Patent Grant
7923428
This application is an application under 35 U.S.C. Section 371 of International Application Number PCT/FR2003/003841 filed on Dec. 19, 2003.
A subject matter of the present invention is a cleaning or rinsing composition intended for the treatment of industrial, domestic or communal hard surfaces, in particular of ceramic, tiling, window, metal, melamine, formica or plastic type, targeted at conferring on the latter in particular persistent antideposition and/or antiadhesion properties with regard to soiling substances; in addition, it can contribute antistatic, gloss or slip-resistance properties to the latter.
A subject matter of the invention is more particularly a cleaning or rinsing composition intended for the treatment of a hard surface, which composition is capable of conferring, on the latter, persistent antideposition and/or antiadhesion properties with regard to soiling substances, so as to prevent the subsequent presence of marks due in particular:
A solution to this problem was provided in EP-A-1 196 527, EP-A-1 196 528 and EP-A-1 196 523 by deposition on the surface, via a cleaning or rinsing formulation, of a water-soluble, amphoteric organic copolymer derived from a cationic monomer and from an anionic or potentially anionic monomer in an amount sufficient to render the surface hydrophilic (or to improve its hydrophilicity, in order to obtain a contact angle which is as low as possible between the hard surface to be treated and a drop of water) but also to ensure the retention of water close to the hard surface thus treated.
Provision has been made to contribute permanent antistatic, soil-release and/or fungicidal properties to articles made of textile fibers (in particular cotton and polyester) by padding said articles at 130-200° C. using a bath (pad-bath solution) comprising a betaine polymer or copolymer, a thermosetting aminoplast condensate and a catalyst, drying and heat treatment at 130-200° C. (U.S. Pat. No. 3,671,305).
Provision has also been made to introduce, into detergent compositions for the washing of textile articles (laundry), zwitterionic polymers, in particular polybetaine polymers, the anionic groups of which are connected to the cationic groups via polyether chains, as additive which makes it possible to remove clayey particulate soiling substances and as antiredeposition additive (EP-B-112 592).
The Applicant Company has now found that the deposition on a hard surface, via a cleaning or rinsing formulation, of polybetaine zwitterions exhibiting one or more permanent positive charges and one or more permanent negative charges on the same monomer unit, the number of positive charges being equal to the number of negative charges on this same monomer unit, makes it possible to confer, on the surface thus treated, persistent antideposition and/or antiadhesion properties with regard to soiling substances which are particularly outstanding; in addition, the presence of polybetaine zwitterions makes it possible to improve the cleaning ability of said formulation.
The term “persistent antideposition and/or antiadhesion properties” is understood to mean that the treated surface retains these properties over time, including after subsequent contacts with a soiling substance (for example rainwater, water from the distribution network, rinsing water to which rinsing products have or have not been added, spattered fats, soaps, and the like). This property of persistence can be observed beyond approximately 10 rinsing cycles, indeed even, in some specific cases where numerous rinsings are carried out (case of toilets, for example), beyond 100 rinsing cycles.
The above expression of “conferring, on the surface thus treated, antideposition properties” means more particularly that the treated surface, brought into contact with a soiling substance in a predominantly aqueous medium, will not have a tendency to “capture” said soiling substance, which thus significantly reduces the deposition of the soiling substance on the surface.
The above expression of “conferring, on the surface thus treated, antiadhesion properties” means more particularly that the treated surface is capable of interacting only very slightly with the soiling substance which has been deposited thereon, which makes possible easy removal of the soiling substances from the soiled treated surface; this is because, during the drying of the soiling substance brought into contact with the treated surface, the bonds developed between the soiling substance and the surface are very weak; thus, to break these bonds requires less energy (thus less effort) during the cleaning operation.
When it is said that the presence of polybetaine zwitterions makes it possible “to improve the cleaning ability” of a formulation, this means that, for the same amount of cleaning formulation (in particular a formulation for washing dishes by hand), the formulation comprising polybetaine zwitterions makes it possible to clean a greater number of soiled objects than a formulation which is devoid thereof.
In addition, the deposition on a hard surface of polybetaine zwitterions makes it possible to contribute antistatic properties to this surface; this property is particularly advantageous in the case of synthetic surfaces.
The presence of polybetaine zwitterions in formulations for the treatment of a hard surface makes it possible to render the surface hydrophilic or to improve its hydrophilicity.
The property of hydrophilization of the surface makes it possible in addition to reduce the formation of condensation on the surface; this advantage can be made use of in cleaning formulations for windows and mirrors, in particular in bathrooms. Furthermore, the rate of drying of the surface, immediately after treatment thereof by the application of the polymer but also after subsequent and repeated contacts with an aqueous medium, is very significantly improved.
A first subject matter of the invention consists of a composition for the cleaning or rinsing in an aqueous or aqueous/alcoholic medium of hard surfaces comprising at least one surface-active agent and at least one polybetaine (B), said polybetaine (B) being characterized in that it:
The term “hard surfaces” is to be taken in the broad sense; it refers to nontextile surfaces which can equally well be domestic, communal or industrial surfaces.
They can be made of any material, in particular of the following types:
The composition according to the invention, capable of contributing, to the hard surfaces to be treated, antideposition and/or antiadhesion properties with regard to soiling substances, can be:
The composition according to the invention can be provided in any form and can be used in multiple ways. Thus, it can be in the form
For satisfactory implementation of the invention, said polybetaine (B) is present in the composition forming the subject matter of the invention in an amount which is effective in contributing, to said surfaces, antideposition and/or antiadhesion properties with regard to soiling substances capable of being deposited on said surfaces.
Said composition forming the subject matter of the invention can comprise, depending on its application, from 0.001 to 10% of its weight of at least one polybetaine (B).
