EP2714876B1 - Neue verwendung von heptylpolyglycosiden zur auflösung von nicht ionischen tensiden in wässrigen sauren reinigungszusammensetzungen und wässrige saure reinigungszusammensetzungen damit - Google Patents

Neue verwendung von heptylpolyglycosiden zur auflösung von nicht ionischen tensiden in wässrigen sauren reinigungszusammensetzungen und wässrige saure reinigungszusammensetzungen damit Download PDF

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EP2714876B1
EP2714876B1 EP12728679.7A EP12728679A EP2714876B1 EP 2714876 B1 EP2714876 B1 EP 2714876B1 EP 12728679 A EP12728679 A EP 12728679A EP 2714876 B1 EP2714876 B1 EP 2714876B1
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equal
composition
formula
less
acid
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French (fr)
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EP2714876A1 (de
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Marie-Françoise GAYRAL CHIRAC
Sébastien KERVERDO
Jérôme GUILBOT
Hervé Rolland
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Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA
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Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA
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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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives 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
    • C11D1/825—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
    • 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
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to the use of an n-heptyl polyglycoside or a mixture of n-heptyl polyglycosides for solubilizing low-foaming nonionic surfactants in compositions that are stable in an acid medium, especially used for cleaning and the descaling of hard surfaces.
  • solubilizing agent any substance or chemical composition capable of solubilizing in water or in aqueous phases, chemical compounds poorly soluble or insoluble in water or in these aqueous phases.
  • the expression "poorly soluble or insoluble chemical compounds in water or in aqueous phases” designates compounds which, added to a predominantly or totally water phase, do not make it possible to obtain a totally clear solution or composition. is transparent, isotropic, homogeneous and stable at a desired temperature for a desired time. This solubility defect is in particular due to the chemical structure of the compound in question and / or the presence of acidic agents in the aqueous phase in which it is desired to solubilize said compound.
  • hydrophobic compounds such as, for example, oils, essential oils, fragrances, pigments, anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.
  • Solubilizing agents are particularly useful for preparing cleaning compositions for hard surface detergents for household or industrial applications.
  • alkaline aqueous cleaning compositions which are characterized by a pH above 7.0
  • acidic aqueous cleaning compositions which are characterized by a pH less than or equal to 7.0.
  • Acidic aqueous cleaning compositions are used to clean hard surfaces, i.e. not only to remove soils from said hard surfaces, but also to descale said surface.
  • Such compositions are particularly suitable for cleaning and descaling installations in the food industry, such as the dairy, bra and wineries industries. They are also suitable for cleaning and descaling household appliances such as dishwashers and coffee machines. These industrial installations and these appliances include circuits and tanks, which after a operating of a certain duration, are soiled with organic materials, such as for example fats, and more particularly phospholipids, proteins, tannins, and by mineral deposits of calcium salts, more particularly carbonates, phosphates and calcium oxalates.
  • aqueous acidic cleaning compositions are also particularly suitable for cleaning and descaling the enamel of toilets, washbasins, baths and showers.
  • aqueous acidic cleaning compositions are also used for the treatment of metal surfaces or cast or forged metal parts, to remove deposits formed by the corrosion or oxidation of metals, such as rust, oxide layers, green de-gris, or deposits of soot, limestone ..
  • acidic aqueous cleaning compositions are also used in cleaning operations to remove concrete or cement residues, and for grease cleaning operations present in depth on concrete surfaces prior to any painting operation of said concrete surfaces.
  • aqueous acidic cleaning compositions must not generate the formation of a large foam during the cleaning operation in the presence of the soil to be treated, show good wetting properties and also good detergency in acidic medium.
  • the detergent surfactants used in acidic aqueous cleaning compositions intended for the hard surface detergent give them the ability to remove soiling on hard surfaces and keep them in suspension, for then be eliminated during the rinsing step.
  • These detergent surfactants may be of anionic, cationic, amphoteric or nonionic nature.
  • Nonionic surfactants are particularly used for the preparation of hard surface detergent compositions in view of their foaming power, which is generally inferior to other ionic surfactants and also to their improved environmental characteristics.
