EP0291869A2 - Détergent sans phosphate à tendence d'incrustation réduite - Google Patents

Détergent sans phosphate à tendence d'incrustation réduite Download PDF

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Publication number
EP0291869A2
EP0291869A2 EP88107689A EP88107689A EP0291869A2 EP 0291869 A2 EP0291869 A2 EP 0291869A2 EP 88107689 A EP88107689 A EP 88107689A EP 88107689 A EP88107689 A EP 88107689A EP 0291869 A2 EP0291869 A2 EP 0291869A2
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EP
European Patent Office
Prior art keywords
weight
acid
composition according
alkali metal
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.)
Withdrawn
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EP88107689A
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German (de)
English (en)
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EP0291869A3 (fr
Inventor
Günther Dr. Vogt
Hans Dr. Andree
Gertrud Nienhaus
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0291869A2 publication Critical patent/EP0291869A2/fr
Publication of EP0291869A3 publication Critical patent/EP0291869A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • Phosphate-free detergents with a content of finely crystalline aluminosilicates as a phosphate substitute, sodium carbonate or sodium silicates as washing alkali and polyanionic compounds from the class of the aminoalkane polyphosphonic acids and the homo- or copolymeric polycarboxylic acids derived from acrylic acid, methacrylic acid, maleic acid and olefinically unsaturated, copolymerizable compounds are known.
  • the preferred phosphonic acids or phosphonic acid salts are ethylene diamine tetramethylene phosphonate (EDTMP) and diethylene triamine pentamethylene phosphonate, mostly in the form of their sodium salts.
  • Preferred polymeric polycarboxylic acids are copolymers of maleic acid with vinyl methyl ethers and in particular maleic acid with acrylic acid in a ratio of 1: 5 to 1: 1 with a molecular weight of 10,000 to 150,000. These polyacids are also usually present in the compositions as sodium salts.
  • the amounts of aminoalkanephosphonates used are usually 0.1 to 1% by weight, those of copolymers 3 to 6% by weight, based on the composition.
  • the complexing and retarding properties (so-called threshold effect) of these additives are often not sufficient to limit the formation of fiber incrustations to the desired extent. It has been shown that the incrustations increase with frequent washing of the textiles with hard water and can eventually reach an undesirable extent. This increase in incrustations manifests itself in an increasing hardening and graying of the tissue and can be followed quantitatively by determining the tissue ash.
  • the task was therefore to reduce the tendency to form such incrustations.
  • a detergent that contains less than 0.1% inorganically bound phosphorus is understood to be phosphate-free.
  • An essential feature of the invention is the joint use of the aminoalkane polyphosphonates and / or polymer carboxylic acids listed under (d) together with the hydroxyalkane diphosphonate mentioned under (f). It is true that the use of the hydroxyalkane phosphonate (component f) in washing and cleaning detergents have long been known, but after the aminoalkane phosphonates listed under (d1) or the polymers according to (d2) were found, this compound was not used in modern phosphate-free agents, since the hydroxyalkane phosphonate is known to have a much lower sequestering capacity than the aminoalkane phosphonates according to (d1) and also has practically no threshold properties comparable to the polymers according to (d2).
  • Suitable aminoalkanephosphonic acids according to component (d1) are preferably ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetrimainpentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. Their proportion in the compositions, calculated on free acid, is preferably 0.1 to 1% by weight, in particular 0.1 to 0.5% by weight.
  • ETMP ethylenediamine tetramethylenephosphonate
  • DTPMP diethylenetrimainpentamethylenephosphonate
  • Their proportion in the compositions, calculated on free acid is preferably 0.1 to 1% by weight, in particular 0.1 to 0.5% by weight.
  • Suitable as (co) polymeric polycarboxylates are polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those made from 50% to 90% acrylic acid and 50% to 10% maleic acid.
  • the molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a particularly be preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%.
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponifying to give the sodium or potassium salts.
  • polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
  • the content of (co) polymeric polycarboxylic acids in the composition, based on free acid (component d2), is preferably 0.5 to 5% by weight and in particular 1 to 4% by weight.
  • the agents can contain component (d1) and (d2) individually or both simultaneously, with simultaneous use being preferred.
