EP0025147B1 - Flüssiges, phosphatarmes und umweltfreundliches Waschmittel - Google Patents

Flüssiges, phosphatarmes und umweltfreundliches Waschmittel Download PDF

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Publication number
EP0025147B1
EP0025147B1 EP80104929A EP80104929A EP0025147B1 EP 0025147 B1 EP0025147 B1 EP 0025147B1 EP 80104929 A EP80104929 A EP 80104929A EP 80104929 A EP80104929 A EP 80104929A EP 0025147 B1 EP0025147 B1 EP 0025147B1
Authority
EP
European Patent Office
Prior art keywords
phosphate
ionic surface
ethylene oxide
ethoxylation
agent according
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
Application number
EP80104929A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0025147A1 (de
Inventor
Rolf M. Dr. Schwiete
Peter Dr. Pfeiffer
Manfred Ochsenschläger
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.)
Van Baerle & Co KG
Original Assignee
Van Baerle & Co KG
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6079336&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0025147(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Van Baerle & Co KG filed Critical Van Baerle & Co KG
Priority to AT80104929T priority Critical patent/ATE5895T1/de
Publication of EP0025147A1 publication Critical patent/EP0025147A1/de
Application granted granted Critical
Publication of EP0025147B1 publication Critical patent/EP0025147B1/de
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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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/38—Cationic compounds
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
    • 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
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the invention relates to a liquid, low-phosphate and therefore environmentally friendly detergent which contains washing-active sulfonates, salts of fatty acids, nonionic surfactants, inorganic silicates and sequestering agents.
  • DE-A-2530727 discloses a detergent which is free from phosphates and nitrilotriacetic acid and which contains washing-active sulfonates, nonionic polyglycol ethers, fatty acids and inorganic silicates and a content of 5 to 40% tall oil fatty acid or another saturated and / or unsaturated fatty acid at least 10 carbon atoms, 2 to 40% alkanesulfonate and / or alkylarylsulfonate, 10 to 50% of ethoxylated fatty alcohol with 3 to 8 mol of ethylene oxide and / or ethoxylated alkylphenol, and 5 to 60% of a quaternized fatty amine polyglycol ether based on higher fatty amines, the Ethylene oxide degree is about 10.
  • Such detergents are particularly suitable for cleaning heavily oil and grease soiled textiles; they can be referred to as high-performance detergent preparations.
  • the present invention is therefore based on the object of finding such a detergent which is capable of achieving a solids content of more than 50%, based on the total detergent, in a liquid combination of surfactants with certain builders. Furthermore, the detergent is said to have an excellent emulsifying power for fats and oils, and it should also be able to be used for the complete cleaning of white and colored laundry, i.e. It is an object of the present invention to achieve in a detergent of the type mentioned at the outset that even delicate items to be washed after fifty washes have a damage factor ⁇ 1, a loss of tensile strength less than 30% and a maximum ash content of 1%.
  • the detergent has a content of 2 to 40% by weight of alkanesulfonates and 5 to 98% by weight of nonionic surfactants, based on the surfactant combination, and is characterized by a content of sequestering agent, the nature of which will be described in detail below.
  • the detergent according to the invention is characterized in that it contains, as non-ionic surfactants, ethoxylation products of mono- and / or polyhydric alcohols, amines, carboxylic acids and carboxamides, each having 6 to 20 carbon atoms.
  • a further preferred embodiment is characterized in that the degree of ethoxylation of the nonionic surfactants is 2 to 20 moles of ethylene oxide.
  • the agent according to the invention is characterized in that it contains, as non-ionic surfactants, fatty alcohol polyglycol ether having 6 to 18 carbon atoms and a degree of ethoxylation of 7 to 10 mol of ethylene oxide.
  • a further preferred embodiment of the detergent according to the invention is finally characterized in that it contains nonylphenol ethoxylates as nonionic surfactants with a degree of ethoxylation of 2 to 20, preferably 7 to 10, moles of ethylene oxide.
  • a further preferred embodiment of the subject matter of the invention is characterized in that the detergent as sequestering agent contains higher polymer sodium phosphates of the formula (NaP0,) " , where n is greater than or equal to 3, preferably sodium hexametaphosphates and / or salts of aminocarboxylic acids and / or salts of Polycarboxylic acids.
  • polymeric phosphates in higher concentrations as sequestering agents into liquid, silicate builders with solids contents> 10%.
