EP0625567B1 - Agent de nettoyage pour le lavage de la vaisselle en machine - Google Patents

Agent de nettoyage pour le lavage de la vaisselle en machine Download PDF

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Publication number
EP0625567B1
EP0625567B1 EP94105346A EP94105346A EP0625567B1 EP 0625567 B1 EP0625567 B1 EP 0625567B1 EP 94105346 A EP94105346 A EP 94105346A EP 94105346 A EP94105346 A EP 94105346A EP 0625567 B1 EP0625567 B1 EP 0625567B1
Authority
EP
European Patent Office
Prior art keywords
formulations
use according
weight
acid
monomers
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
EP94105346A
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German (de)
English (en)
Other versions
EP0625567A2 (fr
EP0625567A3 (fr
Inventor
Rudolf Beck
Frank Dr. Krause
Udo Dr. Schoenkaes
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.)
Stockhausen GmbH and Co KG
Original Assignee
Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen GmbH
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Application filed by Stockhausen GmbH and Co KG, Chemische Fabrik Stockhausen GmbH filed Critical Stockhausen GmbH and Co KG
Publication of EP0625567A2 publication Critical patent/EP0625567A2/fr
Publication of EP0625567A3 publication Critical patent/EP0625567A3/fr
Application granted granted Critical
Publication of EP0625567B1 publication Critical patent/EP0625567B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—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

