Patent Application
20240084229
The present invention relates to a detergent composition (F) comprising at
least one surfactant and, as thickening agent, a composition (CA) in the form of an emulsion of self-invertible water-in-oil type and to the process for preparing such a composition.
Polymers are widely used today in detergent compositions and represent the second most widely used family of products in compositions of this type. Detergent compositions contain polar phases, for example phases consisting of water, and in most cases require the use of rheology modifiers, for example polymers, to increase the viscosity of these polar phases, and also to impart well-defined rheological behavior.
Among the polymers that modify the rheology of polar phases, mention may be made of natural polymers, for example polysaccharides based on monosaccharides or polysaccharides based on monosaccharide derivatives, or else synthetic polymers of linear or branched, crosslinked or noncrosslinked, anionic or cationic or amphiphilic polyelectrolyte type. Predominantly 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 linear or branched, crosslinked or noncrosslinked polymer backbone. These rheology modifiers bring both an increase in the viscosity of the polar phase, and also a certain consistency and/or a stabilizing effect imparted to the detergent composition.
In order to meet the needs of formulators and to improve performance, various recent scientific studies have reported the development of new, innovative and varied polymeric systems. Thus, the polymers used in the detergent industries can play a functional role as film-forming agents, rheology modifiers, enabling stabilization of the fatty phases in emulsions of water-in-oil type and of the oil-in-water type, stabilization of solid particles (pigments and fillers) or as agents having an impact on the appearance of the formula (transparency, translucency, opacity).
Polymers that modify the rheology of polar phases, and more particularly of aqueous phases, are mainly polyelectrolytes resulting from the free-radical polymerization of (meth)acrylic monomers, i.e. acrylic acid or methacrylic acid, ester derivatives of acrylic acid or methacrylic acid, or else derivatives of acrylamide or methacrylamide.
Developing new biobased and biodegradable rheology modifiers that are as efficient as the synthetic polymers currently used still constitutes a major challenge today. Indeed, until now the solutions mainly used for thickening aqueous phases involve ingredients originating from petrochemical materials and in particular acrylic acid and derivatives thereof, or methacrylic acid and derivatives thereof.
Given the growing consumer concern for a sustainable and responsible economy and development, the replacement of raw materials of petrochemical origin with raw materials of renewable origin for preparing polymers is a priority research area.
To date, the literature has described the use of various natural polymers or polymers originating from renewable raw materials, the monomer units of which come from the family of sugars (glucose, arabinose, xylose, galactose, mannose, ribose, glucuronic acid, etc.) or from the family of amino acids (glutamic acid, aspartic acid, lysine, etc.). These polymers are mostly linear or branched depending on the plant from which they come or according to their manufacturing process.
As an example of a polymer of natural origin, mention may be made of polyglutamic acid (PGA), which is currently the subject of numerous research studies. It is a predominantly linear polymer and consists of glutamic acid (GA) monomer units. Glutamic acid is an amino acid characterized by an amine function in the a position and by two carboxylic acid functions (or carboxylates depending on the pH) in the a and y positions (cf. chemical formula No. 1).
One of the ways to increase the branching of a synthetic or natural polymer or of a polymer of natural origin consists in performing crosslinking reactions. The aim of the crosslinking of the polymer chains is to connect several polymer chains to one another which, when added to a polar phase, and more particularly to water, take the form of a three-dimensional network that is insoluble in water but is water-swellable, thus resulting in a chemical gel being obtained.
Crosslinked polymers may be prepared:
Various reactions exist for the crosslinking of polyglutamic acid (PGA), which makes it possible to obtain polymers of natural origin with improved thickening properties in polar media, and notably in aqueous media. Among the crosslinking agents known to be used in the (PGA) crosslinking reaction, polyepoxide derivatives are the most widely described since they make it possible to carry out crosslinking processes under environmentally friendly conditions (moderate temperatures, reaction in aqueous media and in the absence of harmful solvents).
However, the implementation of these processes requires diluting the (PGA) to high levels, which leads to the production of an aqueous gel comprising, per 100% of its mass, a content by mass of less than or equal to 10% of a polymer (P), which is difficult for formulators to implement.
Proceeding from this, a problem that arises is that of providing an easy-to-use detergent composition comprising polymers of natural origin, the raw materials of which are renewable and which have thickening properties for polar media and particularly for aqueous media.
One solution of the present invention is a detergent composition (F) for domestic or industrial use comprising at least one detergent surfactant and, as thickening agent, a composition (CA) in the form of an emulsion of self-invertible water-in-oil type comprising, per 100% of its mass, a content by mass of greater than or equal to 20% of a polymer (P) consisting of monomer units derived from partially or totally salified glutamic acid (GA) and of units derived from at least one crosslinking agent (XLA) bearing at least two glycidyl functions.
For the purposes of the present invention, the term “detergent surfactants” denotes surfactants that give the detergent liquid aqueous composition (F) its ability to remove soiling present on the solid surfaces and to keep it in suspension, in order for it to then be removed during the rinsing step.
For the purposes of the present invention, the term “emulsion of water-in-oil type” denotes 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.
For the purposes of the present invention, the term “emulsion of self-invertible water-in-oil type” denotes an emulsion of 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 has been added to a polar phase, for instance water, the direction of the emulsion will change from water-in-oil form to oil-in-water form, thereby placing the polymer (P) in contact with the polar phase to be thickened.
In the polymer (P) present in the composition (CA) which is the subject of the present invention, the monomer units derived from partially or totally salified glutamic acid (GA) are linked together:
In general, PGA may be prepared chemically according to peptide synthesis methods known to those skilled in the art, in particular proceeding via steps of selective protection, activation, coupling and deprotection. The coupling generally consists of a nucleophilic attack of the amine function of a glutamic acid monomer unit on an activated carboxylic acid function of another glutamic acid monomer unit.
PGGA can also be obtained via processes comprising at least one microbial fermentation step involving the use of at least one bacterial strain.
For the purposes of the present invention, in the polymer (P) as defined previously, the term “salified” indicates that the “pendent” carboxylic acid function present on each glutamic acid (GA) monomer unit of the polymer (in the gamma position in the case of PAGA or in the alpha position in the case of PGGA) is in an anionic or carboxylate form. The counterion of this carboxylate function is a cation derived, for example, from alkali metal salts such as sodium, potassium or salts of nitrogenous bases such as amines, lysine or monoethanolamine (HO—CH2—CH2—NH2).
According to one particular aspect, in the composition (CA) which is the subject of the present invention, the content by mass 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 forms depend on the inter- and intra-molecular hydrogen bonds and thus on the pH, the polymer concentration, the ionic strength of the solution, and also the temperature. The PGGA chains may thus take the form of α helix, β sheet, aggregates or else be in a disordered and random state.
According to one particular aspect, in the composition (CA) which is the subject of the present invention, the polymer (P) is in a helical conformation when it is present in a solution at a content by mass of less than or equal to 0.1% and of which said solution has a pH of less than or equal to 7.
According to one particular aspect, in the composition (CA) which is the subject of the present invention, the polymer (P) is in sheet conformation when it is present in a solution at a content by mass of less than or equal to 0.1% and of which said solution has a pH of greater than 7.
For the purposes of the present invention, the term “crosslinking agent (XLA)” denotes a chemical molecule the structure of which enables it to bond covalently to at least two polymer chains.
For the purposes of the present invention, the term “crosslinking agent (XLA) bearing at least two glycidyl functions” denotes a crosslinking agent (XLA) as defined above, the molecular structure of which comprises at least two glycidyl units or functions of formula (I′):
The crosslinking of the polymer chains of the polymer (P) is performed according to a reaction between the terminal free amine function (—NH2) 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 (XLA) bearing at least two glycidyl functions.
The crosslinking agent (XLA) may be chosen from the members of the group consisting of:
Ethylene glycol diglycidyl ether of formula (I):
The compound of formula (II):
with R representing a hydrogen atom or the glycidyl radical
and n representing an integer of greater than or equal to 1 and less than or equal to 10,
When R represents a hydrogen atom and n is equal to 1, the compound of formula (II) is more particularly the compound of formula (IIa) or glycerol diglycidyl ether:
When R represents the glycidyl radical and n is equal to 1, the compound of formula (II) is more particularly the compound of formula (IIb) or glycerol triglycidyl ether:
When R represents a hydrogen atom and n is equal to 2, the compound of formula (II) is more particularly the compound of formula (IIc) or diglycerol diglycidyl ether:
When R represents the glycidyl radical
and n is equal to 2, the compound of formula (II) is more particularly the compound of formula (IId) or diglycerol tetraglycidyl ether:
1,3-Propanediol diglycidyl ether of formula (III):
1,2-Propanediol diglycidyl ether of formula (IV):
1,4-Butanediol diglycidyl ether of formula (V):
1,2-Butanediol diglycidyl ether of formula (VI):
1,3-Butanediol diglycidyl ether of formula (VII):
1,6-Hexanediol diglycidyl ether of formula (VIII):
The compound of formula (IX):
When R1 represents a hydrogen atom, the compound of formula (IX) is more particularly the compound of formula (IXa) or trimethylolethane diglycidyl ether:
When R1 represents the glycidyl radical
The compound of formula (X):
When R1 represents a hydrogen atom, the compound of formula (X) is more particularly the compound of formula (Xa) or trimethylolpropane diglycidyl ether:
When R1 represents the glycidyl radical
the compound of formula (X) is more particularly the compound of formula (Xb) or trimethylolpropane triglycidyl ether:
The compound of formula (XI):
When R1 and R2 each represent a hydrogen atom, the compound of formula (XI) is more particularly the compound of formula (XIa) or pentaerythritol diglycidyl ether:
When R1 represents a hydrogen atom and R2 represents the glycidyl radical
the compound of formula (XI) is more particularly the compound of formula (XIb) or pentaerythritolorooane triglycidyl ether:
When R1 and R2 each represent the glycidyl radical
the compound of formula (XI) is more particularly the compound of formula (XIc) or pentaerythritolpropane tetraglycidyl ether:
The compound of formula (XII):
The compound of formula (XIII):
and x, y, z, o, p and q independently of one another representing an integer of greater than or equal to 2 and less than or equal to 10.
Depending on the case, the detergent composition (F) may have one or more of the following characteristics:
functionalized or non-functionalized hydrocarbon-based radical comprising from 6 to 22 carbon atoms.
According to one particular aspect, R4 represents a hydrocarbon-based radical selected from the elements of the group consisting of heptyl, octyl, nonyl, decyl, undecyl, undecenyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, hydroxyoctadecyl, oleyl, linoleyl, linolenyl, eicosyl and dodecosyl radicals.
According to another particular aspect, in said polymer (P), per 100% of the mass of monomer units derived from partially or totally salified glutamic acid (GA), the monomer units derived from the compound of formula (X′) represent from 1% to 50% by mass.
The detergent composition (F) comprises between 0.1% and 10% by mass of said composition (CA) and more particularly between 0.1% and 8%.
The present invention also provides a process for preparing a detergent composition (F) comprising the following two distinct steps:
According to a more particular aspect of the process, for the purposes of the present invention, the term “volatile oil” denotes an element of the group consisting of branched alkanes, comprising from 7 to 40 carbon atoms, such as isododecane, isopentadecane, isohexadecane, isoheptadecane, isooctadecane, isononadecane or isoeicosane, or mixtures of some of them, such as those mentioned 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.
According to an even more particular aspect of the process, for the purposes of the present invention, the term “volatile oil” denotes at least one element of the group consisting of isododecane, isohexadecane, C7-8 Isoparaffin, C8-9 Isoparaffin, C9-11 Isoparaffin, C11-13 Isoparaffin and C11-14 Isoparaffin.
According to another even more particular aspect of the process, the volatile oil is selected from an element of the group consisting of C8-9 Isoparaffin, C9-11 Isoparaffin, C11-13 Isoparaffin and C11-14 Isoparaffin.
According to another even more particular aspect of the present invention, the “volatile oil” is selected from an element of the group consisting of the isoparaffins sold under the brand names Isopar™ G, Isopar™ L, Isopar™ H and Isopar™ J.
According to a more particular aspect of the process, for the purposes of the present invention, the term “non-volatile oil (H)” denotes an element of the group consisting of:
linear alkanes and cycloalkanes and less than or equal to 100% comprising from 15 to 19 carbon atoms, and
For the purposes of the present invention, the term “linear alkanes” present in the mixture (M1) as defined above, and comprising from 15 to 19 carbon atoms, more particularly denotes the elements selected from the group consisting of n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane and n-nonadecane.
For the purposes of the present invention, the term “branched alkanes” present in the mixture (M1) as defined above, and comprising from 15 to 19 carbon atoms, more particularly denotes the elements selected from the group consisting of isopentadecane, isohexadecane, isoheptadecane, isooctadecane and isononadecane.
The mixture (M1) is more particularly the mixture sold under the brand name Emogreen™ L15 by SEPPIC or else the mixture sold under the brand name Emogreen™ L19.
Z1—O—Z2 (XIV)
in which Z1 and Z2, which may be 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-dimethylbutyl) tetradecyl ether, (1,3-dimethylbutyl) hexadecyl ether, bis(1,3-dimethylbutyl) ether or dihexyl ether.
R′1—(C═O)—O—R′2 (XV)
in which R′1—(C═O) represents a saturated or unsaturated, linear or branched, acyl radical comprising from 8 to 24 carbon atoms and R′2 represents, independently of R′1, a saturated or unsaturated, linear or branched, hydrocarbon chain comprising from 1 to 24 carbon atoms, for example methyl laurate, ethyl laurate, propyl laurate, isopropyl laurate, butyl laurate, 2-butyl laurate, hexyl laurate, methyl cocoate, ethyl cocoate, propyl cocoate, isopropyl cocoate, butyl cocoate, 2-butyl cocoate, hexyl cocoate, methyl myristate, ethyl myristate, propyl myristate, isopropyl myristate, butyl myristate, 2-butyl myristate, hexyl myristate, octyl myristate, methyl palmitate, ethyl palmitate, propyl palmitate, isopropyl palmitate, butyl palmitate, 2-butyl palmitate, hexyl palmitate, octyl palmitate, methyl oleate, ethyl oleate, propyl oleate, isopropyl oleate, butyl oleate, 2-butyl oleate, hexyl oleate, octyl oleate, methyl stearate, ethyl stearate, propyl stearate, isopropyl stearate, butyl stearate, 2-butyl stearate, hexyl stearate, octyl stearate, methyl isostearate, ethyl isostearate, propyl isostearate, isopropyl isostearate, butyl isostearate, 2-butyl isostearate, hexyl isostearate or isostearyl isostearate,
R′3—(C═O)—O—CH2—CH(OH)—CH2—O—(C═O)—R′4 (XVI)
R′5—(C═O)'O—CH2—CH[O—(C═O)—R′6]—CH2—OH (XVII)
in which R′7—(C═O), R′4—(C═O), R′5—(C═O) and R′6—(C═O), which may be identical or different, represent a saturated or unsaturated, linear or branched acyl group comprising from 8 to 24 carbon atoms.
R′7—(C═O)—O—CH2—CH[O—(C═O)—R″8]—CH2—O—(C═O)—R″9 (XVIII)
in which R′7—(C═O), R′8—(C═O) and R′9—(C═O), which may be identical or different, represent a saturated or unsaturated, linear or branched acyl group comprising from 8 to 24 carbon atoms.
According to another particular aspect of the present invention, said non-volatile oil (H) is selected from:
According to another aspect, in step c) of the process that is the subject of the present invention, the term “emulsifying surfactant of water-in-oil type (S1)” denotes an emulsifying surfactant having an HLB value (Hydrophilic-Lipophilic Balance) that is low enough to induce the formation of an emulsion of water-in-oil type, namely an emulsion in which the aqueous phase will be dispersed and stabilized in the oily organic phase.
As emulsifying surfactant of water-in-oil type, examples that may be mentioned include anhydrohexitol esters of linear or branched, saturated or unsaturated aliphatic carboxylic acids comprising from 12 to 22 carbon atoms, optionally substituted with one or more hydroxyl groups, and more particularly esters of anhydrohexitols selected from anhydrosorbitols and anhydromannitols and of linear or branched, saturated or unsaturated aliphatic carboxylic acids comprising from 12 to 22 carbon atoms, optionally substituted with one or more hydroxyl groups.
In step c) of the process that is the subject of the present invention, the emulsifying system (S1) of water-in-oil type is more particularly selected from the elements of the group consisting of:
The alkoxylated polyglycerol esters of formula (XX):
in which Z1 represents an acyl radical of formula R′2—C(═O)—, in which R′2 represents a saturated or unsaturated, linear or branched, aliphatic hydrocarbon-based radical, comprising from 11 to 35 carbon atoms, and more particularly a radical selected from the dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, eicosanoyl, docosanoyl, oleyl, linoleyl, linolenoyl or isostearyl radicals, Z′1 represents the acyl radical of formula R′2—C(═O)—as defined above, with Z′1 identical to or different from Z1, or a hydrogen atom, R3 represents a hydrogen atom, the methyl radical or the ethyl radical, y1 represents an integer of greater than or equal to 2 and less than or equal to 20, v1, v2 and v3, which may be identical or different, represent an integer of greater than or equal to 0 and less than or equal to 50, and the sum [(y1·v1)+(y1·v2)+v3] is an integer of greater than or equal to 1 and less than or equal to 50.
The polyglycol polyhydroxystearates of formula (XXI):
in which y2 represents an integer of greater than or equal to 2 and less than or
equal to 50, Z4 represents a hydrogen atom, the methyl radical or the ethyl radical, and Z3 represents a radical of formula (XXII):
in which y′2 represents an integer of 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, with Z′3 identical to or different from Z3, or a hydrogen atom.
Examples of emulsifying surfactant of water-in-oil type of formula (XXI) that may be used for preparing the emulsifying system (S1) include PEG-30 dipolyhydroxystearate, sold under the name Simaline™ WO, or else the mixtures comprising PEG-30 dipolyhydroxystearate and sold under the names Simaline™ IE 201 A and Simaline™ IE 201 B, or else the mixture comprising trimethylolpropane-30 tripolyhydroxystearate sold under the name Simaline™ IE 301 B.
The polyglycerol polyhydroxystearates represented by formula (XXIII):
in which Z3 represents a radical of formula (XXIII) as defined above, Z′3 represents a radical of formula (XXII) as defined above, where Z3′ may be identical to or different from Z3, or a hydrogen atom, y3 represents an integer of greater than or equal to 2 and less than or equal to 20.
The alkoxylated polyglycerol polyhydroxystearates represented by formula (XXIV):
in which Z4 represents a radical of formula (XXII) as defined above, Z′4 represents a radical of formula (XXII) as defined above, with Z′4 being identical to or different from Z4, or a hydrogen atom, y4 represents an integer of greater than or equal to 2 and less than or equal to 20, v′1, v′2 and v′3, which may be identical or different, represent an integer of greater than or equal to 0 and less than or equal to 50, and the sum [(y4·v′1)+(y4·v′2)+v′3)] is an integer of greater than or equal to 1 and less than or equal to 50.
According to another aspect, in step g) of the process which is a subject of the present invention, the term “emulsifying surfactant of oil-in-water type (S2)” denotes an emulsifying surfactant having a sufficiently high HLB value to induce the formation of an emulsion of oil-in-water type, namely an emulsion in which the oily organic phase will be dispersed and stabilized in the aqueous phase.
According to another aspect, in step g) of the process which is a subject of the present invention, as surfactant of oil-in-water type (S2), mention may be made of:
The polyethoxylated fatty alcohols denoted by the compounds of formula (XXV):
R″—O—(CH2—CH2—O)n′—OH (XXV)
with R″ representing a linear or branched, saturated or unsaturated hydrocarbon-based radical, which may bear hydroxyl groups, comprising from 6 to 22 carbon atoms, and with n′ representing an integer of greater than or equal to 4 and less than or equal to 100. According to a more particular aspect, in formula (XXV), R″ represents a linear or branched, saturated hydrocarbon-based radical comprising from 10 to 22 carbon atoms. According to an even more particular aspect, the compound of formula (XXV) is a linear decyl alcohol ethoxylated with 6 mol of ethylene oxide, a linear decyl alcohol ethoxylated with 8 mol of ethylene oxide, a linear lauryl alcohol ethoxylated with 6 mol of ethylene oxide, a linear lauryl alcohol ethoxylated with 7 mol of ethylene oxide, a linear lauryl alcohol ethoxylated with 8 mol of ethylene oxide, a linear tridecyl alcohol ethoxylated with 6 mol of ethylene oxide, a linear tridecyl alcohol ethoxylated with 8 mol of ethylene oxide, or a linear tridecyl alcohol ethoxylated with 9 mol of ethylene oxide. Polyethoxylated hexitan esters, and particularly polyethoxylated sorbitan
esters, the aliphatic hydrocarbon-based chain of which comprises from 12 to 22 carbon atoms and in which the number of ethylene oxide units is between 5 and 40, for example sorbitan oleate ethoxylated with 20 mol of ethylene oxide, sold under the trade name Montanox™ 80, or sorbitan laurate ethoxylated with 20 mol of ethylene oxide, sold under the trade name Montanox™ 20.
R″1—O-(G)x-H (XXVI)
in which x, or the mean degree of polymerization, represents a decimal
number of between 1.05 and 5, G represents a reducing sugar residue, and R″1 represents a saturated or unsaturated, linear or branched aliphatic hydrocarbon-based radical, optionally substituted with one or more hydroxyl groups, comprising from 12 to 36 carbon atoms, said composition (C1) consisting of a mixture of compounds represented by formulae (XXVI1), (XXVI2), (XXVI3), (XXVI4) and (XXVI5):
R″1—O-(G)1-H (XXVI1)
R″1—O-(G)2-H (XXVI2)
R″1—O-(G)3-H (XXVI3)
R″1—O-(G)4-H (XXVI4)
R″1—O-(G)5-H (XXVI5)
in the respective molar proportions a1, a2, a3, a4 and a5 such that:
The term “saturated or unsaturated, linear or branched aliphatic hydrocarbon-based radical comprising from 12 to 36 carbon atoms, optionally substituted with one or more hydroxyl groups” denotes, for the radical R″1 in formula (XXVI) as defined above more particularly the n-dodecyl radical, the n-tetradecyl radical, the n-hexadecyl radical, the n-octadecyl radical, the n-eicosyl radical, the n-docosyl radical or the 12-hydroxyoctadecyl radical.
The term “reducing sugar” in the definition of formula (XXVI) as defined above denotes saccharide derivatives that do not have in their structures any glycoside bonds established between an anomeric carbon and the oxygen of an acetal group as defined in the reference work: “Biochemistry”, Daniel Voet/Judith G. Voet, p. 250, John Wiley & Sons, 1990. The oligomeric structure (G)x can exist in all forms of isomerisms, whether it is optical isomerism, geometrical isomerism or positional isomerism. It can also represent a mixture of isomers.
In formula (XXVI) as defined above, the group R1—O— is linked to G via the anomeric carbon of the saccharide residue, so as to form an acetal function.
According to a particular aspect in the definition of formula (XXVI) as defined above, G represents a reducing sugar residue selected from glucose, dextrose, sucrose, fructose, idose, gulose, galactose, maltose, isomaltose, maltotriose, lactose, cellobiose, mannose, ribose, xylose, arabinose, lyxose, allose, altrose, dextran and tallose; and more particularly, G represents a reducing sugar residue selected from glucose, xylose and arabinose residues.
According to an even more particular aspect, in the definition of formula (XXVI) x, or mean degree of polymerization, represents a decimal number of 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 more particularly still greater than or equal to 1.25 and less than or equal to 2.0.
The compositions (C2) comprising, per 100% of their mass: from 10% to 50% by mass, more particularly from 15% to 40% by mass and
more particularly still from 20% to 30% by mass, of at least one composition (C1) represented by formula (XXVI) as defined previously,
R′″1—OH (XXVII)
in which R′″1, which may be identical to or different from R″1, represents a saturated or unsaturated, linear or branched aliphatic hydrocarbon-based radical, optionally substituted with one or more hydroxyl groups, comprising from 12 to 36 carbon atoms and preferably from 12 to 22 carbon atoms.
The polyglycerol esters of formula (XXVIII):
R12—(C═O)—[O—CH2—CH(OH)—CH2]p12—OH (XXVIII)
in which p12 represents an integer of greater than or equal to 1 and less than
or equal to 15 and in which the group R1—(C═O)— represents a saturated or unsaturated and linear or branched aliphatic radical comprising from 6 to 22 carbon atoms.
The compositions (C3) comprising, per 100% of their mass:
HO—[CH2—CH(OH)—CH2—O]n12—H (XXIX)
in which n12 represents an integer of greater than or equal to 1 and less than or equal to 15, and
defined previously.
Lastly, the present invention also provides for:
The use of said composition (CA) as defined above, as thickening and/or emulsifying and/or stabilizing agent for a detergent liquid aqueous composition for domestic or industrial use.
According to another particular aspect, said use of the composition (CA), which is a subject 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.
According to another particular aspect, said use consists in stabilizing an emulsion of oil-in-water type, or of water-in-oil type, giving said emulsion a homogeneous appearance during storage under various conditions, and more particularly at 25° C. for a time at least equal to one month, and more particularly at 4° C. for a time at least equal to one month, and more particularly at 45° C. for a time at least equal to one month.
According to another particular aspect, said use consists in stabilizing solid particles in detergent liquid aqueous compositions for domestic or industrial use.
These solid particles to be suspended may have various regular or irregular geometries, and may be in the form of pearls, beads, rods, flakes, leaflets or polyhedra. These solid particles are characterized by an apparent mean diameter of between 1 μm and 5 mm, more particularly between 10 μm and 1 mm.
Among the solid particles that may be suspended and stabilized with the self-invertible inverse latex as defined above in detergent liquid aqueous compositions for domestic or industrial use are micas, iron oxide, titanium oxide, zinc oxide, aluminum oxide, talc, silica, kaolin, clays, boron nitride, calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, inorganic coloured pigments, polyamides such as Nylon-6, polyethylenes, polypropylenes, polystyrenes, polyesters, acrylic or methacrylic polymers such as polymethyl methacrylates, polytetrafluoroethylene, crystalline or microcrystalline waxes, porous spheres, selenium sulfide, zinc pyrithione, starches, alginates, plant fibers, loofah particles and sponge particles.
Said detergent liquid aqueous composition (F) that is the subject of the present invention is notably 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 else in the form of an aerosol. It may be applied directly by soaking, by spraying or by vaporizing onto the surface to be cleaned or else by means of any type of support intended to be placed in contact with the solid surface to be cleaned (paper, wipe, textile).
In general, said detergent liquid aqueous composition (F) which is a 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 nonionic polymers, thickeners, enzymes, bleaching agents, anticorrosion agents, solvents, acidic agents, alkaline agents, anti-limescale agents, preserving agents, fragrances, colorants, repellents, oxidizing agents, detergency adjuvants, anti-soiling agents or anti-redeposition agents.
Among the detergent surfactants capable of being used for the preparation of the detergent liquid aqueous composition (F) as defined above, mention may be made of surfactants that give the detergent liquid aqueous composition (F) their ability to remove soiling present on the solid surfaces and to keep it in suspension, in order for it to then be removed during the rinsing step.
These detergent surfactants may be of anionic, cationic, amphoteric or nonionic nature.
Among the anionic detergent surfactants capable of being used for the preparation of the detergent liquid aqueous composition (F) as defined above, mention may be made of alkali metal salts, alkaline-earth metal salts, ammonium salts, amine salts, amino alcohol salts of alkyl ether sulfates, of alkyl sulfates, of alkylamido ether sulfates, of alkylaryl polyether sulfates, of monoglyceride sulfates, of alpha-olefin sulfonates, of paraffin sulfonates, of alkyl phosphates, of alkyl ether phosphates, of alkyl sulfonates, of alkylamide sulfonates, of alkylaryl sulfonates, of alkyl carboxylates, of alkyl sulfosuccinates, of alkyl ether sulfosuccinates, of alkylamide sulfosuccinates, of alkyl sulfoacetates, of alkyl sarcosinates, of acyl isethionates, of N-acyl taurates, of acyl lactylates, of N-acylated derivatives of amino acids, of N-acylated derivatives of peptides, of N-acylated derivatives of proteins, and of fatty acids.
Among the amphoteric detergent surfactants capable of being used for the preparation of the detergent liquid aqueous composition (F) as defined above, mention may be made of alkylbetaines, alkylamidobetaines, sultaines, alkylamidoalkylsulfobetaines, imidazoline derivatives, phosphobetaines, amphopolyacetates and amphopropionates.
Among the foaming and/or detergent amphoteric surfactants that may be associated with said self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of alkylbetaines, alkylamidobetaines, sultaines, alkylamidoalkylsulfobetaines, imidazoline derivatives, phosphobetaines, amphopolyacetates, amphopropionates, and sodium N-(2-carboxyethyl)-N-(2-ethylhexyl)-β-alaninate sold under the brand name Tomamine® 30 Amphoteric 400 Surfactant.
Among the cationic detergent surfactants capable of being used for the preparation of the detergent liquid aqueous composition (F) as defined above, mention may particularly be made of quaternary ammonium derivatives.
Among the nonionic detergent surfactants capable of being used for the preparation of the detergent liquid aqueous composition (F) as defined above, mention may particularly be made of alkyl polyglycosides containing a linear or branched, saturated or unsaturated aliphatic radical comprising from 8 to 16 carbon atoms, castor oil derivatives, polysorbates, coconut amides and N-alkylamines. Mention may also be made of alkoxylated monoglycerides, alkoxylated diglycerides, alkoxylated terpenic hydrocarbons such as ethoxylated and/or propoxylated α- or β-pinenes, containing from 1 to 30 oxyethylene and/or oxypropylene units, products resulting from the condensation of ethylene oxide or of propylene oxide with ethylenediamine, such as the Tetronic™ products sold by BASF, ethoxylated and/or propoxylated C8-C18 fatty acids containing from 5 to 25 mol of ethylene oxide and/or propylene oxide, ethoxylated fatty amides containing from 5 to 30 mol of ethylene oxide, ethoxylated amines containing from 5 to 30 mol of ethylene oxide, alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25 and most particularly from 2 to 20 mol of ethylene oxide and/or propylene oxide. Mention may also be made of block copolymers of ethylene oxide and of propylene oxide, and most particularly the block copolymers of ethylene oxide and of propylene oxide sold under the brand name Pluronic™ by the company BASF, for instance Pluronic™ PE 6100 and Pluronic™ PE 6200. It is also possible to incorporate defoaming nonionic surfactants of formula (A1):
R1—X—[(CH2—CH(CH3)—O)u′—(CH2—CH2—O)v′—Y]w′ (A1)
in which R1 represents a saturated or unsaturated, linear or branched hydrocarbon-based aliphatic radical comprising from 6 to 18 carbon atoms, X represents a nitrogen atom or an oxygen atom, u′ and v′, which may be identical or different, each represent an integer of between 1 and 50, w′ is either equal to 1 if X represents an oxygen atom, or equal to 1 or to 2 if X represents a nitrogen atom, and Y represents a blocking functional group selected from the elements of the group consisting of linear alkyl radicals comprising from 4 to 8 carbon atoms, for instance the butyl radical, the benzyl radical or a butylene oxide group. Among the defoaming nonionic surfactants of formula (A1), mention may be made of the products sold under the brand name Tergitol™ by the company Dow Chemical, for instance Tergitol™ L61E and Tergitol™ L64E, Other sparingly foaming nonionic surfactants may have the following formula (A2):
R8—O-(S′)q′-H (A2)
Among the mineral acids that are particularly selected as acidic agents in said detergent liquid aqueous composition (F), mention may be made of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, 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 and hydrofluoric acid.
