DE19937345A1 - Mixed powder or mixed granules based on glycine-N, N-diacetic acid - Google Patents
Mixed powder or mixed granules based on glycine-N, N-diacetic acidInfo
- Publication number
- DE19937345A1 DE19937345A1 DE1999137345 DE19937345A DE19937345A1 DE 19937345 A1 DE19937345 A1 DE 19937345A1 DE 1999137345 DE1999137345 DE 1999137345 DE 19937345 A DE19937345 A DE 19937345A DE 19937345 A1 DE19937345 A1 DE 19937345A1
- Authority
- DE
- Germany
- Prior art keywords
- mixed
- acid
- powder
- weight
- mixed powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 29
- 239000011812 mixed powder Substances 0.000 title claims abstract description 23
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 239000003599 detergent Substances 0.000 claims description 18
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- 239000011976 maleic acid Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000013042 solid detergent Substances 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 claims description 2
- 229940091181 aconitic acid Drugs 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 229940018557 citraconic acid Drugs 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229960002598 fumaric acid Drugs 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims 1
- 239000012459 cleaning agent Substances 0.000 abstract description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- -1 Alkali metal salts Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical class CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000004697 chelate complex Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/30—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using agents to prevent the granules sticking together; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Die Erfindung betrifft ein Mischpulver oder Mischgranulat auf Basis von Glycin- N,N-diessigsäure oder Derivaten davon.The invention relates to a mixed powder or mixed granules based on glycine N, N-diacetic acid or derivatives thereof.
Zur Herstellung von Waschmitteln, insbesondere Textilwaschmitteln oder Reinigungsmitteln, insbesondere Geschirreinigungsmitteln können feste oder flüssige Formulierungen gewählt werden. Feste Formulierungen können beispielsweise als Pulver oder Granulate vorliegen. Die Herstellung von einzelnen pulver- oder granulatförmigen Waschmittelbestandteilen oder Bestandteilsgemischen kann je nach Art der Bestandteile schwierig oder unmöglich sein. Die Pulver oder Granulate dürfen bei der Herstellung, beim Mischen und beim Lagern der Mittel nicht zusammenbacken und die Streu- oder Rieselfähigkeit des Pulvers oder Granulats nicht beeinträchtigen.For the production of detergents, in particular textile detergents or Detergents, especially dish detergents, can be solid or liquid formulations can be selected. Fixed formulations can for example in the form of powder or granules. The manufacture of individual powder or granular detergent ingredients or Mixtures of ingredients can be difficult or difficult depending on the type of ingredients be impossible. The powders or granules may be used in the production, Do not mix and do not cake when storing the agents and the spreading or Do not impair the flowability of the powder or granules.
Der Einsatz von Chelatbildnern in Waschmitteln in fester Form ist bekannt. Die WO 95/29216 betrifft Detergenspulverzusammensetzungen, die einen Metallion- Chelat-Komplex und ein anionisches funktionalisiertes Polymer enthalten. Das Detergenspulver enthält einen Komplex aus einem Chelatbildner und einem Metallion, ausgewählt aus Magnesium, Calcium, Strontium, Zink und Aluminium sowie ein Polymer, das insbesondere Carboxylgruppen aufweist. Das Pulver wird durch Sprühtrocknen hergestellt. Die Chelatbildner können dabei aus einer Vielzahl von Verbindungen ausgewählt sein, Glycin-N,N-diessigsäure-Derivate sind jedoch nicht erwähnt. Unter den verwendbaren Polymeren sind Polycarboxylate aufgeführt, die wasserlösliche Salze von Homo- und Copolymeren von aliphatischen Cabonsäuren enthalten.The use of chelating agents in detergents in solid form is known. The WO 95/29216 relates to detergent powder compositions which contain a metal ion Chelate complex and an anionic functionalized polymer contain. The Detergent powder contains a complex of a chelating agent and one Metal ion selected from magnesium, calcium, strontium, zinc and aluminum and a polymer which has, in particular, carboxyl groups. The powder will made by spray drying. The chelating agents can be from one Variety of compounds can be selected, glycine-N, N-diacetic acid derivatives are not mentioned, however. Among the polymers that can be used are Listed polycarboxylates, the water-soluble salts of homo- and Contain copolymers of aliphatic cabonic acids.
