EP0637627B1 - Formulations détergentes - Google Patents

Formulations détergentes Download PDF

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Publication number
EP0637627B1
EP0637627B1 EP94109139A EP94109139A EP0637627B1 EP 0637627 B1 EP0637627 B1 EP 0637627B1 EP 94109139 A EP94109139 A EP 94109139A EP 94109139 A EP94109139 A EP 94109139A EP 0637627 B1 EP0637627 B1 EP 0637627B1
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EP
European Patent Office
Prior art keywords
detergent formulations
weight
formulations according
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
EP94109139A
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German (de)
English (en)
Other versions
EP0637627A2 (fr
EP0637627A3 (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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Filing date
Publication date
Application filed by Stockhausen GmbH and Co KG, Chemische Fabrik Stockhausen GmbH filed Critical Stockhausen GmbH and Co KG
Publication of EP0637627A2 publication Critical patent/EP0637627A2/fr
Publication of EP0637627A3 publication Critical patent/EP0637627A3/fr
Application granted granted Critical
Publication of EP0637627B1 publication Critical patent/EP0637627B1/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
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the invention relates to detergent formulations which are free of phosphates, zeolites and crystalline Layered silicates and, as builder substances, contain polymers with biodegradability.
  • the function of the detergent builder is mainly that of water or the dirt-derived calcium and magnesium ions by complexing, dispersing and Eliminate sequestration from the washing process and support the washing effect of the surfactants.
  • the builders prevent tissue deposits, reduce the incrustation of the textiles and improve them Primary washing action.
  • the zeolites or crystalline layered silicates contained in the aforementioned agents are not environmentally hazardous, but they have the disadvantage that they lead to a significant increase in the amount of sewage sludge contribute. That is why there have been attempts in the past in phosphate-free detergent powders also to do without the use of water-softening silicates.
  • the published patent application DE 39 30 791 describes phosphate- and zeolite-free detergents, which as Incrustation inhibitors contain polycarboxylates, in particular copolymers of acrylic acid and maleic acid.
  • a disadvantage of the claimed polymeric builder substances is the low biodegradability.
  • the published patent application DE 40 22 005 claims the combination of citrate and polycarboxylates as Builder in zeolite-free mild detergents.
  • the polymers used with molecular weights of 30,000 - 120,000 g / mol also have only low biodegradability and can therefore only be used for small parts can be mineralized in the sewage treatment plant.
  • formulations which are surfactants, biodegradable Contain copolymers, washing alkalis, adjusting agents and other functional auxiliaries.
  • the detergents according to the invention can contain anionic, nonionic or cationic surfactants a contain. Mixtures of anionic and nonionic products are typically used in Central Europe used, which show synergistic washing effects and are often combined with soaps. It can but also exclusively anionic or nonionic surfactants are used.
  • the amount of surfactant a is preferably 5 to 40% by weight, with contents of 7 to 25% by weight being particularly preferred become.
  • Sulfonate type surfactants are e.g. B. C 11 -C 13 alkyl benzene sulfonates, C 13 -C 17 alkane sulfonates and ester sulfonates with chain lengths of 12 to 20 carbon atoms.
  • Suitable surfactants of the sulfate type are, for example, the sulfuric acid monoesters from fatty alcohols of synthetic and native origin, such as. B. coconut fatty alcohol, tallow fatty alcohol, oleyl alcohol or C 10 -C 20 oxo alcohols.
  • fatty alcohol ether sulfates such as. B. lauryl ether sulfate can be used.
  • anionic surfactants are also soaps, for. B. saturated fatty acid soaps, such as the alkali or Alkanolamine soaps of lauric acid, myristic acid, palmitic acid and stearic acid are useful.
  • Prefers are made from natural fatty acids, e.g. B. from coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • Suitable nonionic surfactants are, for example, adducts of ethylene oxide and / or propylene oxide with alkylphenols, oxo alcohols or native fatty alcohols, fatty acids, fatty amines and fatty acid amides.
  • alkylphenols oxo alcohols or native fatty alcohols
  • fatty acids fatty acids
  • fatty amines and fatty acid amides fatty acid amide
  • the addition products of 3 to 15 mol of ethylene oxide with coconut and tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18 carbon atoms are particularly important.
  • surfactants of the C 8 -C 18 alkyl polyglucoside type such as. B.
  • C 10 -C 12 and C 12 -C 16 alkyl polyglucosides, and amine oxides can be used.
  • cationic surfactants and amphoteric products such as ampholytes and betaines, be used.
  • the detergents according to the invention also contain the copolymers b.
  • the amount of b is preferably 5 to 40% by weight, proportions of 5 to 20% by weight being very 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.
  • the copolymers are produced by radical polymerization in an aqueous medium. Such a polymerization is described in German patent application 43 00 772, published on July 21, 1994. This is followed by 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. inorganic and organic peroxides, Persulfates, azo compounds and so-called redox catalysts.