  • the mixing ratio (d1): (d2) is, for example, 1: 1 to 1:30, preferably 1: 5 to 1:20.
  • the 1-hydroxyethane-1,1-diphosphonate (component f) is also preferably present as the sodium salt.
  • the disodium salt reacts neutrally, the tetrasodium salt alkaline (pH 9). Its proportion, based on acid, is 0.05 to 1, preferably 0.1 to 0.7% by weight and in particular 0.1 to 0.5% by weight.
  • the weight ratio of (d1) to (f) is 3: 1 to 1: 6, preferably 2: 1 to 1: 4 and of (d2) to (f) 40: 1 to 2: 1, preferably 20: 1 to 4: 1.
  • the agents according to the invention contain anionic or nonionic surfactants (component a) as further constituents. These include soaps, surfactants of the sulfonate and sulfate type as well as nonionic compounds, e.g. B. from the class of polyglycol ether derivatives.
  • the content of the agent in component (a) is 5 to 35, preferably 8 to 20% by weight.
  • Suitable soaps are derived from natural or synthetic, saturated or monounsaturated fatty acids with 12 to 22 carbon atoms. Are particularly suitable from natural fatty acids such. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C12 ⁇ 18 fatty acid soaps and 0 to 50% of oleic acid soap.
  • Useful sulfonate type surfactants are linear alkyl benzene sulfonates (C9 ⁇ 13 alkyl) and olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from C12 ⁇ 18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtainable from C12 ⁇ 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, and also alpha-sulfo fatty acids and their esters, e.g. B. the alpha-sulfonated hydrogenated coconut, palm kernel or tallow fatty acids and their methyl or ethyl esters and mixtures thereof.
  • 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 Ste aryl alcohol, or the C10 ⁇ 18 oxo alcohols and the sulfuric acid esters of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable.
  • Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
  • Surfactants containing sulfonate groups are preferred, and among these in turn the alkylbenzenesulfonates, alpha-sulfofatty acid ester salts and the alpha-sulfofatty acid ester disalts.
  • the anionic surfactants are usually in the form of their sodium salts. Their proportion, based on the composition, is generally 2 to 15% by weight, preferably 5 to 12% by weight.
  • Addition products of 2 to 20, preferably 3 to 15 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols and alkylphenols can be used as nonionic surfactants.
  • non-fully or not fully water-soluble polyglycol ethers with 2 to 6 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.
  • Further suitable nonionic surfactants are alkyl glycosides or alkyl polyglycosides, the alkyl group of which has 8 to 18, preferably 10 to 16, carbon atoms.
  • the content of the agents in nonionic surfactants or nonionic surfactant mixtures is preferably 3 to 10% by weight and in particular 3 to 7% by weight.
  • Component (b) consists of finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 22 24 837). Their particle size is usually in the range from 1 to 10 ⁇ m.
  • the content of (b) is 10 to 40, preferably 12 to 25% by weight.
  • Their proportion in the agents can be 1 to 8% by weight, in particular 2 to 5% by weight.
  • the sodium silicate improves the grain stability and the grain structure of the powdery or granular agents and has a favorable effect on the washing-in and dissolving behavior of the agents when they are put into washing machines. It also has an anti-corrosive effect and improves washability. It was known that larger proportions, i.e. H.
  • washing alkali is sodium carbonate, the proportion of which is up to 15% by weight, preferably 2 to 12% by weight and in particular 5 to 10% by weight.
  • the total amount of sodium silicate and sodium silicate is 4 to 20% by weight, preferably 5 to 15% by weight and in particular 7 to 12% by weight.
  • graying inhibitors Dirt carriers
  • bleaching agents bleach activators
  • optical brighteners foam inhibitors
  • enzymes enzymes
  • textile-softening substances as well as neutral salts and water.
  • the washing and cleaning agents can contain graying inhibitors, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
  • graying inhibitors 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. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • Carboxymethyl cellulose (Na salt), methyl cellulose and mixtures thereof are preferably used. The proportion of the compounds is generally 0.2 to 2, preferably 0.5 to 1.5,% by weight.
  • H2O2 sodium perborate tetrahydrate
  • NaBO2. H2O2. 3 H2O sodium perborate tetrahydrate
  • NaBO2. H2O2 monohydrate
  • H2O2 supplying borates, for example the perborax Na2B4O7. 4 H2O2.
  • These compounds can be partially or completely by other active acid carriers, especially by peroxy hydrates, such as peroxycarbonates (Na2CO3.