Auch die EP-A-0 618 289 betrifft hochaktive granulatförmige Detergenszusammensetzungen, die Chelate und Polymere enthalten. Die Zusammensetzung weist ein anionisches Tensid, einen Chelatbildner und ein Polymer oder Copolymer auf. Die Chelatbildner können wiederum aus einer Vielzahl von Verbindungen ausgewählt sein. Glycin-N,N-diessigsäure-Derivate sind jedoch nicht aufgeführt. Unter den Polymeren sind insbesondere Polycarboxylate wie Polyacrylate aufgeführt.EP-A-0 618 289 also relates to highly active granular ones Detergent compositions containing chelates and polymers. The Composition includes an anionic surfactant, a chelating agent and Polymer or copolymer. The chelating agents can in turn be from a Variety of connections can be selected. Glycine-N, N-diacetic acid derivatives are not listed, however. Among the polymers are in particular Polycarboxylates such as polyacrylates listed.
Die Verwendung von Glycin-N,N-diessigsäure-Derivaten als Komplexbildner für Erdalkali- und Schwermetallionen in Wasch- und Reinigungsmitteln ist in der EP- A-0 845 456 beschrieben. Hier wird insbesondere die Herstellung von kristallinen Feststoffen aus Glycin-N,N-diessigsäure-Derivaten (MGDA-Derivaten) beschrieben. Hierbei wird ein spezielles Kristallisationsverfahren angewendet.The use of glycine-N, N-diacetic acid derivatives as complexing agents for Alkaline earth and heavy metal ions in detergents and cleaning agents is in the EP A-0 845 456. Here in particular the production of crystalline Solids from glycine-N, N-diacetic acid derivatives (MGDA derivatives) described. A special crystallization process is used here.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Glycin-N,N- diessigsäure-Derivate enthaltenden Mischpulvern oder Mischgranulaten für die Verwendung in festen Wasch- und Reinigungsmitteln. Dabei soll insbesondere die Schütt- und Rieselfähigkeit der Pulver oder Granulate erhalten bleiben.The object of the present invention is to provide glycine-N, N- mixed powders or mixed granules containing diacetic acid derivatives for the Use in solid detergents and cleaning agents. In particular, the Powder and granules remain free-flowing and free-flowing.
Die Aufgabe wird erfindungsgemäß gelöst durch ein Mischpulver oder
Mischgranulat, enthaltend mindestens 80 Gew.-% eines Gemisches aus
The object is achieved according to the invention by a mixed powder or mixed granules containing at least 80% by weight of a mixture
-
a) 5 bis 70 Gew.-% mindestens eines Glycin-N,N-diessigsäure-
Derivats der allgemeinen Formel (I)
MOOC-CHR-N(CH2COOM)2 (I)
mit der Bedeutung
R C1-12-Alkyl
M Alkalimetalla) 5 to 70% by weight of at least one glycine-N, N-diacetic acid derivative of the general formula (I)
MOOC-CHR-N (CH 2 COOM) 2 (I)
with the meaning
RC 1-12 alkyl
M alkali metal - b) 30 bis 95 Gew.-% mindestens eines Polycarboxylates, in dem bis zu 40 mol-% der Carboxylgruppen neutralisiert sind.b) 30 to 95 wt .-% of at least one polycarboxylate in which to 40 mol% of the carboxyl groups are neutralized.
Der verbleibende Mengenanteil kann auf weitere Hilfsstoffe entfallen, wie übliche Waschmittelzusatzstoffe oder Füllstoffe. Vorzugsweise besteht die Mischung im wesentlichen, besonders bevorzugt nur aus den Komponenten (a) und (b).The remaining proportion can be attributed to other auxiliaries, as usual Detergent additives or fillers. The mixture preferably consists of essential, particularly preferably only from components (a) and (b).