  • cleaning compositions comprise large amounts of acidic agents, it is difficult to dissolve large amounts of detergent surfactants to obtain a stable composition with no dephasing on storage.
  • solubilizing agents such as ethanol, xylenesulphonates and cumenesulphonates.
  • Ethanol is an effective solubilizing agent but it however has a certain explosive character in acidic place.
  • the European patent application published under the number EP 0 524 075 A1 discloses the efficacy of aqueous acidic cleaning compositions comprising an anionic hydrotrope or solubilizing agent and nonionic surfactants.
  • agents Anionic solubilizers such as xylenesulfonates and cumenesulfonates, are not very effective for large amounts of surfactants and also do not exhibit the biodegradability properties required to comply with the new environmental regulations.
  • alkylpolyglycosides are also described as solubilizing agents of nonionic defoaming surfactants.
  • the international publication WO 96/33255 A1 discloses anti-foaming compositions comprising a particular alkyl polyglucoside, the alkyl chain of which is constituted by the 2-ethyl hexyl radical and non-ionic defoaming surfactants chosen from those comprising one or more groups chosen from mono-ethoxylated or poly-lower alkyl groups; ethoxylated, mono-propoxylated or polypropoxylated groups. It is taught that 2-ethyl hexyl-chain alkylpolyglucosides are more effective than hexyl-chain alkyl polyglycosides in solubilizing non-ionic defoaming surfactants.
  • the international publication WO 99/21948 A1 discloses clear and stable compositions with high alkaline concentrations, whose foaming properties are controlled, containing a large amount of nonionic surfactants based on alkylene oxide and a hexyl glycoside as a hydrotrope or solubilizing agent. These compositions are characterized by good wetting power and good detergent properties of hard surfaces. It is taught that hexyl glycosides, and more particularly n-hexyl polyglucoside, are solubilizing agents for nonionic surfactants in a strongly alkaline medium and that n-hexyl glucoside is characterized by a solubilizing power of a nonionic surfactant.
  • the Applicant has therefore endeavored to develop a new technical solution, consisting of the use of an n-heptyl polyglycoside or a mixture of n-heptyl polyglycosides, having a non-flammable character and non-ecotoxic and biodegradable properties, for solubilizing nonionic surfactants in stable aqueous compositions in acidic medium, especially used for cleaning and hard surface scaling.
  • aqueous acid composition designates any aqueous composition having a pH of less than or equal to 7.
  • reducing sugar in the composition represented by the formula (I), saccharide derivatives which do not have in their glycosidic bonding structures established between an anomeric carbon and oxygen of an acetal group as defined in the reference work: "Biochemistry”, Daniel Voet / Judith G. Voet, p. 250, John Wyley & Sons, 1990 .
  • the oligomeric structure (G) p can be in all forms of isomerism, whether it is optical isomerism, geometric isomerism or isomerism of position; it can also represent a mixture of isomers.
  • solubilizing agent any substance or chemical composition capable of solubilizing in water or in aqueous phases, chemical compounds poorly soluble or insoluble in water or in these aqueous phases.
  • the expression "poorly soluble or insoluble chemical compounds in water or in aqueous phases” designates compounds which, added to a predominantly or totally water phase, do not make it possible to obtain a totally clear solution or composition. is transparent, isotropic, homogeneous and stable at a desired temperature for a desired time.
  • the group R 1 -O is linked to G by the anomeric carbon of the saccharide residue, so as to form an acetal function.
  • G represents the remainder of a reducing sugar chosen mainly from glucose, dextrose, sucrose, fructose, idose, gulose, galactose, maltose, isomaltose, maltotriose, lactose, cellobiose, mannose, ribose, xylose, arabinose, lyxose, allose, altrose, dextran or tallose.
  • the subject of the invention is the use as defined above for which, in the formula (I), p represents a decimal number greater than or equal to 1.05 and less than or equal to 2 5.
  • the subject of the invention is the use as defined above for which, in formula (I), G represents the residue of a reducing sugar and chosen from the residues of glucose, xylose and arabinose, and more particularly chosen from the remains of glucose or xylose.
  • Stage A) is generally carried out in a reactor in the presence of an acidic catalyst system, by controlling the stoichiometric ratio between the two reactants, and more particularly by introducing a molar excess of n-heptanol, and with mechanical stirring in predetermined temperature and partial vacuum conditions, for example at a temperature between 70 ° C and 130 ° C and under a partial vacuum between 300 mbar (3.10 4 Pa) and 20 mbar (2.10 3 Pa).