  • H2O2 peroxypyrophosphates, citrate perhydrates, urea-H2O2- or melamine-H2O2 compounds as well are replaced by H2O2-delivering peracidic salts or peracids such as perbenzoates, peroxyphthalates, diperazelaic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the preparations.
  • N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetyl-ethylenediamine, and also carboxylic anhydrides, such as benzoic anhydride and Phthalic anhydride and esters of polyols such as glucose pentaacetate.
  • the detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or similarly structured compounds which have a instead of the morpholino group Carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; e.g. the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can adsor on carriers be beer and / or embedded in coating substances to protect them against premature decomposition.
  • Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
  • Bis-acylamides derived from C12 ⁇ 20 fatty acids and C2 ⁇ 6 diamines or from C12 ⁇ 20 alkylamines and C2 ⁇ 6 dicarboxylic acids are also useful.
  • Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicones and paraffins or waxes or from bis-acylamides and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • Layered silicates from the bentonite and smectite class e.g. B. those according to DE 23 34 899 and EP 26 529.
  • synthetic layered silicates which, after suspension in water (16 ° dH, room temperature), have a swelling capacity - which is the quotient of the sediment volume (V s ) / total volume (V) after previous treatment with excess soda solution, careful washing and 20 hours after the slurry in 9 parts by weight of water / one part by weight of layered silicate - of V s / V less than 0.6, in particular less than 0.4, and synthetic layered silicates, which are mixed-crystalline and have structure-determining saponite and / or hectorite-like crystal phases, which are interspersed in an irregular arrangement with crystalline alkali polysilicate.
  • Layered silicates of this type are characterized in more detail in DE 35 26 405.
  • the layered silicate content can be, for example, 5 to 20% by weight.
  • the agents can be prepared in the customary manner, ie by spray drying the constituents which are stable under these conditions and then admixing the heat-sensitive components, such as bleaching agents, enzymes, fragrances and foam inhibitors.
  • Other suitable processes are the granulation of the constituents, water, salt solutions, polymer solutions and / or nonionic surfactants being able to be used as the granulation liquid.
  • the proportion of alkali silicate can be increased to proportions of more than 2.5 to 3% by weight without risk of increased ash formation, and thus the grain strength and pourability of the finished granular powder can be increased , because the addition of HEDP counteracts ash formation.
  • Granular detergents of the following composition were produced and tested.
  • the constituents mentioned in the 1st to 9th place and the main amount of sodium sulfate were mixed to form an aqueous spray batch and spray-dried in a test tower.
  • the perborate, the bleach activator and the granules were subsequently added to the spray product.
  • the amounts relate to% by weight.
  • the test was carried out under practical conditions in household washing machines.
  • the machines were loaded with 3.5 kg of normally soiled household linen (bed linen, table linen, underwear) and 0.5 kg of test fabric.
  • Strips of standardized cotton fabric (Krefeld laundry research institute), nettle, knitwear (cotton jersey) and terry toweling were used as the test fabric. Washing conditions: tap water of 16 ° C (equivalent to 160 g CaO / liter), prewash 5 g / l at 15 to 30 ° C, main wash 7.5 g / l at 25 to 92 ° C (heating time 15 min., 15 min. at 92 ° C), liquor ratio (kg of laundry to liter of wash liquor) in the main wash cycle 1: 4, rinse 5 times with tap water, spin off and tumble dry. After 50 washing cycles, the ash content of the textile samples was determined quantitatively.
  • EDTMP stands for the hexasodium salt of ethylenediaminetetramethylenephosphonic acid (1 g salt corresponds to 0.77 g free acid)
  • HEDP stands for the tetrasodium salt of 1-hydroxy-1,1-ethanediphosphonic acid (1 g salt corresponds to 0.7 g free acid )
  • AMC for the sodium salt of a copolymer of acrylic acid and maleic acid in a molar ratio of 4: 1, molecular weight 70,000, pH 9 (partially neutralized, 1 g of salt corresponds to approximately 0.82 g of free acid).
  • the amounts of the salts used (and the proportion calculated for free acid in parentheses) are given in percent by weight. The difference in quantity of up to 5% by weight is attributable to sodium sulfate.
  • the mean value of the ash content determined from all textile samples was 9.2% by weight after 50 washes in the absence of the 3 components.
  • the amounts in Table 2 relate to the salts.
  • the difference up to 5% consists of sodium sulfate.
  • the experiment S represents the standard.

