EP0070192B1 - Detergenszusätze und diese enthaltende Detergenszusammensetzungen - Google Patents

Detergenszusätze und diese enthaltende Detergenszusammensetzungen Download PDF

Info

Publication number
EP0070192B1
EP0070192B1 EP82303676A EP82303676A EP0070192B1 EP 0070192 B1 EP0070192 B1 EP 0070192B1 EP 82303676 A EP82303676 A EP 82303676A EP 82303676 A EP82303676 A EP 82303676A EP 0070192 B1 EP0070192 B1 EP 0070192B1
Authority
EP
European Patent Office
Prior art keywords
weight
soap
detergent
detergent additive
chain length
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
EP82303676A
Other languages
English (en)
French (fr)
Other versions
EP0070192B2 (de
EP0070192A1 (de
Inventor
Reginald Vear Scowen
Thomas Stirling
Gordon Joseph Welch
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.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10523262&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0070192(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to AT82303676T priority Critical patent/ATE15499T1/de
Publication of EP0070192A1 publication Critical patent/EP0070192A1/de
Application granted granted Critical
Publication of EP0070192B1 publication Critical patent/EP0070192B1/de
Publication of EP0070192B2 publication Critical patent/EP0070192B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 temperatures, 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.
  • supplementary builders are generally materials that are efficiency sequestrant 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 a specific organic sequestrant builder (nitrilotriacetic acid or a salt thereof) and a specific organic precipitant builder (a defined soap or soap blend).
  • a specific organic sequestrant builder nitrilotriacetic acid or a salt thereof
  • a specific organic precipitant builder a defined soap or soap blend
  • the complexing agent is able to take up polyvalent water hardness ions (notably Ca2+, but also Mg 2+ ) 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 of:
  • Component (b) (ii) will hereinafter be referred to as NTA.
  • the subject of the invention is a ternary builder system consisting of aluminosilicate, soap and NTA.
  • GB 1 498492 Henkel
  • DE 25 39 110 Henkel
  • detergent compositions built with aluminosilicate and NTA, in which the detergent-active system includes soap; the soap is, however, present only in small quantities.
  • GB 1 528 943 discloses spray-dried detergent powders containing coap as a part of the detergent-active system and built with zeolite and sodium tripolyphosphate (1: 1); the powders exemplified contain very low levels of NTA.
  • EP 38 591 discloses detergent compositions built with aluminosilicate in which the detergent-active agents used include soaps of C 167 -C 22 unsaturated fatty acids. These soaps function in the compositions as detergent-active agents, assisting in soil removal and cool-water detergency; the aluminosilicate is said to assist in keeping the unsaturated soap from forming an insoluble curd.
  • the unsaturated soaps are not, accordingly, functioning as builders by precipitating calcium from the wash liquor as an insoluble calcium soap.
  • the soap compositions disclosed in EP 38 591 may contain some unsaturated soap, but only at low levels so as not to detract from the detergent activity of the preferred unsaturated materials.
  • the unsaturated soaps disclosed in EP 38 591 are unsuitable for use in the compositions of the present invention, because their calcium salts are not sufficiently insoluble in water.
  • the predominantly saturated soaps used according to the invention on the other hand, have highly insoluble calcium salts. Calcium present in the wash liquor is removed in the form of insoluble calcium soaps; the soaps themselves thus function as builders rather than as detergent-active agents.
  • the soaps used in the compositions of the invention consist to an extent of at least 60%, preferably at least 80%, of saturated soaps.
  • Advantageously 100% saturated material may be used.
  • the soap preferably contains both longer-chain (C 18 and above) and shorter-chain (C 14 and below) material.
  • the longer the chain the higher the insolubility of the calcium salt, and thus the greater the efficiency of the soap as a builder.
  • Shorter chain-length soaps although forming less insoluble calcium salts, can also be effective detergency builders because of their lower molecular weight and accordingly greater weight-effectiveness. The shorter-chain soaps are especially valuable under low temperature washing conditions.
  • Shorter-chain soaps themselves also have better solubility then the longer-chain materials, and the presence of some short-chain material along with longer-chain soaps can enhance overall soap solubility.
  • the soap used in the detergent additive of the invention preferably contains at least 5% by weight, more preferably at least 8%, of material having a chain length of C 18 and above. It may also be advantageous, from the point of view of solubility, for the soap used in the detergent additive of the invention to contain at least 1 %, preferably at least 3%, of material being a chain length of C 14 and below.
  • the soap or mixture of soaps contains at least 60% by weight, preferably at least 80% by weight, of material having a chain length of C 18 and above. It is also advantageous from the point of view of solubility, for the soap to contain at least 1 %, preferably at least 3%, of material having a chain length of C 14 and below. This is not essential, however, for products intended for use in conventional medium or high-temperature washing, where the solubility of the soap itself (the sodium or other soluble salt) is not a problem.
  • soaps examples include hardened tallow (67% C 18 and above) and hardened rapeseed (96.5% C 18 and above).
  • the soap or mixture of soaps contains at least 60% by weight, preferably at least 70% by weight, of material having a chain length of C 14 and below. It preferably also contains at least 5%, more preferably at least 8%, of material having a chain length of C 18 and above. Such a composition is especially beneficial for lower-temperature washing where the solubility of the soap itself is important in determining good detergency building.
  • soaps examples include coconut (82% C 14 and below) and palm kernel (73.5% C 14 and below).
  • the detergent additive of the invention also includes a water-insoluble aluminosilicate cation exchange material.