  • 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 polymers obtained in aqueous solution can, if necessary, be dried by drying methods, in particular spray drying processes, are converted into powdery products.
  • 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 their biodegradability out. On the use of previously used complexing and dispersing agents, such as. B. of phosphates, Phosphonates, poorly degradable polyacrylates, nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid and their salts, which have ecological disadvantages, can generally be dispensed with or the amounts of the aforementioned agents can be reduced.
  • complexing and dispersing agents such as. B. of phosphates, Phosphonates, poorly degradable polyacrylates, nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid and their salts, which have ecological disadvantages, can generally be dispensed with or the
  • 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%.
  • Usable washing alkalis c are water-soluble, alkaline salts, such as
  • Alkali carbonates, alkali bicarbonates and alkali hydroxides The group of washing alkalis also includes water-soluble alkali metal silicates, which also have corrosion-inhibiting properties, such as. B. Sodium metasilicates and sodium disilicates. The proportion of washing alkalis in the agents is preferably 5 to 50% by weight.
  • inorganic neutral salts such as e.g. B. sodium sulfate or sodium chloride, Find use. If such products are used, they are preferably in Amounts of 5 to 60 wt .-% metered.
  • the detergent formulations can be further below contain functional auxiliaries described.
  • peroxo compounds such as sodium perborate mono- and tetrahydrate and percarbonates used.
  • the bleaching agents are dosed in proportions of 0 to 30% by weight, amounts of 5 to 20 % By weight are preferred.
  • oxygen bleaching can be carried out by activators such.
  • B. Tetraacetylethylenediamine (TAED) can be improved.
  • the bleach activator TAED is usually used in amounts of 0 to 10 wt .-% used, proportions of 2 to 7 wt .-% are preferred.
  • the formulations can also contain further dispersing and complexing agents.
  • Suitable products are, for example, citrates, phosphonates, and biodegradable homopolymers and copolymers of acrylic acid, isoserine diacetic acid, polyaspartic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid as well as the alkali salts of the aforementioned substances.
  • Such substances are in the detergents in concentrations of 0 to 50% by weight, preferably in amounts of 0.5 to 20% by weight.
  • Graying inhibitors such as carboxymethyl cellulose and carboxymethyl starches, can also be used.
  • the products increase the dirt-carrying capacity of the washing liquors and are typically in quantities contain from 0 to 2 wt .-%.
  • the formulations can optionally also contain enzymes, in particular proteases, amylases and Lipases. These enzymes are typically dosed in amounts of 0 to 5% by weight.
  • detergent formulations according to the invention defoamers, pouring aids, optical brighteners, color transfer inhibitors and fragrances and dyes are included.
  • the detergents according to the invention can be powdery types or granules act.
  • the powder detergents can be prepared by mixing the solid ingredients and optionally by spraying on the liquid constituents or by spray drying an aqueous, liquid to pasty approach of the starting components.
  • Granulated products can e.g. B. can be produced by extrusion of pasty premixes.
  • the formulations according to the invention can be used as textile detergents in the household sector and in commercial cleaning processes can be used.
  • the copolymers contained in the formulations b have an excellent binding capacity for alkaline earth ions and a high dispersing capacity, so that the use of water-softening silicates, such as zeolites or crystalline layered sodium silicates, can be dispensed with.
  • the detergents according to the invention cause good dirt removal and dirt dispersion and only lead to a slight incrustation when washing the Textiles with hard water.
  • the agents can be highly foaming formulations, such as the Hand wash can be used, or even foam regulating surfactant systems used in machine washing Find use.
  • the formulations according to the invention are better in their effectiveness or at least the same Good.
  • the formulations now claimed also have an improved biological Degradability.
  • 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.
  • detergents of the following composition are produced (data in% by weight): Detergent powder 1 % 2% n-alkylbenzenesulfonate, Na salt 5.0 4.5 C 12 -C 14 fatty alcohol ethoxylate-7-EO 7.0 5.0 Soap 5.0 7.0 Copolymer, powdery 15.0 10.0 sodium 30.0 25.0 Sodium bicarbonate - 25.0 Sodium perborate tetrahydrate 15.0 15.0 Sodium sulfate, light 23.0 8.5 Detergent powder 3% 4% 5% C 12 -C 18 fatty alcohol sulfate, Na salt - 2.0 15.0 C 12 -C 14 fatty alcohol oxyethylate-7-EO - 5.0 4.0 C 13 oxo alcohol ethoxylate mixture (9 EO, 3 EO) 9.0 - - Soap - 5.0 2.0 Copolymer, powdery 15.0 20.0 8.0 sodium 15.0 25.0 8.0 Sodium bicarbonate 26.0
  • a comparative formulation V1 is prepared using the commercially available polycarboxylate Sokalan CP 5 (BASF, acrylic acid-maleic acid copolymer, Na salt, average molar mass 70,000 g / mol): Comparative formulation V1% n-alkylbenzenesulfonate, Na salt 5.0 C 12 -C 14 fatty alcohol ethoxylate-7-EO 7.0 Soap 5.0 Polycarboxylate, powdery 15.0 sodium 30.0 Sodium perborate tetrahydrate 15.0 Sodium sulfate, light 23.0
  • Table 1 shows the ash content as a measure of the deposits.
  • formulation 1 2nd 3rd V1 Ash content (%) 0.47 0.46 0.43 0.51

