EP0010247A1 - Produit pour le lavage sans phosphates et procédé pour sa fabrication - Google Patents

Produit pour le lavage sans phosphates et procédé pour sa fabrication Download PDF

Info

Publication number
EP0010247A1
EP0010247A1 EP79103848A EP79103848A EP0010247A1 EP 0010247 A1 EP0010247 A1 EP 0010247A1 EP 79103848 A EP79103848 A EP 79103848A EP 79103848 A EP79103848 A EP 79103848A EP 0010247 A1 EP0010247 A1 EP 0010247A1
Authority
EP
European Patent Office
Prior art keywords
water
weight
powder
optionally
component
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.)
Granted
Application number
EP79103848A
Other languages
German (de)
English (en)
Other versions
EP0010247B1 (fr
Inventor
Markus Dr. Berg
Jochen Dr. Kaufmann
Dieter Dr. Jung
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Priority claimed from DE19782844455 external-priority patent/DE2844455A1/de
Priority claimed from DE19792908305 external-priority patent/DE2908305A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT79103848T priority Critical patent/ATE2848T1/de
Publication of EP0010247A1 publication Critical patent/EP0010247A1/fr
Application granted granted Critical
Publication of EP0010247B1 publication Critical patent/EP0010247B1/fr
Expired 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
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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