Es wurde erfindungsgemäß gefunden, daß eine Kombination von Alkalimetallsalzen von Glycin-N,N-diessigsäure-Derivaten mit Polycarboxylaten zu Pulvern oder Granulaten führt, die eine geringe Hygroskopizität und ein gutes Lagerverhalten aufweisen und damit vorteilhaft in festen Wasch- und Reinigungsmitteln eingesetzt werden können. Die Mittel sind sehr lagerstabil und auch nach langen Zeiträumen noch schütt- und rieselfähig.It was found according to the invention that a combination of Alkali metal salts of glycine-N, N-diacetic acid derivatives with polycarboxylates leads to powders or granules that have low hygroscopicity and good Have storage behavior and thus advantageous in solid washing and Detergents can be used. The agents are very stable in storage and Free-flowing and free-flowing even after long periods.
Erfindungsgemäß einsetzbare Glycin-N,N-diessigsäure-Derivate sind beispielsweise in EP-A-0 845 456 beschrieben. In den Verbindungen der allgemeinen Formel (I) bedeutet M ein Alkalimetall, vorzugsweise Natrium oder Kalium, insbesondere Natrium.Glycine-N, N-diacetic acid derivatives which can be used according to the invention are described for example in EP-A-0 845 456. In the connections of the general formula (I) M is an alkali metal, preferably sodium or Potassium, especially sodium.
R ist vorzugsweise ein C1-6-Alkylrest, insbesondere ein Methyl- oder Ethylrest. Speziell bevorzugt wird Methylglycindiessigsäure (MGDA) eingesetzt, vorzugsweise als Trinatriumsalz.R is preferably a C 1-6 alkyl radical, in particular a methyl or ethyl radical. Methylglycinediacetic acid (MGDA) is particularly preferably used, preferably as the trisodium salt.
Die Herstellung derartiger Glycin-N,N-diessigsäure-Derivate ist bekannt, vgl. EP- A-0 845 456 und darin zitierte Literatur. The preparation of such glycine-N, N-diacetic acid derivatives is known, cf. EP- A-0 845 456 and literature cited therein.
Als Komponente (b) wird ein Polycarboxylat eingesetzt, in dem bis zu 40 mol-% der Carboxylgruppen neutralisiert sind. Dabei handelt es sich vorzugsweise um ein Homo- oder Copolymer, das zu mindestens 50 Gew.-% aus den Monomeren Maleinsäure, (Meth)acrylsäure, Itaconsäure, Mesaconsäure, Fumarsäure, Aconitsäure, Citraconsäure und/oder Methylenmalonsäure oder deren Anhydriden aufgebaut ist. Bevorzugte Monomere sind dabei Maleinsäure, Fumarsäure, Acrylsäure und (Meth)acrylsäure, insbesondere Maleinsäure und Acrylsäure. Geeignete Polycarboxylate sind beispielsweise in US 3,308,067 beschrieben. Besonders bevorzugt wird ein Polycarboxylat eingesetzt, das zu mindestens 70 Gew.-% aus Acrylsäure und Maleinsäure oder deren Anhydriden aufgebaut ist. Besonders bevorzugt ist ein Copolymer aus Acrylsäure und Maleinsäure. Dabei beträgt der Anteil an Acrylsäure vorzugsweise 50 bis 80 Gew.-%. Das Molekulargewicht der Polycarboxylate beträgt vorzugsweise 1500 bis 100 000, besonders bevorzugt 2000 bis 80 000, insbesondere 3000 bis 70 000.A polycarboxylate is used as component (b) in which up to 40 mol% the carboxyl groups are neutralized. These are preferably a homopolymer or copolymer which consists of at least 50% by weight of the monomers Maleic acid, (meth) acrylic acid, itaconic acid, mesaconic acid, fumaric acid, Aconitic acid, citraconic acid and / or methylene malonic acid or their anhydrides is constructed. Preferred monomers are maleic acid, fumaric acid, Acrylic acid and (meth) acrylic acid, especially maleic acid and acrylic acid. Suitable polycarboxylates are described for example in US 3,308,067. It is particularly preferred to use a polycarboxylate which has at least 70 % By weight is composed of acrylic acid and maleic acid or their anhydrides. A copolymer of acrylic acid and maleic acid is particularly preferred. there the proportion of acrylic acid is preferably 50 to 80% by weight. The Molecular weight of the polycarboxylates is preferably 1500 to 100,000, particularly preferably 2,000 to 80,000, in particular 3,000 to 70,000.