  • acidic catalytic system strong acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hypophosphorous acid, methanesulfonic acid, (para-toluene) sulfonic acid , (trifluoromethane) sulfonic acid, or ion exchange resins.
  • Stage B) of removal of n-heptanol from said mixture obtained at the end of stage A) is generally carried out according to methods known to those skilled in the art, such as, for example, distillation, distillation on thin film, molecular distillation or solvent extraction.
  • Such a preparation process can be completed, if necessary or if desired, by neutralization, filtration and bleaching operations.
  • n represents an integer greater than or equal to 0 and less than or equal to 6, plus particularly greater than or equal to 0 and less than or equal to 3, and even more particularly greater than or equal to 0 and less than or equal to 2.
  • the subject of the invention is the use as defined above for which, in formula (II), m represents an integer greater than or equal to 1 and less than or equal to 9, more particularly greater than or equal to 2 and less than or equal to 6, and even more particularly greater than or equal to 2 and less than or equal to 4.
  • the compounds of formula (II) for which R 'represents a methyl or ethyl radical and n represents an integer greater than or equal to 1 are prepared according to a process comprising if necessary a step a) of alkoxylation by reaction of n molar equivalents d an alkylene oxide or an alkylene carbonate with one molar equivalent of alcohol of formula (IV): R-OH (IV) in which the radical R represents a linear or branched, saturated or unsaturated, hydrocarbon-based aliphatic radical containing from 8 to 14 carbon atoms, optionally substituted with one or more hydroxyl groups, as defined above, to obtain the alkoxylated alcohol of formula (V): R- (O-CH (R ') - CH 2 ) n -OH (V) in which R 'represents a methyl or ethyl radical; and / or if necessary a step b) of ethoxylation by reaction of a molar equivalent of the al
  • the alkylene oxide is chosen from the group consisting of propylene oxide and butylene oxide.
  • the alkylene carbonate is selected from the group consisting of propylene carbonate and butylene carbonate.
  • the compounds of formula (II) for which n is equal to 0 are prepared according to a process implementing a step a ') of ethoxylation by reaction of m mole equivalent of ethylene oxide or of ethylene carbonate with l alcohol of formula (IV) as defined above.
  • n and m represent the integers described above in the definition of compounds of formula (II).
  • alkoxylation reactions of step a) and of ethoxylation of steps a ') and b), as defined above, are generally carried out in a reactor in the presence of a basic catalyst such as hydroxides.
  • a basic catalyst such as hydroxides.
  • alkali metals such as, for example, sodium hydroxide, potassium hydroxide, alkali metal alkoxides, for example sodium or potassium methoxide, sodium or potassium tertiobutylate, Lewis bases, for example triphenylphosphine, catalysts such as, for example, organometallic complexes based on cobalt and / or zinc, or in the presence of an acidic catalyst such as a Lewis acid such as, for example, boron trifluoride, aluminum trichloride or tetrachloride, 'tin.
  • a Lewis acid such as, for example, boron trifluoride, aluminum trichloride or tetrachloride, 'tin.
  • Such processes for the preparation of the compounds of formula (II) can be completed, if necessary or if desired, by neutralization, demineralization, filtration and bleaching operations.
  • the subject of the present invention is the use as defined above, in which the mass ratio between said nonionic surfactant of formula (II) and said composition (C) is lower or equal to 15/1 and greater than or equal to 1/1.
  • mineral acids particularly chosen as acidic agents in the composition (C 1 ) which is the subject of the present invention mention may be made of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and hypophosphorous acid. phosphorous acid, hypochlorous acid, perchloric acid, carbonic acid, boric acid, manganic acid, permanganic acid, chromic acid, periodic acid, iodic acid, hypoiodous acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid.
  • organic acids that are particularly chosen as acidic agents in the composition (C 1 ) that is the subject of the present invention, mention may be made of formic acid, acetic acid, propionic acid, benzoic acid and salicylic acid.
  • the acidic agent is selected from hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid , hypochlorous acid, formic acid, acetic acid, salicylic acid, oxalic acid, citric acid, tartaric acid, gluconic acid, peracetic acid, glycolic acid , lactic acid.
  • the mass ratio between the compound of formula (II) and said composition (C) is less than or equal to 15/1 and greater than or equal to 1 / 1.
  • the subject of the invention is the use of a composition (C 1 ) as defined above, for cleaning hard surfaces.
  • hard surfaces means any action intended to allow the removal of dirt present on surfaces made of various materials.
