[go: up one dir, main page]

EP1076683B1 - Produit solide pour lave-vaisselle, a base de phosphate et de silicates lamellaires cristallins - Google Patents

Produit solide pour lave-vaisselle, a base de phosphate et de silicates lamellaires cristallins Download PDF

Info

Publication number
EP1076683B1
EP1076683B1 EP99922118A EP99922118A EP1076683B1 EP 1076683 B1 EP1076683 B1 EP 1076683B1 EP 99922118 A EP99922118 A EP 99922118A EP 99922118 A EP99922118 A EP 99922118A EP 1076683 B1 EP1076683 B1 EP 1076683B1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
quantities
builder
acid
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 - Lifetime
Application number
EP99922118A
Other languages
German (de)
English (en)
Other versions
EP1076683A1 (fr
Inventor
Rainer Sorg
Christian Nitsch
Jürgen Härer
Harald Volk
Thomas Müller-Kirschbaum
Peter Krings
Harald Bauer
Josef Holz
Günther Schimmel
Lothar Westermann
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
Clariant Produkte Deutschland GmbH
Original Assignee
Henkel AG and Co KGaA
Clariant Produkte Deutschland GmbH
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
Application filed by Henkel AG and Co KGaA, Clariant Produkte Deutschland GmbH filed Critical Henkel AG and Co KGaA
Publication of EP1076683A1 publication Critical patent/EP1076683A1/fr
Application granted granted Critical
Publication of EP1076683B1 publication Critical patent/EP1076683B1/fr
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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/2082—Polycarboxylic 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/16—Phosphates including polyphosphates