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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)

Claims (8)

  1. Formulations détergentes, qui ne contiennent pas de zéolites ni de silicates à structure cristalline lamellaire et qui contiennent
    a) 3 à 70 % en poids d'agents tensioactifs,
    b) 1 à 60 % en poids de copolymères facilement biodégradables, dont le taux de dégradation est ≥ 60 % déterminé par le test d'OECD-Sturm modifié, obtenus par polymérisation radicalaire en milieux aqueux :
    A. d'acides dicarboxyliques éthyléniquement insaturés et/ou de leurs sels,
    B. d'acides monocarboxyliques éthyléniquement insaturés et/ou de leurs sels,
    C. de monomères simplement insaturés et
    D. de 0 à 15 % en poids d'autres monomères copolymérisables en façon radicalaire,
    et présentant par hydrolyse ou saponification ultérieure des unités monomères C. un ou plusieurs groupes hydroxyles dans la chaíne carbonée du polymère C-C, et
    c) 0 à 60 % en poids d'un agent de lavage alcali à l'exception de 5 % en poids de métasilicate de sodium,
    d) 0 à 70 % en poids de charges et
    e) le complément jusqu'à 100 % d'autres agents secondaires fonctionnels.
  2. Formulations détergentes d'après la revendication 1, caractérisées en ce qu'elles contiennent les composants a) en une proportion de 5 à 40 % en poids.
  3. Formulations détergentes d'après la revendication 1, caractérisées en ce qu'elles contiennent les composants a) en une proportion de 7 à 25 % en poids.
  4. Formulations détergentes d'après la revendication 1, caractérisées en ce qu'elles contiennent les composants b) en une proportion de 5 à 40 % en poids.
  5. Formulations détergentes d'après la revendication 1, caractérisées en ce qu'elles contiennent les composants b) en une proportion de 5 à 20 % en poids.
  6. Formulations détergentes d'après la revendication 1, caractérisées en ce qu'elles contiennent des agents de lavage alcalis en une proportion de 5 à 50 % en poids.
  7. Formulations détergentes d'après la revendication 1, caractérisées en ce qu'elles contiennent des charges en une proportion de 5 à 60 % en poids.
  8. Utilisation des formulations d'après la revendication 1 en tant que détergent pour les textiles.
EP94109139A 1993-08-04 1994-06-15 Formulations détergentes Expired - Lifetime EP0637627B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4326129 1993-08-04
DE4326129A DE4326129A1 (de) 1993-08-04 1993-08-04 Waschmittelformulierungen