Als Polycarboxylat kann zudem auch eine derivatisierte Zellulose wie eine carboxy-niedere Alkyl-Zellulose eingesetzt werden. Besonders bevorzugt wird in diesem Fall Carboxymethylzellulose eingesetzt.A derivatized cellulose such as a can also be used as the polycarboxylate carboxy-lower alkyl cellulose can be used. Is particularly preferred in In this case, carboxymethyl cellulose is used.
In den Polycarboxylaten sind bis zu 40 mol-% der Carboxylgruppen neutralisiert. Damit kann auch die reine Säure (0% Neutralisierung) eingesetzt werden. Die Neutralisierung kann mit geeigneten Basen wie Alkalihydroxiden oder Aminen erfolgen. Sie können auch als Ammoniumsalze vorliegen.Up to 40 mol% of the carboxyl groups are neutralized in the polycarboxylates. This means that the pure acid (0% neutralization) can also be used. The Neutralization can be done with suitable bases such as alkali hydroxides or amines respectively. They can also be present as ammonium salts.
Der Anteil der Komponente (a) beträgt 5 bis 70 Gew.-%, vorzugsweise 10 bis 60 Gew.-%. Beispielhafte Anteile der Komponente (a) sind 30 oder 60 Gew.-%. Entsprechend liegt die Komponente (b) in einer Menge von 30 bis 95 Gew.-%, vorzugsweise 40 bis 90 Gew.-% vor. Beispielhaft sind Mengen von 40 oder 70 Gew.-%. The proportion of component (a) is 5 to 70% by weight, preferably 10 to 60 % By weight. Exemplary proportions of component (a) are 30 or 60% by weight. Accordingly, component (b) is in an amount of 30 to 95% by weight, preferably 40 to 90% by weight. Quantities of 40 or 70 are exemplary % By weight.
Das erfindungsgemäße Mischpulver oder Mischgranulat reagiert in wässriger Lösung vorzugsweise sauer. Vorzugsweise weist eine wässrige Lösung des Mischpulvers oder Mischgranulats einen pH-Wert kleiner 7 auf. Hierdurch kann die Hygroskopizität des Mischpulvers oder Mischgranulats auf einen sehr kleinen Wert verringert werden.The mixed powder or mixed granulate according to the invention reacts in aqueous Solution preferably acidic. Preferably, an aqueous solution of the Mixed powder or mixed granules have a pH of less than 7. This can the hygroscopicity of the mixed powder or mixed granules to a very small Value can be decreased.
Die erfindungsgemäßen Mischpulver oder Mischgranulate können hergestellt werden durch Lösen der Komponenten (a) und (b) in einem Lösungsmittel und Sprühtrocknen des erhaltenen Gemisches, wobei sich ein Granulierungsschritt anschließen kann. Dabei können die Komponenten (a) und (b) getrennt gelöst werden, wobei die Lösungen nachfolgend vermischt werden, oder ein Pulvergemisch der Komponenten kann in Wasser gelöst werden.The mixed powders or mixed granules according to the invention can be produced are by dissolving components (a) and (b) in a solvent and Spray drying the mixture obtained, during which a granulation step can connect. Components (a) and (b) can be solved separately be, the solutions are subsequently mixed, or a Powder mixture of the components can be dissolved in water.
Die erfindungsgemäßen Mischpulver oder Mischgranulate werden vorzugsweise zur Herstellung von festen Wasch- und Reinigungsmitteln, bei der Wäsche von Textilien oder bei der Reinigung von Geschirr verwendet. Die Komponente (a) kann dabei als biologisch gut abbaubarer Komplexbildner wirken, während die Komponente (b) als Builder wirken kann. Damit entfalten beide Komponenten der Mischpulver oder Mischgranulate eine Wirkung in Wasch- und Reinigungsmitteln.The mixed powders or mixed granules according to the invention are preferred for the production of solid detergents and cleaning agents, for the washing of Textiles or used in the cleaning of dishes. Component (a) can act as a biodegradable complexing agent, while the Component (b) can act as a builder. Both components of the Mixed powder or mixed granules have an effect in washing and Detergents.
