EP2714876A1

EP2714876A1 - Novel use of heptylpolyglycosides for solubilizing non-ionic surfactants in aqueous acidic cleaning compositions, and aqueous acidic cleaning compositions comprising same

Info

Publication number: EP2714876A1
Application number: EP12728679.7A
Authority: EP
Inventors: Marie-Françoise GAYRAL CHIRAC; Sébastien KERVERDO; Jérôme GUILBOT; Hervé Rolland
Original assignee: Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA
Current assignee: Societe dExploitation de Produits pour les Industries Chimiques SEPPIC SA
Priority date: 2011-05-27
Filing date: 2012-05-14
Publication date: 2014-04-09
Anticipated expiration: 2032-05-14
Also published as: CN103562367A; WO2012164190A1; US20140113850A1; DK2714876T3; FR2975703A1; US9080132B2; CN103562367B; EP2714876B1; FR2975703B1

Abstract

The subject matter of the invention is the use a composition (C) represented by formula (I): Ri-O-(G)p-H (I) in which G is a reducing sugar residue, Ri is a heptyl radical and p is a decimal number greater than 1, and less than or equal to 5, wherein said composition (C) consists of a mixture of compounds represented by the formulae (h), (l2), (l3), (U) and (l5): RrO-(G)i-H (h), RrO-(G)2-H (l2), RrO-(G)3-H (l3), RrO-(G)4-H (l4), RrO-(G)5-H (l5), in the respective molar proportions ai, a2, a3, a4 and a5, such that: the sum ai+ a2 + a3 + a4 + a5 is equal to 1 and that the sum ai + 2a2 + 3a3 + 4a4 + 5a5 is equal to p, as an agent for solubiliZing at least one non-ionic surfactant of formula (II): R-(O-CH(R')-CH₂)_n-(O-CH₂-CH₂)_m-O-H (II), in which R is an aliphatic radical containing from 8 to 14 carbon atoms, R' is a methyl or ethyl radical, n is greater or equal to 0 and less than or equal to 15, m is 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 acidic composition. The subject matter of the invention is also the compositions (Ci) comprising, for 100% of the weight thereof, from 0.2% to 40% by weight of at least one composition represented by formula (I); and from 0.2% to 80% by weight of at least one non-ionic surfactant of formula (II), and the use thereof for cleaning hard surfaces.

Description

BACKGROUND OF THE INVENTION The present invention relates to the use of an n-heptyl polyglycoside or a mixture of n-heptyl polyglycosides. The present invention relates to the use of an n-heptyl polyglycoside or a mixture of n-heptyl polyglycosides. for solubilizing non-ionic, low-foaming surfactants in compositions that are stable in an acid medium, especially used for the cleaning and scaling of hard surfaces.

By solubilizing agent is meant any substance or chemical composition capable of solubilizing in water or in aqueous phases, poorly soluble or insolubble chemical compounds in water or in these aqueous phases. The expression "poorly soluble or insoluble chemical compounds in water or in aqueous phases" designates compounds which, added to a predominantly or totally water phase, do not make it possible to obtain a totally clear solution or composition. is transparent, isotropic, homogeneous and stable at a desired temperature for a desired time. This solubility defect is in particular due to the chemical structure of the compound in question and / or the presence of acidic agents in the aqueous phase in which it is desired to solubilize said compound.

Among the poorly soluble or insoluble compounds in water, mention may be made of hydrophobic compounds such as, for example, oils, essential oils, fragrances, pigments, anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants. .

Solubilizing agents are particularly useful for preparing cleaning compositions for hard surface detergents for household or industrial applications.

Among the cleaning compositions for hard surface detergents for household or industrial applications, alkaline aqueous cleaning compositions, which are characterized by a pH above 7.0, and acidic aqueous cleaning compositions which are characterized by a pH less than or equal to 7.0.

Acidic aqueous cleaning compositions are used to clean hard surfaces, i.e. not only to remove soils from said hard surfaces, but also to descale said surface. Such compositions are particularly suitable for cleaning and descaling installations in the food industry, such as the dairy, bra and wineries industries. They are also suitable for cleaning and descaling household appliances such as dishwashers and coffee machines. These industrial installations and these appliances include circuits and tanks, which after a operating of a certain duration, are soiled with organic materials, such as for example fats, and more particularly phospholipids, proteins, tannins, and by mineral deposits of calcium salts, more particularly carbonates, phosphates and calcium oxalates.

These aqueous acidic cleaning compositions are also particularly suitable for cleaning and descaling the enamel of toilets, washbasins, baths and showers.

These aqueous acidic cleaning compositions are also used for the treatment of metal surfaces or cast or forged metal parts, to remove deposits formed by the corrosion or oxidation of metals, such as rust, oxide layers, green de-gris, or deposits of soot, limestone ..

These acidic aqueous cleaning compositions are also used in cleaning operations to remove concrete or cement residues, and for grease cleaning operations present in depth on concrete surfaces prior to any painting operation of said concrete surfaces.

These aqueous acidic cleaning compositions must not generate the formation of a large foam during the cleaning operation in the presence of the soil to be treated, show good wetting properties and also good detergency in acidic medium.

Due to their amphiphilic structure, the detergent surfactants used in acidic aqueous cleaning compositions intended for the hard surface detergent, give them the ability to remove soiling on hard surfaces and keep them in suspension, for then be eliminated during the rinsing step. These detergent surfactants may be of anionic, cationic, amphoteric or nonionic nature. Nonionic surfactants are particularly used for the preparation of hard surface detergent compositions in view of their foaming power, which is generally inferior to other ionic surfactants and also to their improved environmental characteristics.