Definitions

  • the present invention relates to a machine dishwashing detergent which is in solid form and contains a builder combination of conventional phosphates and crystalline layered silicates.
  • Such agents despite their phosphate content improved protection for sensitive items, especially glasses and decorated items with known good cleaning performance and even partially improved cleaning performance compared to conventional phosphate-containing dishwashing detergents.
  • European patent application EP-A-0 504 091 (Viking) describes phosphate-free automatic dishwashing detergents with very good cleaning performance on tea stains.
  • the cleaners contain about 5 to 15 wt .-% crystalline layered silicates and additionally 10 to 15 wt .-% citric acid and additionally (co) polymeric polycarboxylates.
  • the total cleaning performance of such low alkaline dishwashing detergents is not sufficient in the case of problem soiling apart from tea.
  • the tea cleaning performance is good, but it can be increased.
  • Machine dishwashing detergents which are described in the international patent application WO-A-94/16047 (Procter & Gamble) show by the use of builders, in a certain time released bleach and paraffin oil in amounts of 0.05 to 2.5 parts by weight. % Improvements in silver protection. Citrate-containing agents are clearly preferred. Other builders may be aluminosilicates, phosphates or else crystalline phyllosilicates. Combinations of phosphates and crystalline phyllosilicates are not suggested or advantages are not mentioned by the use of such builder combinations.
  • European Patent Application EP-A-0 416 366 discloses a machine dishwashing detergent containing 30% by weight sodium tripolyphosphate, 30% by weight crystalline layered sodium silicate, preferably as proton donor mineral acid and / or polycarboxylic acids and / or hydroxypolycarboxylic acids and / or Phosphonic acids and / or their acid salts or esters and overall has a relatively low pH. Although such automatic dishwashing detergents already have good cleaning performance.
  • agents which contain crystalline layered silicates as a builder raw material also have the disadvantage that, because of the low rate of dissolution of the crystalline layered silicate, lime deposits on glass and dishes may occur.
  • the raw material is very finely divided and with high dust content, which can lead to production problems both in the powder and granule production and in the production of dishwasher tablets.
  • the object of the present invention was therefore to provide a machine dishwashing detergent which does not have the abovementioned disadvantages, ie which does not cause damage to glass even after repeated use, at the same time has good tea cleaning performance, but also excellent total cleaning performance and both in the powder and Granule production as well as in the production of tablets without production problems can be produced.
  • the present invention accordingly provides a solid machine dishwashing detergent which comprises conventional phosphates and further customary ingredients, wherein the agent comprises, in addition to the phosphates, as a further builder a granular additive which contains as essential constituents a crystalline layered silicate of the general formula (I) NaMSi x O 2x + 1 yH 2 O (I), wherein M represents sodium or hydrogen, x is an integer from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33, and contains (co) polymeric polycarboxylic acid.
  • the agent comprises, in addition to the phosphates, as a further builder a granular additive which contains as essential constituents a crystalline layered silicate of the general formula (I) NaMSi x O 2x + 1 yH 2 O (I), wherein M represents sodium or hydrogen, x is an integer from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33, and contains (co) poly
  • the conventional phosphates useful as builders in automatic dishwashing detergents include in particular alkali phosphates and polymeric alkali phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts.
  • alkali phosphates and polymeric alkali phosphates which may be in the form of their alkaline neutral or acidic sodium or potassium salts.
  • examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium tripolyphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts , Particularly preferred are the salts of tripolyphosphate.
  • Their amounts are based on the total formulation and
  • the crystalline layer-form silicates of the formula (I) are sold by Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na. SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
  • Na-SKS for example Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na. SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
  • Na-SKS-5 ⁇ -Na 2 Si 2 O 5
  • Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-9 NaH-Si 2 O 5 ⁇ H 2 O
  • Na-SKS-10 NaHSi 2 O 5 ⁇ 3H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 Na-SKS-13 (NaHSi 2 O 5 )
  • Na-SKS-6 ⁇ -Na 2 Si 2 O 5
  • crystalline phyllosilicates are introduced into the machine dishwashing detergent according to the invention via the builder additive used according to the invention.
  • the crystalline layer-form silicates of the formula (I) are introduced into the machine dishwashing compositions according to the invention exclusively via the builder additive used according to the invention.
  • the automatic dishwashing agents contain the crystalline layered silicate of the formula (I), introduced via the builder additive, in amounts of from 2 to at most 30% by weight, preferably in amounts of from 3 to 25% by weight and in particular in amounts of 4 to 20 wt .-%.
  • a (co) polymeric polycarboxylic acid is understood as meaning a homopolymer or copolymer which is not or only partially neutralized.
  • These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with other ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, ethylacrylic acid, vinylacetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, meth (allylsulfonic acid), vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid and phosphorous groups Monomers such as vinylphosphonic acid, allylphosphoric acid and acrylamidomethylpropanephosphonic acid and salts thereof, and hydroxyethyl (meth) acrylate sulfates, allyl alcohol sulfates and allyl alcohol phosphates.
  • Such polymers are described,
  • Preferred (co) polymers have an average molar mass of from 1000 to 100000 g / mol, preferably from 2000 to 75000 g / mol and in particular from 2000 to 35000 g / mol.
  • the degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%.
  • Particularly suitable polymers include homopolymers of acrylic acid and copolymers of (meth) acrylic acid with maleic acid or maleic anhydride.
  • copolymers are derived from terpolymers which are obtained by polymerization of 10 to 70% by weight of monoethylenically unsaturated dicarboxylic acids having 4 to 8 C atoms or salts thereof, 20 to 85% by weight of monoethylenically unsaturated monocarboxylic acids having 3 to 10 C atoms or their salts, 1 to 50 wt .-% of monounsaturated monomers which release after hydrolysis hydroxyl groups on the polymer chain, and 0 to 10 wt .-% of further free-radically copolymerizable monomers.
  • graft polymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides are also suitable.
  • the graft polymers disclosed in the European patent application with proteins of animal or vegetable origin, in particular with modified proteins, are likewise very suitable.
  • Copolymers are selected from the group of the graft copolymers preferably used of sugar and other polyhydroxy compounds, and a monomer mixture of the following composition 45 to 96 wt .-% of monoethylenically unsaturated C 3 - to C 10 monocarboxylic acid or mixtures of C 3 - to C 10 monocarboxylic acids and or their salts with monovalent cations, monomers containing 4 to 55% by weight of monoethylenically unsaturated monosulfonic acid groups, monoethylenically unsaturated sulfuric esters, vinylphosphonic acid and / or the salts of these acids with monovalent cations and 0 to 30% by weight of water-soluble, monoethylenically unsaturated compounds, with 2 to 50 moles of alkylene oxide per mole of monoethylenically unsaturated compound are modified.
  • Such compounds are described in DE-A-42 21 381 and in DE-A-43 43 993.
  • polyaspartic acids or their derivatives are polyaspartic acids or their derivatives in non-neutralized or partially neutralized form.
  • the polyaspartic acids are obtained in the form of their alkali metal or ammonium salts. From these it is possible to obtain the products which have not been neutralized or only partially neutralized by addition of appropriate amounts of organic or inorganic acids and, if appropriate, separation of the resulting salts.
  • Such products can also be obtained by the thermal reaction of maleic acid and ammonia or by the condensation of aspartic acid and the subsequent hydrolysis of the resulting polysuccinimide.
  • the production of such products is described for example in DE-A-36 26 672, DE-A-43 07 114, DE-A-44 27 287, EP-A-0 612 784, EP-A-0 644 257 and WO -A-92/14753.
  • graft polymers of acrylic acid, methacrylic acid, maleic acid and other ethylenically unsaturated monomers to salts of polyaspartic acid as usually obtained in the hydrolysis of the polysuccinimide described above. This can be dispensed with the otherwise necessary addition of acid for the preparation of only partially neutralized form of polyaspartic acid.
  • the amount of polyaspartate is usually chosen so that the degree of neutralization of all incorporated in the polymer carboxyl groups does not exceed 80%, preferably 60%. Products of the type mentioned are described in more detail in International Patent Application WO-A-94101486.
  • compositions according to the invention are determined by the content of the builder additives used according to the invention and their content of these polymers.
  • the builder additive used according to the invention contains the crystalline layered silicate of the formula (I) and the (co) polymeric polycarboxylic acid preferably in weight ratios of (40 to 1): 1, in particular of (20 to 2): 1, where ratios of 7 : 1 to about 3: 1, in each case based on the anhydrous calculated active substances, may be particularly advantageous.
  • the water content of the builder additives used according to the invention is preferably from 4 to 20% by weight, the upper meaningful value is made dependent on the water content thereof, that the builder additive should be stable and free-flowing even after storage at elevated temperatures of for example 40 ° C and should not clump. It has been found that the lower value for the water content influences the dissolving behavior of the builder additive.
  • additives which contain from 5 to 15% by weight of water and in particular from 7 to 12% by weight of water.
  • the determination of the water content takes place at a temperature of 140 ° C and a duration of 4 hours.
  • the builder additives used according to the invention can be prepared by simply contacting the crystalline layered silicate of the formula (I) with an aqueous solution, preferably a concentrated aqueous solution of the (co) polymeric polycarboxylic acid and optionally subsequent drying to the desired water content.
  • an aqueous solution preferably a concentrated aqueous solution of the (co) polymeric polycarboxylic acid
  • Conventional mixing and granulating devices such as the ploughshare mixer from Lödige or a Schugi mixer or an Eirich mixer or a Lödige recycler CB 30 and other apparatus known to those skilled in the art, which allow in particular the jetting of a liquid onto a solid, are just as suitable as fluidized bed apparatus.
  • the polymer solution serves as an agglomeration aid.
  • the builder additives used according to the invention have only a slightly reduced starting alkalinity, but a significantly lower residual alkalinity than the pure crystalline layered silicate of the formula (I).
  • the residual alkalinity can be adjusted accordingly by the content of the additives of polymer acid.
  • the builder additive can therefore be used as a buffer substance in automatic dishwashing detergents.
  • the builder additives may contain high levels of (co) polymeric polycarboxylic acid, with amounts between 2 and 40% by weight being preferred and amounts between 5 and 30% by weight being particularly preferred, and amounts between 10 and 25% by weight being quite are particularly preferred.
  • the content of the builder additives on the crystalline layered silicates of the formula (I) is preferably 50 to 90% by weight, more preferably 60 to 90% by weight and most preferably 65 to 85% by weight.
  • the calcium binding capacity of the additives is preferably above 185 mg CaCO 3 / g.
  • the pH of a 0.1% strength by weight aqueous solution is preferably above 10, but below 20 ° C. of 12.
  • the bulk density of the additives used according to the invention varies according to the nature of its preparation and is usually in the range from above 400 to about 700 g / l. While pure crystalline layered silicate of the formula (I) such as SKS6® usually obtains very finely divided and also has high amounts of dust fractions, the builder additive used according to the invention is a coarse-grained powder to agglomerate / granules, which is finer when prepared in the fluidized bed and coarser, for example when made in a high speed mixer.
  • Coarser-grained additives have, for example, an average particle size (d50) of about 450 to 900 ⁇ m, while finer-particle additives have an average particle size (d50) of between about 280 and 330 ⁇ m. But even with the finely divided additives, the dust content is significantly lower than in the commercially available pure crystalline layered silicates of the formula (I), in particular as in SKS6®.
  • the content of the automatic dishwashing agents according to the invention in these builder additives can be varied within a wide range and depends both on the content of the dishwashing detergent formulation on crystalline layered silicates of the formula (I) and on the content of the selected builder additive in this crystalline layered silicate , Usual levels of the phosphate-containing automatic dishwashing agents on these builder additives are about 2 to 40 wt .-%, with contents of 5 to 35 wt .-% and in particular to 30 wt .-% are preferred.
  • the automatic dishwashing compositions according to the invention may contain, in addition to the ingredients used according to the invention, in principle all known ingredients customary in such agents.
  • the agents according to the invention may in particular be further builders, surface-active surfactants, bleaches based on organic and / or in particular inorganic peroxygen compounds, bleach activators, enzymes, sequestering agents, electrolytes, pH regulators and / or further auxiliaries, for example silver corrosion inhibitors, foam regulators and dyes and fragrances contain.
  • conventional disintegrating agents can be used in conventional amounts.
  • the automatic dishwasher detergents according to the invention may also contain one or more further builder substances from the group consisting of carbonates, bicarbonates, amorphous silicates, crystalline layered silicates, which have not been introduced via the additive, and the polyfunctional carboxylic acids or their Salts, especially citric acid or citrate.