Die Mischpulver oder Mischgranulate können in pulverförmige Wasch- und Reinigungsmittel eingearbeitet werden, ohne daß diese verklumpen oder verbacken.The mixed powder or mixed granules can be in powdered washing and Detergents can be incorporated without clumping or bake.
Die Erfindung betrifft auch ein festes Waschmittel, enthaltend ein wie vorstehend beschriebenes Mischpulver oder Mischgranulat und mindestens ein Tensid. Geeignete Waschmittelzusammensetzungen sind bekannt und beispielsweise in WO 95/29216 und EP-A-0 618 289 beschrieben. The invention also relates to a solid detergent containing one as above described mixed powder or mixed granules and at least one surfactant. Suitable detergent compositions are known and, for example, in WO 95/29216 and EP-A-0 618 289.
Die Erfindung betrifft ferner ein festes Geschirrreinigungsmittel, das ein Mischpulver oder Mischgranulat, wie es vorstehend beschrieben ist, enthält und zudem mindestens ein Tensid. Die Mittel liegen dabei vorzugsweise in Pulver- oder Granulatform vor.The invention further relates to a solid dishwashing detergent, the one Mixed powder or mixed granules, as described above, contains and also at least one surfactant. The agents are preferably powdered or granular form.
Die Erfindung wird nachstehend anhand von Beispielen näher erläutert.The invention is explained in more detail below with the aid of examples.
Als Komponente (a) wurde MGDA in Form des Trinatriumsalzes eingesetzt.MGDA in the form of the trisodium salt was used as component (a).
Als Komponente (b) wurde zum einen ein Acrylsäure/Maleinsäure-Copolymer aus 70 Gew.-% Acrylsäure und 30 Gew.-% Maleinsäure mit einem Molgewicht von 70 000 eingesetzt, das zu 40% teilneutralisiert war (Natriumsalz) (Komponente b1). Zum anderen wurde ein Acrylsäure/Maleinsäure-Copolymer mit 50 Gew.-% Acrylsäureanteil und 50 Gew.-% Maleinsäureanteil in der reinen Säureform eingesetzt (Molekulargewicht 3000) (Komponente b2).On the one hand, component (b) was an acrylic acid / maleic acid copolymer from 70 wt .-% acrylic acid and 30 wt .-% maleic acid with a molecular weight of 70,000 used, which was 40% partially neutralized (sodium salt) (Component b1). The other was an acrylic acid / maleic acid copolymer with 50% by weight of acrylic acid and 50% by weight of maleic acid in the pure Acid form used (molecular weight 3000) (component b2).
Die erfindungsgemäße Mischung 1 wurde durch Sprühtrocknen einer wässrigen Lösung eines Gemisches aus 70 Gew.-% der Komponente b1 und 30 Gew.-% MGDA erhalten. Entsprechend wurde Mischung 2 durch Sprühtrocknen einer wässrigen Lösung eines Gemisches aus 40 Gew.-% Komponente b2 und 60 Gew.-% MGDA erhalten.Mixture 1 according to the invention was prepared by spray drying an aqueous Solution of a mixture of 70% by weight of component b1 and 30% by weight MGDA received. Accordingly, mixture 2 was spray-dried aqueous solution of a mixture of 40% by weight of components b2 and 60 Wt .-% MGDA obtained.
Zur Bestimmung der Hygroskopizität und des Lagerverhaltens wurde die Gewichtszunahme bei 22°C und 68% relativer Feuchte für einen längeren Zeitraum bestimmt. Dabei wurde untersucht, ob das Produkt rieselfähig (R), fest und nicht rieselfähig (F) oder klebrig und nicht rieselfähig (K) war. Die Ergebnisse für die einzelnen Komponenten und für die erfndungsgemäßen Mischungen sind in der nachstehenden Tabelle zusammengefaßt. To determine the hygroscopicity and storage behavior, the Weight gain at 22 ° C and 68% relative humidity for a longer one Period determined. It was examined whether the product was free-flowing (R), solid and was not free-flowing (F) or sticky and not free-flowing (K). The Results for the individual components and for the inventive Mixtures are summarized in the table below.