Definitions

  • the invention relates to the use of formulations for in particular phosphate-free cleaning agents with improved biodegradability for the machine dishwashing.
  • Machine dishwashers have the task of cleaning leftovers from dishes, cutlery, glasses, Kitchen appliances etc. to remove.
  • the cleaning agent must wet the surfaces to be cleaned convey and disperse and emulsify water-insoluble dirt particles in the washing liquor.
  • the cleaner suppresses the foam caused by food residues, the residue is more visible Prevent stains on the wash items as far as possible, remove coffee and tea stains, build up of Films of dirt on the surface of dishes and glassware prevent water hardness Bind substances from water and food waste and destroy bacteria.
  • phosphate-free dishwashing detergents have been reduced Developed alkalinity, which often does without the use of chlorine-releasing substances.
  • This "Mild" dishwashing detergents are usually based on trisodium citrate combined with polycarboxylates as the most important phosphate substitute.
  • the products contain low-foam non-ionic surfactants, Enzymes, oxygen-based bleaches (e.g. sodium perborate) and bleach activators such as.
  • B. Tetraacetylethylenediamine Tetraacetylethylenediamine.
  • phosphate substitutes did not show sufficient cleanability, other substances, such as B. EDTA, are used little for ecological reasons.
  • polycarboxylates in particular homopolymers of acrylic acid and copolymers of acrylic acid, have proven to be and maleic acid, as suitable phosphate substitutes and are used today in commercially available cleaning agents used.
  • dishwashing detergents containing polycarboxylates are found in the products as Phospha35 Acrylic polymers used as a substitute have only a low biodegradability and therefore mineralized only to a small extent in the sewage treatment plant.
  • the present invention was therefore based on the object of providing dishwashing detergents which do not have the ecological disadvantages mentioned.
  • the formulations contain component a, the copolymers, at 1 to 60% by weight, preferably 2 to 30% by weight, with proportions of 2 to 15% by weight being very particularly preferably set.
  • Monomers of group A are monoethylenically unsaturated C 4 -C 8 dicarboxylic acids, their anhydrides or their alkali and / or ammonium salts and / or amine salts.
  • Suitable dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and methylene malonic acid.
  • Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the corresponding sodium, potassium or ammonium salts of maleic or itaconic acid are preferably used.
  • the group A monomers are preferably present in the monomer mixture in an amount of 10 to 70% by weight, more preferably 20 to 60% by weight and very particularly preferably 25 to 55% by weight.
  • Monomers of group B are monoethylenically unsaturated C 3 -C 10 monocarboxylic acids and their alkali and / or ammonium salts and / or amine salts. These monomers include, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, vinyl acetic acid and allylacetic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, their mixtures and the sodium, potassium or ammonium salts or mixtures thereof.
  • the group B monomers are preferably present in the monomer mixture in an amount of 20 to 85% by weight, more preferably 25 to 60% by weight and very particularly preferably 30 to 60% by weight.
  • the group C monomers include those after copolymerization and one subsequent hydrolysis or saponification of the polymer one or more hydroxyl groups are covalently bonded directly to the C-C polymer carbon chain. Examples include: Vinyl acetate, vinyl propionate, methyl acetate, methyl vinyl ether, ethylene glycol monovinyl ether and Vinylidene carbonate.
  • the group C monomers are preferably 1 to 50% by weight, particularly preferably 4 to 40% by weight and very particularly preferably 8 to 30% by weight in the monomer mixture available.
  • group D monomers which can be used to modify the copolymers are z.
  • Group D monomers can also - because of required solubility, however, only in a limited amount - double ethylenically unsaturated non-conjugated Compounds and polyalkylene glycol esters of (meth) acrylic acid and polyalkylene glycol ether with (Meth) allyl alcohol, which may or may not be end-capped, can be used.
  • the monomers Group D may contain up to 15% by weight, preferably up to 10% by weight, in the monomer mixture available.
  • copolymers are produced by radical polymerization in an aqueous medium. Such a polymerization is described in the German patent application DE-A-43 00 772.4, which was published on July 21, 1994.
  • monoethylenically unsaturated dicarboxylic acids and / or their salts and / or dicarboxylic acid anhydrides monoethylenic unsaturated monomers after hydrolysis or Saponification to form monomer units with one or more at the C-C chain covalently bonded hydroxyl groups are converted can and optionally other radically copolymerizable Contain monomers in aqueous solution at 40 to 180 ° C in Radically polymerized presence of polymerization initiators with subsequent hydrolysis and saponification, likewise in an aqueous medium.
  • polymerization initiators Compounds used under the polymerization conditions Form radicals, e.g. B.
  • the monomer components are used for the polymerization either submitted in total in aqueous solution and by Polymerized addition of the initiator system or over a period of 1 to 10 hours in the polymerization reactor dosed.
  • dicarboxylic anhydride can be hydrolyzed prior to polymerization and be at least partially neutralized.
  • the final one Hydrolysis or alkaline saponification can take place in the presence of peroxides, e.g. Hydrogen peroxide, or with Sulfur dioxide is preferably carried out after the polymerization become.
  • the copolymers act as dispersants and complexing agents. With them, polyvalent metal ions, e.g. B. Ca, Mg and Fe ions, bound in water-soluble complexes. Disperse the copolymers unusual water hardness and dirt particles. The products are characterized by good environmental compatibility out. On the use of previously used complexing and dispersing agents, such as. B. Phosphates, phosphonates, non-degradable polyacrylates, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), which have ecological disadvantages, can usually be dispensed with or the Amounts of the aforementioned funds can be reduced.