  • the invention relates to a powdered textile detergent which contains large amounts of water-insoluble, finely divided alkali alumosilicate cation exchangers and small amounts of certain water-soluble organic complexing agents, and an alkali silicate.
  • the invention also relates to a method for producing this powdery agent.
  • the bound water produced synthetically containing crystalline alkali metal aluminosilicates of the composition from 0.7 to 1, 5 Me 2 O ⁇ Al 2 O 3 ⁇ 1.3 to 4 SiO 2, and in particular of the composition from 0.7 to 1.1 Me 2 O ⁇ Al 2 O 3 ⁇ 1.3-3.3 SiO 2 , each based on their anhydrous form, where Me is sodium or potassium.
  • sodium aluminosilicates are generally preferred.
  • the cation-exchanging aluminosilicates are advantageously used together with water-soluble complexing agents to improve and accelerate the washing process.
  • German Offenlegungsschrift 25 40 510 describes a detergent for cold and 60 ° C. washing which essentially comprises 5-20% by weight of a cation-exchanging aluminosilicate, 4-12% by weight of a surfactant component made from paraffin sulfonate and olefin sulfonate and 12- 30% by weight of a sodium silicate of the composition Na 2 O.1.6-2.8 SiO 2 , and preferably contains no soluble complexing agents, in particular no detergent phosphates.
  • this detergent has an unsatisfactory primary and secondary washing ability at all washing temperatures. The properties of this detergent cannot be significantly improved either by adding an active oxygen compound and when used under the conditions of the hot wash.
  • German Offenlegungsschrift 26 56 009 which contains a phosphate-free detergent containing 12-25% by weight of a water-insoluble aluminosilicate zeolite, in particular of type 4A, 12-25% by weight, leads to a similar result.
  • Sodium perborate or percarbonate, 5 - 20 wt .-% of a sodium silicate of Zu-. composition Na 2 0 - 1 - 3.2 Si0 2 , and 5 - 25 wt .-% of a conventional alkyl benzene sulfonate surfactant describes.
  • undesired deposits of the water-insoluble zeolite particles on the laundry are to be prevented by a detergent with this combination.
  • these agents which are preferably produced by spray drying, the presence of an additional water-soluble builder is not provided; however, phosphorus-free organic and inorganic Builders such as alkali carbonate, borax, sodium nitrilotriacetate, sodium citrate, etc. are present.
  • this disadvantage is related to the use of a conventional alkali silicate, in particular a sodium silicate of the composition Na 2 O.2.0-3.4 SiO 2 , in small amounts of approximately 0.5-3% by weight on the entire detergent formulation - avoided o
  • a conventional alkali silicate in particular a sodium silicate of the composition Na 2 O.2.0-3.4 SiO 2
  • the effect found is described in this reference using detergent examples which, in addition to 18% by weight of the water-insoluble aluminosilicate, contain 24% by weight sodium triphosphate and 1-3% by weight Na 2 O.3.2 Si0 2 as well as conventional surfactants, and which have been produced by spray drying.
  • Comparable washing results should also be obtained if, instead of the sodium triphosphate, other builders, e.g. Sodium pyrophosphate or sodium nitrilotriacetate, specific polyphosphonates such as e.g. the alkali salts of ethane-1-hydroxy-1,1-diphosphonic acid or ethane-1,1,2-triphosphonic acid, or polyacetates, such as e.g. Sodium ethylenediaminetetraacetate and sodium nitrilotriacetate, carboxylates such as e.g. the alkali citrates, polycarboxylates, e.g. polymeric compounds based on maleic acid, and also inorganic salts such as alkali carbonates and bicarbonates, in amounts of 5-50, preferably 10-55,% by weight, based on the total detergent, are used.
  • other builders e.g. Sodium pyrophosphate or sodium nitrilotriacetate
  • specific polyphosphonates such as
  • German Offenlegungsschrift 25 42 704 discloses detergents containing water-insoluble aluminosilicate cation exchangers and alkali pyrophosphate as a soluble builder. These agents contain an alkali silicate of the composition M 2 O.1.6-4 SiO 2 (M stands for sodium or potassium), which has been converted into a polymer with certain poor solubility properties by dehydration. This measure ensures that when the wash liquor is prepared, the pyrophosphate first reacts with the hardness constituents of the water and this precipitates before the silicate polymer is split into a more soluble product by rehydration.
  • the polymeric, sparingly soluble alkali silicate can be used in the known detergents in amounts of 1-30% by weight, the water-insoluble. Liche aluminosilicate in amounts of 1 - 40 wt .-% may be included.
  • German Offenlegungsschrift 27 11 375 describes a powdered washing and cleaning agent which contains no tripolyphosphate and pyrophosphate builders.
  • this agent can contain 5-50% by weight of a water-insoluble aluminosilicate cation exchanger in combination with 4-40% by weight of one Magnesium ion-insensitive surfactant and larger amounts (about 13 - 40 wt .-%) of a readily soluble alkali silicate of the composition M 2 O ⁇ 1.4 - 2.7 SiO 2 (where M means sodium or potassium).
  • M means sodium or potassium
  • the magnesium ions in the wash solution are to be bound with this alkali silicate, which is used in larger quantities.
  • the constituents are mixed in an aqueous batch and preferably spray-dried.
  • the subject of the applicant's older, unpublished German patent application P 28 14 083.2 is a further developed phosphate-free, bleaching detergent based on cation-exchanging alkali alumosilicate, which, in addition to a selected surfactant component, contains certain water-soluble organic complexing agents of the type of the substituted phosphonic acids and their alkali salts selected from the group of the substituted alkane and triphosphonic acids in amounts of less than 1 wt .-% total.
  • compositions of this earlier patent application can additionally contain customary water-soluble sodium silicates of the composition Na 2 O.1-3.5 SiO 2 , in particular of the composition Na 2, in amounts of up to 7% by weight, preferably in amounts of 2-5% by weight 0: SiO 2 as 1: 2 to 1: 3.35, as a corrosion inhibitor.
  • the alkali silicates and, in particular, the sodium silicates are known to perform a number of functions as detergent components.
  • the most important properties of the alkali silicates include their action as alkali carriers and buffer substances, the promotion of dirt detachment by means of the same electrostatic charging of the surfaces of the fibers and the dirt particles, the ability to emulsify and disperse the dirt, and the ability to trace heavy metals, especially Iron and manganese to be removed from the wash water and so existing perborate stabilize, but also to a certain extent bind the water hardness.
  • Another chemical property of great importance when using modern detergents is the effect of the alkali silicates as corrosion inhibitors on the metal parts of the washing machines.
  • Another important property of alkali silicates would be in the manufacture of detergent powders. the method of hot spray drying to name the positive influence on the strength of the resulting hollow spherical particles.
  • the aim of the present invention is to further develop the use of the cation-exchanging alkali alumosilicates in detergents and to completely dispense with the usual detergent phosphates.
