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WO1996014387A1 - Agent de rinçage contenant des produits d'oxydation de polyglucosanes - Google Patents

Agent de rinçage contenant des produits d'oxydation de polyglucosanes Download PDF

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Publication number
WO1996014387A1
WO1996014387A1 PCT/EP1995/004246 EP9504246W WO9614387A1 WO 1996014387 A1 WO1996014387 A1 WO 1996014387A1 EP 9504246 W EP9504246 W EP 9504246W WO 9614387 A1 WO9614387 A1 WO 9614387A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
mol
oxidation products
radical
iii
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.)
Ceased
Application number
PCT/EP1995/004246
Other languages
German (de)
English (en)
Inventor
Christian Nitsch
Willi Buchmeier
Peter Jeschke
Konrad Engelskirchen
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
Publication of WO1996014387A1 publication Critical patent/WO1996014387A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised

Definitions

  • the invention relates to the use of polyglucosan oxidation products in rinse aid for dishwashers.
  • rinse aids are mixtures of low-foaming fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (for example cumol sulfonate), organic acids (for example citric acid) and solvents (for example ethanol).
  • solubilizers for example cumol sulfonate
  • organic acids for example citric acid
  • solvents for example ethanol
  • limescale or silicate deposits can also form on the items to be washed and in the interior of the machine. Disturbing lime or silicate deposits occur in particular if the washing water in the dishwasher is not or not sufficiently softened and a water hardness of 4 ° d is exceeded.
  • the object of the present invention is therefore to provide rinse aid, the use of which provides spotless dishes;
  • the rinse aid should be low-foaming, have a high phase stability and be easily biodegradable.
  • European patent application EP-Al-542496 discloses the use of oxidized starch as a builder in textile and dishwashing detergents. It has now been found that the addition of polyglucosan oxidation products to conventional rinse aid significantly improves the properties of this rinse aid with regard to the above criteria.
  • the present invention therefore relates to the use of oxidation products of polyglucosans in rinse aids.
  • oxidation products of polyglucosans are understood to mean polymers of monosaccharides which at least partially consist of oxidized anhydroglucose units with one, two or three carboxyl groups per unit. These oxidized anhydroglucose units correspond to the constitutional formulas I, II or III:
  • polyglucosan oxidation products which are produced by the processes described in German Offenlegungsschriften DE 4203 923 AI or DE 43 17 519 AI or by the processes described in European patent application EP 0 548 399 AI or international application WO92 / 18542 become.
  • the reaction is preferably carried out in a closed reaction system at pressures of 1 to 10 bar, preferably 2 to 6 bar, measured at the reaction temperature, oxygen preferably in an inert carrier gas in an amount of 1 to 30% by volume, in particular 3 to 10 vol.% Is included.
  • the polyglucosan oxidation products from polysaccharides are oxidized with Nitrogen dioxide / dinitrogen tetroxide is produced by converting at least a portion of the primary alcohol groups of the polysaccharides into carboxyl groups, the oxidation reaction being carried out in a continuous process at a temperature above 80 ° C. in the presence or absence of oxygen and a residence time of the reaction mixture in the reaction zone of 1 to 30 min, preferably 5 to 30 min and in particular 10 to 30 min.
  • the preferred reaction temperature is between 100 ° and 160 ° C., in particular 110 ° to 130 ° C.
  • the preferred reaction pressure is 1 to 40 bar, in particular 3 to 15 bar.
  • polyglucosan oxidation products are produced by oxidation of carbohydrates with an oxygen-containing gas in an alkaline medium, the oxidation reaction being carried out by homogeneous catalysis of a salt of Cu, Cr, Co, Ni, Fe, V, Ti or Mn is catalyzed.
  • polyglucosan oxidation products are obtained by oxidizing carbohydrates with an oxygen-containing gas in an alkaline aqueous medium in the presence of catalytically effective amounts of a salt of copper, silver or a metal from the group VIII of the periodic table and a metal ion ligand, e.g. B. a polydentate amine ligand.
  • oxidizing agents are used for the oxidation of polyglucosans. Examples include (air) oxygen, hydrogen peroxide, sodium hypochlorite or bromite, periodic acid or periodates, lead (IV) acetate, nitrogen dioxide and cerium (IV) salts. These oxidizing agents react very differently with the anhydroglucose units, cf. for example the formula pictures in Houben-Weyl loc. cit. p. 2124. It is known that when nitrogen dioxide acts on cellulose, the oxidation of the primary alcohol group to the carboxy group is the predominant reaction.
  • the oxidizing agent can be used in gaseous form or dissolved in an inert organic solvent, cf.
  • monocarboxyl starches with a freely selectable degree of conversion of the primary alcohol groups can be produced by their selective oxidation with nitrogen dioxide at low temperatures even without auxiliary agents, for example solvents or catalysts.
  • auxiliary agents for example solvents or catalysts.
  • the almost quantitative and largely selective implementation of the building blocks of the starch molecule is also possible.
