DK2714876T3 - Hidtil ukendt anvendelse af heptylpolyglycosider til solubilisering af non-ioniske overfladeaktive stoffer i vandige sure rengøringssammensætninger, og vandige sure rengøringssammensætninger omfattende samme - Google Patents

Description

NOVEL USE OF HEPTYLPOLYGLYCOSIDES FOR SOLUBILISING NON-IONIC SURFACTANTS IN AQUEOUS ACIDIC CLEANING COMPOSITIONS. AND AQUEOUS ACIDIC CLEANING COMPOSITIONS COMPRISING SAME

The present invention relates to the use of an n-heptyl polyglycoside or of a mixture of n-heptyl polyglycosides for solubilising low-foaming non-ionic surfactants, in stable compositions in an acidic medium, in particular used for cleaning and descaling hard surfaces.

Solubilising agent means any substance or chemical composition able to solubilise, in water or in aqueous phases, chemical compounds that are only slightly soluble or insoluble in water or in these aqueous phases. The expression "chemical compounds that are only slightly soluble or insoluble in water or in aqueous phases" means compounds which, added to a phase mainly or completely consisting of water, do not make it possible to obtain a completely clear, transparent, isotropic, homogeneous solution of composition that is stable at a required temperature for a required period. This lack of solubility is in particular due to the chemical structure of the compound concerned and/or to the presence of acid agents in the aqueous phase in which it is wished to solubilise said compound.

Among the compounds that are only slightly soluble or insoluble in water, mention can be made of hydrophobic compounds such as for example oils, essential oils, fragrances, pigments, anionic surfactants, cationic surfactants, non-ionic surfactants and amphoteric surfactants.

Solubilising agents are particularly used for preparing cleaning compositions intended for cleaning hard surfaces for household or industrial applications.

Among the cleaning compositions intended for cleaning hard surfaces for household or industrial applications, a distinction can be made between alkaline aqueous cleaning compositions, which are characterised by a pH above 7.0, and acidic aqueous cleaning compositions, which are characterised by a pH less than or equal to 7.0.

Acidic aqueous cleaning compositions are used for cleaning hard surfaces, that is to say not only eliminating dirt from said hard surfaces but also descaling said surface. Such compositions are particularly suitable for the cleaning and descaling of food industry installations, such as the milk, brewing and wine-making industries. They are also suitable for cleaning and descaling domestic electrical equipment, such as dishwashers and coffee machines. These industrial installations and domestic electrical equipment comprise circuits and reservoirs which, after functioning for a certain length of time, are soiled by organic materials, such as for example greases, and more particularly phospholipids, proteins and tannins, and by mineral deposits of calcium salts, more particularly calcium carbonates, phosphates and oxalates.

These acidic aqueous cleaning compositions are also particularly suitable for cleaning and descaling enamel in toilets, wash basins, baths and showers.

These acidic aqueous cleaning compositions are also used for treating metal surfaces or cast or forged metal parts, for eliminating the deposits formed by the corrosion or oxidation of metals, such as rust, layers of oxides, verdigris or deposits of soot and lime.

These acidic aqueous cleaning compositions are also used in cleaning operations intended for eliminating residues from concrete or cement, and for operations of cleaning greases present in depth on concrete surfaces before any operation of painting said concrete surfaces.

These acidic aqueous cleaning compositions must not generate the formation of a significant amount of foam during the cleaning operation in the presence of the dirt to be treated, and must show good wetting properties and also good detergent power in an acidic medium.

Because of their amphiphilic structure, the detergent surfactant agents used in acidic aqueous cleaning compositions intended for cleaning hard surfaces confer on the latter the ability to eliminate dirt present on the hard surfaces and to keep it in suspension, in order then to be eliminated during the rinsing step. These detergent surfactants may be of anionic, cationic, amphoteric or non-ionic nature. Non-ionic surfactants are particularly used for preparing detergent compositions for hard surfaces because of their foaming capacity that is generally lower than other ionic surfactants and also because of their improved environmental characteristics.

As these cleaning compositions comprise large quantities of acidic agents, it is difficult to dissolve large quantities of detergent surfactants for obtaining a stable composition not exhibiting any phase separation during storage.

In order to improve the solubility of chemical compounds that are only slightly soluble or insoluble in water or in aqueous phases, persons skilled in the art use solubilising agents such as ethanol, xylene sulfonates and cumene sulfonates. Ethanol is an effective solubilising agent but it does however have a certain explosive character in an acidic environment. The European patent application published under the number EP 0 524 075 A1 describes the efficacy of acidic aqueous cleaning compositions comprising an anionic hydrotropic or solubilising agent and non-anionic surfactants. However, anionic solubilising agents, such as xylene sulfonates and cumene sulfonates, are not very effective for large quantities of surfactants and also do not have the biodegradability properties required for being in conformity with new environmental regulations.

Alkyl polyglycosides are also described as solubilising agents for foam-reducing non-anionic surfactants.

The international publication WO 96/33255 A1 describes anti-foam compositions comprising in particular an alkyl polyglucoside, the alkyl chain of which consists of the 2-ethyl hexyl radical, and foam-reducing non-anionic surfactants chosen from those comprising one or more groups chosen from monoethoxylated and polyethoxylated groups or monopropoxylated or polypropoxylated groups. It is taught therein that alkyl polyglucosides with a 2-ethyl hexyl chain or more effective than alkyl polyglucosides with a hexyl chain for solubilising foam-reducing non-ionic surfactants.

