EP4274883A1 - Waschmittelzusammensetzung mit einer zusammensetzung mit polaren medienverdickungseigenschaften als verdickungsmittel - Google Patents

Waschmittelzusammensetzung mit einer zusammensetzung mit polaren medienverdickungseigenschaften als verdickungsmittel

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Publication number
EP4274883A1
EP4274883A1 EP21836214.3A EP21836214A EP4274883A1 EP 4274883 A1 EP4274883 A1 EP 4274883A1 EP 21836214 A EP21836214 A EP 21836214A EP 4274883 A1 EP4274883 A1 EP 4274883A1
Authority
EP
European Patent Office
Prior art keywords
composition
formula
detergent composition
acid
grams
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.)
Pending
Application number
EP21836214.3A
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English (en)
French (fr)
Inventor
Miruna BODOC
Stéphane MONTEILLET
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.)
Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA
Original Assignee
Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA
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Application filed by Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA filed Critical Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA
Publication of EP4274883A1 publication Critical patent/EP4274883A1/de
Pending 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C11D2111/14—

Definitions

  • the present invention relates to a detergent composition (F) comprising at least one surfactant and, as thickening agent, a composition (C A ) in the form of an emulsion of the self-reversing water-in-oil type and the method of preparation of such a composition.
  • Detergent compositions contain polar phases such as, for example, phases consisting of water, and in most cases require the use of rheology modifying agents, such as, for example, polymers, to increase the viscosity of these polar phases, as well as only to impart a well-defined rheological behavior.
  • polar phases such as, for example, phases consisting of water
  • rheology modifying agents such as, for example, polymers
  • rheology-modifying polymers of the polar phases we can cite natural polymers, such as for example polysaccharides based on oses or polysaccharides based on derivatives of oses, or else synthetic polymers, of the polyelectrolyte type, anionic or cationic, amphiphilic, linear or branched, cross-linked or non-cross-linked.
  • synthetic polymers Mainly present on the market, synthetic polymers have the property of being deployed in the polar phase, under the effect of electrostatic repulsions due to the presence of charges (negative and/or positive) on the polymeric skeleton, linear or branched, uncrosslinked or crosslinked.
  • These rheology modifiers provide both an increase in the viscosity of the polar phase, as well as a certain consistency and/or a stabilizing effect conferred on the detergent composition.
  • the polymers used for the purpose of the detergent industries can play a functional role as film-forming agents, rheology modifying agents, allowing the stabilization of the fatty phases in emulsions of the water-in-oil type and of the oil-in-water, stabilization of solid particles (pigments and fillers) or as agents having an impact on the appearance of the formula (transparency, translucency, opacity).
  • the rheology-modifying polymers of polar phases, and more particularly of aqueous phases are mainly polyelectrolytes, which result from the radical polymerization of monomers of the (meth)acrylic type, that is to say acrylic acid or methacrylic acid, esters derived from acrylic acid or methacrylic acid, or alternatively acrylamide or methacrylamide derivatives.
  • Glutamic acid As an example of a polymer of natural origin, we can cite polyglutamic acid (PGA), which is today the subject of numerous research works. It is a predominantly linear polymer and consists of monomeric glutamic acid (GA) units. Glutamic acid is an amino acid characterized by an amine function in the ⁇ position and by two carboxylic acid functions (or carboxylates depending on the pH) in the ⁇ and ⁇ positions (cf chemical formula n°1).
  • the cross-linking of polymer chains aims to connect several polymer chains to each other which, when added to a polar phase, and more particularly to water, appear as a three-dimensional network insoluble in water. water, but swellable with water and then leading to obtaining a chemical gel.
  • the preparation of cross-linked polymers can be carried out:
  • PGA polyglutamic acid
  • crosslinking agents known to be used in the crosslinking reaction of (PGA) the polyepoxide derivatives are the most described, because they make it possible to implement crosslinking processes under conditions that respect the environment (moderate temperature, reaction in aqueous media and in the absence of harmful solvents).
  • a solution of the present invention is a detergent composition (F) for household or industrial use comprising at least one detergent surfactant and, as thickening agent, a composition (C A ) in the form of a water-in-oil type emulsion.
  • self-inverting compound comprising, for 100% of its mass, a mass content greater than or equal to 20% of a polymer (P) consisting of monomeric units derived from glutamic acid (GA), partially or totally salified, and in units derived at least one cross-linking agent (RA) bearing at least two glycidyl functions.
  • detergent surfactants denotes, within the meaning of the present invention, the surfactants which give the aqueous liquid detergent composition (F) its ability to remove the dirt present on solid surfaces and to keep them in suspension in order to then be removed. during the rinsing step.
  • emulsion of the water-in-oil type is meant within the meaning of the present invention a heterogeneous mixture of two immiscible liquids, one being dispersed in the form of small droplets in the other, said mixture being thermodynamically unstable and stabilized by the presence of a surfactant system comprising at least one emulsifying surfactant.
  • emulsion of the water-in-oil self-reversible type is meant within the meaning of the present invention an emulsion of the water-in-oil type as defined above, in which the emulsifying surfactants present give the emulsion a hydrophilic-lipophilic balance (HLB) such that once said emulsion is added to a polar phase, such as water, the direction of the emulsion will change from the water-in-oil form to the oil- in water, then making it possible to bring the polymer (P) into contact with the polar phase to be thickened.