  • a particular object of the present invention is to have the small amounts of alkali silicate required for corrosion inhibition present in the powder detergent in such a form that even when these agents are used under very critical washing conditions, residues such as those described below are found on the washed textiles of the prior art literature discussed above are not to be feared.
  • the teachings of the prior art which deal with the incorporation and functioning of alkali silicate in detergents containing alumosilicate, could not give any useful suggestions.
  • the sodium silicate powder according to (iii) generally has a bulk density of 350-800 g / l, preferably 350 to 450 g / 1 and in particular approximately 400 g / l, its particle size distribution is in the range from 1 mm to 0.05 mm, wherein at least 80% of the particles are smaller than 0.5 mm.
  • Such readily water-soluble sodium silicate powder can be produced by spray drying or roller drying an aqueous 35-50% solution at a temperature of 100 to 120 ° C. in spray drying and 100 to 140 ° C. in roller drying.
  • Particularly preferred detergents contain a roller-dried sodium silicate, which is prepared by drying a 40 to 50% strength aqueous solution on a heated roller at 100 to 140 ° C. to a residual water content of 15 to 23, in particular 18 to 21% by weight Has.
  • Such a product is adjusted to a bulk density of 350-450 g / l, in particular approximately 400 g / l. It has excellent solubility properties, so that after the solubility test given above, it is already after 3 minutes in cold water 20 ° C is at least 99% dissolved.
  • a product with these properties is commercially available under the name Portil AW.
  • organic complexing agents from the group of substituted alkanedi- and triphosphonic acids - which also include heterocyclically substituted compounds - include in particular those alkanedi- and triphosphonic acids or their alkali and alkaline earth metal salts, the alkane group of which is substituted by the hydroxyl, amino, phenyl or is substituted by a phenyl group carrying hydroxyl, amino or halogen groups.
  • the alkane and triphosphonates from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-di-phosphonic acid, 3-amino-1-hydroxyropane-1,1-diphosphonic acid are particularly preferred.
  • 1-amino-1-p-chlorophenylmethane-1,1-diphosphonic acid 1-hydroxy-1-p-chlorophenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid, 1- Hydroxybutane-1,1-diphosphonic acid and aminotrimethylene triphosphonic acid in the form of their alkali metal salts, especially the sodium salts.
  • the sodium and calcium salts of 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxybutane-1,1-diphosphonic acid and aminotrimethylene triphosphonic acid are particularly preferred.
  • the detergent in powder component A) preferably contains conventional optical brighteners in the usual amounts.
  • Suitable cation-exchanging alkali alumosilicates are in principle the crystalline products described in the above-mentioned DE-OS 24 12 837, which generally have particle sizes below 50 ⁇ , essentially below 40 ⁇ and mostly in the range from 20-0 , Have 1 ⁇ .
  • crystalline sodium aluminosilicates of the composition 0.7 to 1.1 Na 2 O. 1, 0 Al 2 O 3 ⁇ 1, 3 to 2.4 Si0 2, their water content depending on .the Processing conditions can fluctuate and is generally 18-22% by weight in the finished washing powder.
  • Such aluminosilicates are also referred to as "zeolite NaA".
  • Such products are these Composition and crystal structure used, in the production of which by appropriate selection of the starting conditions it was ensured that the resulting crystallites have rounded corners and edges and their particle size is below 30 ⁇ and at least 80% in the range of 8-0.01 ⁇ , and the average particle diameter is 3 - 6 ⁇ .
  • Such aluminosilicates with rounded corners and edges are described in DE-OS 25 31 342.
  • both the calcium and the magnesium ions of the washing water are present - those which are generally present in a Ca: Mg ratio of about 5: 1 at average degrees of hardness are equally bound by the aluminosilicate. Effortless removal of calcium hardness and magnesium hardness is also achieved in artificially applied hot wash liquors of 16 ° d and a ratio of calcium to magnesium ions of 1: 1.
  • a sodium aluminosilicate of the composition 0.7-1.35 Na 2 O 1.0 Al 2 O 3 .1.3-2.4 Si0 2 uses, which is a binary mixture of 40 - 90% particles of the zeolite NaA and 10 to 60% particles of the zeolite HS (hydrosodalite).
  • Such an aluminosilicate already has a calcium binding capacity of 100-165 mg CaO / g and a magnesium binding capacity of 50-110 mg MgO / g - in each case based on the anhydrous substance - in the heated wash liquor from a temperature of 50 ° C.
  • the detergents according to the invention which contain a surfactant component according to (ba), show an excellent foam regulation during the entire boil washing program and when rinsing the washing liquor, particularly when used in drum washing machines.
  • Detergents containing mixtures of the surfactant components (ba) and (bb) are also preferred. Preference is also given to detergents whose surfactant content consists of a mixture of the surfactant component (ba) and a surfactant type (bb3), i.e. Compounds of the formula I exist, the surfactant type (bb3) being able to make up 5-25% by weight of the surfactant mixture and preferably consisting of coconut fatty acid monoethanolamide.
  • the anionic surfactants of the sulfonate and / or sulfate type of the surfactant component (ba) preferably consist of alkylbenzenesulfonates and / or of alkanesulfonates.
  • the use of wash-active alkanesulfonates in the context of this surfactant component is particularly preferred in view of their rapid and complete biodegradation in the waste water and because of their low toxicity.
  • the foam security during washing and rinsing is also ensured if the stated amounts of alkylbenzenesulfonate and / or alkanesulfonate are up to a third of their amount due to the more foaming anionic surfactants of the type of the ⁇ -sulfofatty acid esters, the olefin sulfonates, the fatty alcohol sulfates and the fatty alcohol polyglycol ether sulfates, which likewise have good biodegradability and low toxicity.
  • the nonionic surfactants contained in the combinations (ba) and (bb) from the group of ethoxylated aliphatic C 10 -C 20 alcohols with a degree of ethoxylation of 2-20 preferably consist of binary mixtures of separately produced ethylene oxide addition products with average degrees of ethoxylation on the one hand of 2-7 and on the other hand from 8-20 moles of EO and a ratio of the low ethoxylated to the higher ethoxylated compound of 3: 1 to 1: 3.
  • Preferred nonionic surfactants are those whose aliphatic group is derived from primary alkanols and alkenols and which come from natural and synthetic sources.
  • the ethoxylation products of natural fatty alcohols with in particular C 12 -C 18 alkyl and alkenyl groups are particularly preferred because of their good biodegradability in connection with the easy accessibility.
  • oxo alcohols which are obtained from olefins by hydroformylation and hydrogenation, and which are primary aliphatic alcohols with an ⁇ -methyl branch which does not impair biodegradability. If an ethoxylated fatty alcohol is replaced by an ethoxylated oxo alcohol with the same ratio of the hydrophobic and hydrophilic part of the molecule in the two surfactant components (ba) and (bb) defined above, the washability of hydrophobic dirt is improved with equivalent replacement.