The international publication WO 99/21948 A1 discloses clear compositions stable at high alkaline concentrations, the foaming properties of which are controlled, containing a large quantity of non-ionic surfactants based on alkylene oxide and a hexyl glycoside as a hydrotropic or solubilising agent. These compositions are characterised by good wetting capability and good detergent properties for hard surfaces. It is taught therein that hexyl glycosides and more particularly n-hexyl polyglucoside are solubilising agents for non-ionic surfactants in a highly alkaline medium and that n-hexyl glucoside is characterised by a capability of solubilising a non-ionic surfactant the structure of which results from the ethoxylation by 4 moles of ethylene oxide of a mixture of linear and branched alcohols, with a proportion of linear alcohols of approximately 80%, comprising from 9 to 11 carbon atoms, superior to 2-ethyl hexyl glucoside and Exxal 7 glucoside in the presence of quantities of soda of between 10% and 40%.

The American patent published under the number US 5 205 959 describes a mixture comprising, for 100% of its weight: (i) from 1.5% to 30% by weight alkyl polyglycosides the alkyl chain of which comprises from 6 to 12 carbon atoms and the degree of polymerisation of which is between 1 and 2, (ii) from 5% to 70% by weight alcohols comprising from 16 to 20 carbon atoms, branched at position 2, polyethoxylated, with a number of ethylene oxide units between 5 and 9, the terminal hydroxyl function of which is linked by an ether function with an alkyl chain comprising 4 to 8 carbon atoms, (iii) from 5% to 70% by weight alcohols, comprising an even number of carbon atoms between 12 and 20, polyethoxylated with a number of ethylene oxide units between 2 and 5.

The applicant therefore set out to develop a novel technical solution consisting of the use of an n-heptyl polyglycoside or of a mixture of n-heptyl polyglycosides, having a non-flammable character and non-ecotoxic and biodegradable properties, to solubilise non-ionic surfactants in aqueous compositions stable in an acid medium, particularly used for cleaning and descaling hard surfaces.

This is why, according to a first aspect, the subject matter of the invention is the use of a composition (C) represented by the formula (I):

in which G represents the remainder of a reducing sugar,

Ri represents the n-heptyl radical, and p represents a decimal number greater than 1, and less than or equal to 5, said composition (C) consisting of a mixture of compounds represented by the formulae (Ii), (I2), (I3), (I4) and (Is):

in the following respective molar proportions: ai for the compound of formula (Ii), 32 for the compound of formula (I2), a3 for the compound of formula (I3), 34 for the compound of formula (I4), and as for the compound of formula (Is), such that: the sum ai+a2+a3+a4+a5 is equal to 1 and such that the sum ai+2a2+3a3+4a4+5as is equal to p, as an agent for solubilising at least one non-ionic surfactant of formula (II):

in which R represents a hydrocarbon aliphatic radical, saturated or unsaturated, linear or branched, comprising from 8 to 14 carbon atoms, R' represents a methyl or ethyl radical, and preferably the n-heptyl radical, n represents an integer number greater than or equal to 0 and less than or equal to 15, m represents an integer number greater than or equal to 0 and less than or equal to 15, it being understood that the sum n + m is greater than zero, in an aqueous acid composition.

In the definition of the use that is the subject matter of the present invention, the expression "aqueous acid composition" designates any aqueous composition having a pH of less than or equal to 7.

Reducing sugar means, in the composition represented by formula (I), the saccharidic derivatives that do not have, in their glycoside bonding structures 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)P, may be in any form of isomerism, where their optical isomerism, geometric isomerism or position isomerism; it may also represent a mixture of isomers.

Solubilising agent designates any substance or chemical composition able to solubilise, in water or in aqueous phases, chemical compounds that are only slightly soluble or insoluble in water or in these aqueous phases. The expression "chemical compounds that are only slightly soluble or insoluble in water or in aqueous phases" designates compounds which, added to a phase mainly or completely consisting of water, do not make it possible to obtain a solution or composition that is totally clear, transparent, isotropic, homogeneous and stable at a required temperature for a required period.

In formula (I) as defined above, the group Ri-0 is bonded to G by the anomeric carbon of the saccharide remainder, so as to form an acetal function. G represents the remainder of a reducing sugar chosen mainly from glucose, dextrose, saccharose, fructose, idose, gulose, galactose, maltose, isomaltose, maltotriose, lactose, cellobiose, mannose, ribose, xylose, arabinose, lyxose, allose, altrose, dextran or tallose.

According to a particular aspect of the present invention, the subject matter thereof is the use as defined previously for which, in formula (I), p represents a decimal number greater than or equal to 1.05 and less than or equal to 2.5.

According to another particular aspect of the present invention, the subject matter therefore is the use as defined previously for which, in formula (I), G represents the remainder of reducing sugar chosen from the remainders of glucose, xylose and arabinose, and more particularly chosen from the remainders of glucose or xylose.

The composition represented by formula (I) is prepared in particular according to a method comprising the following successive steps: - a step A) of reaction of a reducing sugar of formula (III):

in which G represents the remainder of a reducing sugar, with a molar excess of n-heptanol of formula Rl-OH, to form a mixture of compounds of formula (I) as defined above and of n-heptanol; - a step ΒΊ of elimination of n-heptanol from said mixture obtained at step A).

Step A) is generally implemented in a reactor in the presence of an acid catalytic system, controlling the stoichiometric ratio between the two reactants, more particularly by introducing a molar excess of n-heptanol, and under mechanical stirring under predetermined conditions of temperature and partial vacuum, for example at a temperature of between 70°C and 130°C and under a partial vacuum of between 300 mbar (3.104 Pa) and 20 mbar (2.103 Pa). Acid catalytic system means strong acids such as sulphuric acid, hydrochloric acid, phosphoric acid, nitric acid, hypophosphorous acid, methanesulphonic acid, (para-toluene) sulphonic acid, (trifluoromethane) sulphonic acid, or ion exchange resins.

Step B) elimination of n-heptanol from said mixture obtained at the end of step A) is generally implemented in accordance with methods known to persons skilled in the art, such as for example distillation, thin-film distillation, molecular distillation or solvent extraction.

Such a preparation method may be supplemented, if necessary or if desired, by neutralisation, filtration and decolouration operations.

In the use as defined above, hydrocarbon aliphatic radical, saturated or unsaturated, linear or branched, comprising from 8 to 14 carbon atoms, optionally substituted with one or more hydroxyl groups, means, for the radical R in formula (II): - Linear alkyl radicals, for example the n-octyl, n-decyl, n-dodecyl or n-tetradecyl radicals; - The radicals issuing from isoalkanols of formula (1):

in which r represents an integer number between 4 and 10, for example the isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl or isotetradecyl radicals; - The 2-ethyl hexyl radical or the branched alkyl radicals issuing from Guerbet alcohols of formula (2):

in which t is an integer number between 4 and 10, s is an integer number between 2 and 10 and the sum s + t is greater than or equal to 6, and less than or equal to 12, for example the 2-ethyl decyl, 2-butyl octyl, 2-ethyl dodecyl, 2-butyl decyl, 2-hexyl octyl, 2-butyl decyl or 2-hexyl octyl radicals; or the radicals issuing from homologues of Guerbet alcohols, for example the 2-propyl heptyl radical. - Radicals issuing from the branched alcohols of formula (3):

in which R" represents a hydrogen atom or a methyl radical, and z represents an integer number greater than or equal to 3 and less than or equal to 15; - The unsaturated linear radicals such as the undecenyl, dodecenyl or tetradecenyl radicals, such as for example the 10-undecenyl, 4-dodecenyl or 5-dodecenyl unsaturated radicals; - The saturated or unsaturated, linear or branched aliphatic radicals comprising from 8 to 14 carbon atoms substituted by one or two hydroxyl groups, such as the hydroxyl octyl, hydroxydecyl or hydroxydodecyl radicals, for example the 8-hydroxy octyl, 10-hydroxydecyl or 12-hydroxydodecyl radicals.

According to another particular aspect of the present invention, the subject matter thereof is the use as defined above for which, in formula (II), the R radical represent a radical chosen from the octyl, decyl, dodecyl, tetradecyl, 2-ethyl hexyl, 2-butyl octyl, 2-butyl decyl, 2-hexyl octyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl or 2-propylheptyl radicals.

According to another particular aspect of the present invention, the subject matter thereof is the use as defined above for which, in formula (II), n represents an integer number greater than or equal to 0 and less than or equal to 6, more particularly greater than or equal to 0 and less than or equal to 3, and even more particularly greater than or equal to 0 and less than or equal to 2.

According to another particular aspect of the present invention, the subject matter thereof is the use as defined above for which, in formula (II), m represents an integer number greater than or equal to 1 and less than or equal to 9, more particularly greater than or equal to 2 and less than or equal to 6, and even more particularly greater than or equal to 2 and less than or equal to 4.

The compounds of formula (II) for which R' represents a methyl or ethyl radical and n represents an integer number greater than or equal to 1 are prepared according to a method comprising if necessary a step a! of alkoxylation by reaction of n molar equivalents of an alkylene oxide or of an alkylene carbonate with a molar equivalent of alcohol of formula (IV): R-OH (IV) in which the R radical represents a hydrocarbon aliphatic radical, saturated or unsaturated, linear or branched, comprising from 8 to 14 carbon atoms, optionally substituted with one or more hydroxyl groups, as defined above, in order to obtain the alkoxylated alcohol of formula (V):

in which R' represents a methyl or ethyl radical; and/or if necessary a step b) of ethoxylation by reaction of a molar equivalent of the alkoxylated alcohol of formula (V) obtained at the end of step a) with m molar equivalents of ethylene oxide or of ethylene carbonate.

In step a) of the method for preparing compounds of formula (II) as described above, the alkylene oxide is chosen from the elements in the group consisting of propylene oxide and butylene oxide, and the alkylene carbonate is chosen from the elements in the group consisting of propylene carbonate and butylene carbonate.

The compounds of formula (II) for which n is equal to 0 are prepared according to a method using a step a'l of ethoxylation by reaction of m molar equivalents of ethylene oxide or ethylene carbonate with the alcohol of formula (IV) as defined above.

In the methods described above, n and m represent the integer numbers described above in the definition of the compounds of formula (II).

The alkoxylation reactions of step a) and of ethoxylation of steps a') and bl. as defined above, are generally carried out in a reactor in the presence of a basic catalyst such as alkaline metal hydroxides such as for example soda, potash, alcoholates of alkaline metals, such as for example sodium or potassium methylate, sodium or potassium tert-butylate, Lewis bases such as for example triphenylphosphine, coordination catalysts such as for example organometallic complexes based on cobalt and/or zinc, or in the presence of an acid catalyst such as a Lewis acid such as for example boron trifluoride, aluminium trichloride or tin tetrachloride.

Such methods for preparing the compounds of formula (II) may be supplemented, if necessary or if desired, by neutralisation, demineralisation, filtration and decolouration operations.

According to another particular aspect of the present invention, the subject matter thereof is the use as defined previously, in which the ratio by weight between said non-ionic surfactant of formula (II) and said composition (C) is less than or equal to 15/1 and greater than or equal to 1/1.

According to another aspect, the subject matter of the invention is a composition (Ci) comprising, for 100% of its weight: a) from 0.2% to 40% by weight of said (C) represented by formula (I):

in which G represents the remainder of a reducing sugar,

Ri represents the n-heptyl radical, and p represents a decimal number greater than 1, and less than or equal to 5, said composition (C) consisting of a mixture of compounds represented by the formulae (Ii), (I2), (I3), (I4) and (Is):

in the following respective molar proportions: ai for the compound of formula (Ii), 32 for the compound of formula (I2), a3 for the compound of formula (I3), a4 for the compound of formula (I4), and as for the compound of formula (Is), such that: the sum ai+a2+a3+a4+as is equal to 1 and such that the sum ai+2a2+3a3+4a4+5as is equal to p, b) from 0.2% to 80% by weight, more particularly from 0.2% to 40% by weight, and even more particularly from 0.2% to 20% by weight of at least one non-ionic surfactant of formula (II):

in which R represents a hydrocarbon aliphatic radical, saturated or unsaturated, linear or branched, comprising 8 to 14 carbon atoms, R' represents a methyl or propyl radical, n represents an integer number greater than or equal to 0 and less than or equal to 15, m represents an integer number greater than or equal to 0 and less than or equal to 15, it being understood that the sum n + m is greater than zero; c) from 1% to 50% by weight, more particularly from 1% to 40% by weight, and even more particularly from 1% to 35% by weight of at least one acid agent chosen from the elements in the group consisting of mineral acids and organic acids; and d) from 1% to 98.6% by weight, more particularly from 20% to 98.6% by weight, and even more particularly from 40% to 98.6% by weight of water.

Among the mineral acids particularly chosen as acid agents in the composition (Ci) that is the subject matter of the present invention, mention can be made of hydrochloric acid, nitric acid, phosphoric acid, sulphuric 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, hydriodic acid and hydrofluoric acid.

Among the organic acids that are particularly chosen as acid agents in the composition (Ci) that is the subject matter of the present invention, mention can be made of formic acid, acetic acid, propionic acid, benzoic acid, salicyclic 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, isopropyl 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 and gluconic acid.

According to a more particular aspect, in the composition (Ci) that is the subject matter of the present invention, the acid agent is chosen from hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hypochlorous acid, formic acid, acetic acid, salicylic acid, oxalic acid, citric acid, tartaric acid, gluconic acid, peracetic acid, glycolic acid, lactic acid.

According to a particular aspect, in the composition (Ci) that is the subject matter of the present invention, the ratio by weight between the compound of formula (II) and said composition (C) is less than or equal to 15/1 and greater than or equal to 1/1.

According to another aspect, a subject matter of the invention is the use of a composition (Ci) as defined above, for cleaning hard surfaces.

The expression "for cleaning hard surfaces" designates any action intended to eliminate dirt present on surfaces consisting of various materials. Hard surfaces means for example floors, vertical surfaces, tiles, domestic electric appliances such as for example dishwashers and coffee machines, taps, sinks, wash basins, baths, showers, WCs, urinals, containers for storing food or agricultural products, vehicles (cars, motor bikes, lorries, etc.), industrial installations such as for example heat exchangers, sea-water evaporators, pipes, heating circuits, cooling circuits, civil engineering equipment soiled by cement or concrete such as for example concrete mixers, shapers for cement and concrete, metal surfaces and cast or forged metal parts.

The materials constituting these hard surfaces are for example glass (soda-lime, fluorocalcium, borosilicate, crystal), enamel, porcelain, earthenware, ceramic, polycarbonate plastics, polypropylenes, stainless steel, silver, copper, aluminium and more particularly highly oxidised aluminium, brasses and copper alloys, precious metals such as for example gold, silver, platinum, wood, synthetic resins, vitreous ceramic or linoleum, and may be coated with paints or varnishes.

As an example of dirt present on these hard surfaces and to be eliminated by cleaning, mention can be made for example of food residues such as for example deposits caused by milk products and sugary food residues, fats such as for example phospholipids, proteins, tannins, algae, heavy and light hydrocarbons, burnt residues, soap residues, germs, carbonaceous traces such as for example soot, mineral deposits of calcium salts such as for example calcium carbonate, calcium phosphate or calcium oxalate, scale, limescale, deposits of metal oxides such as for example rust, verdigris, residues of glues, residues of mortars, residues of cements, residues of lime.

The composition (Ci) that is the subject matter of the present invention is in particular in the form of an aqueous solution, an emulsion or a microemulsion with aqueous continuous phase, an emulsion or a microemulsion with oil continuous phase, an aqueous gel or a foam, or in the form of an aerosol.

The composition (Ci) that is the subject matter of the present invention may be applied directly by soaking, spraying or vaporisation on the surface to be cleaned or by means of any type of medium intended to be put in contact with the hard surface to be cleaned (paper, cloth, textile) comprising said composition (Ci).

The composition (Ci) that is the subject matter of the present invention used for cleaning hard surfaces generally has a pH of less than or equal to 7, more particularly less than or equal to 6, more particularly less than or equal to 4 and even more particularly less than or equal to 2.

In general the composition (Ci) that is the subject matter of the present invention also comprises ingredients normally used in the field of cleaning hard surfaces, such as non-ionic surfactants, cationic surfactants, amphoteric surfactants, cationic polymers, non-ionic polymers, thickening agents, enzymes, bleaches, anticorrosion agents, solvents, preservatives, perfumes, dyes, repellents or oxidants.

As examples of non-ionic surfactants present in the composition (Ci) that is the subject matter of the present invention, mention can be made of: - Block copolymers of ethylene oxide and propylene oxide, and particularly the block copolymers of ethylene oxide and propylene oxide sold under the brand name Pluronic™ by the company BASF, such as for example Pluronic™ PE 6100 and Pluronic™ PE 6200, - Anti-foaming non-ionic surfactants of formula (Ai):

in which: - Ri represents a hydrocarbon aliphatic radical, saturated or unsaturated, linear or branched, comprising from 6 to 18 carbon atoms, - X represents a nitrogen atom or an oxygen atom, - v represents an integer number between 1 and 50, - u represents an integer number between 1 and 50, - w represents an integer number equal to 1 if X represents an oxygen atom, and w represents an integer number equal to 1 or 2 if X represents a nitrogen atom, - Y represents a blocking functional group chosen from the elements in the group consisting of the linear alkyl radicals comprising from 4 to 8 carbon atoms, such as for example the butyl radical, the benzyl radical, or a butylene oxide group.