The pH of the composition or the pH of use of the composition according to the invention can vary, depending on the applications and the surfaces to be treated, from 1 to 14, indeed even from 0.5 to 14. Extreme pH values are conventional in the applications of industrial or communal cleaning type. In the field of domestic applications, the pH values range instead from 1 to 13, depending on the applications.
Said composition can be employed for the cleaning or rinsing of hard surfaces in an amount such that, after optional rinsing and after drying, the amount of polybetaine (B) deposited on the surface is from 0.0001 to 10 mg/m2, preferably from 0.001 to 5 mg/m2, of surface treated.
Unless otherwise indicated, when molar mass is referred to, the reference will be to the weight-average molar mass, expressed in g/mol. The latter can be determined by aqueous gel permeation chromatography (GPC) or by light scattering (DLS or alternatively MALLS), with an aqueous eluent or an organic eluent (for example dimethylacetamide, dimethylformamide, and the like), depending on the composition of the polymer.
By definition, polybetaines are polymeric zwitterions carrying one or more positive charges and one or more negative charges on the same betaine monomer unit. On the same betaine monomer unit, the number of positive charge(s) is equal to the number of negative charge(s).
According to the invention, the polybetaine (B) exhibits a permanent anionic charge and a permanent cationic charge both at highly acidic pH and at highly basic pH; these charges are permanent within a pH range from 1 to 14.
The permanent anionic charge can be contributed by one or more sulfonate, phosphate, phosphonate, phosphinate or ethenolate anions, and the like.
The cationic charge can be contributed by one or more onium or inium cations of the nitrogen (ammonium, pyridinium or imidazolinium cations), phosphorus (phosphonium, and the like) or sulfur (sulfonium, and the like) family.
Preferably, the betaine functional groups of the polybetaine (B) are carried by pendent groups.
For the same betaine monomer unit, the atom carrying the permanent cationic charge is preferably connected to the anion carrying the permanent anionic charge via an optionally substituted polyvalent hydrocarbon group, in particular an alkylene group, optionally substituted by one or more hydroxyl groups. The groups carrying equal permanent positive and negative charges exhibit one or more betaine functional groups which can be represented,
in the case of the cations of the nitrogen family, by the following formulae (I) to (V), exhibiting a cationic charge at the center of the functional group and an anionic charge at the end of the functional group, and the formula (VI), exhibiting an anionic charge at the center of the functional group and a cationic charge at the end of the functional group:
—N(+)(R1)(R2)—R-A-O(−) (I)
—(R3)C═N(+)(R4)—R-A-O(−) (II)
—(R3)(R)C—N(+)(R4)(R5)—R-A-O(−) (III)
—N(+)(═R6)—R-A-O(−) (IV)
—N(+)(R1)(R2)—R—W(−) (V)
—R-A′(—O(−))—R—N(+)(R1)(R2)(R7) (VI)
The betaine functional groups can be connected to the carbon atoms of the hydrocarbon chain (also known as backbone) of the polybetaine (B) in particular via a divalent or polyvalent hydrocarbon unit (for example alkylene or arylene unit) optionally interrupted by one or more heteroatoms, in particular oxygen atoms, an ester unit or an amide unit or else via a valency bond.
Preferably, the hydrocarbon chain (or backbone) of the polybetaine (B) is a (linear or branched) polyalkylene chain optionally interrupted by one or more nitrogen and/or sulfur heteroatoms.
The polybetaine (B) according to the invention can be a homopolymer formed of identical betaine units or a copolymer formed of betaine units, at least two of which are different.
Said polybetaine (B) can additionally comprise at least one unit which is nonionic or nonionogenic at the pH of the composition or at the pH of use of the composition comprising the polybetaine (B) and/or at least one unit which is anionic or potentially anionic at the pH of the composition or at the pH of use of the composition comprising the polybetaine (B). These units can be hydrophilic or hydrophobic. They can represent up to 80% by weight or more specifically up to 90 mol % of the polybetaine (B) polymer.
However, preferably, the nonionic, nonionogenic, anionic or potentially anionic units are limited in number in order for said polybetaine (B) to retain its main characteristic of zwitterion.
Preferably, the polybetaine (B) can comprise less than 50% of its weight or more specifically less than 70 mol % of nonionic, nonionogenic, anionic or potentially anionic units; very preferably, the polybetaine (B) can comprise less than 50 mol % and more particularly less than 30 mol % of nonionic, nonionogenic, anionic or potentially anionic units.
Mention may be made, among the nonionic units which can be present, of those derived from ethylenically unsaturated nonionic monomers, such as acrylamide, vinyl acetate (capable of forming vinyl alcohol units by hydrolysis), C1-C4 alkyl esters of acrylic acid and of methacrylic acid, C1-C4 hydroxyalkyl esters of acrylic acid and of methacrylic acid, in particular ethylene glycol and propylene glycol acrylate and methacrylate, polyalkoxyl esters of acrylic acid and of methacrylic acid, in particular polyethylene glycol and polypropylene glycol esters, and the like.
Mention may be made, among the units which are nonionogenic at a pH of less than or equal to 3 or which are potentially anionic at a higher pH, of those derived from ethylenically unsaturated monomers, such as
Mention may be made, among the units which are nonionogenic at a pH of greater than or equal to 9, of those derived from ethylenically unsaturated monomers, such as
Mention may be made, among the anionic units (the first pKa of which is less than 3), of
Preferably, the polybetaine (B) does not comprise monomer units other than betaines carrying as many permanent anionic charges as permanent cationic charges at a pH ranging from 1 to 14. If other units are present, they are rather potentially anionic units in an amount of less than 50 mol %, preferably of less than 30 mol %.