  • the compounds (bb3) of the formula I contained in the surfactant component (bb) are the optionally still ethoxylated addition products of 1 mol of a low molecular weight amine, in particular mono- or diethanolamine, ethylenediamine, diethylenetriamine or triethylene tetramine, on 1 mol of one end - Or internal C 8 -C 22 epoxyalkane, in particular C 10 -C 18 epoxyalkane.
  • These compounds of the formula I have already been described as detergent additives for detergents in German Offenlegungsschrift 27 03 020.
  • the compounds (bb3) of the formula I also include the ethanolamides of the C 8 -C 18 fatty acids, preferably the C12-C14 fatty acids, and in particular the monoethanolamides, which are also particularly preferred. Accordingly, these compounds of the formula I are also to be regarded in the broadest sense as nonionic surfactants.
  • Ready-formulated compositions of the agents according to the invention generally contain in amounts of 1-50% by weight of further customary additives which improve the utility value, in particular a graying inhibitor, such as . e.g. carboxymethyl cellulose, enzymes, antimicrobials, optical brighteners, fabric softeners, colors and fragrances, sodium sulfate as filler and water, which is bound in the crystals of the water-soluble salts and in particular in the aluminosilicates, and a proportion of about 2-18% by weight of the free-flowing detergent powder.
  • a graying inhibitor such as . e.g. carboxymethyl cellulose, enzymes, antimicrobials, optical brighteners, fabric softeners, colors and fragrances
  • sodium sulfate as filler and water, which is bound in the crystals of the water-soluble salts and in particular in the aluminosilicates, and a proportion of about 2-18% by weight of the free-flowing detergent powder.
  • An essential characteristic of the detergents according to the invention is their presence as a mixture of the powder components A and B defined above, in the case of the detergents with bleaching action another powder component C containing the peroxy bleach component is present in the mixture,
  • the invention therefore also relates to a method for producing the detergents defined above.
  • this process comprises the production of a powder component by heat spray drying an aqueous suspension, the production of a further powder component by a method different from this drying method, and mixing of the powder components, optionally with the addition of a peroxy bleaching component, especially the sodium perborate, as a further powder component characterized in that the above-defined water-insoluble alkali alumino-silicates according to (i) or a), the above-defined surfactant component according to (ii) or b), optionally without or part of the nonionic surfactants, and optionally water-soluble complex-forming framework substances are slurried with water and converted into powder component A by hot atomization, that the sodium silicate powder defined above (iii) or e) is optionally mixed with powdered, water-soluble, complex-forming builders and to this powder optionally adding drying-sensitive nonionic surfactants and optionally further hydrolysis and temperature-sensitive detergent components, and mixing the resulting powder component B with powder component A in a conventional
  • the process for the preparation of the cooking detergent defined above, which contains a stabilizer combination c) in the tower powder component A is further characterized in that the aluminosilicate a), the surfactant component b) and the stabilizer combination c), optionally without part of the nonionic surfactants from b ) and preferably optical brighteners and other additives such as graying inhibitors and sodium sulfate with water slurried and converted into powder component A by hot atomization drying, that the sodium silicate powder defined above according to e) is optionally mixed with non-ionic surfactants sensitive to drying and optionally further hydrolysis and temperature-sensitive detergent components, and the resulting powder component B and the sodium perborate with powder component A are customary Mixed in such a way that the proportions of A, B and C are selected so that the components a) to e) are present in the resulting mixture in the quantitative ranges given above for this detergent.
  • sodium perborate tetrahydrate (NaB0 2 H 2 O 2 .3 H 2 0) is of particular practical importance; the monohydrate compound (NaBO 2 .H 2 O 2 ) can also be used.
  • other borates which produce H 2 O 2 can also be used, for example the perborax Na 2 B 4 O 7 .4H 2 O 2 .
  • These compounds can be partially or completely replaced by other active oxygen carriers, in particular by peroxyhydrates, such as peroxycarbonates (Na 2 CO 3 .1.5 H 2 0 2 ), peroxypyrophosphates, citrate perhydrates, urea-H 2 O 2 - or melamine-H 2 0 2 - Compounds as well as H 2 0 2 -supplying acid salts, such as caroates (KHSO 5 ), perbenzoates or peroxyphthalates.
  • peroxyhydrates such as peroxycarbonates (Na 2 CO 3 .1.5 H 2 0 2 ), peroxypyrophosphates, citrate perhydrates, urea-H 2 O 2 - or melamine-H 2 0 2 - Compounds as well as H 2 0 2 -supplying acid salts, such as caroates (KHSO 5 ), perbenzoates or peroxyphthalates.
  • the magnesium silicates Mg0: SiO 2 4: 1 to 1: 4, which are mostly obtained by precipitation from aqueous solutions, are suitable as water-insoluble peroxystabilizers, which, as part of the stabilizer combination, preferably make up 0.8 to 1.5% of the weight of the entire preparation. preferably 2: 1 to 1: 2 and in particular 1: 1.
  • Suitable water-soluble stabilizers which are preferably present together with the water-insoluble ones, are the organic heavy metal complexing agents of the amino or iminopolycarboxylic acid type, such as, for example, ethylenediaminotetraacetic acid, diethylenetriaminopentaacetic acid or Iminotriessigklad and their alkali and / or alkaline earth metal salts into consideration.
  • the aluminosilicates are expediently used in their still moist state, for example as an aqueous suspension or as a moist filter cake, and preferably by first adding these moist aluminosilicates, optionally with the addition of further water and a Dispersant converted into stable pumpable suspensions with an alumosilicate content of approx. 40% by weight and above - based on the anhydrous substance - and a content of 0.3 - 4% by weight of the dispersant.
  • preferred dispersants are those compounds which are themselves active detergent constituents, and in particular those which are already intended as components of the agent according to the invention.
  • Particularly preferred in the context of the present invention as stabilizing agents for aqueous suspensions of the aluminosilicates are the ethoxylated aliphatic C 10 -C 20 alcohols preferably contained in the surfactant components (ba) and (bb) with an average degree of ethoxylation of 2-7 mol EO or the compound of formula I present in combination (bb) as component (bb3).
  • the suspensions produced by mixing aluminosilicate, water and dispersant are notable for their high stability; they can be stored at room temperature or at higher temperatures, transported through pipelines, in tankers or in some other way before they are used in the process according to the invention for the preparation of powder component A).
  • the remaining constituents of powder component A) are introduced into the initially prepared suspensions of the aluminosilicate and the resulting aqueous, flowable mixture is subjected to spray drying.
