EP0308221B1 - Zusammensetzung, geeignet zur Verwendung als oder in sauren Klarspülmitteln - Google Patents

Zusammensetzung, geeignet zur Verwendung als oder in sauren Klarspülmitteln Download PDF

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EP0308221B1
EP0308221B1 EP88308536A EP88308536A EP0308221B1 EP 0308221 B1 EP0308221 B1 EP 0308221B1 EP 88308536 A EP88308536 A EP 88308536A EP 88308536 A EP88308536 A EP 88308536A EP 0308221 B1 EP0308221 B1 EP 0308221B1
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weight
acid
composition
parts
polymer
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French (fr)
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EP0308221A1 (de
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Paolo Zini
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Rohm and Haas Co
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Rohm and Haas Co
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    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • 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
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • compositions suitable for use as, or in, acidic rinse aids particularly acidic rinse aids for machine dishwashers.
  • the compositions may also be suitable for use as, or in, glass cleaning compositions, for example window cleaning compositions, metal cleaning compositions, textile production, finishing and wash-off compositions, and water treatment compositions, for example in cooling circuits.
  • Rinse aids are invariably used in commercial and institutional machine dishwashers and frequently in household dishwashers.
  • a final rinse of fresh water serves to displace pre-final rinse water and its attendant detergent and soil residues.
  • the final rinse water is normally introduced at a temperature of 80°C or above; the high temperature being used to sanitize as well as to promote rapid flash drying of tableware, glassware or plasticsware (herein collectively referred to as "substrate”) surfaces as they exit the machine.
  • substrate glassware or plasticsware
  • the final rinse water may be used at a lower temperature of about 60°C, amd may contain about 50 parts per million (ppm) of a conventional chlorine-releasing agent for sanitization.
  • ppm parts per million
  • Rinse aid formulations for machine dishwashers are conveniently aqueous solutions containing a low foam nonionic surfactant, and may be injected into the final fresh water rinse at a concentration of about 50 to about 100 ppm.
  • the surfactant in the rinse water lowers the surface tension of the rinse water and improves the wetting action of the rinse water on the somewhat hydrophobic substrate surfaces. Improved wetting reduces the tendency of the rinse water to form drops containing dissolved solids on the substrate surface which give rise to spots upon drying. Accordingly, the functions of the surfactant in the rinse aid are to effectively reduce the surface tension during the draining period and to be low foaming so as to avoid traces of foam on the rinsed substrate which result in a residue upon evaporation.
  • the final rinse water after having been used to rinse the substrates, will be mixed with the circulated pre-final rinse water.
  • the rinse water may also be fed back into the wash water or be used directly as the wash water for the next cycle. Consequently, when a rinse aid is formulated, the surfactant and any other additive should be chosen based on their effect in the wash bath as well as in the rinse water.
  • An additional important aspect of a rinse aid is the ability of the rinse aid to defoam food soils in the alkaline wash bath. Proteinaceous food soils are particularly prone to foam in agitated alkaline wash baths. Foam, or more specifically entrapped air, in the wash spray, will reduce the mechanical efficiency of the spray and interfere with maximum soil removal. Many low foam surfactants are effective soil defoamers. However, other additives may interfere with soil defoaming.
  • Hydrotropes such as sodium xylene sulfonate, cumene sulfonate and short chain alkyl sulfates have been used to permit the formulation of low foam nonionic surfactants into stable aqueous concentrates. (See, for example, US-A-3,563,901 and US-A-4,443,270). These hydrotropes have little effect, however, on compatibilizing low foam surfactants with polycarboxylated polymers in aqueous concentrates. Moreover, even in cases where hydrotropes give limited compatibility, they suffer from the major disadvantage of interfering with the food soil defoaming activity of the surfactants.