Said polybetaine (B) can be obtained in particular by radical polymerization or copolymerization in aqueous solution of ethylenically unsaturated betaine monomers, in particular of ethylenically unsaturated monomers carrying at least one betaine functional group of formula (I) to (X) above, and optionally of other ethylenically unsaturated monomers.
Said monomers can exhibit, by way of examples:
Mention may in particular be made, by way of examples, of polybetaines derived from the following betaine monomers:
the synthesis of which is described in the paper “Sulfobetaine zwitterionomers based on n-butyl acrylate and 2-ethoxyethyl acrylate: monomer synthesis and copolymerization behavior”, Journal of Polymer Science, 40, 511-523 (2002),
the synthesis of which is described in the paper “Synthesis and solubility of the poly(sulfobetaine)s and the corresponding cationic polymers: 1. Synthesis and characterization of sulfobetaines and the corresponding cationic monomers by nuclear magnetic resonance spectra”, Wen-Fu Lee and Chan-Chang Tsai, Polymer, 35 (10), 2210-2217 (1994),
the synthesis of which is described in the paper “Poly(sulphopropylbetaines): 1. Synthesis and characterization”, V. M. Monroy Soto and J. C. Galin, Polymer, 1984, Vol. 25, 121-128,
the synthesis of which is described in the paper “Hydrophobically Modified Zwitterionic Polymers: Synthesis, Bulk Properties, and Miscibility with Inorganic Salts”, P. Koberle and A. Laschewsky, Macromolecules, 27, 2165-2173 (1994),
and 4-vinyl-1-(3-sulfopropyl)pyridinium betaine (4SPV), the synthesis of which is disclosed in the paper “Evidence of ionic aggregates in some ampholytic polymers by transmission electron microscopy”, V. M. Castaño and A. E. González, J. Cardoso, O. Manero and V. M. Monroy, J. Mater. Res., 5 (3), 654-657 (1990):
the synthesis of which is described in the paper “Aqueous solution properties of a poly(vinyl imidazolium sulphobetaine)”, J. C. Salamone, W. Volkson, A. P. Oison, S. C. Israel, Polymer, 19, 1157-1162 (1978),
the synthesis of which is described in the paper “New poly(carbobetaine)s made from zwitterionic diallylammonium monomers”, Favresse, Philippe; Laschewsky, Andre, Macromolecular Chemistry and Physics, 200(4), 887-895 (1999),
the synthesis of which is described in the paper “Hydrophobically Modified Zwitterionic Polymers: Synthesis, Bulk Properties, and Miscibility with Inorganic Salts”, P. Koberle and A. Laschewsky, Macromolecules, 27, 2165-2173 (1994),
the synthesis of which is described in the paper “Hydrophobically Modified Zwitterionic Polymers: Synthesis, Bulk Properties, and Miscibility with Inorganic Salts”, P. Koberle and A. Laschewsky, Macromolecules, 27, 2165-2173 (1994),
The synthesis of MPC and of VPC is disclosed in EP 810 239 B1 (Biocompatibles, Alister et al.).
the synthesis of which is described by M-L. Pujol-Fortin et al. in the paper “Poly(ammonium alkoxydicyanatoethenolates) as new hydrophobic and highly dipolar poly(zwitterions). 1. Synthesis”, Macromolecules, 24, 4523-4530 (1991).
Said polybetaines (B) according to the invention can also be obtained in a known way by chemical modification of a polymer referred to as a precursor polymer. Thus, a polysulfobetaine can be obtained by chemical modification, using a sultone (propane sultone, butane sultone), a haloalkylsulfonate or any other sulfonated electrophilic compound, of a polymer comprising pendent amine functional groups.
A few synthetic examples are given below:
The main routes of access to polysulfobetaines by chemical modification of a precursor polymer by sultones and haloalkylsulfonates are described in particular in the following documents:
The preparation of polyphosphonato- and phosphinatobetaines by chemical modification is reported in “New polymeric phosphonato-, phosphinato- and carboxybetaines”, T. Hamaide, Macromolecular Chemistry, 187, 1097-1107 (1986).
Preferably, the polybetaine B is chosen from alkylsulfonates or hydroxyalkylsulfonates of dialkylammonium alkyl methacrylates or methacrylamides and sulfobetaines derived from a vinylpyridine. More preferably still, they are alkylsulfonates or hydroxyalkylsulfonates of dialkylammonium methacrylamides.
Thus, preferably, the polybetaine B is chosen from:
homopolymers of sulfobetaine which is derived from 2-vinylpyridine of formula
The cleaning or rinsing composition according to the invention additionally comprises at least one surface-active agent. The latter can be nonionic, anionic, amphoteric, zwitterionic or cationic.
Mention may be made, among anionic surface-active agents, by way of examples, of:
A description of nonionic surface-active agents is given in U.S. Pat. Nos. 4,287,080 and 4,470,923. Mention may in particular be made of condensates of alkylene oxide, in particular of ethylene oxide and optionally of propylene oxide, with alcohols, polyols, alkylphenols, fatty acid esters, fatty acid amides and fatty amines; amine oxides; sugar derivatives, such as alkylpolyglycosides or esters of fatty acids and of sugars, in particular sucrose monopalmitate; long-chain (of 8 to 28 carbon atoms) tertiary phosphine oxides; dialkyl sulfoxides; block copolymers of polyoxyethylene and of polyoxypropylene; polyalkoxylated esters of sorbitan; fatty esters of sorbitan; poly(ethylene oxide)s and fatty acid amides modified so as to confer thereon a hydrophobic nature (for example, fatty acid mono- and diethanolamides comprising from 10 to 18 carbon atoms).