  • complexing and dispersing agents such as. B. Phosphates, phosphonates, non-degradable polyacrylates, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), which have ecological disadvantages, can usually be dispensed with or the Amounts
  • the copolymers are biodegradable if they are in the modified OECD Sturm test (EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B) (see e.g. soap-oil-fat waxes 117 (1991), 740 to 744), have a degree of degradation of ⁇ 60%.
  • the formulations also contain alkali formers b.
  • alkali formers b.
  • suitable water-soluble alkali silicates such as alkali metal silicates, alkali disilicates and crystalline alkali layer silicates.
  • alkaline salts such as alkali hydroxides and alkali carbonates. The amount of these alkali-forming substances used is between 3 and 90 % By weight, preferably between 5 and 70% by weight.
  • the formulations can also contain dispersing and complexing agents c.
  • Suitable products include citrates, phosphonates, homo- and copolymers of acrylic acid, isoserine diacetic acid, Ethylenediaminetetraacetic acid and nitrilotriacetic acid and the alkali salts of the aforementioned substances.
  • Such agents when included in the formulations, are up to 60% by weight, preferably in concentrations of 5 to 50% by weight.
  • the use of sodium citrate in concentrations from 10 to 40% by weight is particularly preferred.
  • the formulations can also 0 to 10 wt .-% low-foaming surfactants d, preferably contained in amounts of 0.5 to 5 wt .-%.
  • low-foam nonionic surfactants such as for example fatty alcohol-ethylene oxide-propylene oxide addition products or those blocked with alkyl groups Fatty alcohol ethoxylates used.
  • formulations generally contain other additives in quantities from 0 to 50% by weight, preferably 0 to 25% by weight.
  • Such additives are e.g. B. oxygen-based bleaches, such as sodium perborate or sodium percarbonate, which are generally metered in amounts of 5 to 15% by weight. Because dishwashers are usually work in the temperature range of 40 - 65 ° C, the oxygen bleaching by activators such. B. Tetraacetylethylenediamine (TAED) can be improved. The bleach activator TAED is usually available in quantities from 0 to 10% by weight.
  • additives can also be chlorine-releasing substances, such as dichloroisocyanurate also act as a bleach.
  • Such products are usually in concentrations from 0 to 5 % By weight used.
  • the formulations can also contain enzymes, in particular proteases, amylases and upases. These enzymes are typically dosed in amounts of 0 to 5% by weight.
  • enzymes in particular proteases, amylases and upases. These enzymes are typically dosed in amounts of 0 to 5% by weight.
  • the usual ingredients for such formulations such as. B. fragrances and dyes, Defoamers, flow aids, extenders and extenders, added to the agents according to the invention without problems become. However, they do not contribute to the cleaning effect, but can affect the shelf life of the Improve the wording or positively influence the acceptance of the products by the consumer.
  • Dishwashing detergents can be liquid, powdery products Types and granules or to products pressed into blocks or tablets.
  • the liquid formulations can be prepared by mixing the components.
  • the Powdered products are usually made by mixing the powdered components and, if necessary by spraying on the liquid constituents or by spray drying an aqueous, liquid to paste-like approach of the starting components.
  • the raw materials can first be mixed and / or in Spray mixing devices are pre-processed and then compressed in tabletting machines.
  • the formulations can be used as household dishwashing detergents and be used in the commercial sector.
  • the copolymers contained in the formulations a a good binding capacity for alkaline earth ions and an excellent dispersing and dirt-carrying capacity on.
  • the effectiveness of the cleaner is improved by the use of these polymers.
  • the Cleaning agents according to the invention bring about good dirt detachment and dirt dispersion and reduce deposits of water hardness deposits on the wash ware and machine parts.
  • formulations of the invention are better in their effect or at least the same Good.
  • the formulations now claimed also have improved biodegradability on.
  • the copolymer obtained in aqueous solution is spray-dried into a powder Product transferred.
  • the biodegradability of the copolymers is based on the modified OECD Sturm test EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B.
  • a degree of degradation of over 60% is determined for the substance mentioned in Example 1.
  • polycarboxylates such as. B. homopolyacrylates and copolymers of acrylic acid and maleic acid, have lower biodegradability.
  • Machine dishwashing detergents of the following composition are produced from the copolymer from Example 1 (data in% by weight) Machine dish detergent, powdered 1 % 2% 3% Surfactant (low foam, MARLOX® MO 154) 2.0 2.0 2.0 Copolymer, powdery 10.0 8.0 10.0 Sodium citrate dihydrate - 35.0 - Sodium metasilicate pentahydrate 50.0 - 50.0 Sodium disilicate granules - 20.0 - Sodium hydroxide 10.0 - - Sodium carbonate calc.
  • a comparative formulation V1 is prepared using a commercially available powdered polycarboxylate (polyacrylate, average molecular weight approx. 4,000 g / mol): Comparative formulation V1% Surfactant (low foam, MARLOX® MO 154) 2.0 Polyacrylate (molecular weight approx. 4,000 g / mol) 10.0 Sodium metasilicate pentahydrate 50.0 Sodium hydroxide 10.0 Sodium carbonate calc. 28.0
  • formulation 1 The rinsing performance of formulation 1 according to the invention was tested in comparison with comparative formulation V1 in a commercial dishwasher according to DIN 44 990. Minced meat, spinach, oatmeal, tea, egg, drinking milk and margarine were used as test soils. The dishwasher was operated with drinking water at 13 ° dH. The residues of soiling were evaluated in accordance with the DIN standard and the cleaning index R was calculated as the test result: 1 V1 Cleaning index R (according to DIN 44 990) 4.5 4.2
  • dishwashing detergent formulations according to the invention, it is particularly advantageous to determine that they have a very good cleaning performance and at the same time prevent deposits Contain washware and machine parts of biodegradable polymers as dispersing and complexing agents.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Control And Other Processes For Unpacking Of Materials (AREA)
  • Centrifugal Separators (AREA)