  • Water-miscible solvents such as isopropanol and propylene glycol
  • hydrogen bond-breaking compounds such as urea
  • urea have also been proposed for use in formulating rinse aids containing low foam nonionic surfactants.
  • they have been found to have little or no effect on compatibilizing polycarboxylated polymers with low foam surfactants.
  • Combinations of a hydrotrope and such solvents offer some improvement over the use of either compound alone, but the combinations still result in rinse aids having limited compatibility and adversely affect food soil defoaming activity.
  • Low molecular weight polyelectrolytes have been combined with low foam surfactants in powder detergent formulations.
  • US-A-4,203,858 discloses a low foaming, phosphate-free, dishwashing composition comprising an alkali metal or ammonium carbonate, such as sodium carbonate, a water-soluble salt of a polyelectrolyte having a molecular weight of from about 500 to 4,000, and optionally up to 10 weight percent of a foam-suppressing nonionic surfactant.
  • the weight ratio of polyelectrolyte to carbonate ranges from 5:95 to 20:80.
  • Typical of the polyelectrolytes are acrylic, methacrylic, maleic and itaconic acid polymers.
  • GB-A-2,154,599 discloses detergent compositions comprising a nonionic surfactant and a phase stabilizer such as a maleic acid copolymer. None of these references, however, address or offer solutions for polyelectrolytes with low foam surfactants in rinse aid concentrates.
  • a rinse aid is dependent upon the hardness of the water used in the dishwashing machine.
  • the rinse aid conveniently has a pH of 7 or above (herein referred to as an alkaline rinse aid), and, in the case of hard water which has a high level of hardness, e.g. above about 30 French degrees of hardness, the rinse aid conveniently has a pH of less than 7 (herein referred to as an acidic rinse aid).
  • alkaline rinse aids the problem of compatibilizing low foam nonionic surfactants with polycarboxylated polymers has been overcome, and stable alkaline rinse aids have been produced, by using, as compatibilizer or stabilizer, high molecular weight copolymer formed from monomers comprising methacrylic acid and one or more of C1 to C6 alkyl (meth)acrylates and in which at least 50 percent of the acid groups in the copolymer have been neutralized with alkali (see our EP-A-0245987).
  • Such high molecular weight copolymers are, however, unsuitable for compatibilizing low foam nonionic surfactant with polycarboxylated polymer in an acidic rinse aid formulation as phase separation is found to occur.
  • low foam nonionic surfactant can be compatibilized with polycarboxylated polymer, and a stable acidic rinse aid can be formed, by using, as compatibilizer or stabilizer, further nonionic surfactant.
  • a stable composition suitable for use as, or in, an acidic rinse aid which comprises:
  • the present invention also provides a method of stabilizing an aqueous composition having a pH of less than 7 and comprising a mixture of low foam nonionic surfactant (which by its requirement of being low foaming will have a cloud point of less than 70°C) and polymer having a weight average molecular weight of 1,000 to 250,000 and being a homopolymer of acrylic acid, methacrylic acid, maleic acid 2-acrylamido-2-methylpropane sulfonic acid or acrylamide, or being a copolymer formed from two or more of acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid, hydroxyacrylic acid, C1 to C4 alkyl (meth)acrylates or amides, e.g.
  • ethyl acrylate 2 - acrylamido - 2 - methylpropane sulfonic acid (AMPS), styrene, acrylamide, isobutadiene, dimethylaminoethyl methacrylate (DMAEMA), and t-butyl acrylamide (t-BAM), the method comprising incorporating in said composition nonionic cosurfactant having a cloud point of 70°C or above, e.g. 80°C or above.
  • AMPS acrylamido - 2 - methylpropane sulfonic acid
  • DMAEMA dimethylaminoethyl methacrylate
  • t-BAM t-butyl acrylamide
  • the low foam nonionic surfactant may, for example, comprise any known low foam nonionic surfactant useful in machine dishwashing or rinse aid applications.