Mention may very particularly be made of:
Mention may be made, among amphoteric surface-active agents, of:
Mention may be made, among zwitterionic surface-active agents, of those disclosed in U.S. Pat. No. 5,108,660. The preferred zwitterionic surfactants are alkyl dimethyl betaines, alkyl amidopropyldimethyl betaines, alkyl dimethyl sulfobetaines or alkyl amidopropyldimethyl sulfobetaines, such as Mirataine JCHA, Mirataine H2CHA or Mirataine CBS, sold by Rhodia, or those of the same type sold by Sherex Company under the name of “Varion CADG Betaine” and “Varion CAS Sulfobetaine”, or the condensation products of fatty acids and of protein hydrolysates.
Other zwitterionic surfactants are also disclosed in U.S. Pat. No. 4,287,080 and in U.S. Pat. No. 4,557,853.
Mention may in particular be made, among cationic surface-active agents, of the quaternary ammonium salts of formula
R1R2R3R4N+X−
where
Mention may also be made of other cationic surface-active agents, such as:
quaternary ammonium salts of formula
R1′R2′R3′R4′N+X−
where
Additional examples of appropriate surfactants are compounds generally used as surface-active agents denoted in the well-known handbook “Surface Active Agents”, volume I, by Schwartz and Perry, and “Surface Active Agents and Detergents”, volume II, by Schwartz, Perry and Berch.
The surface-active agents represent from 0.005 to 60%, in particular from 0.5 to 40%, of the weight of the composition of the invention, this being according to the nature of the surface-active agent(s) and the destination of the cleaning composition.
Advantageously, the polybetaine (B)/surface-active agent(s) ratio by weight is between 1/1 and 1/1000, advantageously 1/2 and 1/200.
The cleaning or rinsing composition according to the invention can additionally comprise at least one other additive chosen in particular from conventional additives present in compositions for cleaning or rinsing hard surfaces.
Mention may in particular be made of:
The pH of the composition forming the subject matter of the invention or the pH of use of said composition can range from 0.5 to 14, preferably from 1 to 14.
Compositions of alkaline type, with a pH of greater than or equal to 7.5, preferably of greater than 8.5, for domestic applications (very particularly with a pH from 8.5 to 12, in particular from 8.5 to 11.5) are of particular use for the removal of greasy soiling substances and are particularly well suited to the cleaning of kitchens.
They can comprise from 0.001 to 5%, preferably from 0.005 to 2%, of their weight of polybetaine (B).
The alkaline compositions generally comprise, in addition to the polybetaine (B), at least one additive chosen from
Said alkaline compositions can be provided in the form of a ready-for-use formulation or else of a dry or concentrated formulation to be diluted in water in particular before use; they can be diluted from 1- to 10 000-fold, preferably from 1- to 1000-fold, before use.
Advantageously, a formulation for cleaning kitchens comprises:
Compositions of acidic type, with a pH of less than 5, are of particular use for the removal of soiling substances of inorganic type; they are particularly well suited to the cleaning of toilet bowls.
They can comprise from 0.001 to 5%, preferably from 0.01 to 2%, of their weight of polybetaine (B).
The acidic compositions generally comprise, in addition to the polybetaine (B),
Said acidic compositions are preferably provided in the form of a ready-for-use formulation.
Advantageously, a formulation for cleaning toilet bowls comprises:
A few other specific embodiments and forms of application of the composition of the invention are clarified below.
Thus, the composition according to the invention can be employed for making easier the cleaning treatment of glass surfaces, in particular of windows. This treatment can be carried out by the various known techniques. Mention may be made in particular of the techniques for cleaning windows by spraying with a jet of water using devices of the Kärcher® type.
The amount of polybetaine (B) introduced will generally be such that, during the use of the cleaning composition, after optional dilution, the concentration of polybetaine (B) is between 0.001 g/l and 2 g/l, preferably between 0.005 g/l and 0.5 g/l.
The composition for cleaning windows according to the invention comprises:
The cleaning formulations for windows comprising said polymer can also comprise:
The composition of the invention is also advantageous for making easier the cleaning of dishes in an automatic device. Said composition can be either a detergent (cleaning) formulation used in the washing cycle or a rinsing formulation.
The detergent compositions for washing dishes in automatic dishwashers according to the invention advantageously comprise from 0.01 to 5%, preferably 0.1 to 3%, by weight of polybetaine (B).
Said detergent compositions for dishwashers also comprise at least one surface-active agent, preferably a nonionic surface-active agent, in an amount which can range from 0.2 to 10%, preferably from 0.5 to 5%, of the weight of said detergent composition, the remainder being composed of various additives and of fillers, as already mentioned above.
Thus, they can additionally comprise
The compositions for making easier the rinsing of dishes in automatic dishwashers according to the invention can advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5%, by weight of polybetaine (B), with respect to the total weight of the composition.
Said compositions can also comprise from 0.1 to 20%, preferably 0.2 to 15%, by weight, with respect to the total weight of said composition, of a surface-active agent, preferably a nonionic surface-active agent.
Mention may be made, among preferred nonionic surface-active agents of surface-active agents of the following types: polyoxyethylenated C6-C12 alkylphenols, polyoxyethylenated and/or polyoxypropylenated C8-C22 aliphatic alcohols, ethylene oxide/propylene oxide block copolymers, optionally polyoxyethylenated carboxamides, and the like.
Said compositions can additionally comprise from 0 to 10%, preferably from 0.5 to 5%, by weight, with respect to the total weight of the composition, of a calcium-sequestering organic acid, preferably citric acid.
They can also comprise an auxiliary agent of copolymer of acrylic acid and of maleic anhydride or acrylic acid homopolymers type, in a proportion of 0 to 15%, preferably 0.5 to 10%, by weight, with respect to the total weight of said composition.
The pH is advantageously between 4 and 7.
Another subject matter of the invention is a cleaning composition for making easier the washing of dishes by hand.