  • HLB hydrophilic-lipophilic balance
  • the PGA can be prepared chemically according to peptide synthesis methods known to those skilled in the art, in particular passing through stages of selective protection(s), activation, coupling and deprotection(s).
  • the coupling generally consists of a nucleophilic attack of the amine function of a monomeric glutamic acid unit on an activated carboxylic acid function of another monomeric glutamic acid unit.
  • PGGA can also be obtained by processes comprising at least one microbial fermentation step involving the use of at least one bacterial strain.
  • the term “salified” indicates that the “pendent” carboxylic acid function present on each monomeric glutamic acid (GA) unit of the polymer (in the gamma position in the case of PAGA or alpha in the case of PGGA) is in an anionic or carboxylate form.
  • the counter-ion of this carboxylate function is a cation derived, for example, from salts of alkali metals such as sodium, potassium or from salts of nitrogenous bases such as amines, lysine or monoethanolamine (HO-CH 2 - CH2 - NH2 ).
  • the mass content of the polymer (P) is greater than or equal to 20% and less than or equal to 60% and more particularly greater than or equal to 20% and less than or equal to 40%.
  • PGGA can exist in different conformational forms in solution in water. These depend on the inter and intra molecular hydrogen bonds and therefore on the pH, the polymer concentration, the ionic strength of the solution, as well as the temperature.
  • the chains of the PGGA can thus adopt a helix shape , ⁇ -sheet, aggregates or else be in a disordered and random state.
  • the polymer (P) in the composition (C A ) which is the subject of the present invention, is in helical conformation when it is present in a solution at a mass content of less than or equal to 0.1% and of which said solution shows a pH value less than or equal to 7.
  • the polymer (P) in sheet conformation when it is present in a solution at a mass content of less than or equal to 0.1% and of which said solution shows a pH value greater than 7.
  • cross-linking agent RA
  • crosslinking agent (RA) bearing at least two glycidyl functions is meant within the meaning of the present invention a crosslinking agent (RA) as defined above whose molecular structure comprises at least two glycidyl units or functions of formula ( I'):
  • the cross-linking of the polymer chains of the polymer (P) takes place according to a reaction between the terminal free amine function (-NH 2 ) and/or one or more "pendent" or terminal carboxylic or carboxylate functions (-COOH or -COO - ) present in the structure of said polymer (P), and at least one epoxy group present in the structure of the crosslinking agent (AR) bearing at least two glycidyl functions.
  • the crosslinking agent (RA) may be chosen from the members of the group consisting of:
  • R representing the hydrogen atom or the glycidyl radical [ ] and n which represents an integer greater than or equal to 1 and less than or equal to 10,
  • the compound of formula (II) is more particularly the compound of formula (IIa) or Glycerol Diglycidyl Ether:
  • the compound of formula (II) is more particularly the compound of formula (IIb) or Glycerol Triglycidyl Ether:
  • the compound of formula (II) is more particularly the compound of formula (IIc) or Diglycerol Diglycidyl Ether:
  • the compound of formula (II) is more particularly the compound of formula (IId) or Diglycerol Tetraglycidyl Ether:
  • R 1 representing the hydrogen atom or the glycidyl radical
  • the compound of formula (IX) is more particularly the compound of formula (IXa) or Trimethylol Ethane Diglycidyl Ether:
  • R 1 represents the glycidyl radical
  • the compound of formula (IX) is more particularly the compound of formula (IXb) or Trimethylol Ethane Triglycidyl Ether:
  • R1 representing the hydrogen atom or the glycidyl radical
  • the compound of formula (X) is more particularly the compound of formula (Xa) or Trimethylol Propane Diglycidyl Ether:
  • R1 represents the glycidyl radical
  • the compound of formula (X) is more particularly the compound of formula (Xb) or Trimethylol Propane Triglycidyl Ether:
  • R 1 and R 2 independent, which represent the hydrogen atom or the glycidyl radical
  • the compound of formula (XI) is more particularly the compound of formula (XIa) or Pentaerythritol Diglycidyl Ether:
  • R 1 represents the hydrogen atom and R 2 represents the glycidyl radical
  • the compound of formula (XI) is more particularly the compound of formula (XIb) or Pentaerythritol Propane Triglycidyl Ether:
  • the compound of formula (XI) is more particularly the compound of formula (XIc) or Pentaerythritol Propane Tetraglycidyl Ether:
  • R 3 which represents the hydrogen atom or the glycidyl radical and x, y, z, o, p and q, independent of each other, represent an integer greater than or equal to 2 and less than or equal to 10.
  • the detergent composition (F) may have one or more of the following characteristics:
  • R4 representing a linear or branched, saturated or unsaturated, functionalized or unfunctionalized hydrocarbon radical and comprising from 6 to 22 carbon atoms.
  • R4 representing a hydrocarbon radical chosen from the elements of the group consisting of the radical heptyl, octyl, nonyl, decyl, undecyl, undecenyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, hydroxyoctadecyl, oleyl, linoleyl, linolenyl, eicosyl and dodecosyl.
  • the monomeric units derived from the compound of formula (X′) represent from 1 to 50% by weight.
  • a subject of the present invention is also a method for preparing a detergent composition (F) comprising the following two distinct steps:
  • the method according to the invention may have one or more of the characteristics below:
  • R 4 representing a linear or branched, saturated or unsaturated, functionalized or unfunctionalized hydrocarbon radical and comprising from 6 to 22 carbon atoms.