  • the low ethoxylated aliphatic alcohols of the surfactant components and the compounds of the formula I of the surfactant component (bb) have not been used completely as suspension aids, their incorporation into the powder component B) is recommended, for example by spraying, because of their mostly liquid-viscous nature the silicate powder (iii).
  • the aluminosilicates to be used are synthetic crystalline products; Mixtures of crystalline and amorphous products or semi-crystalline products can of course also be used for the purposes of the invention.
  • the aluminosilicates can be prepared, for example, by. Reaction of water-soluble silicates with water-soluble aluminates in the presence of water.
  • aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution.
  • the desired aluminosilicates are also obtained by mixing the two components present in the solid state in the presence of water.
  • Alosilicate can also be produced from Al (OH) 3 , Al 2 O 3 or Si0 2 by reaction with alkali silicate or aluminate solutions. The production can also be carried out by other known processes.
  • Preferred aluminosilicates have a calcium binding capacity in the range of 100-200 mg CaO / g ai, mostly around 100-180 mg CaO / g ai; This is found mainly in compounds of the composition from 0.7 to 1.1 Na20 Al 2 O 3 1.3 to 3.3 Si02.
  • the alumosilicates which are initially still water-moist from their production and which can be in the form of aqueous suspensions or moist filter cakes, can be converted into dry powders in the customary manner by first removing part of the water mechanically and then drying them, e.g. at temperatures of 50 - 400 C. Depending on the drying conditions, the powder product, which looks dry on the outside, contains more or less, mostly 5 - 35% by weight of bound water. Expediently, drying does not exceed 200 ° C. if the aluminosilicate is intended for use in detergents and cleaning agents; such aluminosilicate powders have a water content of about 18-22% by weight.
  • the aluminosilicates do not need to be dried at all after their preparation if, according to the teaching of DE-OS 25 27 388, they are converted into a stable suspension with a certain dispersant and water and used for further processing into detergents. Apart from the energy saving due to the elimination of the drying stage, this processing mode practically completely avoids agglomeration of the primary particles into undesirable larger particles (secondary particles), as is observed in conventional drying and therefore requires grinding and sieving measures.
  • the magnesium binding capacity is calculated as (30 - x) 7.19 mg MgO / g AS.
  • the particle sizes of the aluminosilicates can e.g. determine by means of sedimentation analysis.
  • the surfactants contained in the agents according to the invention have at least one hydrophobic organic residue and one water-solubilizing anionic, amphoteric or zwitterionic or nonionic group in the molecule.
  • the hydrophobic radical is usually an aliphatic hydrocarbon radical with 8-26, preferably 10-22 and in particular 12-18 carbon atoms or an alkyl aromatic radical with 6-18, preferably 8-16, aliphatic carbon atoms.
  • Suitable synthetic anionic surfactants are in particular those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with C 9-15 -alkyl groups and the alkanesulfonates which are obtainable from C 12 -C 18 -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins Consider.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids
  • olefin sulfonates ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as are used for example from monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
  • fatty alcohols such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols or alkylphenols ethoxylated with 1-6 mol ethylene oxide are also suitable.
  • Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
  • the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the nonionic surfactants suitable according to the invention are the adducts of 1-40, preferably 2-20, moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10-20 carbon atoms from the group of alcohols, alkylphenols and carboxylic acids.
  • the adducts of 8-20 moles of ethylene oxide with primary alcohols such as coconut oil or tallow fatty alcohols, with oleyl alcohol, with oxo alcohols of the corresponding chain lengths, or with corresponding secondary alcohols, and with mono- or dialkylphenols with 6-14 C- Atoms in the alkyl radicals.
  • primary alcohols such as coconut oil or tallow fatty alcohols, with oleyl alcohol, with oxo alcohols of the corresponding chain lengths, or with corresponding secondary alcohols, and with mono- or dialkylphenols with 6-14 C- Atoms in the alkyl radicals.
  • water-soluble nonionics non-fully or not fully water-soluble polyglycol ethers with 2-7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants. Because of their good biodegradability, the ethoxylation products of primary aliphatic alkanols
  • EO ethylene oxide
  • tallow fatty alcohol 5-EO oleyl / cetyl alcohol 5-EO (iodine number 30-50 )
  • Tallow fatty alcohol 7-E0 synthetic C 12 -C 16 fatty alcohol 6-EO, C 11 -C 15 oxo alcohol 3-EO, C 14 / C
  • Exemplary representatives for the nonionic surfactants with an average degree of ethoxylation of 8-20, in particular 9-15 are the compounds coconut fatty alcohol-12-EO, synthetic C 12 / C 14 fatty alcohol-9-EO, oleyl / cetyl alcohol-10 -EO, tallow fatty alcohol-14-EO, C 11 -C 15 -oxoalcohol-13-EO, C 15 -C 18 -oxoalcohol-15-EO, iC 15 -C 17 -alkanediol-9-EO, C 14 / C 15 -Oxoalcohol-11-EO, sec.-C 11 -C 15 -Alcohol-9-EO.
  • nonionic surfactants are the water-soluble adducts of ethylene oxide with 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups with polypropylene glycol, alkylenediamine-polypropylene glycol and with alkylpolypropylene glycols with 1-10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic residue.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide, N-tallow alkyl-N , N-dihydroxyethylamine oxide.
  • amphoteric surfactants are compounds which contain both an anionic and a cationic group in the same molecule. Suitable compounds are the derivatives of aliphatic C 8 -C 18 amines with a water-solubilizing group, such as the carboxy, sulfo or sulfato group. Typical representatives of the ampho direct propionic acid surfactants are the sodium salts of 2-Dodecylaminopro- ° and the 3-Dodecylaminopropansulfonklare and similar compounds such as sulfated imidazoline derivatives.
  • Derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C 8 -C 18 radical and another contains an anionic water-solubilizing carboxy, sulfo or sulfato group are preferred as zwitterionic surfactants.
  • Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonio) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetradecyl-N, N-dimethylammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.
  • Foam-suppressing soaps and non-surfactant foam inhibitors come into consideration as foam-inhibiting additives.
  • the foam-suppressing action of the soaps generally increases with the degree of saturation and the C number of the fatty acid residue, so that soaps of natural and synthetic origin are particularly suitable as foam-inhibiting soaps, which have a high proportion of C 18 -C 22 fatty acids, for example the derivatives of hydrogenated fish oil and rapeseed oils.