  • the compositions do not contain any crystalline layered silicates of the formula (I) which have not been incorporated into the formulation via the builder additive.
  • the agents may additionally contain further (co) polymeric polycarboxylates of the conventional type, which are likewise water-soluble and which can serve as co-builders, in particular under hard water conditions.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids may be considered.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • polystyrene resin polystyrene resin
  • POC QUAL AS 2507® Degussa
  • Norasole® such as Norasol LMW 45N®, Norasol SP 02N® or Norasol 470 N® (Rohm & Haas) or Alcosperse 175 N® (Alco).
  • suitable co-builder polymers of native origin include oxidized starch, for example as disclosed in international patent application WO 94/05762 and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxy-succinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • Preferred organic builder components include the salts of citric acid, especially sodium citrate.
  • sodium citrate anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the said co-builder salts may also be present.
  • the automatic dishwasher detergents according to the invention preferably contain not more than 2% by weight of this (co) polymeric polycarboxylates additionally and not via the builder additive; in particular, the agents are even free of such (co) polymeric polycarboxylates introduced additionally and not via the builder additive.
  • the agents according to the invention may contain their sodium and / or potassium salts, for example in an amount of from 10 to 40% by weight, preferably from 15 to 30% by weight, based on the total agent.
  • these alkali carriers are preferably in amounts of less than 4% by weight, in particular less than 2% by weight in the mechanical Dishwashing agents contain, with particularly preferred means advantageously free of amorphous silicates, are also free of metasilicates.
  • Suitable peroxygen compounds are, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing or cleaning conditions, such as perborate, percarbonate and / or persilicate.
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
  • alkali metal percarbonate alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide.
  • a cleaning agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • typical oxygen bleaches are also the organic peracids.
  • organic peracids especially the excellent effective Phthalimidoperoxycapronsäure, but also all other known peracids are principally usable.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and from German patent applications DE 196
  • hydrophilic substituted acyl acetals known from the German patent application DE 196 16 769 and the acyllactams described in the German patent application DE 196 16 770 and the international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Such bleach activators are contained in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, based on the total agent.
  • the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleach catalysts.
  • Suitable transition metal compounds include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salene complexes known from German patent application DE 195 29 905 and their N-analogues known from German patent application DE 196 20 267, which are known from US Pat German Patent Application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl, the described in the German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium , Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium-ammine complexes known from German patent application DE 196 20 411, the manganese described in German patent application DE 44 16 438, Copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese complex known from European patent application EP 0
  • bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
  • a bleach-enhancing active ingredient combination which is obtainable by intimately mixing a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally a peroxygen-based oxidizing agent and inert carrier material is described, for example, in the earlier German patent application P 197 09 284.5 described.
  • chlorine-containing bleaching agents may in principle be present in the compositions according to the invention and the invention also includes chlorine-containing formulations, it is preferred to use exclusively chlorine-free bleaching agents.
  • Automatic dishwashing detergents according to the invention may contain corrosion inhibitors as ingredients for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing.
  • silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
  • organic redox-active compounds such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
  • salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed. These silver protectants may usually be present in amounts of up to about 5% by weight.
  • Enzymes which can be used in the compositions include those from the class of proteases, lipases, cutinases, amylases, pullulanases, oxidases and peroxidases, glucanases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem® , Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast ® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem® , Alcalase®, Esperase®, Savinase®, Dura
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
  • These optionally additionally used enzymes can also be adsorbed on carriers and / or embedded in encapsulating substances, as described, for example, in European patent EP 0 564 476 or in international patent application WO 94/23005, and / or embedded in encapsulating substances in order to protect them against premature inactivation.
  • dishwasher detergents according to the invention are preferably present in the dishwasher detergents according to the invention in amounts of up to 10% by weight, in particular from 0.05% by weight to 5% by weight, particularly preferably enzymes which are stabilized against oxidative degradation, for example from US Pat international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350.
  • Preferred proteases used in agents according to the invention include the enzymes known from international patent applications WO 91/02792, WO 92/21760 and WO 95/23221.
  • surfactants in particular low-foaming nonionic surfactants, optionally in admixture with anionic and / or zwitterionic surfactants, which serve to better remove greasy soilings, as wetting agents and optionally as granulating aids in the preparation of the cleaning agents, may also be added to the compositions according to the invention.
  • Their amount can be up to 10 wt .-%, in particular up to 5 wt .-% and is preferably in the range of 0.5 wt .-% to 3 wt .-%.
  • extremely low-foam compounds are used in particular in detergents for use in automatic dishwashing processes.
  • C 12 -C 18 -Alkylpolyethylenglykolpolypropylenglykolether with in each case to 8 moles of ethylene oxide and propylene oxide in the molecule.
  • you can also use other known low-foam nonionic surfactants such as C 12 -C 18 alkylpolyethylene glycol polybutylenglykolether with up to 8 moles of ethylene oxide and butylene oxide in the molecule, end phenomenonver importancee Alkylpolyalkylenglykolmischether and foaming, but ecologically attractive C 8 -C 14 -Alkylpolyglucoside having a degree of polymerization of about 1 to 4 (eg APG® 225 and APG® 500 from Henkel) and / or C 12 -C 14 alkyl polyethylene glycols having 3 to 8 ethylene oxide units in the molecule.
  • surfactants from the family of glucamides such as, for example, alkyl-N-methylglucamides, in which the alkyl moiety preferably originates from a fatty alcohol with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol alkoxylates or glucamide with alkyl polyglycosides. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in EP-A-0300305. It was found that these hydroxy mixed ether surfactants show an excellent clear rinse effect.
  • nonionic surfactants such as fatty alcohol alkoxylates, for example Dehypon LS 54®, and also in mixtures with Dehydol LS 4®, but also for mixtures of hydroxy mixed ether and APG® or for mixtures of fatty alcohol ethoxylates, hydroxy mixed ethers and alkyl polyglycoside.
  • these surfactant mixtures also contribute to the fact that the stress corrosion cracking of plastic is significantly reduced.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the suifat type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and ⁇ -sulfofatty acid esters formed in the sulfonation of fatty acid methyl or ethyl esters.
  • the cleaning agents may still contain up to 6% by weight, preferably approximately 0.5 wt .-% to 4 wt .-% of a foam-pressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettklareamide, and other further known in the Commercially available defoamers are added.
  • a foam-pressing compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettklareamide, and other further known in the Commercially available defoamers are added.
  • Further optional ingredients in the compositions according to the invention are, for example, perfume oils.
  • the automatic dishwasher detergents according to the invention are in solid form. They may be pulverulent to granular or may be in the form of a shaped body, in particular a tablet. They can be prepared conventionally, for example by mixing, granulating, compacting, such as roll compacting, tabletting and / or spray-drying. In some cases, the ingredients can also be used in precompounded form for the preparation of automatic dishwashing detergents according to the invention.
  • the tablets may be single-phase or multiphase, monochrome or multicolor and in particular consist of one or more layers, in particular two layers, as are already commercially available.
  • the builder additive may be present in multilayer tablets either only in one layer, but also distributed over several to all layers.
  • the procedure is preferably such that all components - optionally one layer - mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with compressive forces in the range of about 50 to 100 kN , preferably compressed at 60 to 70 kN.
  • conventional tablet presses such as eccentric or rotary presses
  • compressive forces in the range of about 50 to 100 kN , preferably compressed at 60 to 70 kN.
  • at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant and yet sufficiently rapidly soluble tablets under application conditions with breaking and bending strengths of normally 100 to 200 N, but preferably above 150 N.
  • a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g up to 30 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of square / cuboid-shaped tablets, which are introduced predominantly via the metering device in the dishwasher depends on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments currently have a footprint of (20 to 30 mm) x (34 to 40 mm), in particular 26 x 36 mm or 24 x 38 mm.
  • the preparation of machine dishwashing detergents in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 750 to 1200 g / l is characterized in that in a first process step, the builder components with at least a proportion of liquid mixture components Increase the bulk density of this premix and subsequently - if desired after an intermediate drying - the other components of the machine dishwashing detergent combined with the thus obtained premix.
  • the addition of the agents according to the invention is carried out either by hand or - as already indicated above - by means of suitable metering devices.
  • the application concentrations in the main cleaning cycle are preferably about 2 to 8 g / l, preferably 2 to 5 g / l.
  • the rinsing program is generally supplemented and terminated by an intermediate rinse with clear water following the cleaning cycle and a rinse cycle, if appropriate with a common rinse aid. After drying, a completely clean, freed from tea and other soiling residues and hygienically perfect dishes. Even after very many rinses, the advantages are significantly recognizable by the use of the agents according to the invention, such as improved glass protection or decorative protection.
  • the automatic dishwashing compositions according to the invention not only show a very good cleaning performance on tea stains;
  • automatic dishwashing detergents with comparable compositions containing phosphates and crystalline layered silicates of the formula (I), but the latter as a powder and not in the form of the builder additive used in the invention, significant improvements in the removal of proteinaceous soils and soils caused by dairy products achieved.
  • Production-technical production of the powders, granules or tablets according to the invention took place without problems, in contrast to formulations which contained finely divided crystalline stratified silicate.
  • Dehypon LS 54® and Dehypon LT 104® are two low-foaming fatty alcohol alkoxylates from Henkel.
  • the terpolymer contained in the builder additive was prepared according to the disclosure of WO-A-94/15978 from 80% by weight of acrylic acid and maleic acid in a weight ratio of 7: 3 and from 20% by weight of vinyl acetate and then saponified in an acidic medium.
  • the terpolymer was purchased from Stockhausen.
  • Tables 2a and 2b clearly show the advantages of the tablet according to the invention TE1 compared to the comparative tablet TV1.
  • Powders of the compositions shown in Table 3 were prepared in a conventional manner, with PE1 to PE3 being the agents of the invention and PV1 being the comparison agent. The powders were tested for material protection and deposit formation. The effects of the powders PE1 to PE3 and PV1 on sensitive items were measured as in Example 1 at a dosage of 25 g to 51 water after 100 (PE1 to PE3 and PV1) and 300 rinsing cycles (only PE1 and PE2, compared to PV1 after 100 Rinsing cycles). The results are shown in Tables 4a and 4b.
  • Tables 4a and 4b clearly show the advantages of the formulations according to the invention PE1 and PE2 compared to PV1. Even with a high content of builder additive of 28.2% by weight in PE3 corresponding to an active substance content of crystalline layered disilicate of 20% by weight, similar values are obtained as for PV1 with 4% by weight of amorphous sodium disilicate , However, as Table 5 shows, PE3 also had significant advantages over PV1 when color loss was measured on decorated glass plates. For this purpose, in addition to the above-mentioned glasses, red-decorated glass plates of the "Arcopol" brand, "Bande rouge" decor were also tested under the same cleaning conditions. The color loss FV was determined after 50 or 150 rinsing cycles.
  • the comparative formulation PV2 Compared to phosphate-free formulations, the comparative formulation PV2 had clear advantages, in particular with minced meat, spinach and tea.
  • the formulation according to the invention improved these services in addition to egg and protein-containing stains and quite clearly to milk and stains of dairy products and oatmeal.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Claims (14)