Claims (8)

  1. Utilisation des formulations pour agents de nettoyage pour lave-vaisselle qui contiennent, rapporté à la substance anhydre :
    a) de 1 à 60 % en poids de copolymères facilement dégradables biologiquement, dont le taux de dégradation déterminé d'après l'essai de Sturm OCDE modifié est ≥ 60 %, qui ont été obtenus par polymérisation radicalaire en milieu aqueux à partir de:
    A. acides dicarboxyliques monoéthylèniquement insaturés et/ou de leurs sels,
    B. acides monocarboxyliques monoéthylèniquement insaturés et/ou de leurs sels,
    C. monomères simplement insaturés et
    D. 0 à 15 % d'autres monomères copolymérisables par voie radicalaire,
    et qui présentent par hydrolyse ou saponification suivante des unités monomères C. un ou plusieurs groupes hydroxyle sur la C-C chaíne des carbons du polymère, et
    b) 3 à 90 % en poids d'agents alcaligènes,
    c) 0 à 60 % en poids d'agents dispersants et d'agents complexants,
    d) 0 à 10 % en poids de tensioactifs peu moussants, et
    e) 0 à 50 % en poids d'autres additifs.
  2. Utilisation d'après la revendication 1, caractérisée en ce que le composant a) est contenu dans une proportion de 2 à 30 % en poids dans les formulations.
  3. Utilisation d'après la revendication 1, caractérisée en ce que le composant a) est contenu dans une proportion de 2 à 15 % en poids dans les formulations.
  4. Utilisation d'après une ou plusieurs des revendications de 1 à 3, caractérisée en ce que les composants b) sont contenus dans une proportion de 5 à 70 % en poids dans les formulations.
  5. Utilisation d'après une ou plusieurs des revendications de 1 à 4, caractérisée en ce que les composants c) sont contenus dans une proportion de 5 à 50 % en poids dans les formulations.
  6. Utilisation d'après une ou plusieurs des revendications de 1 à 5, caractérisée en ce que les composants d) sont contenus dans une proportion de 0,5 à 5 % en poids dans les formulations.
  7. Utilisation d'après une ou plusieurs des revendications de 1 à 6, caractérisée en ce que les composants e) sont contenus dans une proportion de 0 à 25 % en poids dans les formulations.
  8. Utilisation d'après une ou plusieurs des revendications de 1 à 7 pour des agents de lavage pour lave-vaisselle sans phosphates.
EP94105346A 1993-05-19 1994-04-07 Agent de nettoyage pour le lavage de la vaisselle en machine Expired - Lifetime EP0625567B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4316745A DE4316745A1 (de) 1993-05-19 1993-05-19 Phosphatfreie Maschinengeschirreinigungsmittel
DE4316745 1993-05-19

Publications (3)

Publication Number Publication Date
EP0625567A2 EP0625567A2 (fr) 1994-11-23
EP0625567A3 EP0625567A3 (fr) 1995-05-31
EP0625567B1 true EP0625567B1 (fr) 2001-01-17

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Application Number Title Priority Date Filing Date
EP94105346A Expired - Lifetime EP0625567B1 (fr) 1993-05-19 1994-04-07 Agent de nettoyage pour le lavage de la vaisselle en machine

Country Status (3)

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EP (1) EP0625567B1 (fr)
AT (1) ATE198763T1 (fr)
DE (2) DE4316745A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19516957C2 (de) 1995-05-12 2000-07-13 Stockhausen Chem Fab Gmbh Wasserlösliche Copolymere und Verfahren zu ihrer Herstellung und ihre Verwendung
CA2190230A1 (fr) * 1995-11-20 1997-05-21 Thomas Cleveland Kirk Concentres de nettoyage et methode de preparation
DE102005041349A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
BR112019011182B1 (pt) 2016-12-16 2022-12-13 Dow Global Technologies Llc Composição detergente de lavagem automática de louça

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994015978A1 (fr) * 1993-01-14 1994-07-21 Chemische Fabrik Stockhausen Gmbh Copolymeres biodegradables, leur procede de preparation et leur utilisation
EP0622449A2 (fr) * 1993-04-28 1994-11-02 Chemische Fabrik Stockhausen GmbH Compositions pour adoucir l'eau

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4008696A1 (de) * 1990-03-17 1991-09-19 Basf Ag Verfahren zur herstellung von homo- und copolymerisaten monoethylenisch ungesaettigter dicarbonsaeuren und ihre verwendung
US5191048A (en) * 1991-02-01 1993-03-02 Rohm & Haas Company Biodegradable free-radical addition polymers
EP0510944B1 (fr) * 1991-04-22 1998-04-15 Colgate-Palmolive Company Compositions à visco-élasticité linéaire pour lave-vaisselle automatique
DE4316741A1 (de) * 1993-05-19 1994-11-24 Huels Chemische Werke Ag Universalreinigungsmittel mit biologisch abbaubaren Polymeren

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994015978A1 (fr) * 1993-01-14 1994-07-21 Chemische Fabrik Stockhausen Gmbh Copolymeres biodegradables, leur procede de preparation et leur utilisation
EP0622449A2 (fr) * 1993-04-28 1994-11-02 Chemische Fabrik Stockhausen GmbH Compositions pour adoucir l'eau

Also Published As

Publication number Publication date
DE59409637D1 (de) 2001-02-22
EP0625567A2 (fr) 1994-11-23
EP0625567A3 (fr) 1995-05-31
DE4316745A1 (de) 1994-11-24
ATE198763T1 (de) 2001-02-15

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