  • Suitable low foam nonionic surfactants include: C6 to C22 fatty alcohol/ethylene oxide condensates; polyoxypropylene - polyoxyethylene condensates; alkyl polyoxypropylene - polyoxyethylene condensates; alkyl polyoxyethylene - polyoxypropylene condensates; polyoxyalkylene glycols; benzyl ethers of polyoxyethylene condensates of alkyl phenols; and butylene oxide capped alcohol condensates, e.g.
  • R ( OC2H4 ) y ( OC4H8) x OH having the formula: R ( OC2H4 ) y ( OC4H8) x OH where R is a C8 to C18 alkyl group, y has an average value of 3.5 to 10, and x has an average value of 0.5 to 1.5.
  • Typical commercially available low foam nonionic surfactants include: Triton CF-10 (an alkylaryl polyether) and Triton DF-16 (a modified polyoxyalkylated alcohol) manufactured by Rohm and Haas Company; Pluronic L-62 (a polyoxyethylene - polyoxypropylene block copolymer), Lutensol LF 403 and Lutensol LF 404 manufactured by BASF; and Antarox BL-330 (a modified linear aliphatic alcohol polyethoxylated and chloro-terminated compound) manufactured by GAF Corporation.
  • composition of the invention may, for example, comprise at least 1 part by weight, preferably at least 5 parts by weight, and more preferably at least 10 parts by weight, of the low foam nonionic surfactant.
  • Up to 60 parts by weight, preferably up to 50 parts by weight, and more preferably up to 40 parts by weight, of the low foam nonionic surfactant may, for example, be present in the composition.
  • the polymer is a homopolymer of acrylic acid, methacrylic acid or maleic acid, or is a copolymer formed from two or more of acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid, hydroxyacrylic acid, C2 to C4 alkyl (meth)acrylates or amides and 2-acrylamido - 2 - methylpropane sulfonic acid.
  • the polymer, used in the composition of the invention may be a polycarboxylated polymer.
  • the weight average molecular weight of the polymer is at least 1,000 and is preferably up to 100,000, more preferably up to 70,000.
  • the polymer may be used in the free acid form, or in the partially neutralised or neutralised, e.g. alkali metal or ammonium salt, form when producing the composition of the invention, but is preferably used in the partially neutralised form as it may then be unnecessary to carry out a pH adjustment step to achieve the desired acidic pH.
  • Suitable commercially available polymers include Acrysol LMW 45 (an acrylic acid homopolymer which is 20% neutralised and has a weight average molecular weight of 4500), and Acrysol LMW 45N (an acrylic acid homopolymer which is fully neutralised and has a weight average molecular weight of 4500).
  • composition of the invention may, for example, comprise at least 0.5 parts by weight, preferably at least 1 part by weight, of the polymer. Up to 20 parts by weight, preferably up to 10 parts by weight, and more preferably up to 5 parts by weight, of the polymer may be present in the composition.
  • Suitable nonionic cosurfactants include alkyl aryl polyether alcohols having an average of at least ten ethylene oxide units per molecule; and alkyl polyether alcohols having an average of at least ten ethylene oxide units per molecule.
  • the cosurfactant is a reaction product of ethylene oxide with an octyl or nonyl phenol such as a compound of the formula:- or in which x has an average value of at least 10.
  • composition of the invention may, for example, comprise at least 0.1 parts by weight, preferably at least 0.5 parts by weight, of the nonionic cosurfactant. Up to 10 parts by weight, preferably up to 5 parts by weight, of the nonionic cosurfactant may, for example, be present in the composition.
  • composition of the invention may comprise one or more of each of the low foam nonionic surfactant, polymer and nonionic cosurfactant.
  • the total amount of low foam nonionic surfactant, polymer, nonionic cosurfactant and water is 100% by weight of the composition.
  • composition of the invention may comprise other additives, for example, one or more of sequestrants such as nitrilo triacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), phosphonates, citric acid, or sodium citrate, and water-miscible solvents such as isopropanol or propylene glycol.
  • sequestrants such as nitrilo triacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), phosphonates, citric acid, or sodium citrate, and water-miscible solvents such as isopropanol or propylene glycol.