  1. Produit de lavage solide pour lave-vaisselle, contenant des phosphates habituels, ainsi que d'autres constituants habituels, caractérisé en ce qu'il contient comme autre builder, outre les phosphates, un additif granulaire qui contient comme constituants essentiels un silicate lamellaire cristallin de formule générale (I)

            NaMSixO2x+1.y H2O     (I),

    dans laquelle M représente le sodium ou l'hydrogène, x représente un nombre entier allant de 1,9 à 22 et y représente un nombre allant de 0 à 33, et un acide polycarboxylique (co)polymère.
  2. Produit selon la revendication 1, caractérisé en ce qu'il contient un silicate lamellaire cristallin de formule (I), introduit par l'intermédiaire de l'additif builder, à des quantités de 2 à 30 % en poids au maximum, de préférence à des quantités de 3 à 25 % en poids et en particulier à des quantités de 4 à 20 % en poids.
  3. Produit selon la revendication 1 ou 2, caractérisé en ce qu'il contient des phosphates, en particulier des sels de tripolyphosphate, à des quantités, par rapport à l'ensemble de la composition et calculées sous forme de matière active anhydre, situées dans un intervalle allant de plus de 30 % en poids à 65 % en poids, et en particulier de 35 à 60 % en poids.
  4. Produit selon l'une des revendications 1 à 3, caractérisé en ce qu'il contient une ou plusieurs substances builders du groupe des carbonates, carbonates acides, silicates amorphes, silicates lamellaires cristallins, qui n'ont pas été introduits par l'intermédiaire de l'additif, acides carboxyliques polyfonctionnels respectivement leurs sels.
  5. Produit selon l'une des revendications 1 à 4, caractérisé en ce qu'il contient des silicates amorphes, en particulier des silicates de sodium amorphes avec un rapport pondéral Na2O : SiO2 de 1 : 1,8 à 1 : 3,3 à des quantités inférieures à 4 % en poids, de préférence inférieures à 2 % en poids, où l'on préfère en particulier les produits qui sont dépourvus de silicates amorphes.
  6. Produit selon l'une des revendications 1 à 5, caractérisé en ce qu'il se présente sous forme d'article moulé, en particulier sous forme de comprimé.
  7. Produit selon l'une des revendications 1 à 5, caractérisé en ce qu'il se présente sous forme pulvérulente à granulaire.
  8. Produit selon l'une des revendications 1 à 7, caractérisé en ce qu'il contient un additif builder à des quantités de 2 à 40 % en poids, de préférence à des quantités de 5 à 35 % en poids et en particulier à des quantités allant jusqu'à 30 % en poids.
  9. Produit selon l'une des revendications 1 à 8, caractérisé en ce qu'il contient un additif builder qui contient de 50 à 90 % en poids, de préférence de 60 à 90 % en poids et en particulier de 65 à 85 % en poids de silicate lamellaire cristallin de formule (1), de 2 à 40 % en poids, de préférence de 5 à 30 % en poids et en particulier de 10 à 25 % en poids d'acide polycarboxylique polymère et de 4 à 20 % en poids, de préférence de 5 à 15 % en poids et en particulier de 7 à 12 % en poids d'eau.
  10. Produit selon la revendication 9, caractérisé en ce que l'acide polycarboxylique (co)polymère dans l'additif builder présente une masse molaire de 1000 à 100 000 g/mol, de préférence de 2000 à 75 000 g/mol et en particulier de 2000 à 35 000 g/mol, le degré de neutralisation des groupes acides étant de 0 à 90 %, de préférence de 10 à 80% et en particulier de 30 à 70 %.
  11. Produit selon l'une des revendications 1 à 10, caractérisé en ce qu'il contient des agents de blanchiment à base d'hydrogène et/ou des agents de blanchiment à base de chlore ainsi que le cas échéant des activateurs de blanchiment et/ou des catalyseurs de blanchiment.
  12. Produit selon l'une des revendications 1 à 11, caractérisé en ce qu'il contient des agents tensioactifs, de préférence des agents tensioactifs non ioniques faiblement moussants.
  13. Produit selon la revendication 12, caractérisé en ce qu'il contient comme agents tensioactifs non ioniques des éthers d'(alkyle en C12 à C18)-polyéthylèneglycol-polypropylèneglycol avec à chaque fois jusqu'à 8 moles d'unités oxyde d'éthylène et oxyde de propylène dans la molécule, des éthers d'(alkyle en C12 à C18)-polyéthylèneglycol-poybutylèneglycol avec à chaque fois jusqu'à 8 moles d'unités oxyde d'éthylène et oxyde de butylène dans la molécule, des éthers mixtes d'alkylpolyalkylène-glycol à groupes terminaux coiffés, des (alkyle en C8 à C14)-polyglucosides ayant un degré de polymérisation d'environ 1 à 4, des (alkyle en C12 à C14)-polyéthylèneglycols avec de 3 à 8 unités oxyde d'éthylène dans la molécule, des glucamides et/ou des hydroxyéthers mixtes.
  14. Produit selon la revendication 12 ou 13, caractérisé en ce qu'il contient des mélanges d'alcoxylates d'alcools gras et d'hydroxyéthers mixtes ou d'alkylpolyglycoside et d'hydroxyéthers mixtes ou d'éthoxylates d'alcools gras, d'hydroxyéthers mixtes et d'alkylpolyglycoside.
EP99922118A 1998-04-30 1999-04-21 Produit solide pour lave-vaisselle, a base de phosphate et de silicates lamellaires cristallins Expired - Lifetime EP1076683B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19819187 1998-04-30
DE19819187A DE19819187A1 (de) 1998-04-30 1998-04-30 Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
PCT/EP1999/002679 WO1999057237A1 (fr) 1998-04-30 1999-04-21 Produit solide pour lave-vaisselle, a base de phosphate et de silicates lamellaires cristallins

Publications (2)

Publication Number Publication Date
EP1076683A1 EP1076683A1 (fr) 2001-02-21
EP1076683B1 true EP1076683B1 (fr) 2006-06-14

Family

ID=7866196

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99922118A Expired - Lifetime EP1076683B1 (fr) 1998-04-30 1999-04-21 Produit solide pour lave-vaisselle, a base de phosphate et de silicates lamellaires cristallins

Country Status (7)

Country Link
US (1) US6462006B1 (fr)
EP (1) EP1076683B1 (fr)
JP (1) JP2003521553A (fr)
AT (1) ATE329994T1 (fr)
DE (2) DE19819187A1 (fr)
ES (1) ES2267267T3 (fr)
WO (1) WO1999057237A1 (fr)