  • a water-insoluble aluminosilicate cation exchange material This is preferably a crystalline or amorphous material having the general formula: wherein 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 x 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 CaC0 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 third component of the detergent additive of the invention is an organic sequentrant builder, namely, nitrilotriacetic acid or a water-soluble salt thereof (NTA).
  • NTA water-soluble salt thereof
  • This component may be represented by the following structural formula wherein X is hydrogen or a solubilizing cation.
  • These compounds may further contain C-bonded substituents of an inert and innoxious nature such as alkyl, e.g. methyl or ethyl, or haloalkyl, e.g. chloromethyl.
  • alkyl e.g. methyl or ethyl
  • haloalkyl e.g. chloromethyl.
  • the nature of said compounds is not particularly critical with the implicit limitation that such substituents be devoid of any tendency to deleteriously affect the desirable properties of the NTA.
  • Preferred compounds falling within the ambit of the above-described definition and formula are nitrilotriacetic acid and its alkali metal salts, especially trisodium nitrilotriacetate monohydrate, tripotassium nitrilotriacetate, disodium nitrilotriacetate and dipotassium nitrilotriacetate.
  • the soap and NTA together constitute up to 75% by weight of the builder mix detergent additive (of the invention, preferably from 20% to 50%.
  • the ratio of soap to NTA is 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 will be at least 2.5%.
  • the content of the specified organic builders will not exceed 73%, a range of from 5% to 40%, especially from 7% to 27%, being preferred.
  • the preferred range for the content of the soap is from 3% to 20%, especially from 5% to 10%; for the NTA the preferred range is from 1 % to 15%, especially from 2% to 10%.
  • the detergent composition of the present invention are preferably substantially free of inorganic phosphate. This is highly desirable for the environmental reasons mentioned earlier. 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 if avoidance of the possible environmental effects of phosphate is in question the level advantageously does not exceed 10% based on the whole product; levels below 5% and more especially below 3% are of particular interest in this connexion.
  • 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 may if desired contain other builders in addition to the specified ternary builder system of the invention. As indicated previously, these are preferably non-phosphate materials. Examples of suitable materials include the water-soluble salts of the following acids: ethylenediamine tetracetic acid, polyacrylic acid poly(a-hydroxyacrylic) acid, carboxymethyloxy- malonic acid, carboxymethyloxysuccinic acid, oxydiacetic acid, oxydisuccinic acid, citric acid, dipicolinic acid and many more.
  • the polyacetal carboxylates disclosed in US 4,144,126 and US 4,146,495 may also advantageously be used.
  • oxidised polysaccharides disclosed in GB 1,330,121, GB 1,330,122 and GB 1,330,123 may also advantageously be used.
  • the detergent composition of the invention necessarily includes from about 3% to about 90% by weight, preferably from about 5% to about 40% by weight, more preferably from about 10% to about 25% by weight, of synthetic detergent-active material, which may include anionic, nonionic, amphoteric or zwitterionic detergent compounds or mixtures thereof.
  • synthetic detergent-active material which may include anionic, nonionic, amphoteric or zwitterionic detergent compounds or mixtures thereof.
  • suitable detergent-active compounds are commerically 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 (CS-C1s) alcohols produced for example from tallow or coconut oil; sodium and potassium alkyl (C9-CZO) 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 methyl taurine
  • nonionic detergent compounds examples include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (CS-C22) phenols, generally 5 to 25 EO, i.e. 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.
  • CS-C22 alkyl
  • phenols generally 5 to 25 EO, i.e. 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 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, 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 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' - polyacylatedamines mentioned under (a) are of special interest, particularly N,N,N',N' - tetra - acetyl - ethylenediamine (TAED).
  • the activator in granular form, preferably wherein the activator is finely divided as described in GB 2053998B (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. The sedimentation losses, when using an activator with an average particle size of less than 150 pm, are substantially decreased. Even better bleach performance is obtained if the average particle size of the activator is less than 100 ⁇ m. However, too small a particle size gives increased decomposition, dust-formation and handling problems, and although particle sizes below 100 pm 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 ⁇ m, but it should not contain more than 5% by weight of particles >300 pm, and not more than 20% by weight of particles >200 pm, preferably >150 ⁇ m. 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 pm and up to 10% by weight of granules ⁇ 250 pm 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.
  • an alkali metal silicate particularly sodium ortho-, meta- or preferably neutral or alkaline silicate.
  • the presence of such 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 metasilicates 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 example, 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.
  • wash liquor was prepared using the ingredients stated below in the concentrations stated below, in 40°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 ingredients and concentrations were as follows: * The soap was included for lather control purposes and was present in addition to the soap included in the detergent additive according to the invention.
  • the detergent additive according to the invention was used at concentrations of from 2.00 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 4.495 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:
  • compositions containing a ternary builder system (detergent additive) according to the invention were compared, in 40°FH water at a range of concentrations, with those of control compositions containing single or binary builder systems.
  • the aluminosilicate used was zeolite A, the soap was hardened tallow soap, and the NTA was in the form of its trisodium salt. The results were as follows:
  • Example 2 The procedure of Example 1 was repeated using different proportions of zeolite, soap and NTA. The results were as follows:

Landscapes

  • Chemical & Material Sciences (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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (19)

1. Detergenszusatz, umfassend ein kristallines oder amorphes Aluminosilicat-Kationenaustauschmaterial und einen organischen Builder, dadurch gekennzeichnet, daß er besteht aus
a) wenigstens 25 Gew.-% des kristallinen oder amorphen Aluminosilicat-Kationenaustauschmaterials,
b) Rest bestehend aus
(i) einer oder mehreren wasserlöslichen Seifen von Cg-C22-Fettsäuren, wobei wenigstens 60 Gew.-% der gesamten Seife gesättigtes Material sind, und
(ii) Nitrilotriessigsäure oder einem wasserlöslichen Salz von ihr,

wobei das Gewichtsverhältnis von (i) zu (ii) 3:1 bis 1:3 ist und (i) in einer Menge von wenigstens 12 Gew.-%, bezogen auf das Gesamtgewicht von (a) und (b), vorliegt.
2. Detergenszusatz nach Anspruch 1, dadurch gekennzeichnet, daß die Seife (i) in einer Menge von wenigstens 15 Gew.-%, bezogen auf das Gesamtgewicht von (a) und (b), vorliegt.
3. Detergenszusatz nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß wenigstens 80 Gew.-% der Seife (i) gesättigtes Material ist.
4. Detergenszusatz nach Anspruch 3, dadurch gekennzeichnet, daß die Seife (i) im wesentlichen ganz aus gesättigtem Material besteht.
5. Detergenszusatz nach irgend einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Seife (i) wenigstens 5 Gew.-% Material mit einer Kettenlänge von C18 und darüber und wenigstens 1 % Material mit einer Kettenlänge von C14 und darunter enthält.
6. Detergenszusatz nach Anspruch 5, dadurch gekennzeichnet, daß die Seife (i) wenigstens 60 Gew.-% Material mit einer Kettenlänge von C18 und darüber und wenigstens 1 % Material mit einer Kettenlänge von C14 und darunter enthält.
7. Detergenszusatz nach Anspruch 6, dadurch gekennzeichnet, daß die Seife (i) gehärtete Talgseife und/oder gehärtete Rapssamenseife umfaßt.
8. Detergenszustaz nach Anspruch 5, dadurch gekennzeichnet, daß die Seife (i) wenigstens 60% Material mit einer Kettenlänge von C14 und darunter und wenigstens 5% Material mit einer Kettenlänge von C18 und darüber enthält.
9. Detergenszusatz nach Anspruch 8, dadurch gekennzeichnet, daß die Seife (i) Kokosnußseife und/oder Palmkernseife umfaßt.
10. Detergenszusatz nach irgend einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß (ii) ein Alkalimetallsalz von Nitrilotriessigsäure ist.
11. Detergenszusatz nach irgend einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das Aluminosilicat-Kationenaustauschmaterial ein kristallines Material mit einer Einheitszelle der Formel
Figure imgb0014
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 von 10 bis 28 Gew.-% ist.
12. Detergenszusatz nach Anspruch 11, dadurch gekennzeichnet, daß das Aluminosilicat-Kationenaustauschmaterial ein kristallines Material mit einer Einheitszelle der Formel
Figure imgb0015
ist, worin z 20 bis 30 ist.
13. Detergenszusatz nach irgend einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß er 20 bis 50 Gew.-% insgesamt an (i) und (ii) enthält.
14. Detergenszusatz nach irgend einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß das Gewichtsverhältnis von (i) zu (ii) 3:1 bis 1:1 ist.
15. Detergenszusammensetzung, dadurch gekennzeichnet, daß sie 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 insgesamt 5 bis 40 Gew.-% an (i) und (ii) enthält.
17. Detergenszusammensetzung nach Anspruch 15 oder 16, dadurch gekennzeichnet, daß sie 3 bis 20 Gew.-% (i) enthält..
18. Detergenszusammensetzung nach irgend einem der Ansprüche 15 bis 17, dadurch gekennzeichnet, daß sie 1 bis 15 Gew.-% (ii) enthält.
19. Detergenszusammensetzung nach irgend einem der Ansprüche 15 bis 18, dadurch gekennzeichnet, daß sie nicht mehr als 10 Gew.-% anorganisches Phosphat enthält.
EP82303676A 1981-07-15 1982-07-13 Detergenszusätze und diese enthaltende Detergenszusammensetzungen Expired - Lifetime EP0070192B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82303676T ATE15499T1 (de) 1981-07-15 1982-07-13 Detergenszusaetze und diese enthaltende detergenszusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8121837 1981-07-15
GB8121837 1981-07-15