  • R 4 represents a hydrocarbon radical chosen from the elements of the group consisting of the radical heptyl, octyl, nonyl, decyl, undecyl, undecenyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, hydroxyoctadecyl, oleyl , linoleyl, linolenyl, eicosyl and dodecosyl.
  • the content of compound of formula (X') in the polar solution is comprised, for 100% by mass of said aqueous solution, between 0.05 and 35% by mass, it being understood that the sum of the proportions by mass of the polymer (P), of the crosslinking agent (AR), of the water and of the compound of formula (X′) is equal to 100%.
  • volatile oil is meant within the meaning of the present invention an element of the group consisting of branched alkanes, comprising from 7 to 40 carbon atoms such as iso-dodecane, iso- pentadecane, iso-hexadecane, iso-heptadecane, iso-octadecane, iso-nonadecane or iso-eicosane or mixtures of some of them such as those cited below and identified by their INCI name: C7-8 isoparaffin, C8-9 isoparaffin, C9-11 isoparaffin, C9-12 isoparaffin, C9-13 isoparaffin, C9-14 isoparaffin, C9-16 isoparaffin, C10-11 isoparaffin, C10-12 isoparaffin, C10- 13 isoparaffin, C11-12 isoparaffin, C11-13 isoparaffin and C11-14 isoparaffin.
  • volatile oil within the meaning of the present invention at least one element of the group consisting of iso-dodecane, iso-hexadecane, C7-8 isoparaffin, C8 -9 isoparaffin, C9-11 isoparaffin, C11-13 isoparaffin, C11-14 isoparaffin.
  • the volatile oil is chosen from an element of the group consisting of C8-9 isoparaffin, C9-11 isoparaffin, C11-13 isoparaffin, C11-14 isoparaffin.
  • the “volatile oil” is chosen from an element of the group consisting of isoparaffins marketed under the brand names Isopar TM G, IsoparTM L, IsoparTM H or IsoparTM J .
  • non-volatile oil H is meant within the meaning of the present invention an element of the group consisting of:
  • mixture (M1) is characterized in that it comprises for 100% of its mass:
  • linear alkanes present in the mixture (M1) as defined above, and comprising from 15 to 19 carbon atoms, is meant more particularly within the meaning of the present invention the elements chosen from the group consisting of n- pentadecane, n-hexadecane, n-heptadecane, n-octadecane and n-nonadecane.
  • branched alkanes present in the mixture (M1) as defined above, and comprising from 15 to 19 carbon atoms, is meant more particularly within the meaning of the present invention the elements chosen from the group consisting of the iso -pentadecane, iso-hexadecane, iso-heptadecane, iso-octadecane and iso-nonadecane.
  • the mixture (M1) is more particularly the mixture marketed under the brand name EmogreenTML15 by the company Seppic or else the mixture marketed under the brand name EmogreenTML19.
  • Z 1 and Z 2 which are identical or different, represent a linear or branched alkyl radical comprising from 5 to 18 carbon atoms, for example dioctyl ether, didecyl ether, didodecyl ether, dodecyl octyl ether, dihexadecyl ether, (1,3 -dimethyl butyl) tetradecyl ether, (1,3-dimethyl butyl) hexadecyl ether, bis(1,3-dimethyl butyl) ether or dihexyl ether.
  • dioctyl ether didecyl ether
  • didodecyl ether didodecyl ether
  • dodecyl octyl ether dihexadecyl ether
  • (1,3 -dimethyl butyl) tetradecyl ether (1,3-dimethyl butyl) hexadec
  • R' 2 represents, independently of R' 1 , a saturated hydrocarbon chain or unsaturated, linear or branched containing from 1 to 24 carbon atoms, for example methyl laurate, ethyl laurate, propyl laurate, iso-propyl laurate, butyl laurate, 2-butyl laurate, hexyl, methyl cocoate, ethyl cocoate, propyl cocoate, iso-propyl cocoate, butyl cocoate, 2-butyl cocoate, hexyl cocoate, methyl myristate, ethyl myristate, propyl myristate , iso-propyl myristate, butyl myristate, 2-butyl myristate, hexyl myristate, octy
  • said non-volatile oil (H) is chosen from:
  • the term "emulsifying surfactant of the water-in-oil type (S1)” denotes an emulsifying surfactant having an HLB value ("Hydrophile Lipophile Balance ” or hydrophilic-lipophilic balance) weak enough to induce the formation of a water-in-oil type emulsion, namely an emulsion in which the aqueous phase will be dispersed and stabilized in the oily organic phase.
  • HLB value Hydrophilic-lipophilic balance
  • esters of anhydro hexitol and of aliphatic, linear or branched, saturated or unsaturated carboxylic acids comprising from 12 to 22 carbon atoms optionally substituted with one or several hydroxyl groups
  • esters of anhydro hexitol chosen from anhydro-sorbitols and anhydro-mannitols and of aliphatic, linear or branched, saturated or unsaturated carboxylic acids, containing from 12 to 22 carbon atoms optionally substituted with one or more hydroxyl groups are particularly the esters of anhydro hexitol chosen from anhydro-sorbitols and anhydro-mannitols and of aliphatic, linear or branched, saturated or unsaturated carboxylic acids, containing from 12 to 22 carbon atoms optionally substituted with one or more hydroxyl groups.