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  • 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)
EP88107689A 1987-05-21 1988-05-13 Détergent sans phosphate à tendence d'incrustation réduite Withdrawn EP0291869A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873717227 DE3717227A1 (de) 1987-05-21 1987-05-21 Phosphatfreies waschmittel mit reduzierter inkrustierungstendenz
DE3717227 1987-05-21

Publications (2)

Publication Number Publication Date
EP0291869A2 true EP0291869A2 (fr) 1988-11-23
EP0291869A3 EP0291869A3 (fr) 1990-07-18

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Application Number Title Priority Date Filing Date
EP88107689A Withdrawn EP0291869A3 (fr) 1987-05-21 1988-05-13 Détergent sans phosphate à tendence d'incrustation réduite

Country Status (4)

Country Link
US (1) US4919845A (fr)
EP (1) EP0291869A3 (fr)
DE (1) DE3717227A1 (fr)
DK (1) DK279888A (fr)

Cited By (8)

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Publication number Priority date Publication date Assignee Title
BE1003581A5 (fr) * 1989-01-07 1992-04-28 Sandoz Sa Compositions detergentes, sans phosphates ni silicates, pour lavage.
EP0508934A1 (fr) * 1991-04-12 1992-10-14 Cleantabs A/S Composition détergente pour le linge
US5393455A (en) * 1990-10-26 1995-02-28 Henkel Kommanditgesellschaft Auf Aktien Zeolite-based phosphate-free detergent builder composition
EP0735132A1 (fr) * 1995-03-29 1996-10-02 Rhone-Poulenc Chimie S.A. Formulation détergente compacte en poudre pour lavage du linge
WO1997009404A1 (fr) * 1995-06-01 1997-03-13 Henkel Kommanditgesellschaft Auf Aktien Systeme inhibiteur de grisage a base d'enzyme
DE19538028A1 (de) * 1995-10-12 1997-04-17 Sued Chemie Ag Waschmittelzusatz
WO2002098803A1 (fr) * 2001-06-06 2002-12-12 Solutia Inc. Methode pouvant inhiber l'entartrage par le sel de calcium
WO2009092739A1 (fr) * 2008-01-22 2009-07-30 Thermphos Trading Gmbh Composition de traitement de surface contenant des composés d'acide phosphonique

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DE3900207A1 (de) * 1989-01-05 1990-07-12 Basf Ag Verwendung von copolymerisaten aus 1,2-di-alkoxyethylenen und monoethylenisch ungesaettigten dicarbonsaeureanhydriden in waschmitteln und waschmittel, die diese copolymerisate enthalten
US5244988A (en) * 1989-05-17 1993-09-14 Rohm And Haas Company Maleate polymerization process
US5030380A (en) * 1989-06-27 1991-07-09 Lever Brothers Company, Division Of Conopco, Inc. Polymeric electrolyte-hydrogen peroxide adducts
NZ239112A (en) 1991-01-29 1994-12-22 Ecolab Inc Solid alkaline compositions containing the reaction product in water of alkali metal hydroxide and alkali metal silicate; process of manufacture
US5693602A (en) * 1991-05-31 1997-12-02 Colgate-Palmolive Co. Spray dried powered automatic dishwashing composition containing enzymes
US5474699A (en) * 1991-05-31 1995-12-12 Colgate-Palmolive Co. Phosphate containing powered automatic dishwashing composition with enzymes
US5433885A (en) * 1991-07-17 1995-07-18 Church & Dwight Co., Inc. Stabilization of silicate solutions
US5281351A (en) * 1991-12-06 1994-01-25 Lever Brothers Company, Division Of Conopco, Inc. Processes for incorporating anti-scalants in powdered detergent compositions
DE4303320C2 (de) * 1993-02-05 1995-12-21 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
US5352376A (en) * 1993-02-19 1994-10-04 Ecolab Inc. Thermoplastic compatible conveyor lubricant
US5376300A (en) * 1993-06-29 1994-12-27 Church & Dwight Co., Inc. Carbonate built laundry detergent composition
GB2285053A (en) * 1993-12-23 1995-06-28 Procter & Gamble Rinse aid composition
GB2285052A (en) * 1993-12-23 1995-06-28 Procter & Gamble Detergent composition
GB2285051A (en) * 1993-12-23 1995-06-28 Procter & Gamble Rinse aid composition
EP0781320B2 (fr) † 1994-09-13 2013-10-16 Kao Corporation Procede de lavage
KR100322629B1 (ko) * 1994-12-06 2002-08-13 제일제당주식회사 액체세제조성물
WO1996028531A1 (fr) * 1995-03-11 1996-09-19 The Procter & Gamble Company Composition detergente comportant un compose polycarboxylique polymere, un chelateur et une enzyme amylase
US5929018A (en) * 1995-03-11 1999-07-27 Procter & Gamble Co. Detergent composition comprising a polymeric polycarboxylic compound, a chelant, and an amylase enzyme
US5925609A (en) * 1995-03-11 1999-07-20 Procter & Gamble Company Detergent composition comprising source of hydrogen peroxide and protease enzyme
US6063747A (en) * 1995-07-25 2000-05-16 The Procter & Gamble Company Detergent compositions in compacted solid form
GB2303635A (en) * 1995-07-25 1997-02-26 Procter & Gamble Detergent compositions in compacted solid form
DE19528059A1 (de) * 1995-07-31 1997-02-06 Bayer Ag Wasch- und Reinigungsmittel mit Iminodisuccinaten
US5876514A (en) * 1997-01-23 1999-03-02 Ecolab Inc. Warewashing system containing nonionic surfactant that performs both a cleaning and sheeting function and a method of warewashing
US6407050B1 (en) 2000-01-11 2002-06-18 Huish Detergents, Inc. α-sulfofatty acid methyl ester laundry detergent composition with reduced builder deposits
MY138251A (en) * 2001-06-06 2009-05-29 Thermphos Trading Gmbh Method for inhibiting calcium salt scale
WO2002099184A2 (fr) * 2001-06-06 2002-12-12 Solutia Inc. Procede de production de pate amelioree
US7459420B2 (en) * 2004-12-01 2008-12-02 Vlahakis E Van Automatic dishwashing detergent comprised of ethylene oxide adduct and without phosphates
US7485613B2 (en) * 2004-12-01 2009-02-03 Venus Laboratories, Inc. Low foaming carpet-cleaning detergent concentrate comprised of ethylene oxide adduct and without phosphates
US7699905B1 (en) 2006-05-08 2010-04-20 Iowa State University Research Foundation, Inc. Dispersoid reinforced alloy powder and method of making
US8883035B2 (en) 2009-07-27 2014-11-11 Ecolab Usa Inc. Formulation of a ware washing solid controlling hardness
CN105705625A (zh) 2013-11-11 2016-06-22 艺康美国股份有限公司 多用途的酶洗涤剂和稳定使用溶液的方法

