EP0407626A1 - Composition liquide détergente et nettoyante exempte de phosphate - Google Patents

Composition liquide détergente et nettoyante exempte de phosphate Download PDF

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Publication number
EP0407626A1
EP0407626A1 EP89112552A EP89112552A EP0407626A1 EP 0407626 A1 EP0407626 A1 EP 0407626A1 EP 89112552 A EP89112552 A EP 89112552A EP 89112552 A EP89112552 A EP 89112552A EP 0407626 A1 EP0407626 A1 EP 0407626A1
Authority
EP
European Patent Office
Prior art keywords
weight
potassium
sodium
composition according
agents
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.)
Withdrawn
Application number
EP89112552A
Other languages
German (de)
English (en)
Inventor
Walter Schwizer
Vincenzo Dr. Violante
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP89112552A priority Critical patent/EP0407626A1/fr
Priority to PCT/EP1990/001058 priority patent/WO1991000901A1/fr
Priority to PT9463790A priority patent/PT94637A/pt
Publication of EP0407626A1 publication Critical patent/EP0407626A1/fr
Priority to DK001692A priority patent/DK1692A/da
Withdrawn legal-status Critical Current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
    • C11D3/3765—(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 detergent and cleaning agent which contains neither phosphate nor chlorine and 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, preferably potassium hydroxide, 5-30% by weight of alkali metal salts of nitrilotriacetic acid (NTA) and 5-30% by weight of alkali metal pyrophosphate.
  • alkali metal preferably potassium hydroxide
  • NTA nitrilotriacetic acid
  • 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 - 40 wt .-% of a copolymer of isopentene and maleic anhydride and optionally up to 5 wt .-% sodium metasilicate and up to 5 wt .-% 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, 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.
  • these agents are only used in certain areas of application. For example, these agents cannot be used as degreasing and cleaning agents for alkali-sensitive surfaces such as aluminum or in the food industry.
  • 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 its 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 universally usable washing and cleaning agent 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, (B) 1-40% by weight alkali silicate with a molar ratio of M2O: SiO2 of 1: 2 to 1: 4 , where M is sodium or potassium, (C) 1-30% by weight of an organic builder, (D) 1-20% by weight of a polymeric complexing agent and (E) 30-80% by weight of water with which Provided that the components (A) to (D) are calculated as anhydrous substances.
  • the constituents contained in the compositions, which are used in the form of their salts, can be present as sodium and / or potassium salts.
  • the weight ratio of potassium to sodium in the agents according to the invention is preferably at least 3: 1. Weight ratios of potassium to sodium are particularly preferably between 5: 1 and 60: 1, in particular between 7: 1 and 50: 1.
  • the use of all salt-like substances is also advantageous Ingredients 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 of these with a molar ratio of M2O to SiO2 of 1: 2 to 1: 4, where M is 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 salts of polycarboxylic acids such as citric acid, tartaric acid and succinic acid, of nitrilotriacetic acid (NTA) and of polyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriamine-pentamethylenephosphonic acid (DTPMP). 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. , based on the total amount of organic builder substance.
  • 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 salts of citric acid, 2-10% by weight salts of nitrilotriacetic acid and 0.5-2% by weight salts of 1-hydroxyethane-1, 1-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 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, 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 agents according to the invention are preferably clear aqueous solutions with a pH between 11 and 14.
  • the viscosity of the agents at 20 ° C. is below 200 mPa, preferably the viscosity is 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, d. H. no settling of essential components is observed and remains 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 metal hydroxide.
  • the use of potassium hydroxide is preferred in quantities of 0.5-4% by weight, in particular in quantities 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 - Add 3 wt .-%.
  • the agents can contain additional constituents such as dyes and fragrances, optical brighteners, graying inhibitors, such as water-soluble salts of ether carboxylic acids or ether sulfonic acids, cellulose or starch, and bleaching agents.
  • additional constituents such as dyes and fragrances, optical brighteners, graying inhibitors, 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 components in the agents is 0-10% by weight, preferably 0.5-5% by weight.
  • the agents 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 of 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.
  • agents consisting of 22-50% by weight potassium carbonate, 1.5-20% by weight potassium silicate with a molar ratio of K2O: SiO2 of 1: 2 to 1: 4, 2-10% by weight sodium salt nitrilotriacetic acid, 0.5-1.5% by weight sodium salt of 1-hydroxyethane-1,1-diphosphonic acid, 1.5-5% by weight of a copolymer in the form of the sodium salt, preferably a copolymer of acrylic acid and maleic acid or from Maleic anhydride and methyl vinyl ether, 0-15% by weight sodium citrate, 0-4% by weight potassium hydroxide and 35-55% by weight water.
  • the weight ratio of potassium to sodium is greater than 5: 1.
  • compositions 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 between 30 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 systems that have a liquid dosage is preferred, as is the use as a non-corrosive leaching, degreasing and cleaning agent for devices with metal surfaces that contain steel or aluminum, for example, and in which color, food and the metal industry.
  • 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 that does not contain any free alkali hydroxide.
  • 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 (copolymeric sodium salts from acrylic acid and maleic acid, brand name of BASF AG) was replaced.
  • the example describes the production of a washing 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 potassium water glass (30% active substance) 48 kg of sodium salt of nitrilotriacetic acid (92% of active substance), 380 kg of potassium carbonate powder and 68.5 kg of a 35% strength aqueous solution of Sokalan CP2 were added, while stirring, dissolved and filtered.
  • This example describes the application test that was 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 Leaching process water hardness: 14 ° d (140 mg CaO per liter) Detergent dosage: 40 g Textile samples: 2 test strips with the same soiling and 2 kg of clean laundry
  • the tested textile detergent W according to the invention had the following composition: 38% by weight potassium carbonate 9% by weight potassium water glass (30% active substance ) 0.5% by weight potassium hydroxide (90% active substance) 5% by weight of nitrilotriacetic acid trisodium salt (92 active substance) 7% by weight Sokalan CP 5 (acrylic acid-maleic acid copolymer, Na salt; 35% active substance) Rest of water
  • composition of the comparison recipe V a conventional commercial textile detergent with a high alkali hydroxide content, was: 9.5% by weight potassium water glass (30% active substance) 23.5% by weight potassium hydroxide (90% active substance) 5% by weight nitrilotriacetic acid trisodium salt (92% active substance) 8.5% by weight Sokalan CP 5 (35% active substance) Rest of water