Aus den Ergebnissen der vorstehenden Tabelle geht hervor, daß insbesondere die in saurer Form vorliegenden erfindungsgemäßen Mischungen mit dem angegebenen Anteil an Polycarboxylaten eine sehr niedrige Hygroskopizität aufweisen und auch nach längerer Lagerungsdauer rieselfähig bleiben.The results of the table above show that in particular the mixtures according to the invention present in acidic form with the specified proportion of polycarboxylates a very low hygroscopicity have and remain free-flowing even after a long period of storage.
Claims (10)
- a) 5 bis 70 Gew.-% mindestens eines Glycin-N,N-diessigsäure-
Derivats der allgemeinen Formel (I)
MOOC-CHR-N(CH2COOM)2 (I)
mit der Bedeutung
R C1-12-Alkyl
M Alkalimetall - b) 30 bis 95 Gew.-% mindestens eines Polycarboxylates, in dem bis zu 40 mol-% der Carboxylgruppen neutralisiert sind.
- a) 5 to 70% by weight of at least one glycine-N, N-diacetic acid derivative of the general formula (I)
MOOC-CHR-N (CH 2 COOM) 2 (I)
with the meaning
RC 1-12 alkyl
M alkali metal - b) 30 to 95 wt .-% of at least one polycarboxylate in which up to 40 mol% of the carboxyl groups are neutralized.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999137345 DE19937345A1 (en) | 1999-08-11 | 1999-08-11 | Mixed powder or mixed granules based on glycine-N, N-diacetic acid |
| PCT/EP2000/007628 WO2001012768A1 (en) | 1999-08-11 | 2000-08-04 | Mixed powder or mixed granulate based on glycine-n,n-diacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999137345 DE19937345A1 (en) | 1999-08-11 | 1999-08-11 | Mixed powder or mixed granules based on glycine-N, N-diacetic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19937345A1 true DE19937345A1 (en) | 2001-02-15 |
Family
ID=7917578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1999137345 Withdrawn DE19937345A1 (en) | 1999-08-11 | 1999-08-11 | Mixed powder or mixed granules based on glycine-N, N-diacetic acid |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE19937345A1 (en) |
| WO (1) | WO2001012768A1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005105967A1 (en) * | 2004-04-15 | 2005-11-10 | Ecolab Inc. | Binding agent for solidification matrix |
| WO2006003434A1 (en) * | 2004-07-02 | 2006-01-12 | Reckitt Benckiser N.V. | Particulate |
| WO2006002954A1 (en) * | 2004-07-02 | 2006-01-12 | Basf Aktiengesellschaft | Mgda-based powder mixture or granulate mixture |
| WO2009003979A1 (en) * | 2007-07-03 | 2009-01-08 | Basf Se | Process for producing a free-flowing and storage-stable solid comprising essentially alpha-alanine-n,n-diacetic acid and/or one or more derivatives of alpha-alanine-n,n-diacetic acid |
| WO2010076291A1 (en) * | 2008-12-29 | 2010-07-08 | Akzo Nobel N.V. | Coated particles of a chelating agent |
| WO2011079940A1 (en) * | 2009-12-30 | 2011-07-07 | Inprotec Ag | Solid containing glutamic acid-n, n-diacetic acid (glda) or a derivative therefrom and method for the production thereof |
| EP2380961A1 (en) * | 2010-04-23 | 2011-10-26 | The Procter & Gamble Company | Detergent composition |
| WO2011146582A3 (en) * | 2010-05-21 | 2012-01-05 | Dow Global Technologies Llc. | Aminocarboxylate powders with improved purity and flow ability properties |
| US9096820B2 (en) | 2009-12-24 | 2015-08-04 | Akzo Nobel Chemicals International B.V. | Coated particles of a glumatic acid N,N-diacetate chelating agent |
| WO2019162136A1 (en) * | 2018-02-23 | 2019-08-29 | Unilever N.V. | Detergent solid composition comprising aminopolycarboxylate and organic acid |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070015674A1 (en) * | 2005-06-30 | 2007-01-18 | Xinbei Song | Low phosphate automatic dishwashing detergent composition |