  • suitable phosphonates include 1-hydroxy-ethylene-bis-phosphonic acid, nitrilo-tris(methylene phosphonic acid), ethylenediamine tetra (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), and hexamethylene diamine tetra (methylene phosphonic acid).
  • Suitable commercially available phosphonates include Dequest-2006, -2016, -2046, -2056, and -2066, manufactured by Monsanto, and Mykon -P060, -P110, -P200, -P310, and -P400, manufactured by Warwick International.
  • EDTA may be present in an amount of up to 2% by weight
  • NTA may be present in an amount of up to 4% by weight
  • citric acid may be present in an amount of up to 10% by weight
  • phosphonates may be present in an amount of up to 2% by weight. If more than one such sequestering additive is present, then the amounts of such additives present will require appropriate adjustment.
  • the above-mentioned acidic materials, useful as optional additives, can be used in the acid, partially neutralized or fully neutralized form.
  • Table 1 gives examples of a number of formulations according to the present invention, the figures quoted for each component being percentages by weight based on the total weight of the formulation and the balance being water.
  • compositions according to the present invention which remain stable for several weeks at 40°C, for at least 90 days at room temperature, and pass five (5) freeze/thaw cycles. Whilst not wishing to be bound by theory, it is thought that this stability is due to the formation of a microemulsion by the addition of the nonionic cosurfactant.
  • a stable dispersion is spontaneously formed, that is, is formed without input of mechanical energy, e.g. without agitation.
  • a cosurfactant can produce spontaneous formation of a stable dispersion due to the formation of a microemulsion, and it is believed that a similar situation is occurring in the case of the compositions of the present invention.
  • the composition of the invention may promote the wetting of a substrate, and may reduce spotting of the substrate when subsequently dried. These properties of the composition may also make it suitable for other uses, for example, as, or in, glass (e.g. window) cleaning or metal cleaning compositions.
  • This example illustrates the need to utilise a nonionic cosurfactant to stabilise an aqueous composition comprising low foam nonionic surfactant and polymer.
  • a number of formulations were prepared comprising low foam nonionic surfactant, polymer, water, and, in some formulations, nonionic cosurfactant. The stability of these formulations against phase separation at 40°C for 24 hours (or longer) was measured and the results obtained are given in Table 2 below.
  • the total weight of each of the formulations was 100 parts by weight.
  • the presence of the cosurfactant, used in the present invention enables greater concentrations of polymer to be present in the rinse aid, resulting in increased efficiency in inhibition of precipitation of hardness ion salts from water in which the rinse aid is used, without resulting in phase separation of the polymer and the low foam nonionic surfactant. That is, the cosurfactant enables stable compositions comprising low foam nonionic surfactant and polymer to be produced in which higher concentrations of polymer can be present than could be used in the prior art compositions.
  • compositions of the present invention over the prior art composition is attributable to the ability to form, in accordance with the present invention, stable compositions having a higher concentration of polymer than can be used in the prior art composition.
  • Lines (i) and (ii) of the accompanying graph also demonstrate that, the higher the concentration of polymer in the rinse aid, the greater the inhibition of hardness ion salt precipitation, particularly in medium hard and hard water and hence the higher the light transmittance,; line (i) representing the formulation comprising 10 parts by weight of polymer and line (ii) representing the formulation comprising 2 parts by weight of polymer.
  • This example illustrates two procedures for the preparation of the compositions of the present invention.
  • Triton and “Acrysol” are trademarks of Rohm and Haas Company; “Pluronic” and Lutensol” are trademarks of BASF AG; “Antarox” is a trademark of GAF Corporation; “Dequest” is a trademark of Monsanto; and “Mykon” is a trademark of Warwick International.

