WO1991000901A1 - Agents de lavage et de nettoyage liquides exempts de phosphates - Google Patents

Agents de lavage et de nettoyage liquides exempts de phosphates Download PDF

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Publication number
WO1991000901A1
WO1991000901A1 PCT/EP1990/001058 EP9001058W WO9100901A1 WO 1991000901 A1 WO1991000901 A1 WO 1991000901A1 EP 9001058 W EP9001058 W EP 9001058W WO 9100901 A1 WO9100901 A1 WO 9100901A1
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WO
WIPO (PCT)
Prior art keywords
weight
potassium
sodium
composition according
acid
Prior art date
Application number
PCT/EP1990/001058
Other languages
German (de)
English (en)
Inventor
Walter Schwizer
Vincenzo Violante
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1991000901A1 publication Critical patent/WO1991000901A1/fr
Priority to DK001692A priority Critical patent/DK1692A/da

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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
    • C11D3/3765—(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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • the invention relates to a liquid washing and cleaning agent which contains neither phosphate nor chlorine and which can be used universally in particular in commercial and institutional facilities for washing and cleaning textiles and objects with hard surfaces.
  • German patent application 18 06 206 describes a liquid dishwashing detergent which contains 10-50% by weight of alkali metal hydroxide, preferably potassium hydroxide, 5-30% by weight of alkali metal salts of nitrilotriacetic acid (NTA) and 5-30% by weight of alkali metal pyro- contains phosphate.
  • alkali metal hydroxide preferably potassium hydroxide
  • NTA nitrilotriacetic acid
  • alkali metal pyro- contains phosphate.
  • alkaline cleaning agents which are used as automatic dishwashing detergents and contain alkali metal hydroxide, alkali metal carbonate or alkali metal silicate, and as complexing agents the salts of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid or organic phosphonic acids and optionally water.
  • EDTA ethylenediaminetetraacetic acid
  • nitrilotriacetic acid or organic phosphonic acids and optionally water.
  • Japanese patent application 59/227 997 describes liquid cleaning agents for hard surfaces which contain 5-40% by weight of sodium or potassium hydroxide and 2-40% by weight of one Alkali salt of nitrilotriacetic acid, 2 to 40% by weight of a copolymer of isoptenes and maleic anhydride and optionally up to 5% by weight sodium metasilicate and up to 5% by weight of surfactants.
  • US Pat. No. 4,521,332 discloses liquid, alkaline cleaning agent dispersions which contain 10-45% by weight sodium hydroxide, 0.04% by weight of an acrylic polymer as a dispersing agent, 0.5-20% by weight sodium or potassium carbonate, containing 0.25-3% by weight of a complexing agent such as, for example, NTA salts and 0-15% by weight of an alkali metal phosphate former.
  • Known cleaning agents for alkali-sensitive surfaces especially for aluminum, therefore preferably do not contain any free alkali hydroxide.
  • European patent application 282 921 describes liquid, phosphate-free single-phase degreasing agents for aluminum surfaces which contain mixtures of alkali metal carbonates and alkali metal bicarbonates, one or more complexing agents, which include acrylic polymers, EDTA, NTA, citric acid, gluconic acid and their salts.
  • US Pat. No. 4,528,039 discloses aqueous alkaline cleaning agents, especially for cleaning aluminum surfaces, which contain mixtures of carbonate and Metasilicate, preferably in the form of their sodium salts, in a weight ratio of 20: 1 to 1: 2 and optionally further constituents such as, for example, surfactants, thickeners, organic solvents, colorants and fragrances.
  • the object of the invention was to provide a washing and cleaning agent which can be used universally and which is toxic-free and contains a maximum of 5% by weight of free alkali metal hydroxide.
  • the invention relates to a phosphate-free, liquid washing and cleaning agent containing (A) 5-60% by weight potassium carbonate,
  • the constituents contained in the compositions, which are used in the form of their salts, can be present with the exception of (A) as sodium and / or potassium salts.
  • the potassium to sodium weight ratio in the agents according to the invention is preferably at least 3: 1. Potassium to sodium weight ratios between 5: 1 and 60: 1, in particular between 7: 1 and 50: 1 are particularly preferred is also the use of all salt-like components in the form of the potassium salts.