Citations (4)

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BE1003581A5 (fr) * 1989-01-07 1992-04-28 Sandoz Sa Compositions detergentes, sans phosphates ni silicates, pour lavage.
US5393455A (en) * 1990-10-26 1995-02-28 Henkel Kommanditgesellschaft Auf Aktien Zeolite-based phosphate-free detergent builder composition
EP0508934A1 (fr) * 1991-04-12 1992-10-14 Cleantabs A/S Composition détergente pour le linge
EP0735132A1 (fr) * 1995-03-29 1996-10-02 Rhone-Poulenc Chimie S.A. Formulation détergente compacte en poudre pour lavage du linge
WO1996030479A1 (fr) * 1995-03-29 1996-10-03 Rhone-Poulenc Chimie Formulation detergente compacte en poudre pour lavage du linge
FR2732355A1 (fr) * 1995-03-29 1996-10-04 Rhone Poulenc Chimie Formulation detergente compacte en poudre pour lavage du linge
WO1997009404A1 (fr) * 1995-06-01 1997-03-13 Henkel Kommanditgesellschaft Auf Aktien Systeme inhibiteur de grisage a base d'enzyme
DE19538028A1 (de) * 1995-10-12 1997-04-17 Sued Chemie Ag Waschmittelzusatz
WO2002098803A1 (fr) * 2001-06-06 2002-12-12 Solutia Inc. Methode pouvant inhiber l'entartrage par le sel de calcium
US6869503B2 (en) 2001-06-06 2005-03-22 Solutia, Inc. Composition for inhibiting calcium salt scale
US7300542B2 (en) 2001-06-06 2007-11-27 Thermophos Trading Gmbh Method for inhibiting calcium salt scale
AU2002305842B2 (en) * 2001-06-06 2008-08-21 Thermphos Trading Gmbh Method for inhibiting calcium salt scale
WO2009092739A1 (fr) * 2008-01-22 2009-07-30 Thermphos Trading Gmbh Composition de traitement de surface contenant des composés d'acide phosphonique
EP2090646A1 (fr) * 2008-01-22 2009-08-19 Thermphos Trading GmbH Composition de traitement de surface contenant des composés d'acide phosphonique
US8551931B2 (en) 2008-01-22 2013-10-08 Dequest Ag Surface treatment composition containing phosphonic acid compounds
RU2527448C2 (ru) * 2008-01-22 2014-08-27 Италматч Кемикалс СпА Композиция для обработки поверхности, содержащая соединения фосфоновых кислот

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DE3717227A1 (de) 1988-12-01
DK279888D0 (da) 1988-05-20
DK279888A (da) 1988-11-22
US4919845A (en) 1990-04-24
EP0291869A3 (fr) 1990-07-18

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