Since these cleaning compositions comprise large amounts of acidic agents, it is difficult to dissolve large amounts of detergent surfactants to obtain a stable composition with no dephasing on storage.

To improve the solubility of poorly soluble or insoluble chemical compounds in water or in aqueous phases, those skilled in the art use solubilizing agents such as ethanol, xylenesulphonates and cumenesulphonates. Ethanol is an effective solubilizing agent but it however has a certain explosive character in acidic place. European patent application published under the number EP 0 524 075 A1 describes the effectiveness of acidic aqueous cleaning compositions comprising an anionic hydrotrope or solubilizing agent and nonionic surfactants. However, agents Anionic solubilizers, such as xylenesulfonates and cumenesulfonates, are not very effective for large amounts of surfactants and also do not exhibit the biodegradability properties required to comply with the new environmental regulations.

The alkylpolyglycosides are also described as solubilizing agents of nonionic defoaming surfactants.

International Publication WO 96/33255 A1 discloses defoamer compositions comprising a particular alkyl polyglucoside, the alkyl chain of which is constituted by the 2-ethyl hexyl radical and nonionic defoaming surfactants chosen from those comprising one or more groups chosen from mono-ethoxylated or poly-ethoxylated groups, mono-propoxylated or polypropoxylated groups. It is taught that 2-ethyl hexyl-chain alkylpolyglucosides are more effective than hexyl-chain alkyl polyglycosides in solubilizing non-ionic defoaming surfactants.

International Publication WO 99/21948 A1 discloses limpid and stable compositions with high alkaline concentrations, whose foaming properties are controlled, containing a large quantity of nonionic surfactants based on alkylene oxide and a hexyl glycoside as agent. hydrotrope or solubilizer. These compositions are characterized by good wetting power and good detergent properties of hard surfaces. It is taught that hexyl glycosides, and more particularly n-hexyl polyglucoside, are solubilizing agents for nonionic surfactants in a strongly alkaline medium and that n-hexyl glucoside is characterized by a solubilizing power of a nonionic surfactant. whose structure results from the ethoxylation with 4 moles of ethylene oxide of a mixture of linear and branched alcohols, with a linear alcohol content of about 80%, comprising from 9 to 11 carbon atoms , higher than 2-ethyl hexyl glucoside and Exxal 7 glucoside in the presence of soda amounts of between 10% and 40%.

The US patent published under the number US 5,205,959 describes a mixture comprising, for 100% of its mass:

(i) from 1.5% to 30% by weight of alkylpolyglycosides in which the alkyl chain contains from 6 to 12 carbon atoms and whose degree of polymerization is between 1 and 2,

(ii) from 5% to 70% by weight of alcohols having from 16 to 20 carbon atoms, branched in position 2, polyethoxylated, with a number of ethylene oxide units of between 5 and 9, the hydroxyl function of which terminal is linked by an ether function with an alkyl chain having from 4 to 8 carbon atoms, (iii) from 5% to 70% by weight of alcohols, having an even number of carbon atoms of between 12 and 20, polyethoxylated with a number of ethylene oxide units of between 2 and 5.

The Applicant has therefore endeavored to develop a new technical solution, consisting of the use of an n-heptyl polyglycoside or a mixture of n-heptyl polyglycosides, having a non-flammable character and non-ecotoxic and biodegradable properties, for solubilizing nonionic surfactants in stable aqueous compositions in an acid medium, especially used for cleaning and hard surface scaling.

Therefore, according to a first aspect, the subject 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 a 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 formulas (h), (l ₂ ), (l ₃ ), (U) and (l ₅ ):

R O- (G) ₂ -H (l ₂ )

R O- (G) ₃ -H ( _1-3 )

R O- (G) ₄ -H (l ₄ )

R O- (G) ₅ -H (1 to ₅ ),

in the respective molar proportions:

ai for the compound of formula (h),

a ₂ for the compound of formula (I ₂ ),

a ₃ for the compound of formula (I ₃ ),

a ₄ for the compound of formula (I ₄ ) and

to ₅ for the compound of formula (I ₅ ) such that:

the sum ai + a ₂ + a ₃ + a ₄ + a ₅ is equal to 1 and that

the sum ai + 2a ₂ + 3a ₃ + 4a ₄ + 5a ₅ is equal to p,

as solubilizing agent of at least one nonionic surfactant of formula (II):

R- (0-CH (R ') - CH ₂₎ _n - (0-CH ₂ -CH ₂₎ _m -0-H (II) wherein R represents an aliphatic hydrocarbon radical, saturated or unsaturated, linear or branched, having from 8 to 14 carbon atoms,

R 'represents a methyl or ethyl radical, and preferably the n-heptyl radical n represents an integer greater than or equal to 0 and less than or equal to 15, m represents an integer 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 acidic composition.

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

By reducing sugar is meant in the composition represented by the formula (I), saccharide derivatives which do not have in their glycosidic bonding structures established between an anomeric carbon and oxygen of an acetal group as defined in the reference work: "Biochemistry", Daniel Voet / Judith G. Voet, p. 250, John Wyley & Sons, 1990. The oligomeric structure (G) _p, may be in any form of isomerism, whether optical isomerism, geometric isomerism or position isomerism; it can also represent a mixture of isomers.

By solubilizing agent is meant any substance or chemical composition capable of solubilizing in water or in aqueous phases, chemical compounds poorly soluble or insoluble in water or in these aqueous phases. The expression "poorly soluble or insoluble chemical compounds in water or in aqueous phases" designates compounds which, added to a predominantly or totally water phase, do not make it possible to obtain a totally clear solution or composition. is transparent, isotropic, homogeneous and stable at a desired temperature for a desired time.