Publications (3)

Publication Number Publication Date
EP0070192A1 EP0070192A1 (de) 1983-01-19
EP0070192B1 true EP0070192B1 (de) 1985-09-11
EP0070192B2 EP0070192B2 (de) 1990-01-17

Family

ID=10523262

Family Applications (2)

Application Number Title Priority Date Filing Date
EP82303674A Expired EP0070190B1 (de) 1981-07-15 1982-07-13 Detergenszusätze und diese enthaltende Detergenszusammensetzungen
EP82303676A Expired - Lifetime EP0070192B2 (de) 1981-07-15 1982-07-13 Detergenszusätze und diese enthaltende Detergenszusammensetzungen

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP82303674A Expired EP0070190B1 (de) 1981-07-15 1982-07-13 Detergenszusätze und diese enthaltende Detergenszusammensetzungen

Country Status (11)

Country Link
EP (2) EP0070190B1 (de)
JP (2) JPS5823896A (de)
AT (2) ATE16818T1 (de)
AU (2) AU554225B2 (de)
BR (2) BR8204091A (de)
CA (2) CA1197156A (de)
DE (2) DE3266194D1 (de)
DK (2) DK314782A (de)
NO (2) NO822433L (de)
NZ (2) NZ201212A (de)
ZA (2) ZA825006B (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
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
EP0070190B1 (de) 1985-12-04

Similar Documents

Publication Publication Date Title
EP0111963B1 (de) Reinigungsmittelzusammensetzungen
US4695284A (en) Cool water fabric washing process using a particulate detergent containing a nonionic and a fatty acid builder salt
EP0070079B1 (de) Reinigungsmittelzusammensetzung
CA1152846A (en) Detergent compositions
EP0098108B1 (de) Detergenszusammensetzung
CA1316790C (en) Non-phosphorus detergent bleach compositions
EP0070192B1 (de) Detergenszusätze und diese enthaltende Detergenszusammensetzungen
EP0070191B2 (de) Detergenszusätze und diese enthaltende Detergenszusammensetzungen
EP0164778B2 (de) Detergens-Pulverzusammensetzungen die Natriumperboratmonohydrat enthalten
EP0056723B1 (de) Detergenszusammensetzungen
CA1314189C (en) Detergent compositions
CA1182026A (en) Detergent compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER NV

Owner name: UNILEVER PLC

17P Request for examination filed

Effective date: 19830620

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 15499

Country of ref document: AT

Date of ref document: 19850915

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3266194

Country of ref document: DE

Date of ref document: 19851017

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19860713

26 Opposition filed

Opponent name: UNILEVER PLC / UNILEVER N.V.

Effective date: 19860602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19860731

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER PLC/UNILEVER N.V.

26 Opposition filed

Opponent name: AKZO N.V.

Effective date: 19860610

Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

Effective date: 19860610

NLR1 Nl: opposition has been filed with the epo

Opponent name: AKZO N.V.

Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

BERE Be: lapsed

Owner name: UNILEVER NV

Effective date: 19860731

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: UNILEVER PLC / UNILEVER N.V. * 860610 HENKEL KOMMA

Effective date: 19860602

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19900117

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE CH DE FR GB IT LI NL SE

ET3 Fr: translation filed ** decision concerning opposition
NLR2 Nl: decision of opposition
ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
ITTA It: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 82303676.9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19960702

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970613

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19970618

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970623

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970627

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970714

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980714

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980713

EUG Se: european patent has lapsed

Ref document number: 82303676.9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990331

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19990201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO