EP0622449A2 - Compositions pour adoucir l'eau - Google Patents

Compositions pour adoucir l'eau Download PDF

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Publication number
EP0622449A2
EP0622449A2 EP94104833A EP94104833A EP0622449A2 EP 0622449 A2 EP0622449 A2 EP 0622449A2 EP 94104833 A EP94104833 A EP 94104833A EP 94104833 A EP94104833 A EP 94104833A EP 0622449 A2 EP0622449 A2 EP 0622449A2
Authority
EP
European Patent Office
Prior art keywords
weight
water
acid
formulations
salts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94104833A
Other languages
German (de)
English (en)
Other versions
EP0622449A3 (fr
EP0622449B1 (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
Chemische Werke Huels AG
Chemische Fabrik Stockhausen 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 Chemische Werke Huels AG, Chemische Fabrik Stockhausen GmbH filed Critical Chemische Werke Huels AG
Publication of EP0622449A2 publication Critical patent/EP0622449A2/fr
Publication of EP0622449A3 publication Critical patent/EP0622449A3/fr
Application granted granted Critical
Publication of EP0622449B1 publication Critical patent/EP0622449B1/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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the invention relates to water-softening formulations with improved biodegradability.
  • the function of a water softener is to eliminate the calcium and magnesium ions from the water by complexing, dispersing and sequestering from the washing process and thereby supporting the washing action of the surfactants.
  • the softener reduces the build-up of deposits in the washing machine, e.g. B. on the heating elements.
  • Water softeners according to J. Falbe, Surfactants in Consumer Products, 1987, 292-293, usually consist predominantly of phosphates or of mixtures of phosphates, zeolites and polycarboxylates. Although both types of softeners have a good binding capacity for alkaline earth ions and an excellent dispersing and dirt-carrying capacity, they have ecological disadvantages. The pollution of the wastewater with phosphates leads to an over-fertilization of the waters and the problems associated with eutrophication. Combinations of zeolites and polycarboxylates are often used as substitutes for phosphates.
  • DE-A-39 31 871 describes phosphate-free water softening agents which predominantly consist of zeolite, layered silicate and the sodium salt of a polycarboxylic acid, preferably an acrylic acid-maleic acid copolymer.
  • the disadvantage of the polycarboxylates used today is that the polymers have only a low biodegradability and are therefore only mineralized to a small extent in the sewage treatment plant.
  • the object was therefore to provide water-softening formulations which do not have the ecological disadvantages mentioned.
  • the formulations contain component a, the copolymers, preferably to 5 to 80% by weight, proportions of 5 to 30% by weight being very particularly preferably set.
  • Monomers of group A are monoethylenically unsaturated C4-C8 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 C3-C10 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 which, after copolymerization and subsequent hydrolysis or saponification of the polymer, release one or more hydroxyl groups which are covalently bonded directly to the C-C polymer carbon chain. Examples include: vinyl acetate, vinyl propionate, methyl vinyl acetate, methyl vinyl ether, ethylene glycol monovinyl ether and vinylidene carbonate.
  • the group C monomers are preferably present in the monomer mixture in an amount of 1 to 50% by weight, particularly preferably 4 to 40% by weight and very particularly preferably 8 to 30% by weight.
  • group D monomers that can be used to modify the copolymers are, for. B. sulfone groups and sulfate group-containing monomers, such as meth (allylsulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropanephosphonic acid and their salts, and hydroxyethyl (meth) acrylate sulfates, allyl sulfates.
  • sulfone groups and sulfate group-containing monomers such as meth (allylsulfonic acid), vinylsulfonic acid, styrene sulfonic acid, acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid and acrylamidomethylpropan
  • group D monomers it is also possible - because of the required solubility, but only in a limited amount - to use 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.
  • the group D monomers are optionally present in the monomer mixture up to 15% by weight, preferably up to 10% by weight.
  • the copolymers can be prepared by radical polymerization in an aqueous medium. Such a polymerization is described for example in the German patent application with the file number P 43 00 772.4.
  • 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. The copolymers disperse unusual water hardness and dirt particles. The products are characterized by good environmental compatibility. 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 generally be dispensed with.
  • complexing and dispersing agents such as. B. phosphates, phosphonates, non-degradable polyacrylates, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), which have ecological disadvantages, can generally be dispensed with.
  • the copolymers are biodegradable if they are used in the modified OECD Sturm test (EC Directive 84/449 / EEC C 5 and OECD Guideline 301 B) (see, for example, soap-oil-fat waxes 117 (1991), 740 to 744), have a degree of degradation of ⁇ 60%.
  • the formulations also contain water-softening inorganic silicates b, such as, for. B. sodium aluminum silicates of the zeolite A type and / or crystalline sodium silicates with layer structures.
  • the inorganic silicates are preferably present in proportions of 30 to 80% by weight, based on the anhydrous substance.
  • inorganic salts preferably alkali and ammonium salts of sulfuric, hydrochloric and carbonic acid
  • Sodium sulfate can improve the grain structure of powdery products and granules and have a favorable effect on the washing-up behavior in the washing machine.
  • Such inorganic salts if included in the recipes, preferably contain 20 to 60% by weight.
  • Component d is preferably contained in the formulations in an amount of 2 to 40% by weight.
  • Suitable dispersing and complexing agents are, for example, citrates, phosphonates, isoserinediacetic acid, homopolymers and copolymers of acrylic acid, and ethylenediaminetetraacetic acid and nitrilotriacetic acid, and salts of the aforementioned compounds.
  • the formulations can also contain 0 to 5% by weight of anionic, have nonionic or cationic surfactants.
  • formulations generally contain conventional additives, such as. B. water-soluble alkali metal or alkali disilicates as corrosion inhibitors as well as perfume oils and dyes in amounts of a total of 0 to 30 wt .-%.
  • formulations according to the invention can be used as liquids, powdery products or granules.
  • the liquid formulations can be prepared by mixing the components.
  • the powdery products are usually produced by mixing the powdery constituents and, if appropriate, by spraying on the liquid constituents or by spray drying an aqueous, liquid to pasty batch of the starting components.
  • the formulations according to the invention can be used as water softeners. If there is increased water hardness, they can also be added to detergents and cleaning agents.
  • formulations according to the invention are better or at least equally good in their action.
  • the formulations now claimed also have improved biodegradability.
  • a copolymer with an average molar mass of approximately 15,000 g / mol is obtained by radical polymerization of 35% by weight of maleic anhydride in the form of sodium maleate, 45% by weight of acrylic acid and 20% by weight of vinyl acetate in aqueous solution and saponification .
  • the copolymer obtained in aqueous solution is converted into a powdery product by spray drying.
  • the biodegradability of the copolymers is tested in accordance with the modified OECD Sturm test in accordance with 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, on the other hand, have lower biodegradability.
  • Powdery water-softening formulations of the following composition are prepared from the copolymer of Example 1: 1 % 2% 3% Zeolite A 80 60 40 Copolymer, powdery 20th 15 10th Sodium sulfate, light - 20th 30th Sodium citrate dihydrate - - 20th Sodium disilicate - 5 -
  • the claimed formulations are therefore improved in terms of biodegradability and tissue incrustation.

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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
EP94104833A 1993-04-28 1994-03-26 Compositions pour adoucir l'eau Expired - Lifetime EP0622449B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4313908A DE4313908A1 (de) 1993-04-28 1993-04-28 Wasserenthärtende Formulierungen
DE4313908 1993-04-28

Publications (3)

Publication Number Publication Date
EP0622449A2 true EP0622449A2 (fr) 1994-11-02
EP0622449A3 EP0622449A3 (fr) 1994-12-21
EP0622449B1 EP0622449B1 (fr) 1999-05-06

Family

ID=6486594

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94104833A Expired - Lifetime EP0622449B1 (fr) 1993-04-28 1994-03-26 Compositions pour adoucir l'eau

Country Status (6)

Country Link
US (1) US5575946A (fr)
EP (1) EP0622449B1 (fr)
AT (1) ATE179750T1 (fr)
DE (2) DE4313908A1 (fr)
DK (1) DK0622449T3 (fr)
ES (1) ES2132273T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996035728A1 (fr) * 1995-05-12 1996-11-14 Stockhausen Gmbh & Co. Kg Copolymeres solubles dans l'eau, leur procede de production et leur utilisation
EP0625567B1 (fr) * 1993-05-19 2001-01-17 Stockhausen GmbH & Co. KG Agent de nettoyage pour le lavage de la vaisselle en machine