Families Citing this family (176)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19824705A1 (de) 1998-06-03 1999-12-09 Henkel Kgaa Amylase und Protease enthaltende Wasch- und Reinigungsmittel
AU3290300A (en) * 1999-03-25 2000-10-16 Henkel Kommanditgesellschaft Auf Aktien Tablet containing a builder
DE19914811A1 (de) 1999-03-31 2000-10-05 Henkel Kgaa Enzym- und bleichaktivatorhaltige Wasch- und Reinigungsmittel
DE19962859A1 (de) * 1999-12-24 2001-07-12 Cognis Deutschland Gmbh Feste Waschmittel
DE19962885A1 (de) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften
DE19962883A1 (de) * 1999-12-24 2001-07-12 Cognis Deutschland Gmbh Waschmitteltabletten
DE19962886A1 (de) 1999-12-24 2001-07-05 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
US7072945B1 (en) * 2000-06-30 2006-07-04 Nokia Corporation Network and method for controlling appliances
DE10038845A1 (de) * 2000-08-04 2002-02-21 Henkel Kgaa Teilchenförmig konfektionierte Acetonitril-Derivate als Bleichaktivatoren in festen Waschmitteln
DE10101671A1 (de) * 2000-08-25 2002-03-14 Bayer Ag Verfahren zur Konditionierung stehender und fließender Wassersysteme
DE10153553A1 (de) 2001-07-07 2003-06-12 Henkel Kgaa Nichtwäßrige "3in1"-Geschirrspülmittel II
AU2002331215A1 (en) 2001-08-17 2003-03-03 Henkel Kommanditgesellschaft Auf Aktien Dishwasher detergent with improved protection against glass corrosion
DE10225116A1 (de) * 2002-06-06 2003-12-24 Henkel Kgaa Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz II
US20050113271A1 (en) * 2002-06-06 2005-05-26 Ulrich Pegelow Automatic dishwashing detergent with improved glass anti-corrosion properties II
DE10334047A1 (de) * 2003-07-25 2005-02-24 Clariant Gmbh Adsorbat aus Schichtsilicat und seine Verwendung
US7271138B2 (en) * 2003-10-16 2007-09-18 The Procter & Gamble Company Compositions for protecting glassware from surface corrosion in automatic dishwashing appliances
DE102004003286A1 (de) * 2004-01-22 2005-09-29 Henkel Kgaa System zur Wasserenthärtung durch Fällenthärtung
KR101329837B1 (ko) * 2005-05-04 2013-11-14 디버세이, 인크 낮은 수준의 계면활성제를 함유하는 식기세척 시스템
DE102005039580A1 (de) 2005-08-19 2007-02-22 Henkel Kgaa Farbschützendes Waschmittel
WO2007134614A1 (fr) * 2006-05-18 2007-11-29 Henkel Ag & Co. Kgaa Lessive protégeant les couleurs
DE102008000029A1 (de) 2008-01-10 2009-07-16 Lanxess Deutschland Gmbh Geschirrreinigungsmittel
DE102007003885A1 (de) 2007-01-19 2008-07-24 Lanxess Deutschland Gmbh Geschirrreinigungsmittel
DE102007016391A1 (de) 2007-04-03 2008-10-09 Henkel Ag & Co. Kgaa Farbschützendes Wasch- oder Reinigungsmittel
DE102007019457A1 (de) * 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
EP2014757A1 (fr) 2007-07-05 2009-01-14 JohnsonDiversey, Inc. Produit de rinçage
WO2009050123A2 (fr) 2007-10-12 2009-04-23 Basf Se Formulations de détergents pour la vaisselle, contenant un mélange de polycarboxylates à modification hydrophobe et de polycarboxylates à modification hydrophile
CN102300972A (zh) * 2008-12-02 2011-12-28 迪瓦西公司 包含阳离子淀粉的餐具洗涤系统
US9670435B2 (en) 2010-11-23 2017-06-06 Basf Se Copolymers comprising carboxylic acid groups, sulfo groups and polyalkylene oxide groups as a scale-inhibiting additive to washing and cleaning products
WO2012069440A1 (fr) 2010-11-23 2012-05-31 Basf Se Copolymères, qui contiennent des groupes acide carboxylique, des groupes acide sulfonique et des groupes poly(oxyde d'alkylène), en tant qu'additif anti-dépôt à des agents de lavage et de rinçage
BR112013012623B1 (pt) 2010-11-23 2020-06-16 Basf Se Formulação detergente para lavagem de louça em máquina e uso de um copolímero
WO2012098177A1 (fr) 2011-01-21 2012-07-26 Basf Se Utilisation d'alcooléthoxylates de suif en lavage en lave-vaisselle
CN103890158B (zh) 2011-10-19 2018-06-26 巴斯夫欧洲公司 配制剂、其制备方法及其用作或用于制备洗碟洗涤剂的用途
US8709990B2 (en) 2011-10-19 2014-04-29 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
PL2768935T3 (pl) 2011-10-19 2018-04-30 Basf Se Preparaty, ich zastosowanie jako środków do zmywania naczyń lub do wytwarzania środków do zmywania naczyń i ich wytwarzanie
RU2607085C2 (ru) 2011-10-19 2017-01-10 Басф Се Составы, их применение в качестве или для приготовления средств для мытья посуды и получение составов
US8840731B2 (en) 2011-12-09 2014-09-23 Basf Se Preparations, their production and use
CA2850127A1 (fr) 2011-12-09 2013-06-13 Basf Se Utilisation de preparations pour lavage en lave-vaisselle
US8846593B2 (en) 2012-04-25 2014-09-30 Basf Se Dishwashing composition comprising a covalently modified alkyleneimine polymer
BR112014026564A2 (pt) 2012-04-25 2017-06-27 Basf Se formulação, uso de uma formulação, e, processo para a preparação de uma formulação
WO2013160132A1 (fr) 2012-04-25 2013-10-31 Basf Se Formulations solides et production et utilisation desdites formulations
US9732309B2 (en) 2012-04-25 2017-08-15 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
JP6133971B2 (ja) 2012-04-25 2017-05-24 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 配合物、食器洗い洗剤としての又は食器洗い洗剤を製造するためのそれらの使用方法、及びそれらの製造
WO2014173473A1 (fr) 2013-04-23 2014-10-30 Basf Se Formulations, utilisation desdites formulations en tant que liquide vaisselle ou pour la production de liquide vaisselle et production desdites formulations
WO2014005933A1 (fr) 2012-07-06 2014-01-09 Basf Se Formulations et leur utilisation pour nettoyer des surfaces vitrées d'immeubles
US10179891B2 (en) 2012-07-25 2019-01-15 Basf Se Use of branched polyesters based on citric acid as additive in washing compositions, detergents or a formulation for water treatment
KR102041092B1 (ko) 2012-07-25 2019-11-06 바스프 에스이 주방 세제, 세정제, 세제 또는 물 처리용 제형 중의 첨가제로서 시트르산 기재의 분지형 폴리에스테르의 용도
WO2014037255A1 (fr) 2012-09-07 2014-03-13 Basf Se Particules, procédé de fabrication et utilisation
PL2961822T3 (pl) 2013-02-28 2017-09-29 Basf Se Preparaty, ich zastosowanie jako środków do zmywania naczyń lub do wytwarzania środków do zmywania naczyń i ich wytwarzanie
RU2649393C2 (ru) 2013-02-28 2018-04-03 Басф Се Применение алкоксилированного полипропиленимина для ухода за бельем для стирки и композиция на его основе
EP2981600B1 (fr) 2013-04-02 2018-03-21 Basf Se Formules, leur utilisation comme détergent pour lave-vaisselle et leur fabrication
CN105531255B (zh) 2013-09-13 2018-01-02 巴斯夫欧洲公司 对映体混合物以及生产该混合物的方法
ES2851207T3 (es) 2013-09-16 2021-09-03 Basf Se Uso de ácidos poliaspárticos modificados en detergentes
KR20160058139A (ko) 2013-09-16 2016-05-24 바스프 에스이 폴리아스파르트산의 제조 방법
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
US9127236B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid terpolymer for hard water scale control
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
DE102013019269A1 (de) * 2013-11-15 2015-06-03 Weylchem Switzerland Ag Geschirrspülmittel sowie dessen Verwendung
EP3105309B1 (fr) 2014-02-13 2019-04-10 Basf Se Poudre et granulé, procédé de fabrication d'une telle poudre et granulés et leur utilisation
PL3157901T3 (pl) 2014-06-23 2018-08-31 Basf Se Preparaty, ich wytwarzanie i zastosowanie, oraz odpowiednie składniki
MX2017004987A (es) 2014-10-17 2017-07-19 Basf Se Recipiente que comprende una composicion detergente que contiene mgda.
ES2748009T3 (es) 2014-10-17 2020-03-12 Basf Se Soluciones de sales de metal trialcalino de ácidos aminocarboxílicos, su fabricación y uso
JP6907115B2 (ja) 2014-12-12 2021-07-21 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ 予備縮合物を用いてポリアスパラギン酸を製造する方法
ES2731284T3 (es) 2015-02-25 2019-11-14 Basf Se Procedimiento para limpiar superficies de metal ensuciadas y sustancias útiles para tal procedimiento
WO2016142220A1 (fr) 2015-03-11 2016-09-15 Basf Se Mélanges d'agents chélatants, et procédé de fabrication de tels mélanges
US10619125B2 (en) 2015-03-12 2020-04-14 Basf Se Process for making mixtures of enantiomers of MGDA and GLDA
CN107592858A (zh) 2015-05-13 2018-01-16 巴斯夫欧洲公司 制备螯合剂混合物的方法
EP3138895B1 (fr) 2015-09-02 2018-10-17 Basf Se Particules, leur utilisation comme detergent pour lave-vaisselle et leur fabrication
WO2017102483A1 (fr) 2015-12-17 2017-06-22 Basf Se Procédé de fabrication d'un sel de métal alcalin cristallin d'un agent complexant, et agent complexant cristallin
EP3216781A1 (fr) 2016-03-09 2017-09-13 Basf Se Mélanges contenant des sels de potassium d'acide de méthyl glycine diacétique
WO2017167599A1 (fr) 2016-03-30 2017-10-05 Basf Se Concentrés, procédés de fabrication et utilisations
US10676700B2 (en) 2016-04-06 2020-06-09 Basf Se Mixtures of chelating agents, and process for making such mixtures
CN109072134B (zh) 2016-04-27 2021-05-07 巴斯夫欧洲公司 配制剂、其制备和用途及合适的组分
MX2018016289A (es) 2016-06-20 2019-09-16 Basf Se Polvos y granulos, y proceso para preparar tales polvos y granulos.
EP3266859A1 (fr) 2016-07-05 2018-01-10 Basf Se Composition appropriée comme agent d'élimination de dégraissage et/ou de dépôts de type huile grasse
EP3266858A1 (fr) 2016-07-05 2018-01-10 Basf Se Agent anti-grisâtre
RU2744632C2 (ru) 2016-07-15 2021-03-12 Басф Се Способ получения гранул, содержащих mgda и glda, гранулы и их применение
WO2018077649A1 (fr) 2016-10-26 2018-05-03 Basf Se Compositions détergentes sans phosphate et leurs applications
CN109863236A (zh) 2016-11-08 2019-06-07 巴斯夫欧洲公司 适合作为表面活性剂的组合物
ES2839948T3 (es) 2016-11-17 2021-07-06 Basf Se Formulaciones, su preparación y uso
WO2018109200A1 (fr) 2016-12-16 2018-06-21 Basf Se Feuilles multicouches, leur procédé de fabrication et leur utilisation
BR112019017127A2 (pt) 2017-02-24 2020-04-14 Basf Se processo para produção de sal de metal alcalino de diacetato de metilglicina sólido, partículas sólidas de sal de metal alcalino de diacetato de metilglici-na, e, uso de partículas sólidas
CN110582558B (zh) 2017-04-27 2021-10-26 巴斯夫欧洲公司 包含含有mgda和glda的盐的洗涤剂组合物的容器
ES2962909T3 (es) 2017-05-12 2024-03-21 Unilever Ip Holdings B V Composición detergente para lavavajillas automático
CN111465680A (zh) 2017-11-29 2020-07-28 巴斯夫欧洲公司 组合物、其制备和用途
WO2019197315A1 (fr) 2018-04-13 2019-10-17 Basf Se Procédé pour le nettoyage de vaisselle
US20210155754A1 (en) 2018-04-19 2021-05-27 Basf Se Compositions and polymers useful for such compositions
PL3788125T3 (pl) 2018-05-02 2024-07-22 Basf Se Preparaty detergentowe do zmywania naczyń zawierające poli(kwas asparaginowy) i polimery szczepione na bazie oligo- i polisacharydów jako dodatki hamujące powstawanie nalotu
WO2019211170A1 (fr) 2018-05-04 2019-11-07 Basf Se Granules ou poudres et procédés de fabrication associés
WO2019214968A1 (fr) 2018-05-11 2019-11-14 Basf Se Composition détergente comprenant des rhamnolipides et/ou des lipides de mannosylérythritol
EP3802767A1 (fr) 2018-06-06 2021-04-14 Basf Se Formulations, leur préparation et leur utilisation et constituants appropriés
WO2020030623A1 (fr) 2018-08-10 2020-02-13 Basf Se Unité d'emballage comprenant une composition détergente contenant une enzyme et au moins un agent chélatant