Preferred detergent formulations of this type comprise from 0.1 to 10 parts by weight of polybetaine (B) per 100 parts by weight of said composition and comprise from 3 to 50, preferably from 10 to 40, parts by weight of at least one surface-active agent, preferably an anionic surface-active agent, chosen in particular from sulfates of saturated C5-C24, preferably C8-C16, aliphatic alcohols, optionally condensed with approximately from 0.5 to 30, preferably 0.5 to 8, very particularly 0.5 to 5, mol of ethylene oxide, in the acid form or in the form of a salt, in particular an alkali metal (sodium) salt, alkaline earth metal (calcium, magnesium) salt, and the like.
Preferably, they are lathering liquid aqueous detergent formulations for making easier the washing of dishes by hand.
Said formulations can additionally comprise other additives, in particular other surface-active agents, such as:
Another specific embodiment of the invention is a composition for making easier the exterior cleaning, in particular of the bodywork, of motorized vehicles (automobiles, trucks, buses, trains, planes, and the like).
In this case also, the composition can be a cleaning composition proper or a rinsing composition.
The cleaning composition for motor vehicles advantageously comprises from 0.005 to 10% by weight of polybetaine (B), with respect to the total weight of said composition, and:
The composition of the invention is also particularly suitable for making easier the cleaning of hard surfaces of ceramic type (tiling, bath tubs, bathroom sinks, and the like), in particular for bathrooms.
The cleaning formulation advantageously comprises from 0.02 to 5% by weight of polybetaine (B), with respect to the total weight of said composition, and at least one surface-active agent.
Preference is given, as surface-active agents, to nonionic surface-active agents, in particular the compounds produced by condensation of alkylene oxide groups of hydrophilic nature with a hydrophobic organic compound which can be of aliphatic or alkylaromatic nature.
The length of the hydrophilic chain or of the polyoxyalkylene radical condensed with any hydrophobic group can be readily adjusted in order to obtain a water-soluble compound having the desired degree of hydrophilic/hydrophobic balance (HLB).
The amount of nonionic surface-active agents in the composition of the invention can be from 0 to 30% by weight, preferably from 0 to 20% by weight.
An anionic surfactant can optionally be present in an amount of 0 to 30%, advantageously 0 to 20%, by weight.
It is also possible, but not essential, to add amphoteric, cationic or zwitterionic detergents.
The total amount of surface-active compounds employed in this type of composition is generally between 0.5 and 50%, preferably between 1 and 30%, by weight and more particularly between 2 and 20% by weight, with respect to the total weight of the composition.
Said cleaning composition can also comprise other minor ingredients, such as:
The composition according to the invention is also suitable for making easier the rinsing of shower walls. The aqueous compositions for rinsing shower walls comprise from 0.02% to 5% by weight, advantageously from 0.05 to 1%, of polybetaine (B).
The other main active components of the aqueous compositions for rinsing showers of the present invention are at least one surface-active agent, present in an amount ranging from 0.5 to 5% by weight, and optionally a metal-chelating agent as mentioned above, present in an amount ranging from 0.01 to 5% by weight.
The aqueous compositions for rinsing showers advantageously comprise water with, optionally, a major proportion of at least one lower alcohol and a minor proportion of additives (between approximately 0.1 and approximately 5% by weight, more advantageously between approximately 0.5% and approximately 3% by weight and more preferably still between approximately 1% and approximately 2% by weight).
Some surface-active agents which, can be used in this type of application are disclosed in patents U.S. Pat. Nos. 5,536,452 and 5,587,022, the content of which is incorporated by reference in the present description.
Preferred surfactants are polyethoxylated fatty esters, for example polyethoxylated sorbitan monooleates and polyethoxylated castor oil. Specific examples of such surface-active agents are the condensation products of 20 mol of ethylene oxide and of sorbitan monooleate (sold by Rhodia Inc. under the name Alkamuls PSMO-20® with an HLB of 15.0) and of 30 or 40 mol of ethylene oxide and of castor oil (sold by Rhodia Inc. under the names Alkamuls EL-620® (HLB of 12.0) and EL-719® (HLB of 13.6) respectively). The degree of ethoxylation is preferably sufficient to obtain a surfactant with an HLB of greater than 13.
The pH of the composition is advantageously between 7 and 11.
The composition according to the invention can also be employed for making easier the cleaning of glass-ceramic sheets.
Advantageously, the formulations for cleaning glass-ceramic sheets of the invention comprise:
As mentioned above, the composition according to the invention can also be employed in the field of industrial cleaning, in particular for making easier the cleaning of reactors.
Advantageously, said compositions comprise:
A second subject matter of the invention is the use, in a composition comprising at least one surface-active agent for cleaning or rinsing hard surfaces in an aqueous or aqueous/alcoholic medium, of at least one polybetaine (B)
A third subject matter of the invention is a method for improving the properties of compositions comprising at least one surface-active agent for cleaning or rinsing hard surfaces in an aqueous or aqueous/alcoholic medium by addition to said compositions of at least one polybetaine (B)
A fourth subject matter of the invention is a method for facilitating the cleaning or rinsing of hard surfaces by bringing said surfaces into contact with a composition in an aqueous or aqueous/alcoholic medium comprising at least one surface-active agent and at least one polybetaine (B), said polybetaine (B) being characterized in that it:
The polybetaine (B) is employed or is present in said composition in an amount which is effective in contributing to said surfaces antideposition and/or antiadhesion properties with regard to soiling substances capable of being deposited on said surfaces.
The nature and the amounts of the polybetaine (B) present or employed in said composition, as well as the other additives and various forms of application of said composition, have already been mentioned above.
The following examples are given by way of illustration.
The following homopolysulfobetaines B1 to B8 and the following copolysulfobetaines C1 to C7 are prepared in the laboratory according to a solution radical polymerization method well known to a person skilled in the art, the performances of which homopolysulfobetaines and copolysulfobetaines will be tested in the examples below.
The betaine polymers B1 to B8 tested are respectively employed in the form of a solution at a concentration of 200 mg/l in a water/ethanol mixture comprising 5% by volume of ethanol (this in order to facilitate the drying of the solution deposited on the surface to be treated); the solution is brought to pH 3 by addition of hydrochloric acid.
The intrinsic performances of the betaine polymers B1 to B8 according to the invention are tested visually and are compared with those obtained in the absence of betaine polymer B1 to B8, in the presence of a zwitterionic surface-active agent (ZwSurf) of cocamidopropyl hydroxysultaine type (Mirataine CBS from Rhodia), employed in the form of a solution at a concentration of 200 mg/l in a water/ethanol mixture comprising 5% by volume of ethanol; the solution is brought to pH 3 by addition of hydrochloric acid
Test
Use is made of a black-colored ceramic sheet with dimensions of 25 cm×25 cm cleaned beforehand using ethanol, the surface of which is divided into 10 equal parallel fractions F, F′, F1, F2, F3, F4, F5, F6, F7 and F8. The procedure is as follows
It is found that the betaine polymers B1 to B8 and C1 to C7 facilitate the removal of the soiling substances. The polymers B1 to B4, B7 and B8, and C1 to C7, with an Mw of less than 500 000 g/mol, are very effective, very particularly those with an Mw of less than 150 000 g/mol. The SPE/MAA molar ratio of the copolymers C1 to C7 has only a slight impact in this test.
The betaine polymers B1, B5, B7, C1, C2, C4 and C6 tested are employed in the form of solutions at a concentration of 200 mg/l in a water/ethanol mixture comprising 5% by volume of ethanol (this in order to facilitate the drying of the solution deposited on the surface to be treated); the solutions are brought to pH 3 by addition of hydrochloric acid.
The intrinsic performance of the betaine polymers B1, B5, B7, C1, C2, C4 and C6 according to the invention are tested visually and are compared with those obtained
It is found that the betaine polymers, very particularly the polymers B1, B7, C1 and C2, in contrast to a simple zwitterionic surface-active agent, remain on the surface for at least 200 rinsing cycles; the polymers of the invention endure on the surface.
The polymers do not leave at the same time as the soiling substance; without this being related to any one mechanism, it is assumed that the mechanism of antiadhesion of the soiling substance is not “sacrificial”.
4×6 detergent solutions are prepared respectively comprising
Each aqueous solution is sprayed over a black ceramic tile and is then wiped with a commercial cellulose dust cloth. The model soiling substance employed is composed of
The percentage of the soiling substance deposited which has not remained on the surface is evaluated by image analysis.
The results obtained are given in the following table:
It is found that a detergent composition comprising the polymer B1 or C1 according to the invention facilitates the removal of soiling substances of toilet type on ceramics.
The polymer B1 or C1 is particularly effective in the presence of a nonionic or cationic surface-active agent, at pH 3.
The compositions of four cleaning formulations (including two comparative formulations, A and B) used for cleaning windows are reported in the table below.
Four exterior windows with an area of 1 m2 situated side by side are treated as follows with the formulations A, B, C and D respectively.
Each formulation is sprayed over the respective window in a proportion of 5 ml per m2 of surface area and is then directly wiped with a commercial cellulose dust cloth.
After treatment, the appearance of the window, exposed to the effects of the weather for 8 weeks, is recorded over time.
A panel of observers records, over a scale of 1 to 5, the cleanness of the windows (possible marks, sparkle, carbon residues).
A grade of 1 corresponds to a very dirty window and 5 corresponds to the initial appearance, immediately after cleaning.
This test clearly demonstrates that the polybetaine B2 contributes a soil-release property which persists over at least 6 weeks.
The formulations tested appear in the following table:
The formulations A and B are diluted before use in a proportion of 10 g of formulation in 1 liter of water. Half the floor is treated with the formulation A and the other half is treated with the formulation B comprising the additive.
The floor is made of linoleum.
The user records at what rate the floor becomes dry by passing his hand over the latter.
Example A is given by way of comparison. The results for drying rate of the formulations A and B show that the polymer introduces into the formulation a marked improvement in the drying rate for the consumer.
With the formulation comprising the additive, the drying time is reduced by approximately 30%.
The user also finds that the polymer B7 contributes properties of shininess during drying.
Furthermore, the part of the floor treated with the formulation B is markedly less slippery than the part treated with the formulation A, thus conferring slip-resistance properties on the treated surface.
After two weeks of use, the operator is asked to clean the floor with the formulation A.
It is apparent that the removal of soiling substances of soot and carbon black type is facilitated on the part of the floor which has been treated beforehand with the formulation B. Thus, the polymer B7 confers antiadhesion properties with regard to soiling substance on the surfaces treated.
Glasses are placed in an automatic dishwasher and the powder detergent formulation, the composition of which is given in the following table, is placed in the reservoir provided for this purpose with a dosage of 32 g.
No rinsing liquid is used in this test.
These glasses are washed with the “normal” program, which gives a maximum washing temperature of 65° C.
During the washing cycle, an open container holding a mixture of egg, oil, cream, cheese and ketchup is simultaneously introduced into the dishwasher.
At the end of the washing, the dishwasher is kept closed for 3 hours.
After the washing cycle, the performance of the detergent composition is measured in terms of antiredeposition of soiling substances on the surface of the glass (giving rise to a white deposit/veil) and the hydrophilicity of the surfaces thus treated is also measured.
To do this, a solution of water is sprayed over the glass and the time which the film of water takes to drain (to flow homogeneously) or to remain on the surface is evaluated visually.
Furthermore, after washing, the appearance of the glasses is evaluated.