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

According to a particular aspect of the present invention, the subject of the present invention is the use as defined above for which, in the formula (I), p represents a decimal number greater than or equal to 1, 05 and less than or equal to 2 5.

According to another particular aspect of the present invention, the subject of the invention is the use as defined above for which, in formula (I), G represents the residue of a reducing sugar and chosen from the residues of glucose, xylose and arabinose, and more particularly chosen from the remains of glucose or xylose.

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

HO- (G) -H (III)

wherein G represents the residue of a reducing sugar, with a molar excess of n-heptanol of formula R1 -OH, to form a mixture of compounds of formula (I) as defined above and n-heptanol;

a step B) of removing n-heptanol from said mixture obtained in step A).

Stage A) is generally carried out in a reactor in the presence of an acidic catalyst system, by controlling the stoichiometric ratio between the two reactants, and more particularly by introducing a molar excess of n-heptanol, and with mechanical stirring in predetermined temperature and partial vacuum conditions, for example at a temperature between 70 ° C and 130 ° C and under a partial vacuum between 300 mbar (3.10 ⁴ Pa) and 20 mbar (2.10 ³ Pa). By acidic catalytic system are meant strong acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hypophosphorous acid, methanesulfonic acid, (para-toluene) sulfonic acid , (trifluoromethane) sulfonic acid, or ion exchange resins.

Stage B) of removal of the n-heptanol from said mixture obtained at the end of stage A) is generally carried out according to methods known to those skilled in the art, such as, for example, distillation, distillation on thin film, molecular distillation or solvent extraction.

Such a preparation process can be completed, if necessary or if desired, by neutralization, filtration and bleaching operations.

In the use as defined above, by linear or branched, saturated or unsaturated, hydrocarbon-based aliphatic radical comprising from 8 to 14 carbon atoms, optionally substituted with one or more hydroxyl groups, is designated for the radical R in the formula (II):

Linear alkyl radicals, for example the n-octyl, n-decyl, n-dodecyl or n-tetradecyl radicals;

The radicals resulting from the isoalkanols of formula (1):

(CH ₃ ) (CH ₃ ) CH- (CH ₂ ) _r CH ₂ -OH (1) in which r represents an integer between 4 and 10, for example the isooctyl, isononyl, isodecyl, isoundecyl, isododecyl and isotridecyl radicals; or isotetradecyl;

The 2-ethyl hexyl radical or the branched alkyl radicals derived from Guerbet alcohols of formula (2):

CH (C _s H ₂ _s _{+ 1} ) (C _t H _{2t + 1} ) -CH ₂ -OH (2)

in which t is an integer from 4 to 10, s is an integer from 2 to 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, 2-hexyl octyl radicals; or the radicals derived from homologues of Guerbet alcohols, for example the 2-propyl heptyl radical.

Radicals derived from branched alcohols of formula (3):

CH ₃ - [CH (R ")] _{z -} CH ₂ -OH (3) in which R" represents a hydrogen atom or a methyl radical, and z represents an integer greater than or equal to 3 and less than or equal to 15.

Unsaturated linear radicals such as the undecenyl, dodecenyl or tetradecenyl radicals, for example the unsaturated radicals 10-undecenyl, 4-dodecenyl or 5-dodecenyl;

Saturated or unsaturated, linear or branched aliphatic radicals comprising from 8 to 14 carbon atoms substituted with one or two hydroxyl groups, such as the octyl hydroxyl, hydroxydecyl or hydroxydodecyl radicals, for example the 8-hydroxy octyl radicals, hydroxy decyl or 12-hydroxy dodecyl.

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

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

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

The compounds of formula (II) for which R 'represents a methyl or ethyl radical and n represents an integer greater than or equal to 1 are prepared according to a process comprising if necessary a step a) of alkoxylation by reaction of n molar equivalents d an alkylene oxide or an alkylene carbonate with one molar equivalent of alcohol of formula (IV):

R-OH (IV)

in which the radical R represents a linear or branched, saturated or unsaturated, hydrocarbon-based aliphatic radical containing from 8 to 14 carbon atoms, optionally substituted with one or more hydroxyl groups, as defined above, to obtain the alkoxylated alcohol of formula (V):

R- (O-CH (R ') - CH ₂ ) _n -O-H (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 ethylene carbonate.

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

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

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

The alkoxylation reactions of step a) and of ethoxylation of steps a ') and b), as defined above, are generally carried out in a reactor in the presence of a basic catalyst such as hydroxides. alkali metals, such as, for example, sodium hydroxide, potassium hydroxide, alkali metal alkoxides, for example sodium or potassium methoxide, sodium or potassium tertiobutylate, Lewis bases such as triphenylphosphine, coordination catalysts, for example organometallic complexes based on cobalt and / or zinc, or in the presence of an acidic catalyst such as a Lewis acid such as, for example, boron trifluoride, aluminum trichloride or tin tetrachloride.

Such processes for the preparation of the compounds of formula (II) can be completed, if necessary or if desired, by neutralization, demineralization, filtration and bleaching operations.

According to another particular aspect of the present invention, the subject of the present invention is the use as defined above, in which the mass ratio between said nonionic surfactant of formula (II) and said composition (C) is lower or equal to 15/1 and greater than or equal to 1/1.

According to another aspect, the subject of the invention is a composition (Ci) comprising for 100% of its mass:

a) from 0.2% to 40% by weight, more particularly from 0.2% to 20% by weight, and even more particularly from 0.2% to 15% by weight of a composition (Ci) comprising for 100% of its composition; mass : 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 a heptyl radical and

p represents a decimal number greater than 1, and less than or equal to 5,

R O- (G) ₂ -H (l ₂ )

RrO- (G) ₃ -H (la)

R O- (G) ₄ -H (U)

in the respective molar proportions:

ai for the compound of formula (h),

a ₂ for the compound of formula (I ₂ ),

a ₃ for the compound of formula (I ₃ ),

a ₄ for the compound of formula (I ₄ ) and

to ₅ for the compound of formula (I ₅ )

as :

the sum ai + a ₂ + a ₃ + a ₄ + a ₅ is equal to 1 and that

the sum ai + 2a ₂ + 3a ₃ + 4a ₄ + 5a ₅ 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 nonionic surfactant of formula (II ):

R - (O-CH (R ') - CH ₂ ) _n - (O-CH ₂ -CH ₂ ) _m -O-H (II) in which R represents a linear or branched, saturated or unsaturated hydrocarbon aliphatic radical, having 8 to 14 carbon atoms, R 'is methyl or propyl, n is an integer greater than or equal to 0 and less than or equal to 15, m is an integer 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 mass and even more particularly from 1% to 35% by weight of at least one acidic agent chosen from 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 acidic agents in the composition (Ci) which is the subject of the present invention, mention may be made of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and hypophosphorous acid, phosphorous acid, hypochlorous acid, perchloric acid, carbonic acid, boric acid, manganic acid, permanganic acid, chromic acid, periodic acid, iodic acid, hypoiodous acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid.

Among the organic acids that are particularly chosen as acidic agents in the composition (C 1) which is the subject of the present invention, mention may be made of formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, lactic acid and the like. 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-ethylhexanoic acid, capric acid, caproic acid, cresylic acid, dodecylbenzene sulfonic acid, peracetic acid, monochloroacetic acid, acid gluconic.

According to a more particular aspect, in the composition (Ci) which is the subject of the present invention, the acidic agent is chosen from hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and 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 one particular aspect, in the composition (Ci) which is the subject of the present invention, the mass ratio between the compound of formula (II) and said composition (C) is less than or equal to 15/1 and greater than or equal to 1/1 .

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

The expression "for cleaning hard surfaces" means any action intended to allow the removal of dirt present on surfaces made of various materials. Examples of hard surfaces are floors, vertical surfaces, tiles, household appliances such as dishwashers and coffee machines, taps, sinks, washbasins, bathtubs and showers. , toilets, urinals, storage tanks for food or agricultural products, vehicles (automobiles, motorcycles, trucks, ...), industrial installations such as heat exchangers, seawater evaporators, pipes, heating circuits, cooling circuits, public works equipment contaminated by cement or concrete such as concrete mixers, cement and concrete routers, metal surfaces and cast or forged metal parts.

The materials constituting these hard surfaces are for example glass (soda-lime, fluorocalcic, borosilicate, crystal), enamel, porcelain, faience, ceramics, polycarbonate plastics, polypropylenes, stainless steel, silver, nickel copper, aluminum and more particularly highly oxidized aluminum, brasses and copper alloys, precious metals such as gold, silver, platinum, wood, synthetic resins, glass-ceramic, linoleum, and can be coated with paints, varnishes.

Examples of soils present on these hard surfaces and to be eliminated by cleaning include, for example, food residues such as, for example, deposits caused by dairy products and sweetened food residues, fats such as, for example, phospholipids, proteins, tannins, algae, light and heavy hydrocarbons, burnt residues, soap residues, germs, carbonaceous traces such as soot, mineral deposits of calcium salts such as calcium carbonate, phosphate of calcium or calcium oxalate, scale, limestone, metal oxide deposits such as rust, verdigris, glue residues, mortar residues, cement residues, lime residues.

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

The composition (Ci) which is the subject of the present invention may be applied directly by dipping, spraying or spraying on the surface to be cleaned or by means of any type of support intended to be brought into contact with the hard surface to be cleaned. (paper, wipe, textile) comprising said composition (Ci).

The composition (Ci) object of the present invention, used to clean hard surfaces, generally has a pH less than or equal to 7, more particularly less than or equal to 6, more particularly less than or equal to 4 and even more particularly less than or equal to to 2.

In general, the composition (Ci) which is the subject of the present invention also comprises ingredients usually used in the field of cleaning resurfaces, such as nonionic surfactants, cationic surfactants, amphoteric surfactants, cationic polymers, nonionic polymers, thickeners, enzymes, bleaches, anti-corrosion agents, solvents, preservatives, fragrances, dyes, repellents, oxidizing agents. As examples of nonionic surfactants present in the composition (Ci) which is the subject of the present invention, mention may be made of:

Block copolymers of ethylene oxide and of propylene oxide, and particularly the block copolymers of ethylene oxide and propylene oxide sold under the trade name PLURONIC ™ by BASF, as PLURONIC ™ PE 6100 and PLURONIC ™ PE 6200,

Defoaming nonionic surfactants of formula (A-1):

R ₁ -X - [(CH ₂ -CH (CH ₃ ) -O) u- (CH ₂ -CH ₂ -O) vY] w (Ai) in which:

R-irepresente a linear or branched, saturated or unsaturated, hydrocarbon-based aliphatic radical containing from 6 to 18 carbon atoms,

X represents a nitrogen atom or an oxygen atom,

v represents an integer between 1 and 50,

u represents an integer between 1 and 50,

w represents an integer equal to 1 if X represents an oxygen atom, and w represents an integer equal to 1 or 2 if X represents a nitrogen atom.

Y represents a blocking functional group chosen from the group consisting of linear alkyl radicals comprising from 4 to 8 carbon atoms, for example the butyl radical, the benzyl radical or a butylene oxide group.

Among the non-ionic defoaming surfactants of formula (A-i), mention may be made of the products marketed under the trade name TERGITOL ™ by Dow Chemical, such as for example the TERGITOL ™ L61 E and the TERGITOL ™ L64E

Low-foaming nonionic surfactants of formula (A ₂ ):

R ₂ -0- (S) _q -H (A ₂ )

in which :

S represents the remainder of a reducing sugar chosen from the group consisting of glucose, xylose and arabinose,

R ₂ represents a saturated hydrocarbon radical, linear or branched, containing 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 examples of low foaming nonionic surfactants of formula (A ₂ ) present in the composition (Ci) which is the subject of the present invention, mention may be made of hexyl polyglucosides and 2-ethyl polyglucosides.

As an example of amphoteric surfactants present in the composition (Ci) which is the subject of the present invention, mention may be made of the sodium β-alanine, N- (2-carboxyethyl) -N- (2-ethylhexyl) sold under the trade name TOMAMINE®. AMPHOTERIC 400 SURFACTANT. Examples of thickening agents present in the composition (Ci) which is the subject of the present invention include polymeric hydrocolloids of vegetable or biosynthetic origin, such as xanthan gum, scleroglucan, tragacanth, agar-agar, carrageenates, alginic acid, alginates and galactomannans; cellulose and its derivatives such as hydroxypropylmethyl cellulose; dextrin; casein; pectins; gelatin; chitosan; polyethylene glycols having a molecular weight of between 4000 and 35000 grams per mole; ethoxylated ethylene glycol derivatives having a molecular weight of between 300,000 and 7,000,000 grams per mole.

As examples of thickening agents present in the composition (Ci) which is the subject of the present invention, mention may be made of polymeric thickeners such as homopolymers of acrylamide, or copolymers of acrylamide and the sodium salt of 2-acrylamido -2-methylpropanesulphonate, such as for example the thickeners marketed by the company SEPPIC under the brand name of SOLAGUM ™.

Examples of thickening agents present in the composition (C 1) which is the subject of the present invention include inorganic thickeners, for example clays, hectorite, saponite, sauconite, vermiculite or colloidal silica.

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

Examples of abrasive agents present in the composition (Ci) which is the subject of the present invention include mention of materials of natural origin, such as, for example, wood chips or cores, inorganic abrasive materials such as oxides, quartz, diatomaceous earth, colloidal silica dioxides, organic abrasive materials such as polyolefins such as polyethylenes and polypropylenes, polystyrenes, acetonitrile-butadiene-styrene resins, melamines, phenolic resins, epoxy resins polyurethane resins.

The abrasive agents present in the composition (Ci) which is the subject of the present invention are used in amounts of between 5.0% and 30% by weight.

As examples of solvents present in the composition (Ci) which is the subject of the present invention, mention may be made of isopropyl alcohol, benzyl alcohol, 1,3-propanediol, chlorinated solvents, acetone and methyl ethyl ether. methyl isobutyl ether, butyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, aromatic solvents, isoparaffins, isododecane, ethyl lactate, butyl lactate, terpene solvents, rapeseed methyl esters, sunflower methyl esters, propylene glycol n-methyl ether, dipropylene glycol n-methyl ether, tripropylene glycol n-methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol mono methyl ether acetate, propylene glycol di acetate, propylene glycol phenyl ether, ethylene glycol phenyl ether, dipropylene glycol dimethyl ether.

As examples of solvents present in the composition (Ci) which is the subject of the present invention, mention may be made more particularly of the group consisting of propylene glycol n-methyl ether, dipropylene glycol n-methyl ether and 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, methyl esters of sunflower.

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

at least one step a- of applying the composition (Ci) as defined above to said hard surface, followed by at least one step b- of rinsing said hard surface.

In step a- of the cleaning method that is the subject of the invention, the composition (Ci) is applied to the surface comprising the soils to be cleaned by any means such as, for example, in a full bath, by dipping, by spraying, by application by by means of a support consisting of synthetic or natural textile fibers, woven or nonwoven, or paper, previously impregnated with said composition (Ci).

In step b- of the cleaning method that is the subject of the invention, the rinsing of the hard surface on which the composition (Ci) has been applied during step a- is carried out in full bath or by spraying water. .

Step b- of the cleaning method that is the subject of the invention may 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 limiting it. 1) Preparation of compositions represented by formula (I) and evaluation of their surfactant properties.

1.1) Preparation of n-heptylpolyglucosides

2.7 molar equivalents of n-heptanol are introduced into a jacketed glass reactor, in which a coolant circulates, and provided with an effective stirring, at a temperature of 40 ° C. A molar equivalent of anhydrous glucose is then gradually added to the reaction medium to allow it to be homogeneously dispersed, or 0.15%, with the aid of 98% and 0.15% by weight of hypophosphorous acid. 50% for 100% of the mass constituted by the sum of the mass glucose and the mass of n-heptanol are introduced into the homogeneous dispersion prepared beforehand. The reaction medium is placed under a partial vacuum of about 18x10 ³ Pa (180 mbar), and maintained at a temperature of 100 ° C-105 ° C for a period of 4 hours with evacuation of the water formed by means of a distillation assembly. The reaction medium is then cooled to 85 ° C.-90 ° C. and neutralized by addition of 40% sodium hydroxide to bring the pH of a 5% solution of this mixture to a value of approximately 7.0. The reaction medium thus obtained is then drained at a temperature of 70 ° C. and filtered to remove unreacted glucose grains. The filtrate is then introduced into a jacketed glass reactor, in which circulates a heat transfer fluid, provided with an effective stirring and a distillation device. The excess of heptanol is then removed by distillation at a temperature of 120 ° C. under partial vacuum of between about 10 ⁴ Pa (100 mbar) and 5 × 10 ³ Pa (50 mbar). The reaction medium thus distilled is immediately diluted by the addition of a quantity of water so as to reach a reaction medium concentration of about 60%. After homogenization for 30 minutes at a temperature of 50 ° C, the composition (X ₀ ) obtained is drained.

The analytical characteristics of the composition (X ₀ ) thus obtained comprising n-heptylpolyglucosides are collated in Table 1 below.

Tabeau 1

1.2) Evaluation of the foaming properties of n-heptylpolyglucosides

The foaming properties of the composition (X ₀ ) of n-heptylpolyglucosides, obtained according to the process previously described, as well as the compositions (Xi), (X ₂ ), (X ₃ ), and (X ₄ ) of the state of the technique, were evaluated according to a static method by bubbling nitrogen.

- Composition (X-i): Composition of n-hexylpolyglucosides sold under the brand name AG 6206 ™ by the company Akzo Nobel;

Composition (X ₂ ): Composition of 2-ethylhexylpolyglucosides sold under the trade name AG 6202 ™ by the company Noble Akzo; Composition (X ₃ ): Composition of n-octylpolyglucosides / n-decylpolyglucosides sold under the trade name SIMULSOL ™ SL8 (composition X ₃ ) by the company SEPPIC;

Composition (X4): sodium xylene sulphonate (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 the evaluation of foaming power

The foam is formed by introducing a determined volume of nitrogen into a fixed concentration surfactant solution and in the presence of a fixed amount of sodium hydroxide at a specific temperature. The volume of foam generated by the introduction of the volume of nitrogen is measured at the end of the introduction of said volume of nitrogen, then at a duration of 30 seconds, then 120 seconds at the end of the end of the introduction of the nitrogen volume. 1.2.2) Experimental protocol

50 cm ³ of a solution at 5 mg / cm ³ in dry extract of the tested compositions are introduced into a thermostatically graduated test tube of 250 cm ³ and a quantity of 1 2.5 g of sodium hydroxide. The measurements were carried out at 20 ° C and 60 ° C. A gas distribution finger with porosity 3 (Ref. Corning Pyrex 853-1) is positioned such that the end of the sintered tip is one centimeter from the bottom of the specimen. The nitrogen flow rate is then precisely adjusted to 50 liters per hour and the bubbling is carried out for 15 seconds. After this time, the arrival of the nitrogen is cut off and the experimenter notes the initial foam volume as well as the foam volume after 30 seconds and 120 seconds. At least two tests leading to equivalent results were performed in different test pieces for the same surfactant solution.

1.2.3) Expression of results

The results of the volume of foam observed in the sample initially graduated, then at 30 seconds and at 120 seconds are expressed or cm ³ . They are recorded in the following tables:

Table 2: Foaming power at 20 ° C

Table 3: Foaming power at 60 ° C

1.2. 4) Analysis of the results.

The composition (X ₀ ) is characterized by the generation of a very unstable foam at 20 ° C, since the foam volume decreases in 30 seconds by 95% of its initial value, against 92.3% for the composition (Χ ^ 25% for the composition (X ₂ ) and 12% for the composition (X ₃ ).

At 60 ° C., the composition (X ₀ ) of n-heptylpolyglucosides is also characterized by the generation of a very unstable foam since the volume of foam decreases in 30 seconds by 100% of its initial value, against 57.1% for the composition (X ₂ ) and 14% for the composition (X ₃ ). At 60 ° C, the composition (X ₀ ) by the generation of a foam volume lower than that generated by the compositions of the state of the art.

1.3) Evaluation of the solubilizing properties of n-heptylpolyglucosides in an acidic medium

The solubilizing properties in acidic medium of the composition (X ₀ ) were evaluated compared with compositions (Xi), (X ₂ ), (X ₃ ) and (X ₄ ) of the state of the art as previously described according to the evaluation method described below for a nonionic surfactant of formula (II), in the presence of different acidic agents and at different concentrations of said acidic agents.

1.3.1) Principle of the method of evaluation of the solubilizing power in acidic medium This method was able to determine the solubilizing potency of a surfactant composition in acid medium for a nonionic surfactant insoluble in acidic medium relative to surfactant compositions of the state of the art.

1.3.2) Experimental protocol

A quantity of 5 g of dry matter of a nonionic surfactant (Ti) to be solubilized, a quantity of yi grams of acidic agent, is introduced into a 200 cm ³ glass flask so as to obtain the desired concentration of dry matter of said acid agent and a quantity of complementary distilled water so as to obtain a solution of 100 cm ³ . A magnetized magnetic bar is inserted into the glass bottle which is then placed with magnetic stirring at a speed of 100 rpm for a period of 3 minutes at a temperature of 20 ° C. The solubilizing surfactant composition (Xi) to be tested is then progressively introduced so as to obtain a clear visual appearance for the medium present in the glass vial.

1.3.3) Expression of results

When the visual appearance of the solution present in the glass vial is clear, the experimenter notes the amount (in grams) of the added solubilizing composition (Xi) that was required to obtain this clear appearance, and converts it by calculation. in the amount Xi (in grams) of dry matter of the solubilizing agent included in the composition (Xi).

1.3.4) Characterization of the solubilizing power in phosphoric acid medium of the compositions (Xn) (X (ΧΛ (X ^) and (ΧΛ

The experimental protocol described in paragraph 1.3.2) above is used for each of the compositions (X ₀ ) (Xi), (X ₂ ), (X ₃ ) and (X ₄ ), with the composition of polyethoxylated alcohols ( ΤΊ), prepared by the reaction between a molar equivalent of a mixture of alcohols comprising, for 100% of its mass, 85% by weight of n-decanol and 15% by weight of n-dodecanol with 4 molar equivalents of oxide ethylene in the presence of potassium hydroxide as a basic catalyst. The experimental measurements were carried out in the presence of different amounts of phosphoric acid in solution at 85% by weight, so as to obtain a mass content of 10% and 30% of phosphoric acid in dry matter. The quantities x, of the various solubilizing compositions (X ₀ ), (X ₁ ), (X ₂ ), (X ₃ ) and (X ₄ ) added necessary for obtaining a clear solution, were noted by the Experimenter in each case and reported 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) Characterization of the solubilizing power in nitric acid medium of the compositions (Xn) (Xi), (ΧΛ (Χ _Λ ) and (Χ _Λ )

The experimental protocol described in the preceding section 1.3.2) is used for each of the compositions (X ₀ ) (X ₁ ), (X 2), (X ₃ ) and (X 4), with the composition of polyethoxylated alcohols (ΤΊ) . The experimental measurements were carried out in the presence of different amounts of nitric acid in solution at 65% by mass, so as to obtain mass contents of 10% and 20% of nitric acid in dry matter. The quantities x, of the different solubilizing compositions (X ₀ ), (X1), (X2), (X3) and (X4) necessary for obtaining a clear solution, were recorded by the experimenter in each case and reported 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) Characterization of the solubilizing power in citric acid medium of the compositions (Xn), (X-, (Χ), (Xs) and (X4).

The experimental protocol described in the preceding paragraph 1.3.2) is used for each of the compositions (X ₀ ) (X ₁ ), (X 2), (X ₃ ) and (X 4), with the composition of polyethoxylated alcohols (ΤΊ). . The experimental measurements were carried out with a mass content of 10% of citric acid in dry matter. The quantities x of the various solubilizing compositions (X ₀ ), (X ₁ ), (X 2), (X ₃ ) and (X 4) necessary for obtaining a clear solution were recorded by the experimenter in each case. and recorded in Table 8.

Table 8: (Citric acid content: 10%)

1.3.7) Analysis of the results obtained

The comparison between the solubilizing performances observed for the compositions characterized by a low foaming power, namely the compositions

(X ₀ ), (Xi) and (X ₄ ), shows that for a quantity of 10% by mass of phosphoric acid, a quantity of 1.37 g of the composition (X ₀ ) is necessary to solubilize 5 g of the surfactant composition non-ionic (ΤΊ), while 1.83 g of the composition (X ^ and that

1.42 g of the composition (X ₄ ) are necessary to obtain the same result.

Similarly, in the presence of an amount of 10% by weight of nitric acid, a quantity of 0.76 g of the composition (X ₀ ) is necessary to solubilize 5 g of the nonionic surfactant composition (ΤΊ), whereas 2 17 g of the composition (X) and 1.72 g of the composition (X ₄ ) are necessary to obtain the same result, respectively corresponding to mass quantities of 185% and 126% higher than that used for the composition. (X ₀ ).

The com parison between the solubilizing performance observed for the compositions (X ₀₎ and (X ₂₎ shows that for an amount of 10% by mass of phosphoric acid, a amount of 1, 37g of the composition (X ₀₎ is necessary to solubilize 5g of the nonionic surfactant (Ti) composition, while a quantity of 1, 99g of the composition (X ₂ ) is necessary to obtain the same result, ie a mass quantity greater than 45.2% of that used for the composition (X0).

Similarly, in the presence of a quantity of 10% by weight of nitric acid, an amount of 0.76 g of the composition (X ₀ ) is necessary to solubilize 5 g of the nonionic surfactant composition (ΤΊ), while a quantity of 1.13 g of the composition (X ₂ ) is necessary to obtain the same result, ie a mass quantity greater than 48.6% than that used for the composition (X ₀ ).

1.4 Conclusions

The composition (X ₀ ) comprising n-heptylpolyglucosides, characterized by low foaming properties and environmental properties responding to changes in the regulations, shows improved solubilizing properties in acidic medium compared to solubilizing agents known in the state of the art. technical. 2) Examples of aqueous acidic cleaning compositions

2.1) Metal surface remover

2.1.1) Formula

(1) HORDAPHOS ™ MDGB: phosphoric ester marketed by Clariant as a corrosion inhibiting agent

2.1.2) Preparation of the detergent composition and acid stripper

Each ingredient is introduced successively into a mixing tank with moderate mechanical stirring, at room temperature until a homogeneous and clear composition is obtained. Stirring is maintained for 30 minutes at 20 ° C. The composition obtained has a measured pH value of less than 1 and is clear and homogeneous after storage for a period of one month at 40 ° C.

2.1.3) Cleaning process involving the composition according to the invention The composition prepared in the preceding paragraph is diluted to 3% in water and the solution thus obtained is poured into a vessel of suitable size. The metal parts are then soaked for 30 minutes, then rinsed with water.

2.2. Aluminum surface cleaner

2.2.1) Formula

(2) SIMULSOL ™ OX1309L: detergent surfactant composition marketed by the company SEPPIC, comprising polyethoxylated alcohols resulting from the reaction of a molar equivalent of an alcohol marketed under the trade name EXXAL ™ 13 with 9 molar equivalents of 'ethylene.