  • the preferred lower limit for the content of oxidized anhydroglucose units according to formulas I, II and / or III in the polyglucosan derivatives is about 25 mol%, preferably at least about 35 mol% to 40 mol%.
  • the almost quantitative conversion of one, two or three alcohol groups into carboxy groups is possible, so that the upper limit for the corresponding content of oxidized anhydroglucose units is 95 mol% to about 100 mol%.
  • Corresponding oxidation products which are characterized by contents in the range from about 35 mol% to 80 mol% of oxidized anhydroglucose units may be particularly suitable for practical use, in one important embodiment of which their content is in the range from about 40 mol% is up to 60 mol%.
  • the statistical average of the oxidized polyglucosans to be used according to the invention preferably consist of at least 15 mol% of oxidized anhydroglucose units of the formula I and have average molecular weights below 15,000.
  • Rinse aids containing polyglucosan oxidation products show very low foaming, high phase stability and ensure spotless, shiny dishes.
  • Another subject of the invention are rinse aids containing polyglucosan oxidation products with organic carboxylic acids and certain surfactants.
  • the polyglucosan oxidation products are generally in rinse aid. in an amount of 0.1 to 10 wt .-%, preferably 1 to 5 wt .-%, based on the total rinse aid.
  • organic carboxylic acids e.g. aliphatic hydroxy-di- and tricarboxylic acids such as malic acid (monohydroxysuccinic acid), tartaric acid (di-hydroxysuccinic acid); saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid; Gluconic acid (hexane-pentahydroxy-1-carboxylic acid), but preferably anhydrous citric acid. They are used in amounts of about 0.5 to 50, preferably about 1 to 20,% by weight.
  • the surfactant base of the rinse aid according to the invention is formed from a nonionic surfactant which is present in an amount of 0.5 to 50% by weight, preferably 2 to 20% by weight, and which is selected from the group of mixed ethers of the formula I. , the fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula II, the alkyl polyglycosides of the formula III and their mixtures, where in the mixed ethers of the formula I,
  • R1 for a linear or branched, aliphatic alkyl and / or alkenyl radical with 8 to 14 carbon atoms
  • R2 for a linear or branched alkyl radical with 1 to 4 carbon atoms or a benzyl radical
  • a for 0 or numbers from 1 to 2
  • b represents numbers from 5 to 15,
  • R 3 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 8 to 16 carbon atoms, c represents 0 or numbers from 1 to 3 and d represents numbers from 1 to 5,
  • R 4 stands for an alkyl radical with 8 to 22 carbon atoms
  • G stands for a sugar residue with 5 or 6 carbon atoms, preferably a glucose residue
  • p stands for numbers from 1 to 10.
  • Mixed ethers of the formula I are to be understood as meaning known end group-capped fatty alcohol polyglycol ethers which can be obtained by the relevant methods of preparative organic chemistry.
  • Fatty alcohol polyglycol ethers are preferably reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride.
  • Typical examples games are mixed ethers corresponding to formula (I) in which Rl is a technical C ⁇ 2 / i4 cocoalkyl, a is 0, b is 5 to 10 and R is a butyl group (Dehypon (R) LS-54 or LS-104, from Henkel KGaA).
  • the fatty alcohol polypropylene / polyethylene glycol ethers of the formula II are known nonionic surfactants which are obtained by adding initially propylene oxide and then ethylene oxide or exclusively ethylene oxide to fatty alcohols.
  • Typical examples are polyglycol ethers of the formula (II) in which R 3 represents an alkyl radical having 12 to 18 carbon atoms, c represents 0 or 1 and d represents numbers from 2 to 5 (dehydrol ( R ) LS- 2, LS-4, LS-5, Henkel KGaA, Düsseldorf / FRG).
  • the fatty alcohols are preferably only ethoxylated, ie c is zero.
  • Alkyl polyglycosides are known substances which can be obtained by the relevant processes in preparative organic chemistry.
  • APG Alkyl polyglycosides
  • the alkyl polyglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl polyglycosides are thus alkyl polyglucosides.
  • the agents according to the invention can contain nonionic substances such.
  • B. contain the type of fatty acid N-alkylglucamides.
  • Solubilizers, for example cumene sulfonate, and colorants and fragrances are suitable as further additives, and in a preferred embodiment, the agents according to the invention dispense with solubilizers.
  • a polyglucosan oxidation product was used, which was produced as follows in accordance with DE 4203923:
  • Rinse aid formulations of compositions 1 to 6 were produced, compositions 2, 3, 5, 6, 8 and 9 are according to the invention, 1 (V), 4 (V) and 7 (V) are used for comparison.
  • the foam development of the rinse aid was determined with the aid of a circulating pressure measuring device.
  • the rinse aid (3 ml) was dosed by hand in the rinse aid at 50 ° C.
  • the crockery parts were placed outside the dishwasher for 30 minutes to cool and then visually inspected under lighting in a black box. The dried residual drops, streaks, deposits, cloudy films, etc. remaining on the dishes and cutlery were assessed.
  • APG 225 (70% _ _ _ _ aqueous solution)
  • APG 225 (70% - _ 11.4 U.4 11.4 aqueous solution) (8% AS) (8% AS) (8% AS)
  • Examples 2, 3, 5, 6, 8 and 9 are according to the invention, Examples 1 (V), 4 (V) and 7 (V) serve for comparison. - Results of the rinse aid effect studies