Among the anti-foaming non-ionic surfactants of formula (Ai), mention can be made of the products sold under the brand name Tergitol™ by the company Dow Chemical such as for example Tergitol™ L61E and Tergitol™ L64E. - Low-foaming non-ionic surfactants of formula (A2):

in which: - S represents the remainder of a reducing sugar chosen from the elements in the group consisting of glucose, xylose and arabinose, - R2 represents a saturated hydrocarbon radical, linear or branched, comprising from 6 to 10 carbon atoms, - q represents a decimal number greater than or equal to 1.05 and less than or equal to 5.

As an example of low-foaming non-ionic surfactants of formula (A2) present in the composition (Ci) that is the subject matter of the present invention, mention can be made of hexylpolyglucosides and 2-ethylpolyglucosides.

As an example of amphoteric surfactants present in the composition (Ci) that is the subject matter of the present invention, mention can be made of β alanine and sodium N-(2-carboxyethyl)-N-(2-ethylhexyl) sold under the brand name Tomamine® Amphoteric 400 Surfactant.

As examples of thickening agents present in the composition (Ci) that is the subject matter of the present invention, mention can be made of polymeric hydrocolloids of plant or biosynthetic origin, such as xanthan gum, scleroglucan, tragacanth, agar-agar, carraghenates, alginic acid, alginates and galactomannans; cellulose and derivatives thereof such as for example hydroxypropylmethyl cellulose; dextrin; casein, pectins; gelatin; chitosan; polyethylene glycols having a molecular weight of between 4,000 and 35,000 grams per mol; ethoxylated derivatives of ethylene glycol having a molecular weight between 300,000 and 7,000,000 grams per mol.

As examples of thickening agents present in the composition (Ci) that is the subject matter of the present invention, mention can be made of polymeric thickening agents such as a homopolymers of acrylamide, or copolymers of acrylamide and of the sodium salt of 2-acrylamido-2-methylpropanesulfonate, such as for example the thickeners sold by the company Seppic under the brand name Solagum™.

As examples of thickening agents present in the composition (Ci) that is the subject matter of the present invention, mention can be made of the inorganic thickening agents such as for example clays, hectorite, saponite, sauconite, vermiculite or colloidal silica.

The thickening agents present in the composition (Ci) that is the subject matter of the present invention are used in quantities of between 0.1% and 10% by weight.

As examples of abrasives present in the composition (Ci) that is the subject matter of the present invention, mention can be made of materials of natural origin such as for example wood or kernel shavings, inorganic abrasive material such as oxides, quartzes, 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 and polyurethane resins.

The abrasives present in the composition (Ci) that is the subject matter of the present invention are used in quantities of between 5.0% and 30% by weight.

As examples of solvents present in the composition (Ci) that is the subject matter of the present invention, mention can be made of isopropyl alcohol, benzyl alcohol, 1,3 propane diol, 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, terpene solvents, methyl esters of rapeseed oil, methyl esters of sunflower oil, 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 and dipropylene glycol n-propyl ether, propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, ethylene glycol phenyl ether, dipropylene glycol dimethyl ether.

As an example of solvents present in the composition (Ci) that is the subject matter of the present invention, mention can be made more particularly of the elements in 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, methyl esters of rapeseed oil and methyl esters of sunflower oil.

According to another aspect, the subject matter of the invention is a method for cleaning a hard surface, characterised in that it comprises:

At least one step ai) of applying the composition (Ci) as defined above to said hard surface, followed by at least one step bi) of rinsing said hard surface.

In step ai) of the cleaning method that is the subject matter of the invention, the composition (Ci) is applied to the surface comprising the dirt to be cleaned by any means such as for example in a bath, by soaking, by spraying, by application by means of a medium consisting of synthetic or natural textile fibres, woven or non-woven, or paper, impregnated in advance with said composition (Ci).

In step bi) of the cleaning method that is the subject matter of the invention, the rinsing of the hard surface to which the composition (Ci) that was applied during step aij is carried out in a bath or by spraying water. step bij of the cleaning method that is the subject matter of the invention can be carried out at ambient temperature or at a temperature of between 15°C and 80°C, more particularly at a temperature of between 15°C and 65°C.

The following examples illustrate the invention, without however limiting it. 1. Preparation of compositions represented bv formula ill and evaluation of their surfactant properties 1.1) Preparation of n-heptylpolyglucosides 2.7 molar equivalents of n-heptanol is introduced into a double-jacket glass reactor, in which a heat-transfer fluid circulates, and provided with effective stirring, at a temperature of 40°C. One molar equivalent of anhydrous glucose is then added gradually to the reaction medium to allow homogeneous dispersion thereof, and then 0.15% by weight 98% sulfuric acid and 0.15% by weight 50% hypophosphorous acid for 100% of the weight consisting of the sum of the weight of glucose and the weight of n-heptanol, are introduced into the previously prepared homogeneous dispersion. The reaction medium is placed under partial vacuum of approximately 18xl03 Pa (180 mbar), and maintained at a temperature of 100°C-105°C for a period of 4 hours with discharge of the water formed by means of a distillation assembly. The reaction medium is next cooled to 85°C-90°C and neutralised by adding 40% soda, to bring the pH of a 5% solution of this mixture to approximately 7.0. The reaction medium thus obtained is next drained at a temperature of 70°C and filtered in order to eliminate the glucose grains that have not reacted. The filtrate is next introduced into a double-jacket glass reactor in which a heat-transfer fluid is circulating, provided with effective stirring and a distillation device. The excess heptanol is next eliminated by distillation at a temperature of 120°C under partial vacuum of between approximately 104 Pa (100 mbar) and 5xl03 Pa (50 mbar). The reaction medium thus distilled is immediately diluted by adding a quantity of water so as to achieve a constant reaction medium concentration of approximately 60%. After homogenisation for 30 minutes at a temperature of 50°C, the composition (Xo) obtained is drained off.

The analytical characteristics of the composition (Xo) thus obtained comprising n-heptylpolyglucosides are set out in table 1 below.

Table 1

1.2) Evaluation of foaming properties of n-heptylpolyglucosides

The foaming properties of the composition (Xo) of n-heptylpolyglucosides, obtained according to the previously described method, as well as the compositions (Xi), (X2), (X3) and (X4) of the prior art, were evaluated according to a static nitrogen bubbling method. - Composition (Xi): n-hexylpolyglucoside composition sold under the brand name AG 6206™ by the company AkzoNobel; - Composition (X2): 2-ethylhexylpolyglucoside composition sold under the brand name AG 6202™ by the company AkzoNobel; - Composition (X3): n-octylpolyglucoside/n-decylpolyglucoside composition sold under the brand name Simulsol™ SL8 (composition X3 by the company Seppic; - Composition (X4): Sodium xylene sulfonate (composition X4) sold under the brand name Stepanate SXS-E™ by the company Stepan. 1.2.1) Principle of the static nitrogen bubbling method for evaluating foaming capacity

The foam is formed by introducing a given volume of nitrogen into a solution of surfactant at a fixed concentration and in the presence of a fixed quantity of soda, at a specific temperature. The volume of the foam generated by introducing the volume of nitrogen is measured at the end of the introduction of said volume of nitrogen, then at a period of 30 seconds, and then 120 seconds following the end of the introduction of volume of nitrogen. 1.2.2 Experimental protocol 50 cm3 of a 5 mg/cm3 dry extract solution of the compositions tested is introduced into a 250 cm3 thermostatically controlled graduated test tube as well as a quantity of 12.5g of soda. The measurements were carried out at 20°C and 60°. A finger for gas distribution, porosity 3 (ref. Corning Pyrex 853-1) is positioned so that the end of the sintered end piece is situated at one centimetre from the bottom of the test tube. The flow rate of nitrogen is then precisely adjusted to 50 litres per hour and bubbling is carried out for 15 seconds. After this period, the admission of nitrogen is cut off and experimenter notes the volume of initial foam as well as the volume of foam after 30 seconds and 120 seconds. At least two tests leading to equivalent results were carried out in different test tubes for the same surfactant solution. 1.2.3) Expression of the results

The results of the volume of foam observed in the graduated test piece initially, and then at 30 seconds and at 120 seconds, are expressed in cm3. They are set out in the following tables:

Table 2: Foaming capacity at 20°C

Table 3: Foaming capacity at 60°C

1.2.4) Analysis of results

The composition (Xo) is characterised by the generation of a foam that is highly unstable at 20°C since the volume of foam decreases in 30 seconds from 95% of its initial value, as against 92.3% for the composition (Xi), 25% for the composition (X2) and 12% for the composition (X3).

At 60°C, the composition (Xo) of n-heptylpolyglucosides is also characterised by the generation of a highly unstable foam since the volume of foam decreases in 30 seconds from 100% of this initial value, as against 57.1% for the composition (X2) and 14% for the composition (X3). At 60°C, the composition (Xo) by the generation of a volume of foam less than that generated by the compositions of the prior art. 1.3) Evaluation of the solubilising properties of n-heptylpolyglucosides in an acid medium

The solubilising properties in acid medium of the composition (Xo) were evaluated in comparison with the compositions (Xi), (X2), (X3) and (X4) of the prior art as described previously according to the evaluation method described below for a non-ionic surfactant of formula (II), in the presence of various acid agents and at various concentrations of said acid agents. 1.3.1) Principle of the method of evaluating the solubilising capability in an acid medium

The purpose of this method is to determine the solubilising capability of a surfactant composition in an acid medium for a non-ionic surfactant that is insoluble in an acid medium compared with surfactant compositions of the prior art. 1.3.2 Experimental protocol A quantity of 5 g in dry matter of a non-ionic surfactant (Ti) to be solubilised, a quantity of yi grams of acid agents so as to obtain the required concentration of dry matter of said acid agent and a complementary quantity of distilled water so as to obtain a solution of 100 cm3 are introduced into a 200 cm3 glass flask. A magnetised magnetic bar is introduced into the glass flask, which is next put under magnetic agitation at a speed of 100 revolutions/minute for a period of 3 minutes at a temperature of 20°C. Next the solubilising surfactant composition (Xi) to be tested is introduced gradually so as to obtain a clear visual appearance for the medium present in the glass flask. 1.3.3 Expression of the results

When the visual appearance of the solution present in the glass flask is clear, the experimenter notes the quantity (in grams) of the solubilising composition (Xi) added that was necessary to obtain this clear appearance, and converts it by calculation into the quantity xi (in grams) of dry matter of the solubilising agent included in the composition (Xi). 1.3.4 Characterisation of the solubilising capability in a phosphoric acid medium of the compositions (XoT (XiT (X?). (Xi) and fX4)

The experimental protocol described in the above paragraph 1.3.2) is implemented for each of the compositions (Xo), (Xi), (X2), (X3) and (X4), with the polyethoxylated alcohol composition (Ti), prepared by the reaction between a molar equivalent of a mixture of alcohols comprising, for 100% of its weight, 85% by weight n-decanol and 15% by weight n-dodecanol with 4 molar equivalents of ethylene oxide in the presence of potash as a basic catalyst. The experimental measurements were carried out in the presence of different quantities yi of phosphoric acid in an 85% by weight solution, so as to obtain proportions by weight of 10% and 30% phosphoric acid in dry matter. The quantities Xi of the various solubilising compositions (Xi), (X2), (X3) and (X4) added necessary for obtaining a clear solution were recorded by the experimenter in each case and set out in table 4 for a phosphoric acid concentration of 10% and in table 5 for a phosphoric acid concentration of 30%.