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2129852T3 (es) * 1994-09-22 1999-06-16 Crosfield Joseph & Sons Granulos de silicatos y metodo para fabricar los mismos.
DE19961660A1 (de) * 1999-12-21 2001-07-12 Henkel Kgaa Pflegemittel für Wasch- und Geschirrspülmaschinen
EP1451114A4 (fr) * 2001-11-06 2008-04-09 Solutionz International Water Preparation de traitement de refrigerant
GB0304515D0 (en) * 2003-02-27 2003-04-02 Dakocytomation Denmark As Standard
GB2401604A (en) * 2003-05-10 2004-11-17 Reckitt Benckiser Nv Water-softening product
JP4142982B2 (ja) * 2003-05-13 2008-09-03 株式会社Ｐｆｕ 画像読み取り装置
GB0315991D0 (en) * 2003-07-08 2003-08-13 Dakocytomation Denmark As Standard
DK1951060T3 (da) * 2005-11-04 2018-01-29 Arla Foods Amba Koncentrat afledt af et mælkeprodukt beriget med naturligt forekommende sialyllactose og en fremgangsmåde til fremstilling deraf

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH584284A5 (fr) * 1972-03-30 1977-01-31 Henkel & Cie Gmbh
US4473485A (en) * 1982-11-05 1984-09-25 Lever Brothers Company Free-flowing detergent powders
DE3426368A1 (de) * 1984-07-18 1986-01-23 Basf Ag, 6700 Ludwigshafen Copolymerisate fuer wasch- und reinigungsmittel
DE3528460A1 (de) * 1985-08-08 1987-02-19 Basf Ag Verwendung von neutralisierten und amidierten, carboxylgruppen enthaltenden polymerisaten als zusatz zu waschmitteln und reinigungsmitteln
DE3716544A1 (de) * 1987-05-16 1988-11-24 Basf Ag Verwendung von wasserloeslichen copolymerisaten, die monomere mit mindestens zwei ethylenisch ungesaettigten doppelbindungen einpolymerisiert enthalten, in wasch- und reinigungsmitteln
IT1229135B (it) * 1989-04-05 1991-07-22 Ausidet Spa Copolimeri transesterificati dell'anidride maleica, particolarmente utili nel campo della detergenza.
IT1230862B (it) * 1989-06-06 1991-11-08 Ausidet Spa Copolimeri idrosolubili dell'anidride maleica.
DE3931871A1 (de) * 1989-09-23 1991-04-04 Henkel Kgaa Granulares, phosphatfreies wasserenthaertungsmittel
IT1236966B (it) * 1989-10-25 1993-05-07 Ausidet Srl Processo per la produzione di soluzioni acquose di agenti anti-incro- stazione e soluzioni cosi' ottenute
DE4008696A1 (de) * 1990-03-17 1991-09-19 Basf Ag Verfahren zur herstellung von homo- und copolymerisaten monoethylenisch ungesaettigter dicarbonsaeuren und ihre verwendung
DE4029035A1 (de) * 1990-09-13 1992-03-19 Huels Chemische Werke Ag Waschmittel
DE4034131C2 (de) * 1990-10-26 1999-08-26 Henkel Kgaa Gerüststoff für Waschmittel
US5191048A (en) * 1991-02-01 1993-03-02 Rohm & Haas Company Biodegradable free-radical addition polymers
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0625567B1 (fr) * 1993-05-19 2001-01-17 Stockhausen GmbH & Co. KG Agent de nettoyage pour le lavage de la vaisselle en machine
WO1996035728A1 (fr) * 1995-05-12 1996-11-14 Stockhausen Gmbh & Co. Kg Copolymeres solubles dans l'eau, leur procede de production et leur utilisation
US6207780B1 (en) 1995-05-12 2001-03-27 Rohm & Haas Company Interpolymers of unsaturated carboxylic acids and unsaturated sulfur acids

Also Published As

Publication number Publication date
DK0622449T3 (da) 1999-11-15
US5575946A (en) 1996-11-19
EP0622449A3 (fr) 1994-12-21
ATE179750T1 (de) 1999-05-15
DE4313908A1 (de) 1994-11-03
DE59408197D1 (de) 1999-06-10
EP0622449B1 (fr) 1999-05-06
ES2132273T3 (es) 1999-08-16

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