  • fatty acid mixtures with a chain length distribution of C 12 to C 221 are used, which consist of at least 50 % by weight of C 18 -C 22 fatty acid salts (iodine number ⁇ 5).
  • Foam-suppressing soaps of saturated C 12 -C 18 fatty acids in particular predominantly C 16 -C 18 fatty acids, for example the soap of hydrogenated tallow fatty acid, are also suitable for the combination with non-surfactant-like foam inhibitors.
  • these combinations which have a quantity ratio of soap to non-surfactant-like foam inhibitor of 20: 1 to 5: 1, the soap primarily dampens foaming when the wash liquor is rinsed out.
  • non-surfactant foam inhibitors optionally used in combination with the foam-inhibiting soaps are generally water-insoluble, mostly containing aliphatic C 8 -C 22 carbon radicals.
  • Suitable non-surfactant-like foam inhibitors are, for example, the N-alkylaminotriazines, ie reaction products of 1 mole of cyanuric chloride with 2-3 moles of a mono- or dialkylamine with essentially 8-18 C atoms in the alkyl radical.
  • propoxylated and / or butoxylated aminotriazines for example the reaction products of 1 mole of melamine with 5-10 moles of propylene oxide and additionally 10-50 moles of butylene oxide and the aliphatic.
  • ketones such as stearone, the fatty ketones from hydrogenated tranfatty acid or tallow fatty acid etc. and also the paraffins and halogen paraffins with melting points below 100 ° C and polymeric organosilicon compounds of the silicone oil type, especially one activated by finely divided Si0 2 Polydimethylsiloxane.
  • the compounds of the formula I contained in the agents according to the invention with the surfactant combination (bb) are primarily compounds which were prepared in a 1-stage or 2-stage reaction from terminal or internal epoxyalkanes by first reacting with mono- or diethanolamine or mono- or -diisopropanolamine, with ammonia, an alkylenediamine, polyalkylene polyamine or hydroxyalkyl polyamine, and these addition products optionally in a second stage ethoxylated.
  • the epoxyalkanes used as starting materials are obtained in a manner known per se from the corresponding olefins or olefin mixtures.
  • terminal epoxyalkanes used were preferably those with chain lengths in the range of C12-C18 for the preparation of the hydroxyalkylamines of the formula 1.
  • the compounds of the formula I in the surfactant combination (bb) in the case of the fatty acid ethanolamides are preferably fatty acid monoethanolamides composed of individual fatty acids or fatty acid mixtures, in particular of the chain length range C 10 -C 18 , the natural ones or can be of synthetic origin.
  • the fatty acids know to be saturated and unsaturated;
  • Monoethanolamides of mixed fatty acids from natural sources are particularly suitable, such as the derivatives of the fatty acids obtainable from coconut fat, palm kernel oil or tallow.
  • fatty acid monoethanolamides examples include the compounds: lauric acid monoethanolamide, coconut fatty acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, oleic acid monoethanolamide, tallow fatty acid monoethanolamide.
  • the detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead the morpholino group has a diethanolamino group, a methyl ' amino group or a 2-methoxyethylamino group.
  • Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type.
  • Useful polyamide brighteners are also the substituted aminocoumarins, for example 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin.
  • the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyryl are also useful as polyamide brighteners.
  • the brighteners for polyester and polyamide fibers are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho [2,3-b] -thiophene and 1,2-di- ( 5-methyl-2-benzoxazolyl) ethylene suitable.
  • Brighteners of the substituted 4 / 4'-styryldiphenyl type may also be present; for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • the preparations may also contain graying inhibitors which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
  • graying inhibitors which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
  • water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Carboxymethylated cellulose or starch in the form of its sodium salts and / or methyl celluloses are preferred.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
  • color change inhibitors of the polyvinylpyrrolidone type can be used.
  • a manufacturing specification for the aluminosilicates is given; other known methods for producing the aluminosilicates can also be used.
  • the sodium aluminate solution was placed in a vessel with a volume of 15 l and the sodium silicate solution was added with vigorous stirring. Was stirred with a stirrer with a dispersing disc at 3000 revolutions / min. Both solutions were at room temperature.
  • An X-ray amorphous sodium aluminosilicate formed as the primary precipitation product under an exothermic reaction. After stirring for 10 minutes, the suspension of the precipitate was transferred to a crystallization container and heated to 80-130 ° C. for about 6 hours with stirring (250-500 revolutions / min.). After sucking off the lye from the crystal slurry and washing it with deionized water to a pH of approx.
  • the filter cake was either dried - e.g. 24 hours at 100 ° C. - and then crushed to a fine powder, or an aqueous slurry, preferably an aqueous suspension of the aluminosilicate, was used to produce the detergents or cleaning agents. More precise information on the temperature, the duration of heating and the type of workup are given in the manufacturing instructions for the following individual representative aluminosilicate types.
  • Precipitation batch 2.985 kg aluminate solution of the composition: 17.7% Na 2 O, 15.8% Al 2 O 3 , 66.5% H 2 0; 0.150 kg of caustic soda, 9.420 kg of water and 2.445 kg of a 25.8% strength solution of a sodium silicate of the composition 1 Na 2 O ⁇ 6 SiO 2 , freshly prepared from commercially available water glass and slightly alkali-soluble silica; Precipitation: Suspension of the amorphous precipitate was 10 min. stirred with an intensive stirrer (10,000 rpm); Crystallization: 6 hours at 90 ° C; Drying: 24 hours at 100 ° C; Composition: 0.9 Na 2 O.1 Al 2 O 3.
  • the detergents in Table I were generally prepared in such a way that a spray-dried powder component A was prepared from surfactant component, aluminosilicate, CMC, brightener and sodium sulfate via a slurry batch, and this with powder component B consisting of sodium silicate and the phosphonate salt and that consisting of perborate Powder component C mixed.
  • powder component A consisting of sodium silicate and the phosphonate salt and that consisting of perborate Powder component C mixed.
  • a mixture of the aluminum silicate, the surfactants, the constituents of the stabilizer combination and CMC, brightener and sodium sulfate was spray-dried as a slurry batch and this tower powder was mixed with the sodium silicate and the perborate. Enzymes and fragrances were added to these mixtures in the usual way.
  • the insoluble residue on a sieve was determined by dissolving the detergents in water after a certain dissolving time, or the visible residue on black wool was assessed after a delicate wash by hand, Ver Equally good washing and test results were also obtained if the aluminosilicate used there in the detergent formulations in Tables I and II was replaced by the other aluminosilicate types mentioned, or by alumosilicate types of the same composition but produced in a different way.