  • hard surfaces are floors, vertical surfaces, tiles, household appliances such as dishwashers and coffee machines, taps, sinks, washbasins, bathtubs and showers. , toilets, urinals, storage tanks for food or agricultural products, vehicles (automobiles, motorcycles, trucks, ...), industrial installations such as heat exchangers, seawater evaporators, pipes, heating circuits, cooling circuits, public works equipment contaminated by cement or concrete such as concrete mixers, cement and concrete routers, metal surfaces and cast or forged metal parts.
  • the materials constituting these hard surfaces are for example glass (soda-lime, fluorocalcic, borosilicate, crystal), enamel, porcelain, faience, ceramics, polycarbonate plastics, polypropylenes, stainless steel, silver, nickel copper, aluminum and more particularly highly oxidized aluminum, brasses and copper alloys, precious metals such as gold, silver, platinum, wood, synthetic resins, glass-ceramic, linoleum, and can be coated with paints, varnishes.
  • glass sina-lime, fluorocalcic, borosilicate, crystal
  • enamel porcelain
  • faience ceramics
  • polycarbonate plastics polypropylenes
  • stainless steel silver, nickel copper, aluminum and more particularly highly oxidized aluminum, brasses and copper alloys
  • precious metals such as gold, silver, platinum, wood, synthetic resins, glass-ceramic, linoleum, and can be coated with paints, varnishes.
  • soils present on these hard surfaces and to be eliminated by cleaning include, for example, food residues such as, for example, deposits caused by dairy products and sweetened food residues, fats such as, for example, phospholipids, proteins, tannins, algae, light and heavy hydrocarbons, burnt residues, soap residues, germs, carbonaceous traces such as soot, mineral deposits of calcium salts such as calcium carbonate, phosphate of calcium or calcium oxalate, scale, limestone, metal oxide deposits such as rust, verdigris, glue residues, mortar residues, cement residues, lime residues.
  • food residues such as, for example, deposits caused by dairy products and sweetened food residues
  • fats such as, for example, phospholipids, proteins, tannins, algae, light and heavy hydrocarbons
  • burnt residues soap residues, germs
  • carbonaceous traces such as soot
  • mineral deposits of calcium salts such as calcium carbonate, phosphate of calcium or calcium oxalate, scale, limestone
  • composition (C 1 ) which is the subject of the present invention is in particular in the form of an aqueous solution, an emulsion or a microemulsion with an aqueous continuous phase, an emulsion or a microemulsion with an oily continuous phase. , an aqueous gel, a foam, or in the form of an aerosol.
  • composition (C 1 ) which is the subject of the present invention may be applied directly by dipping, spraying or spraying on the surface to be cleaned or by means of any type of support intended to be brought into contact with the hard surface at cleaning (paper, wipe, textile) comprising said composition (C 1 ).
  • composition (C 1 ) object of the present invention used to clean hard surfaces, generally has a pH less than or equal to 7, more particularly less than or equal to 6, more particularly less than or equal to 4 and even more particularly lower or equal to 2.
  • composition (C 1 ) which is the subject of the present invention also comprises ingredients usually used in the field of cleaning hard surfaces, such as nonionic surfactants, cationic surfactants, amphoteric surfactants, polymers and the like.
  • low foaming nonionic surfactants of formula (A 2 ) present in the composition (C 1 ) object of the present invention mention may be made of hexylpolyglucosides and 2-ethylpolyglucosides.
  • amphoteric surfactants present in the composition (C 1 ) which is the subject of the present invention mention may be made of the sodium ⁇ -alanine, N- (2-carboxyethyl) -N- (2-ethylhexyl) sold under the brand name TOMAMINE. ® AMPHOTERIC 400 SURFACTANT.
  • thickening agents present in the composition (C 1 ) which is the subject of the present invention include polymeric hydrocolloids of vegetable or biosynthetic origin, such as xanthan gum, scleroglucan, tragacanth, agar-agar. carrageenates, alginic acid, alginates and galactomannans; cellulose and its derivatives such as hydroxypropylmethyl cellulose; dextrin; casein; pectins; gelatin; chitosan; polyethylene glycols having a molecular weight of between 4000 and 35000 grams per mole; ethoxylated ethylene glycol derivatives having a molecular weight of between 300,000 and 7,000,000 grams per mole.
  • polymeric hydrocolloids of vegetable or biosynthetic origin such as xanthan gum, scleroglucan, tragacanth, agar-agar. carrageenates, alginic acid, alginates and galactomannans; cellulose and its derivative
  • thickening agents present in the composition (C 1 ) which is the subject of the present invention mention may be made of polymeric thickeners such as homopolymers of acrylamide, or copolymers of acrylamide and of the sodium salt of 2- acrylamido-2-methylpropanesulfonate, for example the thickeners marketed by the company SEPPIC under the brand name of SOLAGUM TM.
  • thickening agents present in the composition (C 1 ) which is the subject of the present invention include inorganic thickeners, for example clays, hectorite, saponite, sauconite, vermiculite or colloidal silica.