EP3837340A1 (fr) 2018-08-16 2021-06-23 Basf Se Films polymères hydrosolubles d'homopolymères ou de copolymères d'oxyde d'éthylène, procédé de calandrage pour leur production et leur utilisation
CN112771143A (zh) 2018-09-27 2021-05-07 巴斯夫欧洲公司 制备颗粒或粉末的方法
BR112021005412A2 (pt) 2018-10-05 2021-06-15 Basf Se preparação de enzima, processo para fabricar uma preparação de enzima estável, métodos para reduzir a perda da atividade proteolítica, para preparação de uma formulação detergente, para remover manchas e para aumentar a estabilidade na armazenagem de uma formulação detergente líquida, usos de um composto e da preparação de enzima, e, formulação detergente
WO2020069914A1 (fr) 2018-10-05 2020-04-09 Basf Se Composés stabilisant les amylases dans des liquides
EP3677676A1 (fr) 2019-01-03 2020-07-08 Basf Se Composés de stabilisation d'amylases dans des liquides
BR112021005954A2 (pt) 2018-10-05 2021-06-29 Basf Se preparação enzimática, processo para produzir uma preparação enzimática estável, métodos para reduzir perda de atividade lipolítica de pelo menos uma lipase, para preparar uma formulação de detergente, para remover manchas e para aumentar a estabilidade de armazenagem de uma formulação de detergente líquido, usos de um composto e da preparação enzimática, e, formulação de detergente.
US11920110B2 (en) 2018-10-22 2024-03-05 Dow Global Technologies Llc Automatic dishwashing composition with dispersant polymer
WO2020094480A1 (fr) 2018-11-07 2020-05-14 Basf Se Procédé de fabrication de granulés, granulés et leur utilisation
WO2020104231A1 (fr) 2018-11-19 2020-05-28 Basf Se Poudres et granulés contenant un agent chélatant et une enzyme
CN113227341A (zh) 2018-12-19 2021-08-06 巴斯夫欧洲公司 包含聚乙二醇接枝共聚物和芳香化学品的成型体
CN113544246A (zh) 2019-03-08 2021-10-22 巴斯夫欧洲公司 阳离子表面活性剂及其在洗衣用洗涤剂组合物中的用途
EP3947622B1 (fr) 2019-04-01 2023-03-15 Basf Se Procédé de fabrication d'un granulé ou d'une poudre
PL3822335T3 (pl) 2019-11-15 2023-03-13 Basf Se Kompozycje czyszczące i ich zastosowanie
WO2021105336A1 (fr) 2019-11-29 2021-06-03 Basf Se Compositions comprenant un polymère et une enzyme
MX2022007214A (es) 2019-12-11 2022-07-12 Basf Se Granulos de mgda y homopolimero o copolimero de acido (met)acrilico; proceso para elaborarlos.
CN114846127A (zh) 2019-12-18 2022-08-02 巴斯夫欧洲公司 粉末和颗粒以及制备该粉末和颗粒的方法
WO2021165144A1 (fr) 2020-02-20 2021-08-26 Basf Se Procédé de fabrication de sels de métaux alcalins de diacétate de méthylglycine solide
US20230109638A1 (en) 2020-02-28 2023-04-06 Basf Se Automatic dishwashing composition comprising at least one imidazole-based compound
US20230143616A1 (en) 2020-03-17 2023-05-11 Basf Se Process for making a granule
WO2021191175A1 (fr) 2020-03-24 2021-09-30 Basf Se Formulation d'un détergent sous la forme d'un corps tridimensionnel
US12163110B2 (en) 2020-05-29 2024-12-10 Basf Se Amphoterically-modified oligopropyleneimine ethoxylates for improved stain removal of laundry detergents
JP2023529990A (ja) 2020-06-17 2023-07-12 ビーエーエスエフ ソシエタス・ヨーロピア 複数の利益をもたらす洗浄剤配合物のための両親媒性アルコキシル化ポリエチレン／－プロピレンイミンコポリマー
US20230235250A1 (en) 2020-06-18 2023-07-27 Basf Se Compositions and Their Use
WO2021089888A1 (fr) 2020-07-02 2021-05-14 Basf Se Compositions comprenant un additif non ionique et un tensioactif de rinçage non ionique et leur utilisation pour réduire le dépôt de graisse sur une surface
BR112022026756A2 (pt) 2020-07-02 2023-01-24 Basf Se Composto, processo para preparar composto de fórmula geral e para limpar louça em uma máquina de lavar louça automática, uso de um composto ou de uma combinação de pelo menos dois compostos, e, composição de limpeza
CN115485360A (zh) 2020-07-09 2022-12-16 巴斯夫欧洲公司 组合物及其应用
WO2022083949A1 (fr) 2020-10-20 2022-04-28 Basf Se Compositions et leur utilisation
EP4012010A1 (fr) 2020-12-10 2022-06-15 Basf Se Compositions et leur utilisation dans l'eau chlorée
EP4263777A1 (fr) 2020-12-15 2023-10-25 Basf Se Polymères biodégradables
CN116323751A (zh) 2020-12-23 2023-06-23 巴斯夫欧洲公司 两亲性烷氧基化聚烯亚胺或烷氧基化聚胺
US20240110009A1 (en) 2020-12-23 2024-04-04 Basf Se New alkoxylated polyalkylene imines or alkoxylated polyamines
EP4301504A1 (fr) 2021-03-04 2024-01-10 Basf Se Procédé de fabrication d'un sel organique revêtu de particules, et sel revêtu de particules
MX2023013280A (es) 2021-05-10 2023-11-30 Basf Se Eter sulfatos basados en mezclas isomericas de tridecil alcohol.
WO2022263354A1 (fr) 2021-06-18 2022-12-22 Basf Se Polymères greffés biodégradables
US20240352383A1 (en) 2021-08-12 2024-10-24 Basf Se Biodegradable graft polymers
WO2023017061A1 (fr) 2021-08-12 2023-02-16 Basf Se Polymères greffés biodégradables pour inhibition de transfert de colorant
CN117836337A (zh) 2021-08-12 2024-04-05 巴斯夫欧洲公司 可生物降解的接枝聚合物
EP4134420A1 (fr) 2021-08-12 2023-02-15 The Procter & Gamble Company Composition détergente comprenant un tensioactif détergent et des polymères greffés biodégradables
EP4134421A1 (fr) 2021-08-12 2023-02-15 The Procter & Gamble Company Composition détergente comprenant un tensioactif détergent et un polymère greffé
JP2024531324A (ja) 2021-08-19 2024-08-29 ビーエーエスエフ ソシエタス・ヨーロピア 修飾アルコキシル化ポリアルキレンイミン又は修飾アルコキシル化ポリアミン
MX2024002156A (es) 2021-08-19 2024-03-08 Basf Se Polialquileniminas alcoxiladas modificadas y poliaminas alcoxiladas modificadas que se pueden obtener mediante un proceso que comprende las etapas a) a d).
WO2023021101A1 (fr) 2021-08-19 2023-02-23 Basf Se Polyalkylène-imines alcoxylées modifiées
EP4388031A1 (fr) 2021-08-19 2024-06-26 Basf Se Oligoalkylèneimines alcoxylées modifiées et oligoamines alcoxylées modifiées
WO2023025637A1 (fr) 2021-08-25 2023-03-02 Basf Se Procédé de fabrication d'un granulé ou d'une poudre contenant un agent complexant
US20240400945A1 (en) 2021-10-13 2024-12-05 Basf Se Compositions comprising polymers, polymers, and their use
WO2023066741A1 (fr) 2021-10-20 2023-04-27 Basf Se Composition sans phosphate et leurs procédés de fabrication et leur utilisation
WO2023088777A1 (fr) 2021-11-22 2023-05-25 Basf Se Compositions comprenant des polymères, polymères et leur utilisation
CN118284680A (zh) 2021-11-22 2024-07-02 巴斯夫欧洲公司 包含聚合物的组合物、聚合物及其用途
MX2024006197A (es) 2021-11-22 2024-06-11 Basf Se Composiciones que comprenden polimeros, polimeros y su uso.
WO2023094275A1 (fr) 2021-11-29 2023-06-01 Basf Se Trialkylènes tétramines éthoxylates à modification amphotérique pour l'élimination améliorée des taches par des détergents de blanchisserie
EP4448705A2 (fr) 2021-12-17 2024-10-23 Basf Se Compositions et applications associées
WO2023110611A1 (fr) 2021-12-17 2023-06-22 Basf Se Procédé de fabrication de granulés et de poudres
MX2024007601A (es) 2021-12-20 2024-07-09 Basf Se Polimeros de polipropilenimina (ppi), su preparacion, usos, y composiciones que comprenden dichos ppi.
JP2025505571A (ja) 2022-02-04 2025-02-28 ビーエーエスエフ ソシエタス・ヨーロピア ポリマーを含む組成物、ポリマー及びそれらの使用
WO2023186679A1 (fr) 2022-03-30 2023-10-05 Basf Se Procédé de fabrication de solutions aqueuses contenant un agent complexant à haute concentration
EP4508176A1 (fr) 2022-04-14 2025-02-19 Basf Se Compositions, leur fabrication et leur utilisation
EP4526419A1 (fr) 2022-05-20 2025-03-26 Basf Se Procédé de fabrication d'une poudre ou d'un granulé comprenant au moins un agent chélatant
WO2024017797A1 (fr) 2022-07-21 2024-01-25 Basf Se Polymères greffés biodégradables utiles pour inhiber le transfert des couleurs
WO2024042005A1 (fr) 2022-08-22 2024-02-29 Basf Se Procédé de production d'esteramines sulfatées
WO2024046786A1 (fr) 2022-08-29 2024-03-07 Basf Se Procédé de préparation d'une composition solide comprenant au moins un agent complexant aminocarboxylate
EP4349949A1 (fr) 2022-10-05 2024-04-10 Basf Se Procédé de préparation d'un sel solide de métal alcalin d'un agent complexant aminocarboxylate
WO2024083589A1 (fr) 2022-10-18 2024-04-25 Basf Se Compositions détergentes, polymères et leurs procédés de fabrication
WO2024115754A1 (fr) 2022-12-02 2024-06-06 Basf Se Compositions aqueuses contenant des polyalcoxylates, polyalcoxylates et leur utilisation
WO2024126268A1 (fr) 2022-12-12 2024-06-20 Basf Se Polymères greffés biodégradables pour inhibition de transfert de colorant
WO2024126267A1 (fr) 2022-12-12 2024-06-20 Basf Se Polymères greffés biodégradables
WO2024126270A1 (fr) 2022-12-12 2024-06-20 Basf Se Polymères greffés biodégradables en tant qu'inhibiteurs de transfert de colorant
DE102023135175A1 (de) 2022-12-16 2024-06-27 Basf Se Verfahren zur Herstellung von Aminosäureestern und organischen Sulfonsäuresalzen sowie Aminosäureestern und deren Salzen
EP4389801A1 (fr) 2022-12-20 2024-06-26 Basf Se Procédé de fabrication d'un granulé
EP4389863A1 (fr) 2022-12-20 2024-06-26 Basf Se Procédé de fabrication d'une poudre ou d'un granulé
WO2024132623A1 (fr) 2022-12-20 2024-06-27 Basf Se Procédé de fabrication d'une poudre ou d'un granulé contenant un agent chélatant
WO2024132413A1 (fr) 2022-12-20 2024-06-27 Basf Se Procédé de fourniture d'une composition comprenant au moins un agent complexant aminocarboxylate
WO2024175407A1 (fr) 2023-02-21 2024-08-29 Basf Se Polyalkylène imines alcoxylées modifiées ou polyamines alcoxylées modifiées
WO2024175409A1 (fr) 2023-02-21 2024-08-29 Basf Se Polyalkylène imines alcoxylées hyper-ramifiées modifiées
WO2024175401A1 (fr) 2023-02-21 2024-08-29 Basf Se Polyalkylène imines alcoxylées modifiées ou polyamines alcoxylées modifiées
EP4428217A1 (fr) 2023-03-07 2024-09-11 Basf Se Copolymères greffés pour l'inhibition de la corrosion dans un procédé de lavage automatique de la vaisselle
WO2024188713A1 (fr) 2023-03-13 2024-09-19 Basf Se Polymères contenant de l'azote alcoxylé et leur utilisation
WO2024200177A1 (fr) 2023-03-24 2024-10-03 Basf Se Procédé de préparation d'esters d'acides aminés en tant que sels de sulfate d'organoéther à partir d'alcools alcoxylés
WO2024213626A1 (fr) 2023-04-12 2024-10-17 Basf Se Acétate de vinyle à faible teneur en deutérium
WO2024213450A1 (fr) 2023-04-14 2024-10-17 Basf Se Procédé de fabrication de particules solides comprenant au moins un agent complexant aminocarboxylate
WO2024231110A1 (fr) 2023-05-05 2024-11-14 Basf Se Propoxylates de polyol biodégradables, leur préparation, utilisations et compositions les comprenant
WO2024235718A1 (fr) 2023-05-16 2024-11-21 Basf Se Polymères, compositions aqueuses comprenant de tels polymères, et utilisation en tant que détergents pour lessive
WO2024240517A1 (fr) 2023-05-22 2024-11-28 Basf Se Composition solide comprenant au moins un composé chimique organique et au moins un oxyde céramique
WO2024240520A1 (fr) 2023-05-23 2024-11-28 Basf Se Polymères, compositions aqueuses comprenant de tels polymères, et utilisation en tant que détergents de blanchisserie
WO2024256175A1 (fr) 2023-06-13 2024-12-19 Basf Se Compositions de nettoyage stabilisées comprenant des edds et des enzymes et leur utilisation
WO2025051594A1 (fr) 2023-09-08 2025-03-13 Basf Se Utilisation de compositions contenant des tensioactifs non ioniques et compositions