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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP79103848A 1978-10-12 1979-10-08 Produit pour le lavage sans phosphates et procédé pour sa fabrication Expired EP0010247B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79103848T ATE2848T1 (de) 1978-10-12 1979-10-08 Phosphatfreies waschmittel und verfahren zu dessen herstellung.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19782844455 DE2844455A1 (de) 1978-10-12 1978-10-12 Phosphatfreies waschmittel und verfahren zu dessen herstellung
DE2844455 1978-10-12
DE19792908305 DE2908305A1 (de) 1979-03-03 1979-03-03 Phosphatfreies waschmittel und verfahren zu dessen herstellung
DE2908305 1979-03-03

Publications (2)

Publication Number Publication Date
EP0010247A1 true EP0010247A1 (fr) 1980-04-30
EP0010247B1 EP0010247B1 (fr) 1983-03-23

Family

ID=25776070

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79103848A Expired EP0010247B1 (fr) 1978-10-12 1979-10-08 Produit pour le lavage sans phosphates et procédé pour sa fabrication

Country Status (3)

Country Link
EP (1) EP0010247B1 (fr)
BR (1) BR7906598A (fr)
DE (1) DE2965075D1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028432A1 (fr) * 1979-11-03 1981-05-13 THE PROCTER & GAMBLE COMPANY Compositions de lavage granulaires
EP0061296A1 (fr) * 1981-03-20 1982-09-29 Unilever Plc Procédé pour la préparation de compositions détergentes contenant de l'aluminosilicate de sodium
FR2524901A1 (fr) * 1982-04-08 1983-10-14 Colgate Palmolive Co Composition detergente adoucissante pour le lavage du linge, procede de fabrication de ces compositions et d'un composant de ces compositions
EP0123489A2 (fr) * 1983-04-20 1984-10-31 The Procter & Gamble Company Compositions détergentes
EP0228011A2 (fr) * 1985-12-23 1987-07-08 Henkel Kommanditgesellschaft auf Aktien Détergent granulaire à teneur en phosphates réduite
EP0242141A2 (fr) * 1986-04-14 1987-10-21 Unilever Plc Poudres détergentes et leur procédé de préparation
US4988454A (en) * 1986-04-04 1991-01-29 Lever Brothers Company Division Of Conopco, Inc. Low phosphorus containing detergent powders and process for preparing them: surfactant, aluminosilicate, sodium silicate and polyacrylate
WO1992015663A1 (fr) * 1991-03-05 1992-09-17 Henkel Kommanditgesellschaft Auf Aktien Detergents
US5501814A (en) * 1991-10-23 1996-03-26 Henkel Kommanditgesellschaft Auf Aktien Detergents and cleaning preparations containing selected builder systems
WO2011080540A1 (fr) * 2009-12-30 2011-07-07 Ecolab Inc. Produits de remplacement de phosphate pour des compositions de détergent et/ou de nettoyage compatibles avec des membranes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1474856A (en) * 1974-08-12 1977-05-25 Sifrance Detergent compositions
DE2711375A1 (de) * 1976-03-25 1977-10-06 Procter & Gamble Wasch- und reinigungsmittel
DE2814083A1 (de) * 1977-04-22 1978-11-02 Henkel Kgaa Phosphatfreies waschmittel, insbesondere fuer erhoehte temperaturen
DE2843709A1 (de) * 1977-10-14 1979-04-26 Pq Corp Waschmittelgemische, die silan-zeolith-geruestsubstanzen enthalten

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1474856A (en) * 1974-08-12 1977-05-25 Sifrance Detergent compositions
DE2711375A1 (de) * 1976-03-25 1977-10-06 Procter & Gamble Wasch- und reinigungsmittel
FR2345511A1 (fr) * 1976-03-25 1977-10-21 Procter & Gamble Composition detergente contenant un agent tensio-actif, un silicate et un adjuvant de detergence
DE2814083A1 (de) * 1977-04-22 1978-11-02 Henkel Kgaa Phosphatfreies waschmittel, insbesondere fuer erhoehte temperaturen
DE2843709A1 (de) * 1977-10-14 1979-04-26 Pq Corp Waschmittelgemische, die silan-zeolith-geruestsubstanzen enthalten