  • the emulsifying system (S1) of the water-in-oil type is more particularly chosen from the elements of the group consisting of:
  • R 2 represents an aliphatic hydrocarbon radical, saturated or unsaturated, linear or branched, containing from 11 to 35 carbon atoms and more particularly a radical chosen from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, eicosanoyl, docosanoyl, oleyl, linoleyl, linolenoyl or isostearyl radicals
  • y represents an integer greater than or equal to 2 and less than or equal to 20.
  • the compound of formula (XIX) is chosen from the elements of the group consisting of decaglycerol oleate, decaglycerol iso-stearate, decaglycerol monolaurate, decaglycerol mono-linoleate, decaglycerol mono-myristate.
  • R' 2 represents an aliphatic hydrocarbon radical, saturated or unsaturated, linear or branched, containing from 11 to 35 carbon atoms, and more particularly a radical chosen from the dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, eicosanoyl, docosanoyl, oleyl, linoleyl, linolenoyl or isostearyl radicals
  • R 3 represents the hydrogen atom, the methyl radical, or the ethyl radical
  • y 1 represents an integer greater than or equal to 2 and less than or equal to 20, v 1 , v 2 , v 3
  • y 2 represents an integer greater than or equal to 2 and less than or equal to 50
  • Z 4 represents the hydrogen atom, the methyl radical or the ethyl radical
  • Z 3 represents a radical of formula (XXII):
  • y' 2 represents an integer greater than or equal to 0 and less than or equal to 10, more particularly greater than or equal to 1 and less than or equal to 10 and Z' 3 represents a radical of formula (XXII) as defined above above, with Z'3 identical or different from Z 3 , or the hydrogen atom.
  • an emulsifying surfactant of the water-in-oil type of formula (XXI) which can be used to prepare the emulsifying system (S1) there is PEG-30 dipolyhydroxystearate sold under the name SimalineTM WO, or else the mixtures comprising PEG-30 dipolyhydroxystearate and sold under the names SimalineTMIE 201 A and SimalineTMIE 201 B or else the mixture comprising Trimethylolpropane-30 tripolyhydroxystearate sold under the name SimalineTMIE 301 B.
  • Z 3 represents a radical of formula (XXIII) as defined above
  • Z' 3 represents a radical of formula (XXII) as defined above, with Z3' identical to or different from Z 3 , or the hydrogen atom
  • y 3 represents an integer greater than or equal to 2 and less than or equal to 20.
  • Z 4 represents a radical of formula (XXII) as defined above
  • Z' 4 represents a radical of formula (XXII) as defined above
  • y 4 represents an integer greater than or equal to 2 and less than or equal to 20
  • v' 1 , v' 2 , v' 3 which are identical or different, represent an integer greater than or equal to 0 and less than or equal to 50
  • the sum [(y 4 .v' 1 ) + (y 4 .v' 2 ) + v' 3 )] is an integer greater than or equal to 1 and less than or equal to 50.
  • the term “emulsifying surfactant of the oil-in-water type (S2)” denotes an emulsifying surfactant having a sufficiently high HLB value to induce the formation of an emulsion of the oil-in-water type, namely an emulsion in which the oily organic phase will be dispersed and stabilized in the aqueous phase.
  • step g) of the process which is the subject of the present invention as surfactant of oil-in-water type (S2), mention may be made of:
  • R'' representing a linear or branched, saturated or unsaturated hydrocarbon radical, which may bear hydroxyl groups, and comprising from 6 to 22 carbon atoms, and with n' representing an integer greater than or equal to 4 and less than or equal to 100.
  • R'' represents a linear or branched, saturated hydrocarbon-based radical comprising from 10 to 22 carbon atoms.
  • the compound of formula (XXV) is a linear decyl alcohol ethoxylated with 6 moles of ethylene oxide, a linear decyl alcohol ethoxylated with 8 moles of ethylene oxide, a linear lauryl alcohol ethoxylated with 6 moles of ethylene oxide, linear lauryl alcohol ethoxylated with seven moles of ethylene oxide, linear lauryl alcohol ethoxylated with 8 moles of ethylene oxide, linear tridecyl alcohol ethoxylated with 6 moles of ethylene oxide, a linear tridecyl alcohol ethoxylated with 8 moles of ethylene oxide, a linear tridecyl alcohol ethoxylated with nine moles of ethylene oxide.
  • x or average degree of polymerization, represents a decimal number between 1.05 and 5
  • G represents the residue of a reducing sugar
  • R'' 1 represents an aliphatic hydrocarbon radical, saturated or unsaturated, linear or branched, optionally substituted with one or more hydroxyl groups, containing from 12 to 36 carbon atoms
  • the said composition (C1) consisting of a mixture of compounds represented by the formulas (XXVI1), (XXVI2), (XXVI3), (XXVI4) and ( XXVI5):
  • hydrocarbon-based aliphatic radical saturated or unsaturated, linear or branched, comprising from 12 to 36 carbon atoms, optionally substituted with one or more hydroxyl groups
  • reducing sugar in the definition of formula (XXVI) as defined above, is meant the saccharide derivatives which do not have in their structures a glycoside bond established between an anomeric carbon and the oxygen of an acetal group such as that they are defined in the reference work: “Biochemistry”, Daniel Voet/Judith G. Voet, p. 250, John Wyley & Sons, 1990.
  • the oligomeric structure (G) x can occur in all forms of isomerism, whether optical isomerism, geometric isomerism or positional isomerism. It can also represent a mixture of isomers.
  • R 1 -O- group is linked to G via the anomeric carbon of the saccharide residue, so as to form an acetal function.