2.2.2) Preparation of the cleaning composition of aluminum surfaces

Each ingredient is introduced successively into a mixing tank with moderate mechanical stirring, at room temperature until a homogeneous and clear composition is obtained. Stirring is maintained for 30 minutes at 20 ° C. The resulting composition has a measured pH value of less than 1.0 and is clear and homogeneous after storage for a period of one month at 40 ° C.

2.2.3) Cleaning process involving the composition according to the invention

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.

2.3. Rinse aid for industrial dishwashers 2.3.1) Formulation

Ingredients Mass content

SIMULSOL ™ NW 900 ⁽³⁾ 15%

Composition (X ₀ ) 5%

Citric acid anhydrous 17%

Isopropanol 20%

Water Qs 100%

(3) SIMULSOL ™ NW 900: detergent surfactant composition sold by the company SEPPIC, comprising polyethoxylated alcohols resulting from the reaction of one molar equivalent of an alcohol sold under the trade name EXXAL ™ 10 with 9 molar equivalents of oxide ethylene.

2.3.2) Preparation of the acidic cleaning composition for industrial dishwashers.

Each ingredient is introduced successively into a mixing tank with moderate mechanical stirring, at room temperature until a homogeneous and clear composition is obtained. Stirring is maintained for 30 minutes at 20 ° C. The composition obtained has a pH measured at a value of 1, 3 and is clear and homogeneous after storage for a period of one month at 40 ° C.

2.2.3) Cleaning process involving the composition according to the invention

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

Claims

1 - Use of a Composition (C) represented by the Formula (I)

in which G represents the remainder of a reducing sugar,

R 1 represents a heptyl radical and preferably the n-heptyl radical;

p represents a decimal number greater than 1, and less than or equal to 5,

R O- (G) ₂ -H (l ₂ )

R O- (G) ₃ -H ( _1-3 )

R O- (G) ₄ -H (l ₄ )

R O- (G) ₅ -H (1 to ₅ ),

in the respective molar proportions:

ai for the compound of formula (h),

a ₂ for the compound of formula (I ₂ ),

a ₃ for the compound of formula (I ₃ ),

a ₄ for the compound of formula (I ₄ ) and

to ₅ for the compound of formula (I ₅ )

as :

the sum ai + a ₂ + a ₃ + a ₄ + a ₅ is equal to 1 and that

the sum ai + 2a ₂ + 3a ₃ + 4a ₄ + 5a ₅ is equal to p,

as solubilizing agent of at least one nonionic surfactant of formula (II):

R - (O-CH (R ') - CH ₂ ) _n - (O-CH ₂ -CH ₂ ) _m -O-H (II) in which R represents a linear or branched, saturated or unsaturated hydrocarbon aliphatic radical, having from 8 to 14 carbon atoms,

R 'represents a methyl or ethyl radical,

n represents an integer greater than or equal to 0 and less than or equal to 15,

m represents an integer 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 acidic composition. 2 - Use as defined in claim 1, characterized in that in formula (I), p represents a decimal number greater than or equal to 1, 05 and less than or equal to 2.5. 3 - Use as defined in one of claims 1 or 2, characterized in that in formula (I), G represents the residue of a reducing sugar and chosen from the residues of glucose, xylose and arabinose. 4 - Use as defined in any one of claims 1 to 3, characterized in that in formula (II), the radical R represents a radical selected from the octyl, decyl, dodecyl, tetradecyl, 2-ethyl hexyl radicals , 2-butyl octyl, 2-butyl decyl, 2-hexyl octyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl or 2-propyl heptyl.

5 - Use as defined in any one of claims 1 to 4, characterized in that in formula (II), n represents an integer 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.

6 - Use as defined in any one of claims 1 to 5, characterized in that in formula (II), m represents an integer greater than or equal to 1 and less than or equal to 9, more particularly greater than or equal to at 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.

7 - Use as defined in any one of claims 1 to 6, characterized in that the mass ratio between said nonionic surfactant of formula (II) and said composition (C) is less than or equal to 15/1 and greater than or equal to 1/1.

Composition (Ci) comprising for 100% of its mass

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,

R 1 represents a heptyl radical and preferably the n-heptyl radical;

p represents a decimal number greater than 1, and less than or equal to 5,

R O- (G) ₂ -H (l ₂ )

RrO- (G) ₃ -H (la)

R O- (G) ₄ -H (U)

RrO- (G) ₅ -H Os), in the respective molar proportions:

ai for the compound of formula (h),

a ₂ for the compound of formula (I ₂ ),

a ₃ for the compound of formula (I ₃ ),

a ₄ for the compound of formula (I ₄ ) and

to ₅ for the compound of formula (I ₅ )

as :

the sum ai + a ₂ + a ₃ + a ₄ + a ₅ is equal to 1 and that

the sum ai + 2a ₂ + 3a ₃ + 4a ₄ + 5a ₅ is equal to p,

b) from 0.2% to 80% by weight of at least one nonionic surfactant of formula (II):

c) from 1% to 50% by weight of at least one acidic agent selected from the group consisting of mineral acids and organic acids; and

d) from 1% to 98.6% by weight of water.

9 - Composition (Ci) as defined in claim 8, characterized in that the mass ratio between the compound of formula (II) and said composition (C) is less than or equal to 15/1 and greater than or equal to 1 / 1.

- Use of the composition (Ci) as defined in any one of claims 8 or 9 for cleaning hard surfaces.

1 1 - Method for cleaning a hard surface, characterized in that it comprises:

at least one step a1) of applying the composition (Ci) as defined in one of claims 8 or 9 to said hard surface, followed by

at least one step bi) rinsing said hard surface.