The grading “1” corresponds to a very dirty glass.
The grading “5” corresponds to a “clean” glass.
The results show that, during the washing cycle, the polymer B1 or B7 or the copolymer C3 brings the particles of soiling substance into suspension and prevents their deposition on the surface.
Two comparative tests are carried out between two commercial cleaning formulations for automatic dishwashers (formulations D and E) and two similar formulations (A and B) comprising the polymer B1 or C3.
The compositions of the formulations A, B, D and E are given in the table of the preceding Example 4.
1st Comparative Test
Four automatic dishwashers are available.
A dish made of glass of Pyrex® type and 22 g of a detergent formulation chosen from the formulations A, B, D and E respectively are placed in each.
The dishes are prewashed with the “normal” program at 55° C.
The dishes P thus treated are denoted as follows:
A preparation of “gratin” type is subsequently cooked in each of the dishes.
After having been emptied of their contents, the dishes PA and PD are washed (1 dish per dishwasher) for 3 consecutive cycles using the formulation D (without polybetaine).
After having been emptied of their contents, the dishes PB and PE are washed (1 dish per dishwasher) for 3 consecutive cycles using the formulation E (without polybetaine).
After washing, the dishes are removed from the dishwashers and their appearance is compared.
It is found that the soiling substances adhere less to the dishes prewashed with the formulation A or B.
2nd Comparative Test
Four automatic dishwashers are available.
A batch of plates and 22 g of a detergent formulation chosen from the formulations A, B, D and E respectively are placed in each.
The batches are prewashed with the “normal” program at 55° C.
The batches L thus treated are denoted as follows:
A model soiling substance comprising egg, beef flesh, vegetable fat and proteins is deposited on the 4 batches of prewashed plates. Drying is allowed to take place at 60° C. for 1 hour.
The batches LA and LD are washed (1 batch per dishwasher) for 3 consecutive cycles using the formulation D (without polybetaine).
The batches LB and LE are washed (1 batch per dishwasher) for 3 consecutive cycles using the formulation E (without polybetaine).
After washing, the batches of plates are removed from the dishwashers and their appearance is compared.
The polymers B1 and C3 thus improve the ability of the formulations to prevent the adhesion of soiling substances in automatic dishwashers.
The polymer B1 or the copolymer C3 is introduced into an automatic dishwasher formulation which may or may not comprise sodium tripolyphosphate.
Filming (formation of a white veil by deposition of inorganic calcium salts on the surface) is brought about by the addition of 2 grams of orthophosphate (NaHPO4) at each cycle start in the dishwasher.
The number of washing cycles (with a 35° TH water) necessary for the appearance of a white veil on the glasses is measured.
These results show that the polymer B1 or C3 prevents (inhibits) the deposition of calcium carbonate and phosphate on the dishes.
This type of polymer is recommended for use in dishwasher compositions of 2-in-1 type (washing and rinsing) or even of 3-in-1 type (softening, washing and rinsing).
The washing operation described in Example 6 with the formulation D (without sodium tripolyphosphate and without polymer B1) is repeated.
This operation is followed by a rinsing stage carried out with the rinsing formulations F1 to F3 given in the following table:
The contact angle results obtained with regard to the formulations F2 and F3 show that the polymer B3 introduces into the formulation a hydrophilization of the glass surface in dishwashers which is not encountered with the formulation F1.
The polymer of the invention makes it possible advantageously to substitute the amount of nonionic surfactant by a polymer which contributes sparkling properties to the utensils treated (in particular with regard to glasses).
Two comparative tests are carried out between two commercial formulations for cleaning dishes by hand (formulations A and C) and two formulations (B and D) comprising the polymer B2.
1st Comparative Test
A dish made of glass of Pyrex® type PA is prewashed in a first sink by hand with the formulation A diluted 1000-fold in water.
In the same way, a dish made of glass of Pyrex® type PB is prewashed in a second sink by hand with the formulation B (comprising the betaine polymer B2) diluted 1000-fold in water.
The dishes thus treated with the formulations A and B are subsequently dried in the open air.
A preparation of “gratin” type is cooked in each of the dishes at 180° C. for one hour. They are subsequently emptied of their contents.
The dish PA is left to soak for 1 hour in a first sink filled with the formulation A (without polybetaine) diluted a thousand fold in water.
The dish PB is left to soak for 1 hour in a second sink filled with the formulation A (without polybetaine) diluted a thousand fold in water.
After soaking for one hour, the dishes are removed from the sinks and their appearance is compared.
It is found that the soiling substance adheres much less to the dish PB pretreated with the formulation B than to the dish PA.
2nd Comparative Test
Two batches of 30 plates each are soiled with a model soiling substance comprising egg, beef flesh, vegetable fat and proteins. Drying is allowed to take place at 60° C. for 1 hour.
The first batch of 30 plates (referred to as “Batch C”) is washed with the formulation C (without polybetaine) in 2 liters of faucet water; the number of plates of Batch C which can be cleaned is counted; the amount counted is 15 plates.
The second batch of 30 plates (referred to as “Batch D”) is washed with the formulation D (with polybetaine) in 2 liters of faucet water; the number of plates of Batch D which can be cleaned is counted; the amount counted is 22 plates.
The polymer B2 thus improves the cleaning ability of the formulations for washing dishes by hand.
The formulations employed are given in the following table:
The formulation A (without polybetaine) is sprayed over half the interior surface of a bath tub made of polyester reinforced by glass fibers and over half of a wall surface made of tiling.
The formulation B (with polybetaine) is sprayed over the other half of the interior surface of the bath tub made of polyester reinforced by glass fibers and over the other half of the wall surface made of tiling.
The surfaces are subsequently rinsed with faucet water.