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Claims (18)

1. Stabile Zusammensetzung, geeignet zur Verwendung als oder in einem sauren Spülmittel, enthaltend:
(i) wenig schäumendes nichtionisches Tensid mit einem Trübungspunkt von weniger als 70 °C;
(ii) ein Polymer mit einem Gewichtsmittel des Molekulargewichts von 1.000 bis 250.000, welches ein Homopolymer darstellt aus Acrylsäure, Methacrylsäure, Maleinsäure, 2-Acrylamido-2-methylpropansulfonsäure oder Acrylamid oder ein Copolymer, welches Einheiten enthält, die abgeleitet sind aus zwei oder mehr aus Acrylsäure, Methacrylsäure, Ethacrylsäure, Maleinsäure, Itaconsäure, Hydroxyacrylsäure, C₁-C₄-Alkyl(meth)acrylaten oder -amiden, 2-Acrylamido-2-methylpropansulfonsäure, Styrol, Acrylamid, Isobutadien, Dimethylaminoethylmethacrylat und t-Butylacrylamid;
(iii) ein weiteres nichtionisches Tensid mit einem Trübungspunkt von 70 °C oder darüber, beispielsweise 80 °C oder darüber; und
(iv) Wasser;
und wobei die Zusammensetzung einen pH-Wert von weniger als 7 aufweist.
2. Zusammensetzung nach Anspruch 1, wobei das Polymer (ii) ein Homopolymer aus Acrylsäure, Methacrylsäure oder Maleinsäure ist, oder ein Copolymer, welches gebildet ist aus zwei oder mehr aus Acrylsäure, Methacrylsäure, Ethacrylsäure, Maleinsäure, Itaconsäure, Hydroxyacrylsäure, C₂-C₄-Alkyl(meth)acrylaten oder -amiden und 2-Acrylamido-2-methylpropansulfonsäure.
3. Zusammensetzung nach Anspruch 1 oder 2, wobei das Polymer (ii) ein polycarboxyliertes Polymer ist.
4. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei dem das wenig schäumende nichtionische Tensid (i) eines oder mehr enthält aus C₆-C₂₂-Fettalkohol/Ethylenoxid-Kondensaten; Polyoxypropylen/Polyoxyethylen-Kondensaten; Alkylpolyoxypropylen/Polyoxyethylen-Kondensaten; Alkylpolyoxyethylen/Polyoxypropylen-Kondensaten; Polyoxyalkylenglycolen; Benzylethern von Polyoxyethylen-Kondensaten von Alkylphenolen; und mit Butylenoxid gedeckten Alkoholkondensaten.
5. Zusammensetzung nach Anspruch 4, wobei die mit Butylenoxid gedeckten Alkoholkondensate die Formel

