worin R1 und Y die in Anspruch 1 gegebenen Bedeutungen haben und v und w jeweils ganze Zahlen im Bereich von 1 bis 4 sind.
8. Detergenszusatz nach irgend einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der organische, sequestrierende Builder ein Alkalimetallsalz einer organischen Carbonsäure mit 3 oder mehr Carboxylgruppen ist.
9. Detergenszusatz nach Anspruch 8, dadurch gekennzeichnet, daß der organische, sequestrierende Builder ein Alkalimetallsalz von Nitrilotriessigsäure ist.
10. Detergenszusatz nach Anspruch 8, dadurch gekennzeichnet, daß der organische, sequestrierende Builder ausgewählt ist unter Alkalimetallsalzen von Ethylendiamintetraessigsäure, Polyacrylsäure, Poly(α-hydroxyacryl)säure, Carboxymethyloxymalonsäure, Carboxymethyloxybernsteinsäure, Oxydiessigsäure, Oxydibernsteinsäure, Zitronensäure, Dipicolinsäure, Polyacetalcarboxylaten und oxidierten Polysacchariden.
11. Detergenszusatz nach irgend einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das Aluminosilicat-Kationenaustauschmaterial ein kristallines Material mit einer Einheitszelle der Formel IX
Figure imgb0042
ist, worin x und y ganze Zahlen von wenigstens 6 sind, das Verhältnis von x zu y im Bereich von 1:1 bis 1:2 ist und z so ist, daß der Gehalt an gebundenem Wasser 10 bis 28 Gew.-% ist.
12. Detergenszusatz nach Anspruch 11, dadurch gekennzeichnet, daß das Aluminosilicat-Kationenaustauschmaterial ein kristallines Material mit einer Einheitszelle der Formel X
Figure imgb0043
ist, worin z 20 bis 30 ist.
13. Detergenszusatz nach irgend einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß er 10 bis 60 Gew.-% insgesamt des organischen, fällenden Builders und des organischen sequestrierenden Builders enthält.
14. Detergenszusatz nach irgend einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß das Gewichtsverhältnis des organischen, fällenden Builders zum organischen, sequestrierenden Builder 3:1 bis 1:3 ist.
15. Detergenszusammensetzung, die 3 bis 90 Gew.-% wenigstens eines synthetischen, reinigungsaktiven Materials und 10 bis 97 Gew.-% eines Detergenszusatzes gemäß irgend einem der Ansprüche 1 bis 14 umfaßt.
16. Detergenszusammensetzung nach Anspruch 15, dadurch gekennzeichnet, daß sie weniger als 5 Gew.-% anorganisches Phosphat enthält.
EP82303674A 1981-07-15 1982-07-13 Detergenszusätze und diese enthaltende Detergenszusammensetzungen Expired EP0070190B1 (de)

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GB8121837 1981-07-15
GB8121837 1981-07-15

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GB9008013D0 (en) * 1990-04-09 1990-06-06 Unilever Plc High bulk density granular detergent compositions and process for preparing them
US5508258A (en) * 1990-08-03 1996-04-16 Henkel Kommanditgesellschaft Auf Aktien Use of surface-active alpha-sulfo-fatty acid di-salts in water and oil based drilling fluids and other drill-hole treatment agents
GB9022660D0 (en) * 1990-10-18 1990-11-28 Unilever Plc Detergent compositions
JP4635223B2 (ja) * 2004-09-06 2011-02-23 株式会社古河テクノマテリアル 界面活性剤系組成物
JP5388260B2 (ja) * 2006-03-03 2014-01-15 株式会社古河テクノマテリアル 水添加型の消火剤
JP5207161B2 (ja) * 2006-08-10 2013-06-12 ディバーシー株式会社 自動食器洗浄機への洗浄剤供給方法およびそれに用いられる自動食器洗浄機用タブレット洗浄剤組成物、並びにそれを用いた洗浄方法

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SE419975C (sv) * 1973-04-13 1986-08-07 Henkel Kgaa Tvett- och/eller blekmedel innehallande ett kristallint vattenolosligt silikat forfarande for dess framstellning och dess anvendning
US4605509A (en) * 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
DE2333356C3 (de) * 1973-06-30 1982-03-11 Henkel KGaA, 4000 Düsseldorf Waschmittel
AT335030B (de) * 1974-01-14 1977-02-25 Henkel & Cie Gmbh Verfahren zum waschen von textilien, sowie mittel zur durchfuhrung des verfahrens
JPS5328163B2 (de) * 1974-05-30 1978-08-12
US3985669A (en) * 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
AT375395B (de) * 1974-10-04 1984-07-25 Henkel Kgaa Verfahren zum waschen bzw. bleichen von textilien sowie mittel dazu
AT338948B (de) * 1974-10-10 1977-09-26 Henkel & Cie Gmbh Pulverformige wasch- und reinigungsmittel und verfahren zu ihrer herstellung
JPS5228507A (en) * 1975-08-29 1977-03-03 Nippon Oil & Fats Co Ltd Detergent composition
JPS52117908A (en) * 1976-03-31 1977-10-03 Nitsusan Setsuken Kk Detergent composition
BE5T2 (fr) * 1977-06-21 1980-02-08 Procter & Gamble Europ Wasmiddelrn
IT1160682B (it) * 1977-10-14 1987-03-11 Po Corp. Composizioni detergenti con coadiuvante di silano-zeolite
CA1137076A (en) * 1978-12-13 1982-12-07 John R. Bauer Fluid spray mixer - reactor system
JPS55108496A (en) * 1979-02-13 1980-08-20 Nippon Gousei Senzai Kk Detergent composition
US4265777A (en) * 1980-04-17 1981-05-05 The Procter & Gamble Company Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap

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BR8204091A (pt) 1983-07-05
DK314982A (da) 1983-01-16
DE3267784D1 (en) 1986-01-16
JPS6116315B2 (de) 1986-04-30
AU554225B2 (en) 1986-08-14
CA1197156A (en) 1985-11-26
JPS5823896A (ja) 1983-02-12
NO822433L (no) 1983-01-17
NO822434L (no) 1983-01-17
AU8598582A (en) 1983-01-20
CA1191068A (en) 1985-07-30
EP0070192B2 (de) 1990-01-17
NZ201213A (en) 1985-07-31
ZA825005B (en) 1984-02-29
ATE15499T1 (de) 1985-09-15
JPS5823897A (ja) 1983-02-12
JPH045720B2 (de) 1992-02-03
AU8598482A (en) 1983-01-20
NZ201212A (en) 1985-08-16
EP0070190A1 (de) 1983-01-19
EP0070192A1 (de) 1983-01-19
DE3266194D1 (en) 1985-10-17
ZA825006B (en) 1984-02-29
ATE16818T1 (de) 1985-12-15
DK314782A (da) 1983-01-16
BR8204092A (pt) 1983-07-05
EP0070192B1 (de) 1985-09-11

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