Table 4: (Phosphoric acid content: 10%)

Table 5: (Phosphoric acid content: 30%)

1.3.5 Characterisation of the solubilising capability in a nitric acid medium of compositions (Xnl. (Xi1. (X?1. (Xi) and (X4l

The experimental protocol described in the above paragraph 1.3.2) for each of the compositions (Xo), (Xi), (X2), (X3) and (X4), is implemented with the polyethoxylated alcohol composition (Ti). The experimental measurements were carried out in the presence of different quantities yi of nitric acid in solution at 65% by weight, so as to obtain proportions by weight of 10% and 20% of nitric acid in dry matter. The quantities Xi of the various solubilising compositions (Xo), (Xi), (X2), (X3) and (X4) necessary for obtaining a clear solution were recorded by the experimenter in each case and set out in table 6 for a nitric acid concentration of 10% and in table 7 for a nitric acid concentration of 20%.

Table 6: (Nitric acid content: 10%)

Table 7: (Nitric acid content: 20%)

1.3.6 Characterisation of the solubilising capability in a citric acid medium of compositions (Xol. (Xil. (X?), (X3) and fX4l

The experimental protocol described in the above paragraph 1.3.2) is implemented for each of the compositions (Xo), (Xi), (X2), (X3) and (X4) with the polyethoxylated alcohol composition (Ti). The experimental measurements were carried out with a proportion by weight of 10% of citric acid in dry matter. The quantities Xi of the various solubilising compositions (Xo), (Xi), (X2), (X3) and (X4) necessary for obtaining a clear solution were recorded by the experimenter in each case and set out in table 8.

Table 8: (Citric acid content: 10%)

1.3.7 Analysis of the results obtained

The comparison between the solubilising performances obtained for the compositions characterised by a low foaming capability, namely the compositions (Xo), (Xi) and (X4), shows that, for a quantity of 10% by weight of phosphoric acid, a quantity of 1.37 g of the composition (Xo) is necessary for solubilising 5g of the non-ionic surfactant composition (Ti), whereas 1.83 g of the composition (Xi) and 1.42 g of the composition (X4) are necessary for obtaining the same result.

Likewise, in the presence of a quantity of 10% by weight of nitric acid, a quantity of 0.76 g of the composition (Xo) is necessary for solubilising 5 g of the non-ionic surfactant composition (Ti), whereas 2.17 g of the composition (Xi) and 1.72 g of the composition (X4) are necessary for obtaining the same result, corresponding respectively to quantities by weight of 185% and 126% greater than that used for the composition (Xo).

The comparison between the solubilising performances observed for the compositions (Xo) and (X2) show that, for a quantity of 10% by weight of phosphoric acid, a quantity of 1.37 g of the composition (Xo) is necessary for solubilising 5 g of the non-ionic surfactant composition (Ti), whereas a quantity of 1.99 g of the composition (X2) is necessary for obtaining the same result, that is to say a quantity by weight 45.2% greater than that used for the composition (Xo).

Likewise, in the presence of a quantity of 10% by weight of nitric acid, a quantity of 0.76 g of the composition (Xo) is necessary for solubilising 5 g of the non-ionic surfactant composition (Ti), whereas a quantity of 1.13 g of the composition (X2) is necessary for obtaining the same result, that is to say a quantity by weight 48.6% greater than that used for the composition (Xo). 1.4) Conclusions

The composition (Xo) comprising n-heptylpolyglucosides, characterised by low foaming properties and environmental properties meeting the changes in regulations, show improved solubilising properties in an acid medium compared with the solubilising agents known in the prior art. 2) Examples of aqueous acid cleaning compositions 2.1) Stripping of metal surfaces 2.1.1) Formula

(1) Hordaphos™ MDGB: phosphoric ester sold by the company Clariant as a corrosion-inhibiting agent 2.1.2) Preparation of the detergent and acidic stripping composition

Each ingredient is introduced successively into a mixing vessel under moderate mechanical stirring, at ambient temperature, until a homogeneous clear composition is obtained. The stirring is maintained for 30 minutes at 20°C. The composition obtained has a measured pH below 1 and is clear and homogeneous after storage for a period of one month at 40°C. 2.1.3) Cleaning method using the composition according to the invention

The composition prepared in the previous paragraph is diluted to 3% in water and the solution thus obtained is poured into a vessel of suitable size. The metal parts are then soaked therein for 30 minutes and then rinsed with water. 2.2) Cleaning for aluminium surfaces 2.2.1) Formula

(2) Simulsol™ OX 1309 L: detergent surfactant composition sold by the company Seppic, comprising polyethoxylated alcohols resulting from the reaction of a molar equivalent of an alcohol sold under the brand name Exxal™ 13 with 9 molar equivalents of ethylene oxide. 2.2.2) Preparation of the composition for cleaning aluminium surfaces

Each ingredient is introduced successively into a mixing vessel under moderate mechanical stirring, at ambient temperature, until a homogeneous clear composition is obtained. The stirring is maintained for 30 minutes at 20°C. The composition obtained has a measured pH below 1.0 and is clear and homogeneous after storage for a period of one month at 40°C. 2.2.3) Cleaning method using the composition according to the invention

The composition prepared in the previous paragraph is diluted to 3% in water and the solution thus obtained is spread onto the aluminium wall to be cleaned. This wall is then rinsed with hot water at 60°C. 2.3) Rinsing product for industrial dishwashers 2.3.1) Formulation

(3) Simulsol™ NW 900: detergent surfactant composition sold by the company Seppic, comprising polyethoxylated alcohols resulting from the reaction of molar equivalent of an alcohol sold under the brand name Exxal™ 10 with 9 molar equivalents of ethylene oxide. 2.3.2) Preparation of the acid cleaning composition for industrial dishwashers Each ingredient is introduced successively into a mixing vessel under moderate mechanical stirring, at ambient temperature, until a homogeneous clear composition is obtained. The stirring is maintained for 30 minutes at 20°C. The composition obtained has a measured pH below 1.3 and is clear and homogeneous after storage for a period of one month at 40°C. 2.3.3) Cleaning method using the composition according to the invention

The composition prepared in the previous paragraph is diluted to 0.3% and the solution thus obtained is poured into the dishwasher and used at a temperature of 60°C.