The user is then requested to record after how many days of use of the bath tub he feels the need to clean “the white marks” which appear either on the wall tiling or on the bath tub.
A significant effect of the addition of polybetaine on preventing the appearance of marks on pretreated surfaces is found.
0.05 part by weight of polybetaine B1, B7, B8 or C1 is added to 100 parts by weight of a commercial cleaning formulation for toilet bowls based on
Half of the surface of the bowl is treated using the commercial formulation and the other half is treated using the commercial formulation to which polybetaine has been added.
The bowl is rinsed using the flow of the flush of water.
The model soiling substance of Preliminary Example 1 is deposited over the whole of the bowl using a soft brush and is left to dry for 20 minutes before a further flow of the flush of water.
This deposition of soiling substance/drying/flow of the flush of water stage (“cycle”) is repeated; the number of cycles at the end of which a phenomenon of accumulation of soiling substance (soil buildup) is observed is recorded.
The results obtained are as follows:
The polymer of the invention thus improves the removal and the antiadhesion of soiling substances on toilet bowls.
The polymer B7 of the invention is impregnated onto sodium carbonate and the following two formulations are prepared:
The powder is subsequently diluted 200-fold (i.e., 10 g of powder are dissolved in 2 l of water) before being applied to the automobile using a high-pressure jet of Kärcher type. Half the automobile is treated with the reference formulation and the other half with the formulation to which polymer B7 has been added.
After washing, the appearance of the two sides of the automobile is similar. After using for 1 month, the automobile is rinsed with detergent-free water. The treated and untreated appearances are then compared.
It is clearly apparent that the film of dust has been removed from the side of the part treated with the polymer of the invention.
Preparation of the Soiling Substance
A crosslinking agent is prepared in another beaker by mixing 45 g of isooctane and 1 g of cobalt naphthenate for 30 minutes.
The final soiling substance which will be applied to the surface is obtained by pouring 20.0 g of the crosslinking agent into the 90 g of soiling substance.
The mixture is stirred for 5 hours at ambient temperature before application.
Materials
Several series of 8 squares made of white Formica®, each of 5 cm×5 cm per side and with a thickness of 1.3 cm, are used. Each square is cleaned beforehand with 0.1 ml of ethanol and is left to dry for at least 30 minutes.
Pretreatment Formulation and Pretreatment Method
A solution comprising 0.4% of polymer B7, 0.5% of cationic surfactant, 4% of ethylene glycol monobutyl ether, 5% of isopropanol and 1% of trimethylamine is prepared.
0.1 ml of pretreatment solution is sprayed over the surface of each square to be evaluated; drying is allowed to take place at ambient temperature for 5 minutes. A sponge moistened with water is passed three times over each surface in order to ensure that the pretreatment is homogeneous.
The squares are subsequently allowed to dry for 3 hours.
Final Cleaning Formulation
A formulation comprising 0.5% of cationic surfactant, 4% of ethylene glycol monobutyl ether, 5% of isopropanol and 1% of trimethylamine is prepared.
Equipment
“Scraper”
It is a guiding device in which the 8 squares of each series are aligned horizontally.
The four squares of the center are numbered 3, 4, 5, 6; the squares placed at the ends are numbered 1 and 2, on the one hand, and 7 and 8, on the other hand.
A metal rod is placed above the squares in order to make possible the passage of a cellulose sponge cut to the size of 4 cm×4 cm from one side to the other of the squares; the sponge is capable of being applied to the squares at a constant pressure using a screw and of moving from one side to the other of squares 1 to 8 along the guiding device.
Paint Roller
For applying the soiling substance to the squares.
Test
Each of the 8 squares is cleaned beforehand with 0.1 ml of ethanol and is left to dry for at least 30 minutes.
Four of the 8 squares are subsequently pretreated according to the method given above.
The 8 squares are aligned in the scraper, the four pretreated squares (numbered 3, 4, 5 and 6) being situated at the center of the scraper, the nonpretreated squares (numbered 1 and 2, on the one hand, and 7 and 8, on the other hand) being situated at the ends and being used only to prevent “edge effects”.
A drop of soiling substance is applied to the squares 3 and 5; this soiling substance is subsequently distributed evenly over the squares 3 to 6 by passage of the paint roller.
The 8 squares are subsequently placed in an oven at 250° C. and 30% relative humidity for 24 hours.
Deposition of a “Difficult” Soiling Substance
A drop of soiling substance is applied to the squares 3 and 5; this soiling substance is subsequently distributed evenly over the squares 3 to 6 by passage of the paint roller.
A drop of soiling substance is applied to the squares 4 and 6; this soiling substance is subsequently distributed evenly over the squares 3 to 6 by passage of the paint roller.
The 8 squares are subsequently placed in an oven at 250° C. and 50% relative humidity for 24 hours.
0.1 ml×2 of final cleaning formulation are applied on two occasions using the cellulose sponge to the pretreated tiles 3 to 6.
The cellulose sponge is subsequently moved from one side to another of squares 1 to 8 along the guiding device. One sponge pass is counted when the sponge has passed from square 1 to square 8 or vice versa.
Five to-and-fro movements (10 passes) are carried out.
The removal of the soiling substances is subsequently evaluated visually.
A grading of:
The test is repeated 3 times, the squares to be evaluated (those numbered from 3 to 6) being changed.
The mean grades obtained are as follows: for the reference (i.e. squares treated solely with the formulation not comprising the polymer B7)
| Number | Date | Country | Kind |
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| 03 02079 | Feb 2003 | FR | national |
| 03 09527 | Aug 2003 | FR | national |
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| PCT/FR03/03841 | 12/19/2003 | WO | 00 | 4/18/2006 |
| Publishing Document | Publishing Date | Country | Kind |
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| WO2004/083354 | 9/30/2004 | WO | A |
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