        R(OC₂H₄)y(OC₄H₈)xOH

aufweisen, wobei R eine C₈-C₁₈-Alkylgruppe bedeutet; y einen mittleren Wert von 3,5 bis 10 hat und x einen mittleren Wert von 0,5 bis 1,5 hat.
6. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei dem das wenig schäumende nichtionische Tensid (i) anwesend ist in einer Menge von mindestens 1 Gewichtsteil, bevorzugt mindestens 5 Gewichtsteilen, bevorzugter mindestens 10 Gewichtsteilen, pro 100 Gewichtsteile von (i), (ii), (iii) plus (iv).
7. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der das wenig schäumende nichtionische Tensid (i) anwesend ist in einer Menge von bis zu 60 Gewichtsteilen, bevorzugt bis zu 50 Gewichtsteilen, bevorzugter bis zu 40 Gewichtsteilen, pro 100 Gewichtsteile von (i), (ii), (iii) plus (iv).
8. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Polymer (ii) ein Gewichtsmittel des Molekulargewichts von bis zu 100.000 aufweist, bevorzugt bis zu 70.000.
9. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Polymer (ii) teilweise neutralisiert ist.
10. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Polymer (ii) anwesend ist in einer Menge von mindestens 0,5 Gewichtsteilen, bevorzugt mindestens 1 Gewichtsteil, pro 100 Gewichtsteile von (i), (ii), (iii) plus (iv).
11. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Polymer (ii) anwesend ist in einer Menge von bis zu 20 Gewichtsteilen, bevorzugt bis zu 10 Gewichtsteilen, bevorzugter bis zu 50 Gewichtsteilen pro 100 Gewichtsteile von (i), (ii), (iii) plus (iv).
12. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das weitere nichtionische Tensid (iii) Alkylarylpolyetheralkohole mit einem Mittel von mindestens zehn Ethylenoxideinheiten pro Molekül und Alkylpolyetheralkohole mit einem Mittel von mindestens zehn Ethylenoxideinheiten pro Molekül enthält.
13. Zusammensetzung nach Anspruch 12, wobei die Alkylarylpolyetheralkohole Verbindungen der Formel
Figure imgb0009
 oder
Figure imgb0010
 enthalten, wobei x einen Mittelwert von mindestens 10 hat.
14. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das weitere nichtionische Tensid (iii) anwesend ist in einer Menge von mindestens 0,1 Gewichtsteilen, bevorzugt mindestens 0,5 Gewichtsteilen, pro 100 Gewichtsteile von (i), (ii), (iii) plus (iv).
15. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das weitere nichtionische Tensid (iii) anwesend ist in einer Menge von bis zu 10 Gewichtsteilen, bevorzugt bis zu 5 Gewichtsteilen, pro 100 Gewichtsteile von (i), (ii), (iii) plus (iv).
16. Verfahren zum Stabilisieren einer wäßrigen Zusammensetzung mit einem pH-Wert von weniger als 7, enthaltend ein Gemisch aus einem wenig schäumenden nichtionischen Tensid mit einem Trübungspunkt von weniger als 70 °C und ein Polymer mit einem Gewichtsmittel des Molekulargewichts von 1.000 bis 250.000, welches ein Homopolymer aus Acrylsäure, Methacrylsäure, Maleinsäure, 2-Acrylamido-2-methylpropansulfonsäure oder Arcylamid darstellt oder ein Copolymer, welches Einheiten enthält, die abgeleitet sind aus zwei oder mehr aus Acrylsäure, Methacrylsäure, Ethacrylsäure, Maleinsäure, Itaconsäure, Hydroxyacrylsäure, C₁-C₄-Alkyl(meth)acrylaten oder -amiden, 2-Acrylamido-2-methylpropansulfonsäure, Styrol, Acrylamid, Isobutadien, Dimethylaminoethylmethacrylat und t-Butylacrylamid, wobei man bei dem Verfahren in die Zusammensetzung außerdem ein nichtionisches Tensid mit einem Trübungspunkt von 70 °C oder darüber einbringt, beispielsweise 80 °C oder darüber.
17. Verfahren nach Anspruch 16, wobei das wenig schäumende nichtionische Tensid, das Polymer und das weitere nichtionische Tensid und deren Mengen so sind, wie in einem der Ansprüche 2 bis 15 definiert.
18. Verwendung eines nichtionischen Tensids mit einem Trübungspunkt von 70 °C oder darüber, beispielsweise 80 °C oder darüber, zum Stabilisieren einer wäßrigen Zusammensetzung mit einem pH-Wert von weniger als 7, enthaltend ein wenig schäumendes nichtionisches Tensid mit einem Trübungspunkt von weniger als 70 °C und Polymer, wobei das Polymer so ist wie in den Ansprüchen 1, 2 oder 3 definiert.
EP88308536A 1987-09-18 1988-09-15 Zusammensetzung, geeignet zur Verwendung als oder in sauren Klarspülmitteln Expired - Lifetime EP0308221B1 (de)