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4404279A1 (de) * 1994-02-10 1995-08-17 Henkel Kgaa Tablette mit Buildersubstanzen

Family Cites Families (84)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL157021B (nl) 1973-11-15 1978-06-15 Degussa Werkwijze ter bereiding van polycarboxylaten met verbeterde biologische afbreekbaarheid.
EP0075820B1 (fr) 1981-09-28 1986-08-13 BASF Aktiengesellschaft Procédé de préparation de copolymères d'acides mono- et dicarboxyliques à insaturation oléfinique
US5175361A (en) 1981-09-28 1992-12-29 Basf Aktiengesellschaft Preparation of copolymers of monoethylenically unsaturated monocarboxylic acids and dicarboxylic acids
DE3545947A1 (de) * 1985-12-23 1987-07-02 Henkel Kgaa Phosphatfreies, granulares waschmittel
DE3624336A1 (de) 1986-07-18 1988-01-28 Henkel Kgaa Verfahren zur herstellung von rieselfaehigen alkalischen reinigungsmitteln durch kompaktierende granulation
DE3626672A1 (de) 1986-08-07 1988-02-11 Bayer Ag Polyasparaginamidsaeure
GB8629837D0 (en) 1986-12-13 1987-01-21 Interox Chemicals Ltd Bleach activation
DE3702968A1 (de) * 1987-02-02 1988-08-11 Henkel Kgaa Weichmachendes waschmittel
DE3723873A1 (de) 1987-07-18 1989-01-26 Henkel Kgaa Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung
GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
DK0493398T3 (da) 1989-08-25 2000-05-22 Henkel Research Corp Alkalisk, proteolytisk enzym og fremgangsmåde til fremstilling deraf
DE3929896A1 (de) * 1989-09-08 1991-03-14 Hoechst Ag Geschirrspuelmittel
DE4003172A1 (de) 1990-02-03 1991-08-08 Basf Ag Pfropfcopolymerisate von monosacchariden, oligosacchariden, polysacchariden und modifizierten polysacchariden, verfahren zu ihrer herstellung und ihre verwendung
GB9003741D0 (en) 1990-02-19 1990-04-18 Unilever Plc Bleach activation
US5041232A (en) 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
DE4008696A1 (de) 1990-03-17 1991-09-19 Basf Ag Verfahren zur herstellung von homo- und copolymerisaten monoethylenisch ungesaettigter dicarbonsaeuren und ihre verwendung
DE4009618A1 (de) * 1990-03-26 1991-10-02 Henkel Kgaa Spruehgetrocknetes, avivierend wirkendes waschmitteladditiv
DE69125309T2 (de) 1990-05-21 1997-07-03 Unilever Nv Bleichmittelaktivierung
DE4041752A1 (de) 1990-12-24 1992-06-25 Henkel Kgaa Enzymzubereitung fuer wasch- und reinigungsmittel
US5221733A (en) 1991-02-22 1993-06-22 Donlar Corporation Manufacture of polyaspartic acids
DK166548B1 (da) 1991-03-15 1993-06-07 Cleantabs As Phosphatfrit maskinopvaskemiddel
US5540855A (en) * 1991-04-23 1996-07-30 The Procter & Gamble Company Particulate detergent compositions
US5340735A (en) 1991-05-29 1994-08-23 Cognis, Inc. Bacillus lentus alkaline protease variants with increased stability
ATE155165T1 (de) 1991-07-31 1997-07-15 Ausimont Spa Verfahren zur erhöhung der bleichwirksamkeit eines inorganischen persalzes
DE4128672A1 (de) 1991-08-29 1993-03-04 Henkel Kgaa Verwendung von stark alkalischen mitteln zur verhinderung des anlaufens von silberbestecken in geschirrspuelmaschinen
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
CA2085642A1 (fr) 1991-12-20 1993-06-21 Ronald Hage Activation de blanchiment
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
DE4221381C1 (de) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4221875A1 (de) 1992-07-03 1994-01-05 Basf Ag Modifizierte Polyasparaginsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
ATE376061T1 (de) 1992-07-17 2007-11-15 Genencor Int Hochalkalische serinproteasen
ATE444356T1 (de) 1992-07-23 2009-10-15 Novozymes As Mutierte -g(a)-amylase, waschmittel und geschirrspülmittel
DE4228786A1 (de) 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
DE4300772C2 (de) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
AU6086494A (en) 1993-01-18 1994-08-15 Procter & Gamble Company, The Detergent compositions
NZ262623A (en) * 1993-02-11 1998-03-25 Genencor Int Alpha-amylase mutant, dna and vectors encoding such and detergent compositions thereof
EP0612784B1 (fr) 1993-02-22 1998-11-11 Bayer Ag Procédé de préparation du polysuccinimide et de l'acide polyaspartique
DE4307114A1 (de) 1993-03-06 1994-09-08 Basf Ag Verfahren zur Herstellung von Umsetzungsprodukten aus Polyasparaginsäureamid und Aminosäuren und ihre Verwendung
DE4310506A1 (de) * 1993-03-31 1994-10-06 Cognis Bio Umwelt Enzymzubereitung für Wasch- und Reinigungsmittel
DK39093D0 (da) * 1993-04-01 1993-04-01 Novo Nordisk As Enzym
US5888954A (en) 1993-05-08 1999-03-30 Henkel Kommanditgesellschaft Auf Aktien Corrosion inhibitors for silver
DE4338724A1 (de) 1993-11-12 1995-05-18 Henkel Kgaa Silberkorrosionsschutzmittel II
DE4325922A1 (de) 1993-08-02 1995-02-09 Henkel Kgaa Silberkorrosionsschutzmittel I
BR9406306A (pt) * 1993-05-20 1995-12-26 Procter & Gamble Composições de branqueamento compreendendo ativadores n-acil caprolactama
AU6833394A (en) * 1993-05-20 1994-12-20 Procter & Gamble Company, The Bleaching compounds comprising n-acyl caprolactam for use in hand-wash or other low-water cleaning systems
ATE169003T1 (de) * 1993-05-20 1998-08-15 Procter & Gamble Bleichmittel, welche einen substituierten benzoyl caprolactam bleichaktivator enthalten
US5405413A (en) * 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
DK100893D0 (da) * 1993-09-09 1993-09-09 Novo Nordisk As Enzym
CA2132112A1 (fr) 1993-09-21 1995-03-22 David Elliott Adler Methode de catalysation acide pour l'obtention de polymeres d'acide amine
ATE188989T1 (de) * 1993-11-11 2000-02-15 Procter & Gamble Beim waschen weichmachende zusammensetzungen
DE4338922A1 (de) * 1993-11-15 1995-05-18 Degussa Aktivatoren für anorganische Persauerstoffverbindungen
AU1074295A (en) * 1993-11-25 1995-06-13 Warwick International Group Limited Bleaching compositions
DE4343993A1 (de) 1993-12-22 1995-06-29 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Polyhydroxyverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung
US5534196A (en) * 1993-12-23 1996-07-09 The Procter & Gamble Co. Process for making lactam bleach activator containing particles
JP3922391B2 (ja) * 1994-02-24 2007-05-30 ヘンケル コマンディットゲゼルシャフト アウフ アクティーン 改良酵素とこれを含有する洗剤
MX9604643A (es) * 1994-04-07 1997-11-29 Procter & Gamble Composiciones blanqueadoras que consisten de catalizadores de blanqueo que contienen metal.
DE4415623A1 (de) 1994-05-04 1995-11-09 Basf Ag Verwendung von Pfropfpolymerisaten von monoethylenisch ungesättigten Dicarbonsäuren auf hydrierten Sacchariden als Zusatz zu Wasch- und Reinigungsmitteln
DE4416438A1 (de) 1994-05-10 1995-11-16 Basf Ag Ein- oder mehrkernige Metall-Komplexe und ihre Verwendung als Bleich- und Oxidationskatalysatoren
EP0693550B1 (fr) 1994-07-21 2004-06-16 Ciba SC Holding AG Composition de blanchiment de tissu
DE4427287A1 (de) 1994-08-02 1996-02-08 Basf Ag Verfahren zur Herstellung von Polykondensaten der Asparaginsäure mit verbesserter biologischer Abbaubarkeit und ihre Verwendung
DE4437486A1 (de) * 1994-10-20 1996-04-25 Henkel Kgaa Kristalline Schichtsilikate in maschinellen Geschirrspülmitteln
DE4439978A1 (de) 1994-11-09 1996-05-15 Stockhausen Chem Fab Gmbh Verfahren zur Herstellung von Terpolymeren
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
BR9607008A (pt) * 1995-02-02 1997-10-28 Procter & Gamble Composições de lavagem de prato automática compreendendo catalísadores quelatados por cobalto
DE69617209T2 (de) * 1995-02-02 2002-07-25 The Procter & Gamble Company, Cincinnati Verfahren zur entfernung von teeflecken in geschirrspülern mit zusammensetzungen enthaltend kobalt (iii)- katalysator
CA2212115C (fr) * 1995-02-02 2001-04-24 The Procter & Gamble Company Compositions de lavage automatique de la vaisselle comprenant des catalyseurs a base de cobalt
DK0737738T3 (da) * 1995-04-12 2003-10-20 Cleantabs As Blegemiddeltablet
DE19516957C2 (de) 1995-05-12 2000-07-13 Stockhausen Chem Fab Gmbh Wasserlösliche Copolymere und Verfahren zu ihrer Herstellung und ihre Verwendung
DE19529905A1 (de) 1995-08-15 1997-02-20 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19536082A1 (de) 1995-09-28 1997-04-03 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19605688A1 (de) 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen
TW502064B (en) * 1996-03-11 2002-09-11 Kao Corp Detergent composition for clothes washing
DE19620411A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19613103A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallkomplex-haltige Systeme als Aktivatoren für Persauerstoffverbindungen
DE19616769A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616770A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acyllactame als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616693A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616767A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19620267A1 (de) 1996-05-20 1997-11-27 Henkel Kgaa Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen
DE19709284A1 (de) 1997-03-07 1998-09-10 Henkel Kgaa Katalytisch aktive Wirkstoffkombination zur Verstärkung der Bleichwirkung
JP2001507047A (ja) 1996-11-08 2001-05-29 ハンツマン・アイシーアイ・ケミカルズ・エルエルシー 硬質および軟質ポリウレタン発泡体を製造するための方法
ES2218632T3 (es) * 1996-12-21 2004-11-16 Clariant Gmbh Componente pulverulento de agentes de lavado y limpieza.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4404279A1 (de) * 1994-02-10 1995-08-17 Henkel Kgaa Tablette mit Buildersubstanzen