Among the organic acids that are particularly selected as acidic agents in said detergent liquid aqueous 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, citric acid, sorbic acid, sulfamic acid, dihydroacetic acid, dimethylsulfamic acid, fumaric acid, glutamic acid, isopropylsulfamic acid, valeric acid, benzenesulfonic acid, xylenesulfonic acid, 2-ethylhexanoic acid, capric acid, caproic acid, cresylic acid, dodecylbenzenesulfonic acid, peracetic acid, monochloroacetic acid and gluconic acid.
Among the alkaline agents associated with said self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of the elements of the group consisting of alkali metal or alkaline earth metal hydroxides, for instance sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide.
Among the anti-limescale agents associated with said self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of the elements of the group consisting of sequestrants, for instance sodium tripolyphosphate (TPP), ethylenediaminetetraacetate (EDTA), tetraacetylethylenediamine (TAED), methylglycine diacetate (MGDA), sodium nitrilotriacetate (Na3NTA), sodium or potassium gluconate, sodium or potassium erythorbate, sodium or potassium polycarboxylates, and sodium citrate, of ion-exchange agents, for instance sodium zeolites or aluminosilicates, or lamellar sodium silicates, and precipitating agents, for instance calcium carbonate and sodium metasilicate. According to a more particular aspect, in said detergent liquid aqueous composition (F), the anti-limescale agent is selected from the elements of the group consisting of sodium metasilicate, sodium tripolyphosphate (TPP), ethylenediaminetetraacetate (EDTA), tetraacetylethylenediamine (TAED), methylglycine diacetate (MGDA), sodium nitrilotriacetate (Na3NTA), sodium gluconate, sodium citrate and calcium carbonate. The sequestrants, and more particularly the sequestrants described above,
have the effect of complexing calcium and magnesium ions to form water-soluble complexes which are then removed 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 sequestrants described above, have the effect of removing the ions responsible for the hardness of water by forming insoluble calcium compounds, which are subsequently removed with the soiling on the cleaned surfaces. Among the thickeners and/or gelling agents that may be associated with said
self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of polysaccharides consisting only of monosaccharides, such as glucans or glucose homopolymers, glucomannoglucans, xyloglycans, galactomannans of which the degree of substitution (DS) of the D-galactose units on the main D-mannose chain is between 0 and 1, and more particularly between 1 and 0.25, such as galactomannans originating from cassia gum (DS=1/5), locust bean gum (DS=1/4), tara gum (DS=1/3), guar gum (DS=1/2) or fenugreek gum (DS=1).
Among the thickeners and/or gelling agents that may be associated with said self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of polysaccharides consisting of monosaccharide derivatives, such as sulfated galactans and more particularly carrageenans and agar, uronans and more particularly algins, alginates and pectins, heteropolymers of monosaccharides and of uronic acids, and more particularly xanthan gum, gellan gum, acacia gum exudates and karaya gum exudates, glucosaminoglycans. Among the thickeners and/or gelling agents that may be associated with said self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of cellulose, cellulose derivatives such as methylcellulose, ethylcellulose, hydroxypropylcellulose, silicates, starch, hydrophilic starch derivatives, and polyurethanes.
Among the thickeners and/or gelling agents that may be associated with said self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of inorganic thickeners, for instance clays, hectorite, saponite, sauconite, vermiculite or colloidal silica.
The thickeners present in composition (F) that is a subject of the present invention are used in amounts of between 0.1% and 10% by mass.
Among the abrasive agents that may be associated with said self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of materials of natural origin, for instance wood or kernel chips, inorganic abrasive materials such as oxides, quartzes, diatomaceous earths, colloidal silica dioxides, organic abrasive materials such as polyolefins, for instance polyethylenes and polypropylenes, polystyrenes, acetonitrile-butadiene-styrene resins, melamines, phenolic resins, epoxy resins or polyurethane resins. The abrasive agents present in composition (F) that is a subject of the present invention are used in amounts of between 5.0% and 30% by mass.
Among the solvents that may be associated with said self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of isopropyl alcohol, benzyl alcohol, 1,3-propanediol, chlorinated solvents, acetone, methyl ethyl ether, methyl isobutyl ether, butyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, aromatic solvents, isoparaffins, isododecane, ethyl lactate, butyl lactate, terpenic 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, tripropylene glycol n-butyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, ethylene glycol phenyl ether or dipropylene glycol dimethyl ether. As examples of solvents present in composition (F) that is a subject of the present invention, mention may be made more particularly of the elements of the group consisting of 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, tripropylene glycol n-butyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol phenyl ether, ethylene glycol phenyl ether, dipropylene glycol dimethyl ether, rapeseed methyl esters and sunflower methyl esters.