  • the thickening agents present in the composition (C 1 ) which is the subject of the present invention are used in amounts of between 0.1% and 10% by weight.
  • abrasive agents present in the composition (C 1 ) which is the subject of the present invention include mention of materials of natural origin, for example wood chips or cores, inorganic abrasive materials such as oxides, quartz, diatomaceous earth, colloidal silica dioxides, organic abrasive materials such as polyolefins such as polyethylenes and polypropylenes, polystyrenes, acetonitrile-butadiene-styrene resins, melamines, phenolic resins, resins epoxy, polyurethane resins.
  • materials of natural origin for example wood chips or cores
  • inorganic abrasive materials such as oxides, quartz, diatomaceous earth, colloidal silica dioxides
  • organic abrasive materials such as polyolefins such as polyethylenes and polypropylenes, polystyrenes, acetonitrile-butadiene-styrene resins, melamines, phenolic resin
  • the abrasive agents present in the composition (C 1 ) object of the present invention are used in amounts of between 5.0% and 30% by weight.
  • solvents present in the composition (C 1 ) which is the subject of the present invention mention may be made of isopropyl alcohol, benzyl alcohol, 1,3 propane diol, chlorinated solvents, acetone and methyl ethyl ether.
  • n-heptanol 2.7 molar equivalents of n-heptanol are introduced into a jacketed glass reactor, in which a coolant circulates, and provided with an effective stirring, at a temperature of 40 ° C.
  • a molar equivalent of anhydrous glucose is then gradually added to the reaction medium to allow its homogeneous dispersion, then 0.15% by mass of sulfuric acid at 98% and 0.15% by mass of hypophosphorous acid at 50% for 100% of the mass constituted by the sum of the mass glucose and the mass of n-heptanol are introduced into the homogeneous dispersion prepared beforehand.
  • the reaction medium is placed under a partial vacuum of about 18x10 3 Pa (180 mbar), and maintained at a temperature of 100 ° C-105 ° C for a period of 4 hours with evacuation of the water formed by means of a distillation assembly.
  • the reaction medium is then cooled to 85 ° C.-90 ° C. and neutralized by addition of 40% sodium hydroxide to bring the pH of a 5% solution of this mixture to a value of approximately 7.0.
  • the reaction medium thus obtained is then drained at a temperature of 70 ° C. and filtered to remove unreacted glucose grains.
  • the filtrate is then introduced into a jacketed glass reactor, in which circulates a heat transfer fluid, provided with an effective stirring and a distillation device.
  • the excess of heptanol is then removed by distillation at a temperature of 120 ° C. under partial vacuum of between about 10 4 Pa (100 mbar) and 5 ⁇ 10 3 Pa (50 mbar).
  • the reaction medium thus distilled is immediately diluted by the addition of a quantity of water so as to reach a reaction medium concentration of about 60%. After homogenization for 30 minutes at a temperature of 50 ° C, the composition (X 0 ) obtained is drained.
  • composition (X 0 ) thus obtained comprising n-heptylpolyglucosides are collated in Table 1 below.
  • ⁇ b> ⁇ u> Tab 1 ⁇ / u> ⁇ /b> Composition (X 0 ) Appearance at 20 ° C (visual determination) Liquid Acid Number (NFT Standard 60204) 1.7 Hydroxyl value on dry extract (Standard USP XXI NF XVI 01/01/1995) 813.9 Water (% by mass) (NFT Standard 73201) 58.8% Residual content of n-heptanol (gas chromatography) in% by mass 0.22%
  • the foam is formed by introducing a determined volume of nitrogen into a fixed concentration surfactant solution and in the presence of a fixed amount of sodium hydroxide at a specific temperature.
  • the volume of foam generated by the introduction of the volume of nitrogen is measured at the end of the introduction of said volume of nitrogen, then at a duration of 30 seconds, then 120 seconds at the end of the end of the introduction of the nitrogen volume.
  • composition (X 0 ) is characterized by the generation of a very unstable foam at 20 ° C, since the foam volume decreases in 30 seconds by 95% of its initial value, against 92.3% for the composition (X 1 ), 25% for the composition (X 2 ) and 12% for the composition (X 3 ).
  • the composition (X 0 ) of n-heptylpolyglucosides is also characterized by the generation of a very unstable foam since the volume of foam decreases in 30 seconds by 100% of its initial value, against 57.1% for the composition (X 2 ) and 14% for the composition (X 3 ).
  • the composition (X 0 ) by the generation of a foam volume lower than that generated by the compositions of the state of the art.
  • compositions (X 0 ) were evaluated in comparison with the compositions (X 1 ), (X 2 ), (X 3 ) and (X 4 ) of the state of the art as previously described according to the evaluation method described below for a nonionic surfactant of formula (II), in the presence of different acidic agents and at different concentrations of said acidic agents.
  • the object of this method is to determine the solubilizing power of a surfactant composition in an acidic medium for a nonionic surfactant that is insoluble in an acidic medium compared with surfactant compositions of the state of the art.