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GB8721936 1987-09-18
GB878721936A GB8721936D0 (en) 1987-09-18 1987-09-18 Composition

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EP0308221B1 true EP0308221B1 (de) 1992-04-29

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EP (1) EP0308221B1 (de)
JP (1) JPH01158098A (de)
AU (1) AU607535B2 (de)
CA (1) CA1314187C (de)
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GB (1) GB8721936D0 (de)
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ZA (1) ZA886913B (de)

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WO1992015664A1 (en) * 1991-03-04 1992-09-17 Ciba-Geigy Ag Aqueous textile auxiliary composition
EP0522756A1 (de) * 1991-06-28 1993-01-13 Calgon Corporation Ampholitische Terpolymere mit verbesserten Konditionierungseigenschaften in Shampoozusammensetzungen und Haarpflegemitteln
US5591703A (en) * 1993-04-27 1997-01-07 The Procter & Gamble Company Liquid or granular automatic diswashing detergent compositions containing builder, enzyme and low molecular weight, modified polyacrylate copolymers
US5597789A (en) * 1993-04-27 1997-01-28 The Procter & Gamble Company Liquid or granular automatic dishwashing detergent compositions containing silicate and low molecular weight modified polyacrylate coploymers
US5739099A (en) * 1995-12-06 1998-04-14 Basf Corporation Rinse aid compositions containing modified acrylic polymers
US5753608A (en) * 1996-12-28 1998-05-19 Basf Corporation Rinse aid compositions containing phosphate esters
EP0851021A2 (de) * 1996-12-28 1998-07-01 Basf Corporation Verbesserte Klarspülmittelzusammensetzungen
US5880087A (en) * 1996-12-28 1999-03-09 Zack; Kenneth L. Rinse and compositions containing alkyliminodialkanoates
US6630440B1 (en) 1998-08-03 2003-10-07 The Procter & Gamble Company Rinse-aid formulation
US9809786B2 (en) 2015-01-07 2017-11-07 Ecolab Use Inc. Rinse aid composition comprising a terpolmer of maleic, vinyl acetate and ethyl acrylate
US11118140B2 (en) 2014-08-29 2021-09-14 Ecolab Usa Inc. Solid rinse aid composition comprising polyacrylic acid

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US4826618A (en) * 1984-02-22 1989-05-02 Diversey Corporation Stable detergent emulsions
GB9310365D0 (en) † 1993-05-18 1993-06-30 Unilever Plc Hard surface cleaning compositions comprising polymers
DE4323638A1 (de) * 1993-07-15 1995-01-19 Henkel Kgaa Verhinderung von Wasserflecken bei der technischen Reinigung
EP0638635A1 (de) * 1993-08-12 1995-02-15 Ciba-Geigy Ag Wässrige Textilhilfsmittel
AU6274594A (en) * 1993-10-14 1995-05-04 Ecolab Inc. Rinse agents that form clear coatings on ware
DE4415804A1 (de) * 1994-05-05 1995-11-09 Henkel Kgaa Klarspülmittel mit biologisch abbaubaren Polymeren
EP0778340A3 (de) * 1995-12-06 1999-10-27 Basf Corporation Phosphatfreie Geschirreinigungsmittelzusammensetzungen, enthaltend Copolymere von Alkylenoxid-Addukten von Allylalkohol und Acrylsäure
US6210600B1 (en) * 1996-12-23 2001-04-03 Lever Brothers Company, Division Of Conopco, Inc. Rinse aid compositions containing scale inhibiting polymers
US6730645B1 (en) 1999-01-22 2004-05-04 The Procter & Gamble Company Method for improving dye stability in colored acidic rinse-aid formulations
ES2204523T3 (es) * 1999-01-22 2004-05-01 THE PROCTER & GAMBLE COMPANY Metodo para mejorar la estabilidad de un colorante en formulaciones de ayuda al enjuague acidas, coloreadas.
AU2002214027A1 (en) * 2000-10-25 2002-05-06 Unilever Plc Dish-washing compositions
US7390776B2 (en) 2002-09-13 2008-06-24 Nippon Shokubai Co., Ltd. Liquid detergent builder and liquid detergent containing the same
US7241726B2 (en) * 2003-10-16 2007-07-10 The Procter & Gamble Company Complete-cycle methods for protecting glassware from surface corrosion in automatic dishwashing appliances
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CN107075418B (zh) * 2014-10-09 2020-11-13 罗门哈斯公司 用于在自动餐具洗涤体系中减少污渍的添加剂
AU2015328204B2 (en) * 2014-10-09 2019-04-04 Rohm And Haas Company Additive for reducing spotting in automatic dishwashing systems
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CA666119A (en) * 1960-02-02 1963-07-02 A. Wright William Liquid detergent composition
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ZA851023B (en) * 1984-02-22 1985-09-25 Diversey Corp Stable detergent emulsions
US4678596A (en) * 1986-05-01 1987-07-07 Rohm And Haas Company Rinse aid formulation