Claims (11)

1. Anvendelse afen sammensætning (C) repræsenteret ved formlen (I):

hvor G repræsenterer resten afen reducerende sukkerart, Ri repræsenterer et heptylradikal, og fortrinsvis et n-heptyl-radikal, p repræsenterer et decimaltal større end 1, og mindre end eller lig med 5, hvilken sammensætning (C) består af en blanding af forbindelser repræsenteret ved formlerne (li), (h), (I3), (I4) og (I5):

i de følgende respektive molandele: ai for forbindelsen med formel (li), a2 for forbindelsen med formel (I2), a3 for forbindelsen med formel (I3), a4 for forbindelsen med formel (I4) og as for forbindelsen med formel (Is), således at: summen ai + a2 + a3 + θ4 + as er lig med 1, og at summen ai + 2a2 + 3a3 + 4a4 + 5as er lig med p, mindst ét non-ionisk overfladeaktivt stof med formlen (II) som fortyndingsmiddel:

hvor R repræsenterer et mættet eller umættet, lineært eller forgrenet, alifatisk carbonhydridradikal omfattende fra 8 til 14 carbonatomer, R' repræsenterer et methyl- eller ethyl-radikal, n repræsenterer et heltal større end eller lig med 0 og mindre end eller lig med 15, m repræsenterer et heltal større end eller lig med 0 og mindre end eller lig med 15, hvor summen n + m er større end nul, i en vandig sur sammensætning.

2. Anvendelse ifølge krav 1, kendetegnet ved at i formlen (I) repræsenterer p et decimaltal større end eller lig med 1,05 og mindre end eller lig med 2,5.

3. Anvendelse ifølge et af kravene 1 eller 2, kendetegnet ved at i formlen (I) repræsenterer G resten afen reducerende sukkerart og er valgt blandt resterne af glucose, xylose og arabinose.

4. Anvendelse ifølge et hvilket som helst af kravene 1 til 3, kendetegnet ved at i formel (II) repræsterer radikalet R et radikal valgt blandt radikalerne octyl, decyl, dodecyl, tetradecyl, 2-ethylhexyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, isooctyl, isononyl, isodecyl, isoundecyl, isotridecyl, isotetradecyl eller 2-propylheptyl.

5. Anvendelse ifølge et hvilket som helst af kravene 1 til 4, kendetegnet ved at i formlen (II) repræsenterer n et heltal større end eller lig med 0 og mindre end eller lig med 6, især større end eller lig med 0 og mindre end eller lig med 3, og i særdeleshed større end eller lig med 0 og mindre end eller lig med 2.

6. Anvendelse ifølge et hvilket som helst af kravene 1 til 5, kendetegnet ved at i formlen (II) repræsenterer m et heltal større end eller lig med 1 og mindre end eller lig med 9, især større end eller lig med 2 og mindre end eller lig med 6, og i særdeleshed større end eller lig med 2 og mindre end eller lig med 4.

7. Anvendelse ifølge et hvilket som helst af kravene 1 til 6, kendetegnet ved at masseforholdet mellem det non-ioniske overfladeaktive stof med formlen (II) og sammensætningen (C) er mindre end eller lig med 15: 1 og større end eller lig med 1:1.

8. Sammensætning (Ci) omfattende for 100 % af massen deraf: a) fra 0,2 til 40 masseprocent af sammensætningen (C) repræsenteret ved formlen (I):

hvor G repræsenterer resten af en reducerende sukkerart, Ri repræsenterer et heptyl-radikal, og fortrinsvis et n-heptyl-radikal, p repræsenterer et decimaltal større end 1, og mindre end eller lig med 5, hvilken sammensætning (C) består afen blanding af forbindelser repræsenteret ved formlerne (li), (h), (I3), (I4) og (Is):

i de følgende respektive molandele: ai for forbindelsen med formel (li), da for forbindelsen med formel (I2), 33 for forbindelsen med formel (I3), 34 for forbindelsen med formel (I4) og as for forbindelsen med formel (Is), således at: summen ai + a2 + a3 + a4 + as er lig med 1, og at summen ai + 2a2 + 3a3 + 4a4 + 5as er lig med p, b) fra 0,2 til 80 masseprocent af mindst ét non-ionisk overfladeaktivt stof med formlen (II):

hvor R repræsenterer et mættet eller umættet, lineært eller forgrenet, alifatisk carbonhydridradikal, omfattende fra 8 til 14 carbonatomer, R' repræsenterer et methyl- eller ethyl-radikal, n repræsenterer et heltal større end eller lig med 0 og mindre end eller lig med 15, m repræsenterer et heltal større end eller lig med 0 og mindre end eller lig med 15, hvor summen n + m er større end nul; c) fra 1 til 50 masseprocent af mindst ét surt middel valgt blandt elementerne af gruppen bestående af mineralsyrer og organiske syrer; og d) fra 1 til 98,6 masseprocent vand.

9. Sammensætning (Ci) ifølge krav 8, kendetegnet ved at masseforholdet mellem sammensætningen med formlen (II) og sammensætningen (C) er mindre end eller lig med 15:1 og større end eller lig med 1:1.

10. Anvendelse af sammensætningen (Ci) ifølge et hvilket som helst af kravene 8 eller 9 til rengøring af hårde overflader.

11. Fremgangsmåde til rengøring af en hård overflade, kendetegnet ved at den omfatter: mindst et trin ai) med at påføre sammensætningen (Ci) ifølge et af kravene 8 eller 9 på den hårde overflade, efterfulgt af mindst et trin bi) med at skylle den hårde overflade.