  • a magnetized magnetic bar is inserted into the glass bottle which is then placed with magnetic stirring at a speed of 100 rpm for a period of 3 minutes at a temperature of 20 ° C.
  • the solubilizing surfactant composition (Xi) to be tested is then progressively introduced so as to obtain a clear visual appearance for the medium present in the glass vial.
  • the experimenter notes the amount (in grams) of the added solubilizing composition (Xi) that was required to obtain this clear appearance, and converts it by calculation. in the quantity x 1 (in grams) of dry matter of the solubilizing agent included in the composition (Xi).
  • compositions (X 0 ), (X 1 ) and (X 4 ) show that for a quantity of 10% by mass of phosphoric acid a quantity of 1.37 g of the composition (X 0 ) is necessary to solubilize 5 g of the nonionic surfactant composition (T 1 ), whereas 1.83 g of the composition (X 1 ) and 1.42 g of the composition (X 4 ) are necessary to obtain the same result.
  • composition (X 0 ) in the presence of a quantity of 10% by mass of nitric acid, an amount of 0.76 g of the composition (X 0 ) is necessary to solubilize 5 g of the nonionic surfactant composition (T 1 ), whereas 2.17 g of the composition (X 1 ) and 1.72 g of the composition (X 4 ) are necessary to obtain the same result, respectively corresponding to mass quantities of 185% and 126% greater than that used for the composition (X 0 ).
  • compositions (X 0 ) and (X 2 ) show that, for a quantity of 10% by mass of phosphoric acid, a quantity of 1.37 g of the composition (X 0 ) is necessary for solubilize 5 g of the nonionic surfactant composition (T 1 ), whereas a quantity of 1.99 g of the composition (X 2 ) is necessary to obtain the same result, ie a mass quantity greater than 45.2% of that used for the composition (X0).
  • composition (X 0 ) in the presence of an amount of 10% by mass of nitric acid, an amount of 0.76 g of the composition (X 0 ) is necessary to solubilize 5 g of the nonionic surfactant composition (T 1 ), while an amount of 1.13 g of the composition (X 2 ) is necessary to obtain the same result, ie a mass quantity greater than 48.6% than that used for the composition (X 0 ).
  • composition (X 0 ) comprising n-heptylpolyglucosides, characterized by low foaming properties and environmental properties responding to changes in the regulations, shows improved solubilizing properties in acidic medium compared to solubilizing agents known in the state of the art. technical.
  • Each ingredient is introduced successively into a mixing tank with moderate mechanical stirring, at room temperature until a homogeneous and clear composition is obtained. Stirring is maintained for 30 minutes at 20 ° C.
  • the composition obtained has a measured pH value of less than 1 and is clear and homogeneous after storage for a period of one month at 40 ° C.
  • composition prepared in the preceding paragraph is diluted to 3% in water and the solution thus obtained is poured into a vessel of suitable size. The metal parts are then soaked for 30 minutes, then rinsed with water.
  • SIMULSOL TM OX 1309 L Mass content SIMULSOL TM OX 1309 L (2) 3% Composition (X 0 ) 3% 75% phosphoric acid 40% HORDAPHOS MDGB 1% 5% Di Propylene Glycol Methyl Ether 5% Water Qs 100% (2) SIMULSOL TM OX1309L: detergent surfactant composition marketed by the company SEPPIC, comprising polyethoxylated alcohols resulting from the reaction of a molar equivalent of an alcohol marketed under the trade name EXXAL TM 13 with 9 molar equivalents of 'ethylene.
  • SEPPIC detergent surfactant composition marketed by the company SEPPIC, comprising polyethoxylated alcohols resulting from the reaction of a molar equivalent of an alcohol marketed under the trade name EXXAL TM 13 with 9 molar equivalents of 'ethylene.
  • Each ingredient is introduced successively into a mixing tank with moderate mechanical stirring, at room temperature until a homogeneous and clear composition is obtained. Stirring is maintained for 30 minutes at 20 ° C.
  • the resulting composition has a measured pH value of less than 1.0 and is clear and homogeneous after storage for a period of one month at 40 ° C.
  • composition prepared in the preceding paragraph is diluted to 3% in water and the solution thus obtained is sprayed onto the aluminum wall to be cleaned. This wall is then rinsed with hot water at 60 ° C.
  • SIMULSOL TM NW 900 15% Composition (X 0 ) 5% Anhydrous citric acid 17% isopropanol 20% Water Qs 100%
  • SIMULSOL TM NW 900 detergent surfactant composition sold by the company SEPPIC, comprising polyethoxylated alcohols resulting from the reaction of one molar equivalent of an alcohol sold under the trade name EXXAL TM 10 with 9 molar equivalents of oxide ethylene.
  • Each ingredient is introduced successively into a mixing tank with moderate mechanical stirring, at room temperature until a homogeneous and clear composition is obtained. Stirring is maintained for 30 minutes at 20 ° C.
  • the composition obtained has a pH measured at a value of 1.3 and is clear and homogeneous after storage for a period of one month at 40 ° C.
  • composition prepared in the previous paragraph is diluted to 0.3% in water and the solution thus obtained is poured into the dishwasher and used at a temperature of 60.degree.