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne l'utilisation de produits d'oxydation de polyglucosanes dans des agents de rinçage, ainsi que des agents de rinçage contenant des produits d'oxydation de polyglucosanes.
PCT/EP1995/004246 1994-11-07 1995-10-30 Agent de rinçage contenant des produits d'oxydation de polyglucosanes Ceased WO1996014387A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4439678.3 1994-11-07
DE19944439678 DE4439678A1 (de) 1994-11-07 1994-11-07 Klarspülmittel mit Polyglucosan-Oxidationsprodukten

Publications (1)

Publication Number Publication Date
WO1996014387A1 true WO1996014387A1 (fr) 1996-05-17

Family

ID=6532649

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/004246 Ceased WO1996014387A1 (fr) 1994-11-07 1995-10-30 Agent de rinçage contenant des produits d'oxydation de polyglucosanes

Country Status (2)

Country Link
DE (1) DE4439678A1 (fr)
WO (1) WO1996014387A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3675634A1 (fr) * 2017-09-01 2020-07-08 Syngenta Participations AG Adjuvants

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2556544A1 (de) * 1975-12-16 1977-06-30 Hoechst Ag Maschinengeschirrspuelmittel
EP0511081A1 (fr) * 1991-04-22 1992-10-28 Roquette FrÀ¨res Produit de lavage à teneur réduite ou nulle en zéolithe
EP0542496A1 (fr) * 1991-11-14 1993-05-19 The Procter & Gamble Company Amidon oxydé à C6/C2-C3 utilisé comme ingrédient pour détergent
DE4228786A1 (de) * 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
DE4233699A1 (de) * 1992-10-07 1994-04-14 Henkel Kgaa Klarspüler für das maschinelle Geschirrspülen
WO1994028030A1 (fr) * 1993-05-26 1994-12-08 Henkel Kommanditgesellschaft Auf Aktien Fabrication de polycarboxylates a base de polysaccharides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2556544A1 (de) * 1975-12-16 1977-06-30 Hoechst Ag Maschinengeschirrspuelmittel
EP0511081A1 (fr) * 1991-04-22 1992-10-28 Roquette FrÀ¨res Produit de lavage à teneur réduite ou nulle en zéolithe
EP0542496A1 (fr) * 1991-11-14 1993-05-19 The Procter & Gamble Company Amidon oxydé à C6/C2-C3 utilisé comme ingrédient pour détergent
DE4228786A1 (de) * 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
DE4233699A1 (de) * 1992-10-07 1994-04-14 Henkel Kgaa Klarspüler für das maschinelle Geschirrspülen
WO1994028030A1 (fr) * 1993-05-26 1994-12-08 Henkel Kommanditgesellschaft Auf Aktien Fabrication de polycarboxylates a base de polysaccharides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3675634A1 (fr) * 2017-09-01 2020-07-08 Syngenta Participations AG Adjuvants

Also Published As

Publication number Publication date
DE4439678A1 (de) 1996-05-09

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