Also Published As

Publication number Publication date
EP1076683A1 (fr) 2001-02-21
DE59913558D1 (de) 2006-07-27
ES2267267T3 (es) 2007-03-01
JP2003521553A (ja) 2003-07-15
DE19819187A1 (de) 1999-11-11
ATE329994T1 (de) 2006-07-15
WO1999057237A1 (fr) 1999-11-11
US6462006B1 (en) 2002-10-08
WO1999057237A9 (fr) 2002-08-22

Similar Documents

Publication Publication Date Title
EP1076683B1 (fr) Produit solide pour lave-vaisselle, a base de phosphate et de silicates lamellaires cristallins
DE4232170C2 (de) Schwachalkalische Geschirreinigungsmittel
EP0697036B1 (fr) Produits de protection de l'argent contre la corrosion ii
EP2329000B1 (fr) Utilisation d'oxalates de manganèse comme catalyseur de blanchiment
CH676993A5 (fr)
EP2329001B1 (fr) Mélanges de catalyseurs de blanchiment contenant des sels de manganèse et de l'acide oxalique ou ses sels
EP0827529A1 (fr) Granules acides renfermant des substances a activite redox
EP1322744A1 (fr) Sels enduits et granuleux de n-alkylammoniumacetonitrile et leur utilisation en tant qu'activeurs de blanchiment
WO1996012783A1 (fr) Silicates stratifies cristallins utilises comme agents de rinçage pour le lavage de vaisselle a la machine
WO1996037596A1 (fr) Agents detergents pour lave-vaisselle renfermant des agents anti-corrosion de l'argent
EP1084219B1 (fr) Detergents contenant une amylase et un percarbonate
EP0626996A1 (fr) Procede de fabrication de produits de rin age pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds
DE19824704A1 (de) Amylase und bleichaktivierende Übergangsmetallverbindung enthaltende Wasch- und Reinigungsmittel
EP0569365B1 (fr) Produit de nettoyage sans phosphates
DE4210363A1 (de) Verfahren zur Herstellung niederalkalischer, aktivchlor-, silikat- und phosphatfreier Maschinengeschirrspülmittel in Form von Schwergranulaten
DE4325922A1 (de) Silberkorrosionsschutzmittel I
EP0872543A2 (fr) Composition nettoyant inhibitant la corrosion
WO1995000623A1 (fr) Detergent pour lave-vaisselle contenant des adjuvants
EP0846155B1 (fr) Utilisation de lipase dans des agents faiblement alcalins pour le lavage de vaisselle en machine
EP1224254B1 (fr) Inhibiteur enzymatique de grisaillement
WO1996022353A1 (fr) Nettoyant contenant un agent anticorrosion pour l'argent
DE19547730A1 (de) Schwachalkalische Geschirreinigungsmittel und Builderkombination für Wasch- und Reinigungsmittel
DE19540087A1 (de) Geschirrspülmittel
DE19632283A1 (de) Verwendung von Lipasen in niederalkalischen Mitteln zum Vorspülen im Rahmen des maschinellen Geschirrspülens

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

17P Request for examination filed

Effective date: 20001021

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 20030422

APBN Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2E

APBR Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3E

APBV Interlocutory revision of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNIRAPE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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

Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH

Owner name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060614

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20060614

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59913558

Country of ref document: DE

Date of ref document: 20060727

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20060923

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2267267

Country of ref document: ES

Kind code of ref document: T3

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

26N No opposition filed

Effective date: 20070315

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

BERE Be: lapsed

Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) G.M.B.H.

Effective date: 20070430

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

Effective date: 20070430

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

Ref country code: CH

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

Effective date: 20070430

Ref country code: LI

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

Effective date: 20070430

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

Ref country code: BE

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

Effective date: 20070430

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

Ref country code: AT

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

Effective date: 20070421

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

Ref country code: ES

Payment date: 20140311

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: 20140416

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: 20140418

Year of fee payment: 16

Ref country code: IT

Payment date: 20140422

Year of fee payment: 16

Ref country code: FR

Payment date: 20140409

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 59913558

Country of ref document: DE

Representative=s name: ACKERMANN, JOACHIM KARL WILHELM, DIPL.-CHEM. D, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 59913558

Country of ref document: DE

Representative=s name: ACKERMANN, JOACHIM KARL WILHELM, DIPL.-CHEM. D, DE

Effective date: 20140908

Ref country code: DE

Ref legal event code: R081

Ref document number: 59913558

Country of ref document: DE

Owner name: WEYLCHEM WIESBADEN GMBH, DE

Free format text: FORMER OWNERS: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH, 65929 FRANKFURT, DE; HENKEL AG & CO. KGAA, 40589 DUESSELDORF, DE

Effective date: 20140908

Ref country code: DE

Ref legal event code: R081

Ref document number: 59913558

Country of ref document: DE

Owner name: HENKEL AG & CO. KGAA, DE

Free format text: FORMER OWNERS: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH, 65929 FRANKFURT, DE; HENKEL AG & CO. KGAA, 40589 DUESSELDORF, DE

Effective date: 20140908

Ref country code: DE

Ref legal event code: R081

Ref document number: 59913558

Country of ref document: DE

Owner name: HENKEL AG & CO. KGAA, DE

Free format text: FORMER OWNER: CLARIANT PRODUKTE (DEUTSCHLAND), HENKEL AG & CO. KGAA, , DE

Effective date: 20140908

Ref country code: DE

Ref legal event code: R081

Ref document number: 59913558

Country of ref document: DE

Owner name: WEYLCHEM WIESBADEN GMBH, DE

Free format text: FORMER OWNER: CLARIANT PRODUKTE (DEUTSCHLAND), HENKEL AG & CO. KGAA, , DE

Effective date: 20140908

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59913558

Country of ref document: DE

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

Effective date: 20150421

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: 20151103

Ref country code: IT

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

Effective date: 20150421

Ref country code: GB

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

Effective date: 20150421

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20151231

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: 20150430

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

Ref country code: ES

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

Effective date: 20150422

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20180704