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Claims (11)

  1. Verwendung einer Zusammensetzung (C), für die die Formel (I) steht:

            R1-O-(G)p-H     (I)

    in der G für den Rest eines reduzierenden Zuckers steht,
    R1 für das N-Heptylradikal steht,
    p für eine Dezimalzahl größer 1 und kleiner oder gleich 5 steht,
    wobei die Zusammensetzung (C) aus einer Mischung von Verbindungen besteht, für die die Formeln (I1), (I2), (I3), (I4) und (I5) stehen:

            R1-O-(G)1-H     (I1)

            R1-O-(G)2-H     (I2)

            R1-O-(G)3-H     (I3)

            R1-O-(G)4-H     (I4)

            R1-O-(G)5-H     (I5),

    in den folgenden jeweiligen molaren Anteilen:
    a1 für die Verbindung der Formel (I1),
    a2 für die Verbindung der Formel (I2),
    a3 für die Verbindung der Formel (I3),
    a4 für die Verbindung der Formel (I4), und
    a5 für die Verbindung der Formel (I5),
    so dass:
    die Summe a1 + a2 + a3 + a4 + a5 gleich 1 ist, und dass
    die Summe a1 + 2a2 + 3a3 + 4a4 + 5a5 gleich p ist,
    als Lösungsvermittler von mindestens einem nichtionischen Tensid der Formel (II):

            R-(O-CH(R')-CH2)n-(O-CH2-CH2)m-O-H     (II)

    in der R für ein gesättigtes oder ungesättigtes, geradkettiges oder verzweigtes aliphatisches Kohlenwasserstoffradikal steht, das 8 bis 14 Kohlenstoffatome enthält,
    R' für ein Methyl- oder Ethylradikal steht,
    n für eine Ganzzahl größer oder gleich 0 und kleiner oder gleich 15 steht,
    m für eine Ganzzahl größer oder gleich 0 und kleiner oder gleich 15 steht, wobei die Summe n + m größer Null ist, in einer wässrigen sauren Zusammensetzung.
  2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass in der Formel (I) p für eine Dezimalzahl größer oder gleich 1,05 und kleiner oder gleich 2,5 steht.
  3. Verwendung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass in der Formel (I) G für den Rest eines reduzierenden Zuckers steht und aus den Glukose-, Xylose- und Arabinoseresten ausgewählt ist.
  4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass in der Formel (II) das Radikal R für ein Radikal steht, das aus den Octyl-, Decyl-, Dodecyl-, Tetradecyl-, 2-Ethylhexyl-, 2-Butyloctyl-, 2-Butyldecyl-, 2-Hexyloctyl-, Isooctyl-, Isononyl-, Isodecyl-, Isoundecyl-, Isododecyl-, Isotridecyl-, Isotetradecyl- oder 2-Propylheptypradikalen ausgewählt ist.
  5. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass in der Formel (II) n für eine Ganzzahl größer oder gleich 0 und kleiner oder gleich 6, bevorzugt größer oder gleich 0 und kleiner oder gleich 3, und noch bevorzugter größer oder gleich 0 und kleiner oder gleich 2 steht.
  6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass in der Formel (II) m für eine Ganzzahl größer oder gleich 1 und kleiner oder gleich 9, bevorzugt größer oder gleich 2 und kleiner oder gleich 6, und noch bevorzugter größer oder gleich 2 und kleiner oder gleich 4 steht.
  7. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Massenverhältnis zwischen dem nichtionischen Tensid der Formel (II) und der Zusammensetzung (C) kleiner oder gleich 15/1 und größer oder gleich 1/1 ist.
  8. Zusammensetzung (C1), die auf 100 % ihrer Masse umfasst:
    a) 0,2 bis 40 Masse-% der Zusammensetzung (C), für die die Formel (I) steht:

            R1-O-(G)p-H     (I)

    in der G für den Rest eines reduzierenden Zuckers steht,
    R1 für das N-Heptylradikal steht,
    p für eine Dezimalzahl größer 1 und kleiner oder gleich 5 steht,
    wobei die Zusammensetzung (C) aus einer Mischung von Verbindungen besteht, für die die Formeln (I1), (I2), (I3), (I4) und (I5) stehen:

            R1-O-(G)1-H     (I1)

            R1-O-(G)2-H     (I2)

            R1-O-(G)3-H     (I3)

            R1-O-(G)4-H     (I4)

            R1-O-(G)5-H     (I5),

    in den folgenden jeweiligen molaren Anteilen:
    a1 für die Verbindung der Formel (I1),
    a2 für die Verbindung der Formel (I2),
    a3 für die Verbindung der Formel (I3),
    a4 für die Verbindung der Formel (I4), und
    a5 für die Verbindung der Formel (I5),
    so dass:
    die Summe a1 + a2 + a3 + a4 + a5 gleich 1 ist, und dass
    die Summe a1 + 2a2 + 3a3 + 4a4 + 5a5 gleich p ist,
    b) 0,2 bis 80 Masse-% von mindestens einem nichtionischen Tensid der Formel (II):