  • the polymeric phosphates commercially available as builder substances are sodium pyrophosphates and sodium tripolyphosphates.
  • Sodium silicates and sodium phosphates also have a significantly lower price than the corresponding potassium compounds, i.e. due to the higher efficiency of the detergents based on sodium compounds.
  • the present invention is therefore based on the surprising finding that certain sequestering agents or their solutions can be combined with sodium silicate solutions which contain 60% by weight of solids, calculated as percent by weight Na 2 0 plus percent by weight Si0 2 , in a storage-stable manner.
  • Sequestrants in the sense of the present disclosure are higher polymer sodium phosphates of the formula (Na p 0 3 ) 1 , where n is greater than or equal to 3 and both chain and ring groups can be present.
  • the fine structure of such polymer phosphates has not yet been completely clarified.
  • sodium hexametaphosphates with chain lengths of more than six P0 4 groups act as sequestering agents in the sense of the invention. These are long-chain hexametaphosphates with average chain lengths around 20.
  • the detergent according to the invention or in this application in the washing process they act even in low concentrations as excellent sequestering agents and builder components which, with highly concentrated liquid detergents, enable delicate laundry to be washed in an extremely gentle manner.
  • the mixing ratio of sodium hexametaphosphate and sodium silicate solutions can be varied within wide limits; For example, sodium silicate solutions with a density of 59/60 ° B6 can be mixed with 60% sodium hexametaphosphate solution without restriction.
  • sequestering agents within the meaning of the invention are salts of nitrilotriacetic acid, salts of ethylenediaminetetraacetic acid or a similarly structured amine carboxylic acid, furthermore salts of polycarboxylic acids, such as gluconates, heptonates or citrates.
  • amino carboxylic acids to the detergent according to the invention also acts as an oxygen stabilizer when oxidative bleaching agents are added in the washing process.
  • Inorganic silicates in the sense of the present invention are characterized by a composition where sodium, potassium and quaternary amine can occur for Me.
  • the values for x and y are between 1 and 8; the ratio y: x ranges from 0.5 to 8.
  • the water content is given by the coefficient z. It ranges from 0 in the case of anhydrous silicates to about 20 in the case of liquid water glasses.
  • sodium ortho-, sequi-, meta-, di- and trisilicates can be used in anhydrous or water-containing form, also silicate solutions, so-called water glasses, of which particularly preferred are those which have a ratio S'0 2 : Na 2 0 of 1-2 and have a Na, O + S'0 2 content of at least 30% by weight.
  • Wash-active sulfonates for the purposes of the present invention are alkanesulfonates with 10 to 15 carbon atoms and a degree of sulfonation> 1; with a proportion of di- to polysulfonates.
  • Non-ionic surfactants for the purposes of the present invention are ethylene oxide adducts and monohydric and / or polyhydric alcohols of the aliphatic series and on aromatically substituted aliphatic alcohols, furthermore on amines, carboxylic acids and carboxamides.
  • the carbon skeleton of the molecules to which ethylene oxide is attached consists of 6 to 20 carbon atoms. 2 to 20 molecules of ethylene oxide, preferably 7 to 12 molecules of ethylene oxide, can be attached to a molecule substrate.
  • particular preference is given to ethylene oxide addition products of synthetic alcohols or fatty alcohols having 6 to 18 carbon atoms and obtained from natural fats, the degree of ethylene oxide being 7 to 10.
  • nonylphenol ethoxylates with a degree of ethoxylation of preferably 7 to 10 moles of ethylene oxide / mole of nonylphenol are particularly preferred as nonionic surfactants for the purposes of the present invention.
  • Propylene oxide can also replace ethylene oxide.
  • the detergents according to the invention can also contain the additives which are generally customary in detergents, such as, for example, dirt-carrying agents, fragrances, bleaches, stabilizers, disinfectants, optical brighteners and foam-inhibiting agents or other surfactants, for example Contain amphoteric surfactants or betaines or hydrotropic agents.
  • additives which are generally customary in detergents, such as, for example, dirt-carrying agents, fragrances, bleaches, stabilizers, disinfectants, optical brighteners and foam-inhibiting agents or other surfactants, for example Contain amphoteric surfactants or betaines or hydrotropic agents.
  • test strips were tested in accordance with DIN 53 919. Products of the prior art were tested for comparison. Here too, test strips according to DIN 53 919 were checked after 50 wash cycles. The results were as follows:
  • the phosphorus content is less than 0.1 g per liter.
  • the phosphorus content is 0.2-0.4 g per liter.