Publications (3)

Publication Number Publication Date
EP0637627A2 EP0637627A2 (fr) 1995-02-08
EP0637627A3 EP0637627A3 (fr) 1995-05-31
EP0637627B1 true EP0637627B1 (fr) 2000-11-08

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ID=6494419

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Application Number Title Priority Date Filing Date
EP94109139A Expired - Lifetime EP0637627B1 (fr) 1993-08-04 1994-06-15 Formulations détergentes

Country Status (4)

Country Link
US (1) US5496495A (fr)
EP (1) EP0637627B1 (fr)
AT (1) ATE197468T1 (fr)
DE (2) DE4326129A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK0783561T3 (da) * 1994-09-22 1999-10-11 Crosfield Joseph & Sons Silicatgranulatkorn og fremgangsmåde til fremstilling deraf
US6194367B1 (en) 1995-03-01 2001-02-27 Charvid Limited Liability Co. Non-caustic cleaning composition comprising peroxygen compound and specific silicate and method of making the same in free-flowing, particulate form
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
US5898024A (en) * 1995-03-01 1999-04-27 Charvid Limited Liability Non-caustic cleaning composition comprising peroxygen compound and specific silicate, and method of making the same in free-flowing, particulate form
US5663132A (en) * 1995-03-01 1997-09-02 Charvid Limited Liability Company Non-caustic composition comprising peroxygen compound and metasilicate and cleaning methods for using same
DE19516957C2 (de) * 1995-05-12 2000-07-13 Stockhausen Chem Fab Gmbh Wasserlösliche Copolymere und Verfahren zu ihrer Herstellung und ihre Verwendung
DE69817811T2 (de) 1997-05-30 2004-04-01 Unilever N.V. Rieselfähige körnige waschmittelzusammensetzungen
GB9711356D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
DE10153551A1 (de) * 2001-10-30 2003-05-22 Henkel Kgaa Im wesentlichen sedimentfrei dispergierbares Wasch- oder Reinigungsmittel
US20050176617A1 (en) * 2004-02-10 2005-08-11 Daniel Wood High efficiency laundry detergent
ATE485361T1 (de) * 2005-08-19 2010-11-15 Procter & Gamble Festförmige waschmittelzusammensetzung enthaltend alkylbenzolsulphonat, carbonat-salz und carboxylat-polymer
US20100056404A1 (en) * 2008-08-29 2010-03-04 Micro Pure Solutions, Llc Method for treating hydrogen sulfide-containing fluids

Family Cites Families (12)

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Publication number Priority date Publication date Assignee Title
GB2109398B (en) * 1981-10-22 1985-05-15 Unilever Plc Detergent composition for washing fabrics
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
GB8504733D0 (en) * 1985-02-23 1985-03-27 Procter & Gamble Ltd Detergent compositions
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.
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
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
ATE164623T1 (de) * 1993-02-05 1998-04-15 Henkel Kgaa Gerüststoff für wasch- oder reinigungsmittel
DE4316741A1 (de) * 1993-05-19 1994-11-24 Huels Chemische Werke Ag Universalreinigungsmittel mit biologisch abbaubaren Polymeren

Also Published As

Publication number Publication date
DE4326129A1 (de) 1995-02-09
DE59409578D1 (de) 2000-12-14
US5496495A (en) 1996-03-05
ATE197468T1 (de) 2000-11-11
EP0637627A2 (fr) 1995-02-08
EP0637627A3 (fr) 1995-05-31

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