  • G represents the residue of a reducing sugar chosen from glucose, dextrose, sucrose, fructose, idose, gulose, galactose, maltose, isomaltose, maltotriose, lactose, cellobiose, mannose, ribose, xylose, arabinose, lyxose, allose, altrose, dextran or tallose and more particularly G represents the residue of a reducing sugar chosen from the residues of glucose, xylose and arabinose.
  • x in the definition of formula (XXVI) x, or average degree of polymerization, represents a decimal number greater than or equal to 1.05 and less than or equal to 2.5, more particularly greater than or equal to 1.05 and less than or equal to 2.0 and even more particularly greater than or equal to 1.25 and less than or equal to 2.0.
  • compositions (C2) comprising for 100% of their mass:
  • R''' 1 identical to or different from R'' 1 , represents an aliphatic hydrocarbon radical, saturated or unsaturated, linear or branched, optionally substituted with one or more hydroxyl groups, containing from 12 to 36 carbon atoms and preferably 12 to 22 carbon atoms.
  • n12 represents an integer greater than or equal to 1 and less than or equal to 15, and
  • the present invention also relates to:
  • composition (C A ), object of the present invention consists in thickening polar phases such as, for example, aqueous, alcoholic or aqueous-alcoholic phases or polar phases comprising polyols such as glycerol.
  • said use consists in stabilizing an emulsion of the oil-in-water type, or of the water-in-oil type, by conferring a homogeneous appearance on said emulsion during storage under different conditions, and more particularly at 25 °C for a period at least equal to one month, and more particularly at 4°C for a period at least equal to one month, and more particularly at 45°C for a period at least equal to one month.
  • said use consists in stabilizing solid particles in liquid aqueous detergent compositions for household or industrial use.
  • These solid particles to be suspended can take on different geometries, regular or irregular, and take the form of beads, balls, rods, flakes, lamellae or polyhedrons. These solid particles are characterized by an average apparent diameter of between one micrometer and five millimeters, more particularly between ten micrometers and one millimeter.
  • solid particles which can be suspended and stabilized by the self-inverting inverse latex as defined previously in liquid aqueous detergent compositions for household or industrial use, there are micas, iron oxide, oxide titanium, zinc oxide, aluminum oxide, talc, silica, kaolin, clays, boron nitride, calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, inorganic colored pigments, polyamides such as nylon-6, polyethylenes, polypropylenes, polystyrenes, polyesters, acrylic or methacrylic polymers such as polymethylmethacrylates, polytetrafluoroethylene, crystalline or microcrystalline waxes, porous spheres, selenium sulphide , zinc pyrithione, starches, alginates, vegetable fibers, Loofah particles, sponge particles.
  • micas such as nylon-6, polyethylenes, polypropylenes, polystyrenes, polyesters, acrylic or methacrylic polymers such as polymethylmethacrylates, polytetra
  • Said aqueous liquid detergent composition (F), object 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 oily continuous phase, an aqueous gel, a foam, or else in the form of an aerosol. It can 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 solid surface to be cleaned (paper, wipe, textile).
  • said liquid aqueous detergent composition (F) which is the subject of the present invention, also comprises ingredients usually used in the field of cleaning solid surfaces or textile fibers, such as nonionic, cationic or amphoteric surfactants, cationic or non-ionic polymers, thickening agents, enzymes, bleaching agents, anti-corrosion agents, solvents, acid agents, alkaline agents, anti-scaling agents, preservatives, perfumes, dyes, repellents , oxidizing agents, detergency builders, antifouling agents, anti-redeposition agents.
  • ingredients usually used in the field of cleaning solid surfaces or textile fibers such as nonionic, cationic or amphoteric surfactants, cationic or non-ionic polymers, thickening agents, enzymes, bleaching agents, anti-corrosion agents, solvents, acid agents, alkaline agents, anti-scaling agents, preservatives, perfumes, dyes, repellents , oxidizing agents, detergency builders, antifouling
  • aqueous liquid detergent composition (F) As defined above, mention may be made of surfactants which give the aqueous liquid detergent composition (F) their ability to remove soiling present on the solid surfaces and to keep them in suspension, to be then eliminated during the rinsing step.
  • detergent surfactants can be anionic, cationic, amphoteric or non-ionic in nature.
  • detergent anionic surfactants capable of being used for the preparation of the liquid aqueous detergent composition (F) as defined previously, mention may be made of alkali metal salts, alkaline-earth metal salts, ammonium salts , amine salts, amino alcohol salts of alkyl ether sulphates, alkyl sulphates, alkylamidoether sulphates, alkylaryl polyether sulphates, monoglyceride sulphates, alpha-olefin sulphonates, paraffin sulphonates, alkyl phosphates, alkyl ether phosphates, alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates, alkyl carboxylates, alkylsulfosuccinates, alkylether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, alkyl
  • detergent amphoteric surfactants capable of being used for the preparation of the liquid aqueous detergent composition (F) as defined above, mention may be made of alkylbetaines, alkylamidobetaines, sultaines, alkylamidoalkylsulfobetaines, imidazoline derivatives, phosphobetaines , amphopolyacetates and amphopropionates.
  • foaming and/or detergent amphoteric surfactants that can be combined with said self-inverting inverse latex as defined above in said liquid aqueous detergent composition (F)
  • cationic detergent surfactants capable of being used for the preparation of the liquid aqueous detergent composition (F) as defined previously, mention may be made in particular of the quaternary ammonium derivatives.