            R-(O-CH(R')-CH2)n-(O-CH2-CH2)m-O-H     (II)

    in der R für ein gesättigtes oder ungesättigtes, geradkettiges oder verzweigtes aliphatisches Kohlenwasserstoffradikal steht, das 8 bis 14 Kohlenstoffatome enthält, R' für ein Methyl- oder Propylradikal steht, n für eine Ganzzahl größer oder gleich 0 und kleiner oder gleich 15 steht, m für eine Ganzzahl größer oder gleich 0 und kleiner oder gleich 15 steht, wobei die Summe n + m größer Null ist;
    c) 1 bis 50 Masse-% von mindestens einem sauren Mittel, ausgewählt aus den Elementen der Gruppe, die gebildet wird von den anorganischen Säuren und den organischen Säuren; und
    d) 1 bis 98,6 Masse-% Wasser.
  9. Zusammensetzung (C1) nach Anspruch 8, dadurch gekennzeichnet, dass das Massenverhältnis zwischen der Verbindung der Formel (II) und der Zusammensetzung (C) kleiner oder gleich 15/1 und größer oder gleich 1/1 ist.
  10. Verwendung der Zusammensetzung (C1) nach einem der Ansprüche 8 oder 9 zum Reinigen von harten Oberflächen.
  11. Verfahren zum Reinigen einer harten Oberfläche, dadurch gekennzeichnet, dass es umfasst:
    mindestens einen Schritt a 1 ) des Auftragens der Zusammensetzung (C1) nach einem der Ansprüche 8 oder 9 auf die harte Oberfläche, gefolgt von
    mindestens einem Schritt b 1 ) des Abspülens der harten Oberfläche.
EP12728679.7A 2011-05-27 2012-05-14 Neue verwendung von heptylpolyglycosiden zur auflösung von nicht ionischen tensiden in wässrigen sauren reinigungszusammensetzungen und wässrige saure reinigungszusammensetzungen damit Active EP2714876B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1154653A FR2975703B1 (fr) 2011-05-27 2011-05-27 Nouvelle utilisation d'heptylpolyglycosides pour solubiliser des tensioactifs non-ioniques dans des compositions nettoyantes acides aqueuses, et compositions nettoyantes acides aqueuses les comprenant.
PCT/FR2012/051070 WO2012164190A1 (fr) 2011-05-27 2012-05-14 Nouvelle utilisation d'heptylpolyglycosides pour solubiliser des tensioactifs non-ioniques dans des compositions nettoyantes acides aqueuses, et compositions nettoyantes acides aqueuses les comprenant

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FR2968003B1 (fr) * 2010-11-25 2013-06-07 Seppic Sa Nouvel agent hydrotrope, son utilisation pour solubiliser des tensioactifs no-ioniques, compositions les comprenant.
FR2995610B1 (fr) * 2012-09-14 2014-10-10 Seppic Sa Nouveau procede de forage de cavites souterraines, nouvelles compositions a base d'alkylpolyglycosides et leur utilisation comme agent lubrifiant dans la preparation de fluides de forage aqueux
FR3014683B1 (fr) * 2013-12-18 2017-10-13 Soc D'exploitation De Produits Pour Les Ind Chimiques Seppic Utilisation d'alkylpolyglycosides comme solubilisants de parfums et composition parfumante les comprenant
US10428228B1 (en) 2014-01-20 2019-10-01 Arris Technologies, LLC Pre-treatment and cleaning of equipment used with uncured cementitious materials
US10100206B1 (en) * 2014-01-20 2018-10-16 Arris Technologies, LLC Pre-treatment and cleaning of equipment used with uncured cementitious materials
US10947480B2 (en) 2016-05-17 2021-03-16 Conopeo, Inc. Liquid laundry detergent compositions
FR3088074B1 (fr) 2018-11-06 2021-12-03 Pimpant Composition detergente et kit pour la preparation de lessives

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DE3928602A1 (de) * 1989-08-30 1991-03-07 Henkel Kgaa Alkalistabile und stark alkalisch formulierbare antischaummittel fuer die gewerbliche reinigung, insbesondere fuer die flaschen- und cip-reinigung
DE69217516T2 (de) 1991-07-15 1997-09-11 Cfpi Ind Saures, desinfizierendes und Kesselstein entfernendes Reinigungsmittel und Verfahren zu seiner Herstellung
FR2733246B1 (fr) 1995-04-21 1997-05-23 Seppic Sa Composition anti-mousse comprenant un tensioactif non ionique et un alkylpolyglycoside
SE510989C2 (sv) 1997-10-29 1999-07-19 Akzo Nobel Nv Högakaliska kompositioner innehållande en hexylglykosid som hydrotrop

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WO2012164190A1 (fr) 2012-12-06
DK2714876T3 (da) 2017-10-02
FR2975703B1 (fr) 2013-07-05
US20140113850A1 (en) 2014-04-24
EP2714876A1 (de) 2014-04-09
CN103562367A (zh) 2014-02-05
CN103562367B (zh) 2016-11-23
FR2975703A1 (fr) 2012-11-30
US9080132B2 (en) 2015-07-14

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