Among the enzymes that may be associated with said self-invertible inverse latex as defined above in said detergent liquid aqueous composition (F), mention may be made of proteases, amylases, lipases, cellulases and peroxidases. The enzymes present in composition (F) that is a subject of the present invention are used in amounts of between 0.005% and 0.5% by mass.
According to another aspect, a subject of the invention is the use of said detergent liquid aqueous composition (F) as defined above, for cleaning solid surfaces. The expression for “cleaning solid surfaces” denotes any action intended for removing soiling present on surfaces consisting of various materials. The surfaces to be cleaned may be solid surfaces or textile surfaces. The term “solid surfaces” denotes, for example, floors, walls, window panes, tiles, household electrical appliances, kitchenware, countertops, tapware, sinks, tanks for storing chemical, food or agricultural products, vehicles (motor vehicles, motorbikes, trucks, etc.). The materials constituting these solid surfaces are, for example, glass (soda-lime, fluorocalcium, borosilicate, crystal), porcelain, earthenware, ceramic, polycarbonate or polypropylene plastics, stainless steel, silver, copper, aluminum, wood, synthetic resins, glass-ceramic or linoleum, and may be coated with paints or varnishes. As examples of soiling that is present on these solid surfaces and that is to be removed by cleaning, mention may for example be made of food residues, grease, light and heavy hydrocarbons, burnt residues, dust, sludge, finger marks, soap residues and microorganisms.
According to another aspect, a subject of the invention is a process for cleaning a solid surface, characterized in that it comprises at least one first step a″1) of applying said detergent liquid aqueous composition (F) as defined above, followed by at least one step b″1) of rinsing said solid surface.
In step a″1) of the process as defined above, said detergent liquid aqueous composition (F) is applied to the surface comprising the soiling to be cleaned by any means, for instance by total immersion, by spraying or by application by means of a support consisting of synthetic or natural, woven or nonwoven textile fibers, or paper, impregnated beforehand with said composition.
In step b″1) of the process as defined above, the rinsing of the solid surface onto which composition (F) for domestic or industrial use has been applied during step a″1) is performed by total immersion or by spraying with water. Step b″1) of the cleaning process that is a subject of the invention may be performed at ambient temperature or at a temperature of between 30 and 80° C., more particularly at a temperature of between 30 and 65° C.
The examples that follow illustrate the invention without, however, limiting it.
The synthesis process comprises the following steps:
After homogenization, the composition (CA1) is isolated.
The synthesis process comprises the following steps:
After homogenization, the composition (CA2) is isolated.
The synthesis process comprises the following steps:
→After homogenization, the composition (CA3) is isolated.
The synthesis process comprises the following steps:
After homogenization, the composition (CA4) is isolated.
The synthesis process comprises the following steps:
After homogenization, the composition (CA5) is isolated.
The synthesis process comprises the following steps:
After homogenization, the composition (CA6) is isolated.
The synthesis process comprises the following steps:
After homogenization, the composition (CA7) is isolated.
The synthesis process comprises the following steps:
After homogenization, the composition (CA8) is isolated.
The synthesis process comprises the following steps:
After homogenization, the composition (CA9) is isolated.
The synthesis process comprises the following steps:
After homogenization, the composition (Cato) is isolated.
The synthesis process comprises the following steps:
After homogenization, the composition (CA11) is isolated.
The compositions (CA1) to (CA11) according to the invention are evaluated as described below:
Weigh out 192 grams of water in a 400 ml tall-form beaker.
The results are collated in table 1 below.
Viscosity values of the gels at pH 6.
Dynamic viscosities of the aqueous gels obtained with the compositions (CA1) to (CA11). Compositions (CA1) to (CA11) according to the invention make it possible to obtain thickened aqueous gels compared to the aqueous gel obtained from a non-crosslinked sodium gamma-polyglutamate (“control test”).
Thus, at a polymeric percentage by mass equal to 2%, the aqueous gels obtained with the compositions (CA1) and (CA3) exhibit viscosities of 76 000 and 91 600 mPa·s, respectively, whereas the aqueous gel obtained with non-crosslinked sodium gamma-polyglutamate (“control test”) features a viscosity of 176 mPa·s.
Similarly, at a polymeric percentage by mass of less than 2%, the aqueous gels obtained with the compositions (CA2), (CA4), (CA8), (CA9) and (CA10) respectively exhibit viscosities of 124 000, 117 200, 9540, 91 800 and 78 000 mPa·s, whereas the aqueous gel obtained with 2% by mass of non-crosslinked sodium gamma-polyglutamate (“control test”) features a viscosity of 176 mPa·s.
In the formulations below, the percentages are expressed as percentages by mass per 100% of the mass of the formulation.
The preparation of the composition (F1) involves the following steps:
The cleaning process is as follows:
The composition prepared above is sprayed at ambient temperature onto the walls of an oven soiled with food grease and onto cooking grills also soiled with food grease. After 10 minutes, the walls of the oven and the cooking grills are rinsed with hot water at 60° C. The walls of the oven and the surfaces of the cooking grills thus cleaned no longer have any soiling.
Composition (F2) is prepared as follows:
Each ingredient is successively introduced into a mixing tank under moderate mechanical stirring, at ambient 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 of less than 1.0 and is clear and homogeneous after storage for a period of one month at 40° C.
The cleaning process is as follows:
The 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.
| Number | Date | Country | Kind |
|---|---|---|---|
| FR2100111 | Jan 2021 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/087359 | 12/22/2021 | WO |