  • nonionic detergent surfactants capable of being used for the preparation of the liquid aqueous detergent composition (F) as defined above, mention may be made in particular of the alkylpolyglycosides comprising an aliphatic radical, linear or branched, saturated or unsaturated and comprising 8 with 16 carbon atoms, castor oil derivatives, polysorbates, coconut amides, N-alkylamines.
  • alkoxylated monoglycerides alkoxylated diglycerides, alkoxylated terpene hydrocarbons such as ethoxylated and/or propoxylated ⁇ - or ⁇ -pinenes, containing from 1 to 30 oxyethylene and/or oxypropylene units, the products resulting from the condensation of ethylene oxide or propylene oxide with ethylenediamine, such as TetronicTM marketed by BASF, ethoxylated and/or propoxylated C8-C18 fatty acids containing from 5 to 25 moles of ethylene oxide and/or propylene, ethoxylated fatty amides containing from 5 to 30 moles of ethylene oxide, ethoxylated amines containing from 5 to 30 moles of ethylene oxide, alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, very particularly from 2 to 20 moles of ethylene and/or propylene oxide.
  • alkoxylated monoglycerides alk
  • Block copolymers of ethylene oxide and propylene oxide and very particularly the block copolymers of ethylene oxide and propylene oxide marketed under the brand name PlurinicTM by the company BASF, such as PluronicTMPE 6100 and PluronicTMPE 6200, for example. It is also possible to incorporate nonionic defoaming surfactants of formula (A 1 ):
  • R 1 represents an aliphatic hydrocarbon radical, saturated or unsaturated, linear or branched, containing from 6 to 18 carbon atoms
  • X represents a nitrogen atom or an oxygen atom
  • u' and v', identical or different each represent an integer between 1 and 50
  • w' is either equal to 1 if X represents an oxygen atom, or equal to 1 or 2 if X represents a nitrogen atom
  • Y represents a functional group blocker chosen from the elements of the group consisting of linear alkyl radicals containing from 4 to 8 carbon atoms, such as the butyl radical, the benzyl radical, a butylene oxide group.
  • nonionic defoaming surfactants of formula (A 1 ) mention may be made of the products marketed under the brand name TergitolTM by the Dow Chemical Company, such as for example TergitolTM L61E and TergitolTM L64E.
  • Other low-foaming nonionic surfactants may have the following formula (A 2 ):
  • S' represents the residue of a reducing sugar chosen from the elements of the group consisting of glucose, xylose and arabinose
  • R 8 represents a saturated hydrocarbon radical, linear or branched, containing from 6 to 10 carbon atoms and q' represents a decimal number greater than or equal to 1.05 and less than or equal to 5.
  • low-foaming nonionic surfactants of formula (A 2 ) optionally present in said liquid aqueous detergent composition (F)
  • mineral acids particularly chosen as acid agents in said liquid aqueous detergent composition (F) mention may be made of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, hypophosphorous acid, phosphorous, hypochlorous acid, perchloric acid, carbonic acid, boric acid, manganic acid, permanganic acid, chromic acid, periodic acid, iodic acid, acid hypoiodous, hydrobromic acid, hydroiodic acid, hydrofluoric acid.
  • organic acids particularly chosen as acid agents in said liquid aqueous detergent composition (F) mention may be made of formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, glycolic acid, lactic acid, malic acid, maleic acid, tartaric acid, acid citric acid, sorbic acid, sulfamic acid, dihydroacetic acid, dimethylsulfamic acid, fumaric acid, glutamic acid, iso-propyl sulfamic acid, valeric acid, benzene sulfonic acid , xylene sulfonic acid, 2-ethyl-hexanoic acid, capric acid, caproic acid, cresylic acid, dodecylbenzene sulfonic acid, peracetic acid, monochloroacetic acid, gluconic.
  • alkaline agents associated with the said self-inverting inverse latex as defined above in the said aqueous liquid detergent composition (F) mention may be made of the elements of the group consisting of the hydroxides of alkali metals or alkaline-earth metals such as, for example, the hydroxide sodium, potassium hydroxide, barium hydroxide and calcium hydroxide.
  • anti-limescale agents associated with said self-inverting inverse latex as defined above in said aqueous liquid detergent composition (F) mention may be made of the elements of the group consisting of sequestering agents, such as for example sodium tripolyphosphate (TPP ), ethylenediaminetetracetate (EDTA), tetraacetylethylenediamine (TAED), methyl glycine diacetate (MGDA), sodium nitrolotriacetate (Na 3 NTA), sodium or potassium gluconates, sodium or potassium erythorbates, sodium or potassium polycarboxylates, and sodium citrate, by ion exchange agents such as for example zeolites or sodium aluminosilicates, or lamellar sodium silicates, precipitating agents such as for example calcium carbonate and metasilicate sodium.
  • sequestering agents such as for example sodium tripolyphosphate (TPP ), ethylenediaminetetracetate (EDTA), tetraacetylethylened
  • the anti-limescale agent is chosen from the elements of the group consisting of sodium metasilicate, sodium tripolyphosphate (TPP), ethylenediaminetetracetate (EDTA), tetraacetylethylenediamine (TAED), methyl glycine diacetate (MGDA), sodium nitrolotriacetate (Na3NTA), sodium gluconate, sodium citrate and calcium carbonate.