| PL3061744T3 (en) | 2008-04-01 | 2018-10-31 | Unilever N.V. | Preparation of free flowing granules of methylglycine diacetic acid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3504896A1 (en) * | 1985-02-13 | 1986-08-14 | Basf Ag, 6700 Ludwigshafen | ADDITIVES FOR DETERGENT AND CLEANING AGENTS |
| EP0678572A1 (en) * | 1994-04-20 | 1995-10-25 | The Procter & Gamble Company | Detergent powder compositions |
| ES2130790T3 (en) * | 1995-02-17 | 1999-07-01 | Unilever Nv | SOLID DETERGENT BLOCK. |
| JP3810847B2 (en) * | 1996-01-22 | 2006-08-16 | 花王株式会社 | High density powder detergent composition |
| GB2311536A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Dishwashing and laundry detergents |
-
1999
- 1999-08-11 DE DE1999137345 patent/DE19937345A1/en not_active Withdrawn
-
2000
- 2000-08-04 WO PCT/EP2000/007628 patent/WO2001012768A1/en active Application Filing
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2005238423B2 (en) * | 2004-04-15 | 2010-05-27 | Ecolab Inc. | Binding agent for solidification matrix |
| EP3929271A1 (en) * | 2004-04-15 | 2021-12-29 | Ecolab USA Inc. | Binding agent for solidification matrix |
| EP3536771A1 (en) * | 2004-04-15 | 2019-09-11 | Ecolab USA Inc. | Binding agent for solidification matrix |
| US7442679B2 (en) | 2004-04-15 | 2008-10-28 | Ecolab Inc. | Binding agent for solidification matrix comprising MGDA |
| WO2005105967A1 (en) * | 2004-04-15 | 2005-11-10 | Ecolab Inc. | Binding agent for solidification matrix |
| US7598218B2 (en) | 2004-04-15 | 2009-10-06 | Ecolab Inc. | Method of forming a binding agent for solidification matrix |
| CN100580072C (en) * | 2004-04-15 | 2010-01-13 | 埃科莱布有限公司 | Binding agent for solidification matrix |
| US8048838B2 (en) | 2004-07-02 | 2011-11-01 | Basf Aktiengesellschaft | MGDA-based powder mixture or granulate mixture |
| EP2218769A1 (en) | 2004-07-02 | 2010-08-18 | Reckitt Benckiser N.V. | Particulate |
| US7935668B2 (en) | 2004-07-02 | 2011-05-03 | Reckitt Benckiser N.V. | Particulate |
| WO2006003434A1 (en) * | 2004-07-02 | 2006-01-12 | Reckitt Benckiser N.V. | Particulate |
| WO2006002954A1 (en) * | 2004-07-02 | 2006-01-12 | Basf Aktiengesellschaft | Mgda-based powder mixture or granulate mixture |
| EP3263686A1 (en) | 2004-07-02 | 2018-01-03 | Reckitt Benckiser Finish B.V. | Detergent composition containing mgda |
| CN101687156B (en) * | 2007-07-03 | 2013-08-07 | 巴斯夫欧洲公司 | Process for producing a free-flowing and storage-stable solid comprising essentially alpha-alanine-N,N-diacetic acid and/or one or more derivatives of alpha-alanine-N,N-diacetic acid |
| WO2009003979A1 (en) * | 2007-07-03 | 2009-01-08 | Basf Se | Process for producing a free-flowing and storage-stable solid comprising essentially alpha-alanine-n,n-diacetic acid and/or one or more derivatives of alpha-alanine-n,n-diacetic acid |
| WO2010076291A1 (en) * | 2008-12-29 | 2010-07-08 | Akzo Nobel N.V. | Coated particles of a chelating agent |
| US9096820B2 (en) | 2009-12-24 | 2015-08-04 | Akzo Nobel Chemicals International B.V. | Coated particles of a glumatic acid N,N-diacetate chelating agent |
| US8940678B2 (en) | 2009-12-30 | 2015-01-27 | Basf Se | Method for producing a solid with sufficiently low hygroscopicity which comprises glutamic acid-N,N-diacetic acid (GLDA) or a derivative thereof |
| CN102725389A (en) * | 2009-12-30 | 2012-10-10 | 巴斯夫欧洲公司 | Solid containing glutamic acid-N, N-diacetic acid (GLDA) or a derivative therefrom and method for the production thereof |