  • the proportion of potassium carbonate (A) in the agents according to the invention is 5-60% by weight. Potassium carbonate is preferably used in amounts of 10-55% by weight and in particular 20-50% by weight.
  • the alkali silicates (B) used are sodium or potassium silicates or mixtures thereof with a molar ratio of M2O to SiO 2 of 1: 2 to 1: 4, where M represents the alkali metal cation. Potassium silicates are preferably used.
  • the proportion of alkali silicates (B) in the agents according to the invention is 1-40% by weight, preferably 1.5-20% by weight and in particular 2-10% by weight.
  • the organic builder substances (C) are the alkali metal salts of polycarboxylic acids such as citric acid, tartaric acid and succinic acid, of nitrilotriacetic acid (NTA) and of polyphosphonic acids such as l-hydroxyethane-l, l-diphosphonic acid (HEDP) and diethylenetriamine-pentamethylenephosphonic acid (DTP ). NTA and HEDP are preferably used in the form of their sodium or potassium salts.
  • the proportion of organic builder substances (C) in the agents according to the invention is 1 to 30% by weight, preferably 1 to 20% by weight, polycarboxylates 0 to 100% by weight and phosphonates 0 to 20% by weight.
  • nitrilotriacetic acid in the form of the sodium salt, amounts of 2-10% by weight are preferred. It is also advantageous to use mixtures, for example consisting of 0-15% by weight of salts of citric acid, 2-10% by weight of salts of nitrilotriacetic acid and 0.5-2% by weight of salts of l-hydroxyethane-1 , l-diphosphonic acid.
  • Suitable polymeric complexing agents (D) are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates, polymaleinates and, in particular, copolymeric alkali metal salts of acrylic acid with maleic acid, preferably those with 10 to 50% maleic acid, sodium and potassium salts being equally preferred .
  • the molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 and 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Compounds of this class which are advantageously used are also salts of copolymers of acrylic acid, methacrylic acid or maleic acid or maleic anhydride with vinyl ethers, in which the proportion of the acid is at least 50% by weight.
  • the use of copolymers of maleic anhydride and methyl vinyl ether in the form of their sodium and / or potassium salts has proven to be particularly favorable.
  • the content of polymeric complexing agents (D) in the agents according to the invention is between 1 and 20% by weight.
  • the agents according to the invention preferably contain 1.5-20% by weight and in particular 2-5% by weight (D).
  • the water content of the agents according to the invention is between 30 and 80% by weight, preferably between 30 and 60% by weight and in particular between 35 and 55% by weight.
  • the inventive compositions are preferably clear aqueous Lö ⁇ solutions with a pH 11 to 14
  • the viscosity of the compositions is 20 ⁇ C under 200 Pa, preferably the Vis ⁇ is viscosity by less than 150 mPa.
  • the agents also have the advantage that they are stable in storage even under extreme temperature conditions such as -20 ° C., ie no settling of essential components is observed and remain pourable. In addition, they are free from organic solvents and show no corrosive effects on metallic devices and hard surfaces made of steel or light metals such as aluminum.
  • the agents can contain 0-5% by weight of alkali hydroxide.
  • the use of potassium hydroxide is preferred in amounts of 0.5-4% by weight, in particular in amounts of 0.5-3% by weight.
  • low-foaming, alkali-resistant, customary anionic, nonionic or amphoteric surfactants in amounts of up to 10% by weight, preferably from 0.5 to 5% by weight and in particular from 0.5 to Add 3 wt .-%.
  • the agents can contain additional ingredients such as colorants and fragrances.
  • optical brighteners such as water-soluble salts of ether carboxylic acids or ether sulfonic acids, cellulose or starch, and bleaching agents.
  • the total content of these additional constituents in the agents is 0-10% by weight, preferably 0.5-5% by weight.
  • the compositions consist of 20-55% by weight of potassium carbonate, 1.5-20% by weight of potassium silicate with a molar ratio of K2O: SiO2 of 1: 2 to 1: 4, 3-10% by weight.
  • an organic builder in the form of the sodium salts preferably sodium salts of nitrilotriacetic acid, 1.5-10% by weight of a copolymer in the form of the sodium salt, preferably copolymers of acrylic acid and maleic acid or of maleic anhydride and methyl vinyl ether, and 30-60% by weight .-% Water.