  • TPP sodium tripolyphosphate
  • EDTA ethylenediaminetetracetate
  • TAED tetraacetylethylenediamine
  • MGDA methyl glycine diacetate
  • Na3NTA sodium nitrolotriacetate
  • sodium gluconate sodium citrate and calcium carbonate.
  • the sequestering agents have the effect of complexing the calcium and magnesium ions to form water-soluble complexes which are then eliminated during rinsing.
  • the ion exchange agents and more particularly the ion exchange agents described above, have the effect of exchanging their sodium ions with calcium and magnesium ions.
  • the precipitating agents, and more particularly the sequestering agents described above, have the effect of eliminating the ions responsible for the hardness of the water by forming insoluble calcium compounds, which are subsequently eliminated with the dirt on the cleaned surfaces. .
  • thickening and/or gelling agents that can be combined with said self-inverting inverse latex as defined above in said liquid aqueous detergent composition (F)
  • thickening and/or gelling agents that can be combined with said self-inverting inverse latex as defined above in said liquid aqueous detergent composition (F)
  • ose derivatives such as galactans sulfates and more particularly carrageenans and agar, uronans and more particularly algins, alginates and pectins, heteropolymers of oses and uronic acids and more particularly xanthan gum, gellan gum, gum exudates arabic and karaya gum, glucosaminoglycan
  • thickening and/or gelling agents that can be combined with said self-inverting inverse latex as defined above in said liquid aqueous detergent composition (F)
  • thickening and/or gelling agents that can be combined with said self-inverting inverse latex as defined previously in said liquid aqueous detergent composition (F)
  • inorganic thickening agents such as, for example, clays, hectorite, saponite, sauconite, vermiculite or colloidal silica.
  • the thickening agents present in the composition (F) which is the subject of the present invention are used in quantities of between 0.1 and 10% by weight.
  • abrasive agents that can be combined with said self-inverting inverse latex as defined above in said liquid aqueous detergent composition (F)
  • materials of natural origin such as, for example, wood shavings or , inorganic abrasive materials such as oxides, quartzs, diatomaceous earths, colloidal silica dioxides, organic abrasive materials such as polyolefins such as polyethylenes and polypropylenes, polystyrenes, acetonitrile-butadiene-styrene resins , melamines, phenolic resins, epoxy resins, polyurethane resins.
  • the abrasive agents present in the composition (F) which is the subject of the present invention are used in quantities of between 5.0 and 30% by mass.
  • solvents that can be associated with said self-inverting inverse latex as defined above in said liquid aqueous detergent composition (F) mention may be made of isopropyl alcohol, benzyl alcohol, 1,3- propanediol, chlorinated solvents, acetone, methyl ethyl ether, methyl iso-butyl ether, butyl acetate, ethyl acetate, iso-propyl acetate, iso-acetate -butyl, aromatic solvents, iso-paraffins, iso-dodecane, ethyl lactate, butyl lactate, terpene solvents, rapeseed methyl esters, sunflower methyl esters, propylene glycol n-methyl ether, dipropylene glycol n-methyl ether, tripropylene glycol n-methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, trip
  • enzymes that can be associated with said self-inverting reverse latex as defined above in said liquid aqueous detergent composition (F) mention may be made of proteases, amylases, lipases, cellulases and peroxidases.
  • the enzymes present in the composition (F) which is the subject of the present invention are used in quantities of between 0.005 and 0.5% by weight.
  • the subject of the invention is the use of said liquid aqueous detergent composition (F) as defined above, for cleaning solid surfaces.
  • cleaning solid surfaces designates any action intended to allow the elimination of dirt present on surfaces made of various materials.
  • the surfaces to be cleaned can be solid surfaces or textile surfaces.
  • solid surfaces we mean, for example, floors, walls, window panes, tiles, household appliances, crockery, worktops, taps, sinks, chemical storage tanks, food or agricultural, vehicles (cars, motorcycles, trucks, etc.).
  • the materials constituting these solid surfaces are, for example, glass (soda-lime, fluoro-lime, borosilicate, crystal), porcelain, earthenware, ceramics, polycarbonate plastics, polypropylenes, stainless steel, silver, copper, aluminium, wood, synthetic resins, ceramic glass, linoleum, and can be coated with paints, varnishes.
  • glass silica
  • fluoro-lime fluoro-lime, borosilicate, crystal
  • porcelain earthenware
  • ceramics polycarbonate plastics
  • polypropylenes stainless steel
  • silver copper, aluminium, wood, synthetic resins
  • ceramic glass linoleum
  • paints, varnishes can be coated with paints, varnishes.
  • dirt present on these solid surfaces and to be removed by cleaning mention may be made, for example, of food residues, grease, heavy and light hydrocarbons, burnt residues, dust, mud, fingerprints, soap scum, germs.
  • the subject of the invention is a method for cleaning a solid surface, characterized in that it comprises at least a first step a''1) of application of the said liquid aqueous detergent composition (F) as defined above, followed by at least one step b''1) of rinsing said solid surface.
  • step a''1) of the method as defined above said liquid aqueous detergent composition (F) is applied to the surface comprising the dirt to be cleaned by any means, for example in the full bath, by spraying or by application by means of a support consisting of synthetic or natural textile fibres, woven or non-woven, or of paper, impregnated beforehand with the latter.
  • step b''1) of the process as defined above the rinsing of the solid surface to which the composition (F) for household or industrial use has been applied during step a''1) is carried out in full bath or by sprinkling water.