| RU2560730C2 (en) * | 2009-12-30 | 2015-08-20 | Басф Се | Solid substance containing glutamic acid-n,n-diacetic acid (glda) or derivative thereof, as well as method for production thereof |
| CN102725389B (en) * | 2009-12-30 | 2016-03-02 | 巴斯夫欧洲公司 | Comprise L-glutamic acid-N, solid of N-oxalic acid (GLDA) or derivatives thereof and preparation method thereof |
| WO2011079940A1 (en) * | 2009-12-30 | 2011-07-07 | Inprotec Ag | Solid containing glutamic acid-n, n-diacetic acid (glda) or a derivative therefrom and method for the production thereof |
| WO2011133484A1 (en) * | 2010-04-23 | 2011-10-27 | The Procter & Gamble Company | Detergent composition |
| EP2380961A1 (en) * | 2010-04-23 | 2011-10-26 | The Procter & Gamble Company | Detergent composition |
| US9012684B2 (en) | 2010-05-21 | 2015-04-21 | Dow Global Technologies Llc | Aminocarboxylate powders with improved purity and flowability properties |
| WO2011146582A3 (en) * | 2010-05-21 | 2012-01-05 | Dow Global Technologies Llc. | Aminocarboxylate powders with improved purity and flow ability properties |
| WO2019162136A1 (en) * | 2018-02-23 | 2019-08-29 | Unilever N.V. | Detergent solid composition comprising aminopolycarboxylate and organic acid |
| WO2019162135A1 (en) * | 2018-02-23 | 2019-08-29 | Unilever N.V. | Process of preparing a solid composition comprising aminopolycarboxylate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001012768A1 (en) | 2001-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1765967B1 (en) | Mgda-based powder mixture or granulate mixture | |
| EP1971675B1 (en) | Mixed powder or mixed granule based on glutamic acid-n,n-diacetic acid and salts thereof | |
| DE19937345A1 (en) | Mixed powder or mixed granules based on glycine-N, N-diacetic acid | |
| DE69814388T2 (en) | PRODUCTION OF DETERGENT GRANULES | |
| DE69724336T2 (en) | Water softening tablets | |
| EP0187257B1 (en) | Carpet cleaning agent | |
| DE69226029T2 (en) | Detergents and processes for their manufacture | |
| DE3417820A1 (en) | METHOD FOR PRODUCING A WASHING ADDITIVE IN TABLET FORM | |
| EP0609777A2 (en) | Detergent composition with improved soil removal ability, process for its production and use of a suitable polycarboxylate therefor | |
| DE4313909A1 (en) | Water-softening formulations | |
| CH490490A (en) | Laundry detergent with softening properties | |
| DE19506634A1 (en) | Process for the preparation of finely divided mixtures of amphiphilic polymers and polycarboxylates and their use | |
| DE69533160T2 (en) | Detergent-forming agent, process for its preparation and detergent composition containing the same | |
| DE2551111A1 (en) | GRANULATED OR POWDERY DETERGENT MIXTURE | |
| DE1617172A1 (en) | Soap compositions | |
| CH643590A5 (en) | PARTICULATE BLENDER. | |
| DD298422A5 (en) | LIQUID CLEANER CONCENTRATE CONTAINS A WATER-SOLUBLE COPOLYMER | |
| EP0849355B1 (en) | Powder washing and cleaning components | |
| DE69328688T3 (en) | Dispersant | |
| DE4326129A1 (en) | detergent formulations | |
| DE69230098T2 (en) | Bleaching composition for laundry | |
| DE4313908A1 (en) | Water-softening formulations | |
| EP0578659A1 (en) | Low-alkaline, chlorine and phosphate-free dishwasher detergents in the form of heavy powders and granulates | |
| EP0959175A1 (en) | Compositions comprisisng formamidinesulfinic acid | |
| EP0571436B1 (en) | Granular additive for washing and cleaning agents |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8130 | Withdrawal |