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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)
EP80104929A 1979-08-25 1980-08-20 Flüssiges, phosphatarmes und umweltfreundliches Waschmittel Expired EP0025147B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80104929T ATE5895T1 (de) 1979-08-25 1980-08-20 Fluessiges, phosphatarmes und umweltfreundliches waschmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2934484 1979-08-25
DE19792934484 DE2934484A1 (de) 1979-08-25 1979-08-25 Fluessiges, phosphatarmes und umweltfreundliches waschmittel

Publications (2)

Publication Number Publication Date
EP0025147A1 EP0025147A1 (de) 1981-03-18
EP0025147B1 true EP0025147B1 (de) 1984-01-18

Family

ID=6079336

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80104929A Expired EP0025147B1 (de) 1979-08-25 1980-08-20 Flüssiges, phosphatarmes und umweltfreundliches Waschmittel

Country Status (3)

Country Link
EP (1) EP0025147B1 (enrdf_load_stackoverflow)
AT (1) ATE5895T1 (enrdf_load_stackoverflow)
DE (2) DE2934484A1 (enrdf_load_stackoverflow)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2109892A1 (de) * 1970-03-03 1972-01-27 Lion Fat Oil Co Ltd Wasch- und Reinigungsmittel
DE2530727B2 (de) * 1975-07-10 1977-12-29 Van Baerle & Co Kg, 6084 Gernsheim Waschmittel
DE2749398A1 (de) * 1976-11-29 1978-06-01 Henkel Kgaa Fuer die kaltwaesche geeignetes waschmittel

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE725820C (de) * 1932-09-07 1942-09-30 Ig Farbenindustrie Ag Verfahren zum Waschen und Reinigen
GB1380390A (en) * 1970-12-16 1975-01-15 Unilever Ltd Detergent compositions
DE2242157C3 (de) * 1971-09-01 1981-11-26 Colgate-Palmolive Co., 10022 New York, N.Y. Phosphatfreie olefinsulfonathaltige Waschmittel
BE789405A (fr) * 1971-09-28 1973-03-28 Unilever Nv Compositions detergentes
NL7403806A (enrdf_load_stackoverflow) * 1973-03-23 1974-09-25
AT330930B (de) * 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
NZ188209A (en) * 1977-09-12 1980-04-28 Colgate Palmolive Co Free-flowing, phosphate-free, particulate, heavy-duty laundry detergent
US4162994A (en) * 1977-11-10 1979-07-31 Lever Brothers Company Powdered detergent compositions containing a calcium salt of an anionic surfactant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2109892A1 (de) * 1970-03-03 1972-01-27 Lion Fat Oil Co Ltd Wasch- und Reinigungsmittel
DE2530727B2 (de) * 1975-07-10 1977-12-29 Van Baerle & Co Kg, 6084 Gernsheim Waschmittel
DE2749398A1 (de) * 1976-11-29 1978-06-01 Henkel Kgaa Fuer die kaltwaesche geeignetes waschmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Stüpel "Synthetische Wasch- und Reinigungsmittel", Stuttgart 1957, S. 57, 137-142 *

Also Published As

Publication number Publication date
ATE5895T1 (de) 1984-02-15
DE3066181D1 (en) 1984-02-23
EP0025147A1 (de) 1981-03-18
DE2934484A1 (de) 1981-03-26
DE2934484C2 (enrdf_load_stackoverflow) 1989-09-14

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