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992015664A1 (en) * 1991-03-04 1992-09-17 Ciba-Geigy Ag Aqueous textile auxiliary composition
US5559273A (en) * 1991-03-04 1996-09-24 Ciba-Geigy Corporation Aqueous textile auxiliary compositions
EP0522756A1 (de) * 1991-06-28 1993-01-13 Calgon Corporation Ampholitische Terpolymere mit verbesserten Konditionierungseigenschaften in Shampoozusammensetzungen und Haarpflegemitteln
US5591703A (en) * 1993-04-27 1997-01-07 The Procter & Gamble Company Liquid or granular automatic diswashing detergent compositions containing builder, enzyme and low molecular weight, modified polyacrylate copolymers
US5597789A (en) * 1993-04-27 1997-01-28 The Procter & Gamble Company Liquid or granular automatic dishwashing detergent compositions containing silicate and low molecular weight modified polyacrylate coploymers
US5739099A (en) * 1995-12-06 1998-04-14 Basf Corporation Rinse aid compositions containing modified acrylic polymers
US5753608A (en) * 1996-12-28 1998-05-19 Basf Corporation Rinse aid compositions containing phosphate esters
EP0851021A2 (de) * 1996-12-28 1998-07-01 Basf Corporation Verbesserte Klarspülmittelzusammensetzungen
US5880087A (en) * 1996-12-28 1999-03-09 Zack; Kenneth L. Rinse and compositions containing alkyliminodialkanoates
US6630440B1 (en) 1998-08-03 2003-10-07 The Procter & Gamble Company Rinse-aid formulation
US11118140B2 (en) 2014-08-29 2021-09-14 Ecolab Usa Inc. Solid rinse aid composition comprising polyacrylic acid
US11624043B2 (en) 2014-08-29 2023-04-11 Ecolab Usa Inc. Solid rinse aid composition comprising polyacrylic acid
US9809786B2 (en) 2015-01-07 2017-11-07 Ecolab Use Inc. Rinse aid composition comprising a terpolmer of maleic, vinyl acetate and ethyl acrylate
US10208272B2 (en) 2015-01-07 2019-02-19 Ecolab Usa Inc. Rinse aid composition comprising a terpolmer of maleic, vinyl acetate and ethyl acrylate

Also Published As

Publication number Publication date
NO172751C (no) 1993-09-01
EP0308221A1 (de) 1989-03-22
GB8721936D0 (en) 1987-10-28
AU607535B2 (en) 1991-03-07
NO884074D0 (no) 1988-09-14
NO172751B (no) 1993-05-24
JPH01158098A (ja) 1989-06-21
DE3870560D1 (de) 1992-06-04
AU2231488A (en) 1989-03-23
ZA886913B (en) 1989-05-30
CA1314187C (en) 1993-03-09
NO884074L (no) 1989-03-20

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