  • Step b''1) of the cleaning process which is the subject of the invention can be carried out at ambient temperature or at a temperature of between 30 and 80°C, more particularly at a temperature of between 30 and 65°C.
  • compositions (CA) I- Examples of preparation of compositions (CA):
  • the synthesis process comprises the following steps:
  • composition (CA1) is isolated.
  • the synthesis process comprises the following steps:
  • composition (C A2 ) is isolated.
  • the synthesis process comprises the following steps:
  • composition (C A3 ) is isolated.
  • the synthesis process comprises the following steps:
  • Step e Shearing emulsification with a stirrer equipped with a SilversonTM L4RT rotor/stator system for 2 min at a speed of 7500 (revolutions/min).
  • composition (C A4 ) is isolated.
  • the synthesis process comprises the following steps:
  • Stage f Shearing emulsification with SilversonTM L4RT, for 2 minutes at a speed of 7500 (revolutions/min).
  • composition (C A5 ) is isolated.
  • the synthesis process comprises the following steps:
  • composition (C A6 ) is isolated.
  • the synthesis process comprises the following steps:
  • composition (C A7 ) is isolated.
  • the synthesis process comprises the following steps:
  • composition (C A8 ) is isolated.
  • Example I.9 Preparation of a concentrated reverse latex of cross-linked sodium PGA according to the invention in octyl palmitate
  • the synthesis process comprises the following steps:
  • composition (C A9 ) is isolated.
  • EGDGE Ethylene Glycol Diglycidyl Ether
  • the synthesis process comprises the following steps:
  • composition (C A10 ) is isolated.
  • the synthesis process comprises the following steps:
  • composition (C A11 ) is isolated.
  • compositions (C A1 ) to (C A11 ) according to the invention II- Evaluations of the compositions (C A1 ) to (C A11 ) according to the invention:
  • compositions (C A1 ) to (C A11 ) according to the invention are carried out as described below:
  • compositions (C A1 ) to (C A11 ) according to the invention make it possible to obtain thickened aqueous gels with respect to the aqueous gel obtained from a non-crosslinked sodium gamma-polyglutamate (“control test”).
  • the aqueous gels obtained with the compositions (C A1 ) and (C A3 ) show viscosities of 76,000 and 91,600 mPa.s respectively, whereas the aqueous gel obtained with the gamma- Non-crosslinked sodium polyglutamate (“control test”) is characterized by a viscosity of 176 mPa.s.
  • the aqueous gels obtained with the compositions (C A2 ), (C A4 ), (C A8 ), (C A9 ) and (C A10 ) respectively show viscosities of 124,000 , 117,200, 9,540, 91,800 and 78,000 mPa.s, whereas the aqueous gel obtained with 2% by weight non-crosslinked sodium gamma-polyglutamate (“control test”) is characterized by a viscosity of 176 mPa.s.
  • Example III.1 Composition (F1) cleaner for ovens and cooking grids
  • SimulsolTM OX 1309 L Detergent surfactant composition marketed by Seppic comprising polyethoxylated alcohols resulting from the reaction of a molar equivalent of an alcohol marketed under the brand name ExxalTM 13 with 9 molar equivalents of oxide of 'ethylene.
  • composition (F1) involves the following steps:
  • a pre-gel is prepared at 20° C. by adding SimulsolTM OX 1309 L, then SimulsolTM SL7 G in water.
  • the composition (C A1 ) according to the invention is then introduced into the aqueous solution and mixed until a gel of stable viscosity is obtained.
  • step b) The soda is then gradually introduced with mechanical stirring at a temperature of 20°C until a homogeneous gel is obtained.
  • the gel obtained at the end of step b) has a homogeneous and clear appearance, with a viscosity of 10,000 mPa.s (Brookfield LVT at a speed of 6 revolutions/minute).
  • the gel obtained at the end of step b) of this procedure has a homogeneous and clear appearance, with a viscosity of 12,000 mPa.s (Brookfield LVT, at a speed of 6 rpm).
  • the cleaning process is as follows:
  • composition prepared above is sprayed at room temperature on the walls of an oven soiled by food fats and on the cooking grids also soiled by food fats. After ten minutes, the walls of the oven and the cooking grids are rinsed with hot water at 60°C. The walls of the oven and the surfaces of the cooking grids cleaned in this way no longer show any dirt.
  • Example III.2 Composition (F2) cleaning for aluminum surfaces
  • Hordaphas TM MDGB is a composition based on phosphoric esters, used as an anti-corrosion agent.
  • composition (F2) takes place as follows:
  • Each ingredient is successively introduced 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 1.0 and is clear and homogeneous after storage for one month at 40°C.
  • the cleaning process is as follows:
  • composition prepared in the previous paragraph is diluted to 3% in water and the solution thus obtained is sprayed on the aluminum wall to be cleaned. This wall is then rinsed with hot water at 60°C.

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EP21836214.3A 2021-01-07 2021-12-22 Waschmittelzusammensetzung mit einer zusammensetzung mit polaren medienverdickungseigenschaften als verdickungsmittel Pending EP4274883A1 (de)

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FR2100111A FR3118581A1 (fr) 2021-01-07 2021-01-07 Composition détergente comprenant comme agent épaississant une composition qui présente des propriétés épaississantes de milieux polaires
PCT/EP2021/087359 WO2022148662A1 (fr) 2021-01-07 2021-12-22 Composition détergente comprenant comme agent épaississant une composition qui présente des propriétés épaississantes de milieux polaires

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