  • the weight ratio of potassium to sodium is between 7: 1 and 50: 1.
  • the agents consist of 20-50% by weight of potassium carbonate, 1.5-20% by weight of potassium silicate with a molar ratio of K2O: SiO2 of 1: 2 to 1: 4, 2-10% by weight.
  • % Sodium salts of nitrilotriacetic acid, 1.5-5% by weight of a copolymer in the form of the sodium salt of acrylic acid and maleic acid or of maleic anhydride and methyl vinyl ether, 0.5-4 % By weight sodium or potassium hydroxide and 35-60% by weight water.
  • the weight ratio of potassium to sodium is between 5: 1 and 50: 1.
  • compositions consisting of 22-50% by weight of potassium carbonate, 1.5-20% by weight of potassium silicate with a molar ratio of K2O: S1O2 of 1: 2 to 1: 4, 2-10% by weight.
  • the potassium to sodium weight ratio is greater than 5: 1.
  • Embodiments are also preferred in which the agents contain the above-described constituents in the above amounts and additionally 1-10% by weight of further constituents such as surfactants, colorants and fragrances and bleaches.
  • the invention further relates to a method for producing the detergents and cleaning agents described above, in which the components are mixed with one another in a manner known per se.
  • the alkali metal hydroxide, the alkali metal silicate (both components if provided) and the organic builder substance are preferably dissolved in demineralized water with stirring.
  • a temperature of between 30 is achieved by means of external cooling and set at 60 ° C.
  • the addition of the other constituents such as potassium carbonate, polymeric complexing agent, optionally surfactants, colorants and fragrances, optical brighteners, graying inhibitors and bleaching agents can be carried out in any order.
  • the solution is filtered.
  • the agents according to the invention can be used both as detergents for textiles and as cleaning agents for hard surfaces.
  • the use as a phosphate-free dishwashing detergent in plants which have a liquid dosage is preferred, as is the use as a non-corrosive leaching, degreasing and cleaning agent for devices with metal surfaces, which contain steel or aluminum, for example, and in the dyeing , Food and metal industries are used.
  • the agents can also be used as immersion cleaners or low-foaming spray cleaners for smaller devices.
  • the example describes the production of a detergent and cleaning agent which contains no free alkali metal hydroxide.
  • agents according to the invention were also obtained by completely replacing the sodium salt of nitrilotriacetic acid used in Example 1 with citrates, succinates or tartrates, or by adding 1% by weight, based on the total, of the sodium salt of nitrilotriacetic acid used in Example 1 Agent replaced by the sodium salt of l-hydroxyethane-l, l-diphosphonic acid.
  • Example 1 further agents according to the invention were obtained in that in Example 1 the 35% solution of Sokalan CP2 by a 35% solution of Sokalan CP5 or by Sokalan CP 7 or Sokalan CP 8 (copoly ere sodium salts from acrylic acid and maleic acid, brand name of BASF AG) was replaced.
  • the example describes the production of a detergent and cleaning agent which contains free potassium hydroxide.
  • 8.5 kg of potassium hydroxide (90 * active substance) were dissolved in 410 kg of demineralized water with stirring and external cooling at 55 ° C.
  • 85 kg of Kauai water glass (30 * active substance) 48 kg of sodium salt of nitrilotriacetic acid (92 * active substance)
  • 380 kg of potassium carbonate powder 68.5 kg of a 35% aqueous solution of Sokalan CP2 were added in succession added with stirring, dissolved and filtered.
  • agents according to the invention were also obtained by partially (at 15% by weight, based on the amount of sodium salt of nitrilotriacetic acid used in Example 3), using sodium citrate or potassium citrate or by the sodium salt of 1- Hydroxyethane-l, l-di- phosphonic acid or replaced by diethylenetriaminepentamethyl ⁇ phosphonic acid.
  • This example describes the application test carried out in a household washing machine with a horizontally arranged washing drum (type: Adora 4) under the following conditions:
  • Washing temperature 40 ° C, 60 ° C and 95 ⁇ C single eye process
  • the tested textile detergent W according to the invention had the following composition:
  • composition of the comparison formula V a conventional commercial textile detergent with a high alkali hydroxide content, was as follows:

Abstract

Les agents de lavage et de nettoyage exempts de phosphates et de chlore renferment 5 à 60 % en poids de carbonate de potassium, 1 à 40 % en poids de silicate alcalin, 1 à 30 % en poids d'une substance organique de constitution, 1 à 20 % en poids d'un agent complexant polymère, 30 à 80 % en poids d'eau et 0 à 5 % en poids d'hydroxyde alcalin libre. Ces agents sont d'un emploi universel, ne présentent aucun inconvénient sur le plan toxicité et n'exercent aucune action corrosive vis-à-vis de surfaces métalliques telles qu'en acier ou en aluminium.
PCT/EP1990/001058 1989-07-10 1990-07-02 Agents de lavage et de nettoyage liquides exempts de phosphates WO1991000901A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DK001692A DK1692A (da) 1989-07-10 1992-01-07 Phosphatfrit, flydende vaskek- og rengoeringsmiddel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP89112552.8 1989-07-10
EP89112552A EP0407626A1 (fr) 1989-07-10 1989-07-10 Composition liquide détergente et nettoyante exempte de phosphate

Publications (1)

Publication Number Publication Date
WO1991000901A1 true WO1991000901A1 (fr) 1991-01-24

Family

ID=8201602

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1990/001058 WO1991000901A1 (fr) 1989-07-10 1990-07-02 Agents de lavage et de nettoyage liquides exempts de phosphates

Country Status (4)

Country Link
EP (1) EP0407626A1 (fr)
DK (1) DK1692A (fr)
PT (1) PT94637A (fr)
WO (1) WO1991000901A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994004639A1 (fr) * 1992-08-11 1994-03-03 Unilever Plc Compositions liquides
US7728170B2 (en) 2002-09-18 2010-06-01 Roquette Freres Method for preparing a polycarboxylic composition comprising an electrochemical oxidation stage of a monosaccharide composition

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5433885A (en) * 1991-07-17 1995-07-18 Church & Dwight Co., Inc. Stabilization of silicate solutions
US5234505A (en) * 1991-07-17 1993-08-10 Church & Dwight Co., Inc. Stabilization of silicate solutions
US5234506A (en) * 1991-07-17 1993-08-10 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and method
ZA935690B (en) * 1992-08-28 1995-02-06 Crosfield Joseph & Sons Alkall containing silica solution

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627686A (en) * 1968-09-30 1971-12-14 Chemed Corp Machine dishwashing compositions containing sodium polyacrylate and nta
DE2435479A1 (de) * 1974-07-24 1976-02-12 Henkel & Cie Gmbh Geschirrspuelmittel
GB2086410A (en) * 1980-10-11 1982-05-12 Sandoz Ltd Fabric washing compositions
US4457322A (en) * 1983-02-11 1984-07-03 Lever Brothers Company Alkaline cleaning compositions non-corrosive toward aluminum surfaces
EP0120533A2 (fr) * 1983-03-25 1984-10-03 Unilever N.V. Composition détergente aqueuse alcaline liquide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627686A (en) * 1968-09-30 1971-12-14 Chemed Corp Machine dishwashing compositions containing sodium polyacrylate and nta
DE2435479A1 (de) * 1974-07-24 1976-02-12 Henkel & Cie Gmbh Geschirrspuelmittel
GB2086410A (en) * 1980-10-11 1982-05-12 Sandoz Ltd Fabric washing compositions
US4457322A (en) * 1983-02-11 1984-07-03 Lever Brothers Company Alkaline cleaning compositions non-corrosive toward aluminum surfaces
EP0120533A2 (fr) * 1983-03-25 1984-10-03 Unilever N.V. Composition détergente aqueuse alcaline liquide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994004639A1 (fr) * 1992-08-11 1994-03-03 Unilever Plc Compositions liquides
US7728170B2 (en) 2002-09-18 2010-06-01 Roquette Freres Method for preparing a polycarboxylic composition comprising an electrochemical oxidation stage of a monosaccharide composition

Also Published As

Publication number Publication date
DK1692D0 (da) 1992-01-07
PT94637A (pt) 1991-03-20
DK1692A (da) 1992-01-07
EP0407626A1 (fr) 1991-01-16

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