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP89112552A 1989-07-10 1989-07-10 Composition liquide détergente et nettoyante exempte de phosphate Withdrawn EP0407626A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP89112552A EP0407626A1 (fr) 1989-07-10 1989-07-10 Composition liquide détergente et nettoyante exempte de phosphate
PCT/EP1990/001058 WO1991000901A1 (fr) 1989-07-10 1990-07-02 Agents de lavage et de nettoyage liquides exempts de phosphates
PT9463790A PT94637A (pt) 1989-07-10 1990-07-09 Processo para a preparacao de composicoes de limpeza e de lavagem liquidas e isentas de fosfatos
DK001692A DK1692A (da) 1989-07-10 1992-01-07 Phosphatfrit, flydende vaskek- og rengoeringsmiddel

Applications Claiming Priority (1)

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

Publications (1)

Publication Number Publication Date
EP0407626A1 true EP0407626A1 (fr) 1991-01-16

Family

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Family Applications (1)

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

Country Status (4)

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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0585038A1 (fr) * 1992-08-28 1994-03-02 Crosfield Limited Solution alcaline de silica
US5393448A (en) * 1991-07-17 1995-02-28 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and method
US5397495A (en) * 1991-07-17 1995-03-14 Church & Dwight Co. Inc. Stabilization of silicate solutions
US5433885A (en) * 1991-07-17 1995-07-18 Church & Dwight Co., Inc. Stabilization of silicate solutions

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9217001D0 (en) * 1992-08-11 1992-09-23 Unilever Plc Liquid compositions
FR2844525B1 (fr) 2002-09-18 2005-06-03 Roquette Freres Procede de preparation d'une composition polycarboxylique comprenant une etape d'oxydation electrochimique d'une composition monosaccharidique

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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5393448A (en) * 1991-07-17 1995-02-28 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and method
US5397495A (en) * 1991-07-17 1995-03-14 Church & Dwight Co. Inc. Stabilization of silicate solutions
US5433885A (en) * 1991-07-17 1995-07-18 Church & Dwight Co., Inc. Stabilization of silicate solutions
US5549761A (en) * 1991-07-17 1996-08-27 Church & Dwight Co., Inc. Method for removing rosin soldering flux from a printed wiring board
EP0585038A1 (fr) * 1992-08-28 1994-03-02 Crosfield Limited Solution alcaline de silica

Also Published As

Publication number Publication date
WO1991000901A1 (fr) 1991-01-24
PT94637A (pt) 1991-03-20
DK1692D0 (da) 1992-01-07
DK1692A (da) 1992-01-07

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