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028432A1 (fr) * 1979-11-03 1981-05-13 THE PROCTER & GAMBLE COMPANY Compositions de lavage granulaires
EP0061296A1 (fr) * 1981-03-20 1982-09-29 Unilever Plc Procédé pour la préparation de compositions détergentes contenant de l'aluminosilicate de sodium
US4637891A (en) * 1981-03-20 1987-01-20 Lever Brothers Company Process for the manufacture of detergent compositions containing sodium aluminosilicate
FR2524901A1 (fr) * 1982-04-08 1983-10-14 Colgate Palmolive Co Composition detergente adoucissante pour le lavage du linge, procede de fabrication de ces compositions et d'un composant de ces compositions
EP0123489A2 (fr) * 1983-04-20 1984-10-31 The Procter & Gamble Company Compositions détergentes
EP0123489A3 (en) * 1983-04-20 1987-05-20 The Procter & Gamble Company Detergent compositions
EP0228011A2 (fr) * 1985-12-23 1987-07-08 Henkel Kommanditgesellschaft auf Aktien Détergent granulaire à teneur en phosphates réduite
EP0228011A3 (en) * 1985-12-23 1987-08-26 Henkel Kommanditgesellschaft Auf Aktien Granular detergent with reduced phosphate content
US4988454A (en) * 1986-04-04 1991-01-29 Lever Brothers Company Division Of Conopco, Inc. Low phosphorus containing detergent powders and process for preparing them: surfactant, aluminosilicate, sodium silicate and polyacrylate
EP0242141A2 (fr) * 1986-04-14 1987-10-21 Unilever Plc Poudres détergentes et leur procédé de préparation
EP0242141A3 (fr) * 1986-04-14 1988-11-02 Unilever Plc Poudres détergentes et leur procédé de préparation
WO1992015663A1 (fr) * 1991-03-05 1992-09-17 Henkel Kommanditgesellschaft Auf Aktien Detergents
US5501814A (en) * 1991-10-23 1996-03-26 Henkel Kommanditgesellschaft Auf Aktien Detergents and cleaning preparations containing selected builder systems
WO2011080540A1 (fr) * 2009-12-30 2011-07-07 Ecolab Inc. Produits de remplacement de phosphate pour des compositions de détergent et/ou de nettoyage compatibles avec des membranes

Also Published As

Publication number Publication date
DE2965075D1 (en) 1983-04-28
EP0010247B1 (fr) 1983-03-23
BR7906598A (pt) 1980-06-03

Similar Documents

Publication Publication Date Title
DE2412837C3 (de) Mittel zum Waschen bzw. Bleichen von Textilien unter Einsatz kristalliner wasserunlöslicher Silikate, ihre Herstellung und ihre Verwendung
EP0209840B1 (fr) Silicates en couches à pouvoir gonflant réduit, leur procédé de préparation et leur utilisation dans des agents de lavage et de nettoyage
EP0291869A2 (fr) Détergent sans phosphate à tendence d'incrustation réduite
CH602961A5 (en) Textile cleaning bath contg alumino silicates
CH639691A5 (de) Phosphatfreies waschmittel.
DE2412839A1 (de) Verfahren zum waschen von textilien, sowie mittel zur durchfuehrung des verfahrens
EP0010247B1 (fr) Produit pour le lavage sans phosphates et procédé pour sa fabrication
DE2539110C3 (fr)
CH630322A5 (de) Stabile suspensionen wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln.
DE2538233C3 (fr)
EP0276705A2 (fr) Agglomérat poreux de couche de silicate/sulfate de sodium
DE2644289A1 (de) Wasch- und reinigungsmittel
DE2501113C3 (fr)
DE2844455A1 (de) Phosphatfreies waschmittel und verfahren zu dessen herstellung
EP0277571A2 (fr) Détergent adoucissant
EP0011846B1 (fr) Agent de lavage et de nettoyage, contenant un mélange de sels d'adjuvants ayant une faible teneur en phosphates
DE3632107A1 (de) Phosphatreduziertes waschmittel enthaltend n-alkoxylierte fettsaeureamide
DE2532501A1 (de) Verfahren zum waschen, reinigen bzw. bleichen der oberflaechen fester werkstoffe, insbesondere von textilien und mittel zur durchfuehrung dieses verfahrens
DE3702067A1 (de) Textilweichmachendes waschmittel
AT396691B (de) Verfahren zum waschen bzw. bleichen von textilien sowie mittel dazu und verfahren zu deren herstellung
DE2531342A1 (de) Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien
EP0369317A1 (fr) Agents de lavage et nettoyage contenant sec. dialkyléther sulfates
DE3606828A1 (de) Waschmittel fuer niedere waschtemperaturen
DE2009721A1 (en) Softening detergent
DE2620292A1 (de) Waschmittel mit einem gehalt an feinteiligen alkalialuminiumsilikaten

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 NL SE

17P Request for examination filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

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

REF Corresponds to:

Ref document number: 2848

Country of ref document: AT

Date of ref document: 19830415

Kind code of ref document: T

REF Corresponds to:

Ref document number: 2965075

Country of ref document: DE

Date of ref document: 19830428

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19891010

Year of fee payment: 11

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

Ref country code: SE

Effective date: 19901009

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19920924

Year of fee payment: 14

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

Ref country code: GB

Payment date: 19920928

Year of fee payment: 14

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

Ref country code: FR

Payment date: 19921005

Year of fee payment: 14

Ref country code: DE

Payment date: 19921005

Year of fee payment: 14

Ref country code: AT

Payment date: 19921005

Year of fee payment: 14

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

Ref country code: BE

Payment date: 19921028

Year of fee payment: 14

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

Ref country code: NL

Payment date: 19921031

Year of fee payment: 14

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

Ref country code: GB

Effective date: 19931008

Ref country code: AT

Effective date: 19931008

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

Ref country code: CH

Effective date: 19931031

Ref country code: BE

Effective date: 19931031

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19931031

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

Ref country code: NL

Effective date: 19940501

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

Effective date: 19931008

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19940630

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: DE

Effective date: 19940701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 79103848.2

Effective date: 19910603

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT