EP2176309A2 - Copolymer für verbesserte trocknung - Google Patents

Copolymer für verbesserte trocknung

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Publication number
EP2176309A2
EP2176309A2 EP08786305A EP08786305A EP2176309A2 EP 2176309 A2 EP2176309 A2 EP 2176309A2 EP 08786305 A EP08786305 A EP 08786305A EP 08786305 A EP08786305 A EP 08786305A EP 2176309 A2 EP2176309 A2 EP 2176309A2
Authority
EP
European Patent Office
Prior art keywords
units
copolymer
betaine
group
copolymer according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08786305A
Other languages
English (en)
French (fr)
Inventor
Evelyne Prat
Olivier Anthony
Marie-Pierre Labeau
Chi-Thanh Vuong
Marc Evers
Annick Julia Oscar Mertens
Luca Sarcinelli
Stefano Scialla
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP2176309A2 publication Critical patent/EP2176309A2/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen

Definitions

  • the subject of the present invention is a novel copolymer, a process for its preparation and uses of this copolymer.
  • water or an aqueous composition is applied to the object to be cleaned, it is optionally rinsed and then allowed to dry. This is the case for example when cleaning dishes by hand, or when cleaning dishes automatically using a dishwasher.
  • the drying phase may take a certain time and / or may leave traces of water-soluble or water-dispersible materials (for example traces of mineral matter contained in the water) and / or traces of dirt, generally oily, originating from the water. object to clean.
  • PVP poly (vinyl-pyrrolidone)
  • PVP polystyrene resin
  • dishwashing compositions generally significantly loaded with surfactants, it is indeed poorly dispersible, and / or of low stability in these compositions. In particular, it can affect the transparency of the compositions, whereas transparency is a quality sought by consumers.
  • the quality of drying following the application of a dishwashing composition remains to be improved.
  • dishwashing compositions in particular, having improved drying properties.
  • compounds which can provide such improvements and which can be formulated easily in dishwashing compositions are provided.
  • the present invention satisfies these needs by providing a copolymer comprising zwitterionic units A, and other units B, the units A comprising a betaine group, characterized in that:
  • the betaine group of the A units is a sulphobetaine group
  • the B units are units deriving from vinyl-pyrrolidone.
  • compositions - ease of formulation of the composition, - modularity and / or adaptability to a large number of compositions,
  • progressive dewetting preferably sufficiently slow to be perceptible and / or to avoid traces
  • sulfobetaine group is understood to mean a group comprising an anionic group and a cationic group, at least one of the groups comprising a sulfur atom.
  • the unit derived from a monomer for the different units of the precursor units A, denotes a unit which can be obtained directly from said monomer by polymerization.
  • a unit derived from an acrylic or methacrylic acid ester does not cover a unit of the formula -CH 2 -CH (COOH) -, -CH 2 -C (CH 3 ) (COOH) -, - CH 2 -CH (OH) -, respectively, obtained for example by polymerizing an ester of acrylic or methacrylic acid, or vinyl acetate, respectively, and then hydrolyzing.
  • a unit derived from acrylic or methacrylic acid for example covers a unit obtained by polymerizing a monomer (for example an acrylic or methacrylic acid ester) and then reacting (by by hydrolysis) the polymer obtained so as to obtain units of formula -CH 2 -CH (COOH) -, or -CH 2 -C (CH 3 ) (COOH) -.
  • a unit derived from a vinyl alcohol for example covers a unit obtained by polymerizing a monomer (for example a vinyl ester), then reacting (for example by hydrolysis) the polymer obtained so as to obtain units of formula -CH 2 -CH (OH) -.
  • Units derived from a monomer A may for example have been obtained by polymerization of monomers A pre seu cu r r s and then post-polymerization reaction to obtain units comprising the betaine group.
  • a units are not considered to be units derived from pre- cursor monomers not comprising a betaine group. In the present application, unless otherwise indicated, when we speak of molar mass, it will be the average molar mass in absolute mass, expressed in g / mol.
  • This can be determined by aqueous gel permeation chromatography (GPC), by light scattering (DDL or MALLS for an aqueous eluent), with an aqueous eluent or an organic eluent (for example formamide) according to the composition of the polymer.
  • GPC aqueous gel permeation chromatography
  • DDL or MALLS light scattering
  • MALLS for an aqueous eluent
  • an aqueous eluent or an organic eluent for example formamide
  • the copolymer of the invention comprises zwitterionic units A, and other units B, the units A comprising a betaine group, characterized in that: the betaine group of the units A is a sulphobetaine group, and the units B are units derived from vinyl-pyrrolidone.
  • It is preferably a random copolymer.
  • the units A, B form a polyalkylene hydrocarbon chain optionally interrupted by one or more nitrogen or sulfur atoms.
  • Units A comprising a sulfobetaine group
  • the betaine group of the A units comprises an anionic group and a cationic group, at least one of the groups comprising a sulfur atom.
  • the anionic group can in particular be a carbonate group, a sulfur group such as a sulphonate group, a phosphorus group such as a phosphate, phosphonate or phospinate group or an ethenolate group. Preferably it is a sulfonate group.
  • the cationic group may be an onium or inium group of the nitrogen family of the phosphorus or sulfur, for example an ammonium, pyrididium, imidazolinium, phosphonium or sulfonium group. Preferably it is an ammonium group (preferably quaternary).
  • the betaine group is a sulphobetaine group comprising a sulphonate group and a quaternary ammonium group. It should be noted that it would not be outside the scope of the invention by combining several different betaine groups, by associating in the copolymer several different A units.
  • the betaine groups are typically pendent groups of the copolymer, typically obtained from monomers comprising at least one ethylenic unsaturation.
  • the number of positive charges is equal to the number of negative charges.
  • a units are electrically neutral in at least one pH range.
  • Useful betaine groups can be represented, in the case of the cations of the nitrogen family, by the following formulas (I) to (IV), having a cationic charge at the center of the function and an anionic charge at the end of the function:
  • R 1 , R 2 and R 5 which are identical or different, represent an alkyl radical containing from 1 to 7 carbon atoms, preferably from 1 to 2 carbon atoms - the symbols R 3 and R 4 represent hydrocarbon radicals forming with the nitrogen atom a nitrogenous heterocycle possibly comprising one or more other heteroatoms, in particular nitrogen
  • R 6 represents a hydrocarbon-based radical forming, with the nitrogen atom, a saturated or unsaturated nitrogenous heterocycle optionally comprising one or more other heteroatoms, in particular nitrogen;
  • betaine groups of formulas (VIII) and (IX) may be mentioned:
  • the betaine groups can be linked to the carbon atoms of a macromolecular chain deriving from the polymerization of an ethylenic unsaturation (dorsal, backbone) of the copolymer, especially via a divalent or polyvalent hydrocarbon unit (for example alkylene or arylene). ) optionally interrupted by one or more heteroatoms, oxygen or nitrogen in particular, an ester unit, an amide unit, or by a valency bond.
  • a divalent or polyvalent hydrocarbon unit for example alkylene or arylene.
  • the copolymer may in particular be obtained by radical polymerization
  • monomers A comprising an ethylenically unsaturated betaine group, especially ethylenically unsaturated monomers bearing at least one betaine group of the formulas given above, and vinylpyrrolidone, from which the B units are derived.
  • Said monomers A may, by way of example:
  • one or more mono- or poly-ethylenically unsaturated hydrocarbon radicals (in particular vinyl, allyl, styrenyl, etc.),
  • one or more mono- or poly-ethylenically unsaturated ester radicals in particular acrylate, methacrylate, maleate, etc.
  • mono- or poly-ethylenically unsaturated ester radicals in particular acrylate, methacrylate, maleate, etc.
  • the units A may be derived from at least one betaine monomer A selected from the group consisting of the following monomers:
  • dialkylammonium alkylsulfonates alkyl acrylates or methacrylates, acrylamido or methacrylamido, such as:
  • sulfopropyl dimethylammonium propyl methacrylamide marketed by RASCHIG under the name SPP:
  • sulfopropyl dimethylammonium ethyl methacrylate marketed by RASCHIG under the name SPDA:
  • heterocyclic betaine monomers such as: - sulfobetaines derived from piperazine:
  • alkyl dialkylammonium alkyl allyl such as sulfopropyl methyl diallyl ammonium betaine: whose synthesis is described in the article “New poly (carbobetaine) made from zwitterionic diallylammonium monomers”, Favresse, Philippe; Laschewsky, André, Macromolecular Chemistry and Physics, 200 (4), 887-895 (1999).
  • alkyl dialkylammonium styrenic alkylsulphonates such as:
  • the polymer according to the invention can also be obtained in known manner by chemical modification of a polymer (copolymer) said precursor polymer comprising units A pre cu r r seu to be modified (betainized) by postpolymerization reaction to give the units A presenting a betaine group.
  • sulfobetaine units can be obtained by chemical modification of units of a precursor polymer, preferably by chemical modification of a polymer comprising pendant amine functions, using a sulfonated electrophilic compound, preferably a sultone ( propanesultone, butanesultone), or a haloalkylsulfonate.
  • Poly (sulfobetaine) s and corresponding cationic polymers 3. Synthesis and dilute aqueous solution properties of poly (sulfobetaines) derived from styrene-maleic anhydride), Wen-Fu Lee and Chun-Hsiung Lee, Polymer 38 (4) 971-979 (1997) - "Poly (sulfobetaine) s and corresponding cationic polymers.” Synthesis and aqueous solution properties of a cationic poly (methyl iodide quaternized styrene-N, N-dimethylaminopropyl maleamidic acid) copolymer ", Lee, Wen -Fu; Chen, Yan-Ming, Journal of Applied Polymer Science 80, 1619-1626 (2001)
  • the units A have one of the following formulas:
  • B units are units derived from vinyl-pyrrolidone. Such monomers are known. It is specified that it is preferably N-vinyl-pyrrolidone.
  • the copolymer of the invention may comprise other optional units C different from the units A and B mentioned above.
  • the units A and B can represent from 1% to 100%, preferably from 50 to 100%, preferably from 75 to 100% by mole of the units of the copolymer.
  • the copolymer comprises:
  • the molar ratio between the units A and the units B is between 1/99 and 25/75, preferably between 5/95 and 15/85.
  • the copolymer may in particular comprise, as other C units:
  • the copolymer does not comprise more than 25 mol% in total of such units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 25 mol% in total of C N units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 25 mol% in total of C A units, preferably not at all. According to an advantageous embodiment, the copolymer does not comprise more than 25 mol% in total of C C units, preferably not at all. According to particular embodiments, the copolymer is substantially free (it comprises less than 1 mol%, preferably less than 0.5%, preferably none) of the following units: - units C c, and / or - the C N units chosen from
  • R 6 is a hydrogen atom or a methyl group
  • - X 2 is a group of formula -CO-O-, -CO-NH- or -C 6 H 4 -CH 2 -
  • n is an integer or mean number greater than or equal to 1
  • R 7 is a hydrogen atom, an alkyl group or a tristyrylphenyl group, and / or
  • R 6 is a hydrogen atom or a methyl group
  • X 2 is a group of formula -CO-O-, -CO-NH- or -C 6 H 4 -CH 2 -
  • R 8 is a hydrocarbon group containing at least two carbon atoms, comprising at least two -OH groups, preferably two consecutive carbon atoms, and / or
  • the copolymer may be in any convenient form, for example in solid, dry or vectorized form, for example in the form of a solution or of an emulsion or a suspension, in particular in the form of a aqueous solution.
  • the vectorized form for example an aqueous solution, can in particular comprise from 5 to 50% by weight of the copolymer, for example from 10 to 30% by weight.
  • the aqueous solution can in particular be a solution obtained by a method of preparation in the aqueous phase, in particular a radical polymerization process.
  • the polymer of the invention may in particular have a molar mass ranging from 20,000 g / mol to 1,000,000 g / mol, preferably from 100,000 to 400,000 g / mol.
  • the copolymer of the invention may be prepared by any suitable method.
  • the process will generally comprise a radical polymerization (copolymerization) step, where monomers are brought together, and a source of free radicals.
  • a mixture of monomers A precursor and vinyl-pyrrolidone is polymerized (copolymerization) in the presence of a source of free radicals, to obtain a copolymer comprising units B and units derived from monomers A precursor , then chemically modifies these units to obtain A units (post-polymerization modification). Modifications have been mentioned above, in the section concerning units A.
  • the process comprises a step of copolymerization by bringing together:
  • a monomer A (or A precursor ) comprising an ethylenically unsaturated group and a sulphobetaine-vinyl-pyrrolidone group
  • Radical polymerization processes are known to those skilled in the art.
  • the source of free radicals the amount of free radicals, the introduction phases of the various compounds (monomers, source of radicals, etc.), the polymerization temperature, and other parameters or operating conditions can be varied. known and appropriate way. Some details or indications are given below.
  • the processes can be batch type processes ("batch” in English), semi-batch type ("semi-batch” in English) or even continuous type.
  • a semi-continuous type process typically comprises a phase of gradual introduction of at least one monomer (comonomer), preferably of all the monomers (comonomers), into a reactor, without continuous output of the reaction product, the product of reaction, comprising the polymer, being recovered at once at the end of the reaction.
  • the polymerization may advantageously be carried out in aqueous solution.
  • free radicals can be generated spontaneously, for example by raising the temperature, with appropriate monomers such as styrene.
  • Free radicals can be generated by irradiation, especially by UV irradiation, preferably in the presence of appropriate UV-sensitive initiators. It is possible to use initiators (or "initiators") or initiator systems, of radical type or redox type.
  • the source of free radicals can be water soluble or not. It is preferable to use water-soluble or at least partially water-soluble initiators (for example water-soluble at least 50% by weight).
  • hydrogen peroxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butylperoxyoctoate, t-butylperoxynethodecanoate and t-butylperoxyisobutarate; , lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate,
  • azo compounds such as: 2-2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), 1,1 ' azobis (cyclohexane-carbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis (2-methyl-N-hydroxyethyl) -propionamide, 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dichloride, 2,2'-azobis dichloride (2 -amidinopropane), 2,2'-azobis (N, N'-dimethyleneisobutyramide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide) 2,2'-azobis (2
  • redox systems comprising combinations such as: mixtures of hydrogen peroxide, alkyl, peresters, percarbonates and the like and of any of the iron salts, titanous salts, zinc formaldehyde sulfoxylate or formaldehyde sulfoxylate sodium, and reducing sugars,
  • alkali metal bisulfite such as sodium metabisulphite
  • alkali metal persulfates in combination with an arylphosphinic acid, such as benzene phosphonic acid and the like, and reducing sugars.
  • an arylphosphinic acid such as benzene phosphonic acid and the like
  • the polymerization temperature may especially be between 25 ° C and 95 ° C.
  • the temperature may depend on the source of free radicals. If it is not a UV initiator type source, it will be preferred to operate between 50 ° C and 95 ° C, more preferably between 60 ° C and 80 ° C. In general, the higher the temperature is The higher the polymerization is initiated (it is favored), the lower the molecular weights of the copolymers obtained.
  • compositions for automatic dishwashing generally additionally include a builder agent ("builder"). It is specified that the compositions and processes for cleaning the dishes do not include compositions and processes for cleaning hard surfaces other than dishes (cutlery, plates, dishes, cooking tools, containers, pots, pans, etc.). They do not include compositions and processes for cleaning hard surfaces such as household, industrial and / or institutional surfaces such as floors, walls, windows, sinks, furniture, toilets; the walls of kitchens, the walls of bathrooms.
  • builder agent builder agent
  • the dishwashing detergent composition may comprise in particular from 0.01% to 5%, preferably from 0.05 to 3%, preferably from 0.2% to 1.5%, by weight, of the copolymer of the invention.
  • the composition may be in any form, especially in aqueous or non-aqueous liquid form, preferably concentrated in solid form or in gel form.
  • the composition may be capable of foaming in an aqueous medium. It preferably comprises at least one surfactant (S) selected from anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants or mixtures thereof.
  • S surfactant
  • the amount of surfactant (S), expressed in seconds, can represent from 0.1 to 99%, preferably from 0.5 to 60% of the total mass of composition.
  • the amount of surfactant (S), expressed in dry matter, may represent up to 99%, preferably up to 95% of the total mass of composition; this amount usually represents at least 50% of the total composition mass.
  • the soap bar solids may further contain water and / or a water-compatible solvent in an amount of up to 20% of the mass of said solid.
  • total composition mass is meant the mass of the whole composition including, in addition to the copolymer of the invention and optionally the surfactant (S), the other possible constituents (water, solvents, other additives).
  • anionic surfactant mention may be made in particular
  • R is an alkyl radical C 8-20, preferably C 10 -C 16
  • R' an alkyl radical in C 1 -C 6 , preferably C 1 -C 3 and M an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine ).
  • Mention may in particular be made of methyl ester sulphonates whose R radical is C 14 -C 16 ;
  • alpha-olefin sulfonates comprising from 12 to 16 carbon atoms
  • alkyl sulphates of formula ROSO 3 M in which R represents a C 5 -C 24 or preferably C 10 -C 18 alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above; as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 30 units, preferably from 0.5 to 10 EO and / or OP units;
  • R represents a C 2 -C 22 , preferably C 6 -C 20 , alkyl radical
  • R ' represents a C 2 -C 3 alkyl radical
  • M represents a C 2 -C 3 alkyl radical
  • alkylated or alkylaryl phosphate esters such as RHODAFAC RA600, RHODAFAC PA15 or RHODAFAC PA23 marketed by RHODIA.
  • the amount, expressed in dry form, of anionic surfactant (when present) may range from 0.5 to 90 parts, preferably from 5 to 60 parts, more preferably from 10 to 30 parts by weight per 100 parts by weight. total weight of composition.
  • alkylene oxide condensates especially ethylene oxide with alcohols, polyols, alkylphenols; fatty acid esters; fatty acid amides; fatty amines; amine oxides; sugar derivatives such as alkylpolyglycosides or esters of fatty acids and sugars, especially sucrose monopalmitate; long-chain tertiary phosphine oxides; dialkyl sulfoxides; block copolymers of polyoxyethylene and polyoxypropylene; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly (ethylene oxide) and amides of fatty acids modified so as to confer a hydrophobic character (for example, mono- and diethanolamides of fatty acids containing from 10 to 18 carbon atoms ).
  • alkylene oxide condensates especially ethylene oxide with alcohols, polyols, alkylphenols; fatty acid esters; fatty acid amides; fatty amines; amine oxides; sugar
  • TERGITOL 15-S-9 TERGITOL 24-L-6 NMW marketed by Union Carbide Corp.
  • NEODOL 45-9 NEODOL 23-65, NEODOL 45-7
  • NEODOL 45-4 sold by Shell Chemical Cy.
  • RHODASURF IDO60, RHODASURF LA90, RHODASURF IT070 marketed by Rhodia.
  • amine oxides such as the oxides of alkyl Ci 0 -C 8 dimethylamines, the oxides of alkoxy C 8 -C 22 ethyl dihydroxy ethylamines;
  • Nonionic surfactants when present may represent from 0.1 to 20%, preferably from 0.1 to 15%, more particularly from 0.5 to 10% (in dry) of the total mass of said composition.
  • anionic and / or nonionic surfactant there may be present in the detergent composition one or more cationic, amphoteric or zwitterionic surfactants.
  • Cationic surfactants include alkylammonium salts of the formula
  • X " represents a halogen ion, CH 3 SO 4 " or C 2 H 5 SO 4 "
  • R 1 and R 2 are the same or different and represent a C 1 -C 20 alkyl radical, an aryl or benzyl radical
  • R 3 and R 4 are identical or different and represent an alkyl radical in C 1 -C 2 0, aryl or benzyl radical or a condensate of ethylene oxide and / or propylene (CH 2 CH 2 O) x - (CH 2 CHCH 3 O -H, where x and y are from 0 to 30 and are never zero together, such as cetyltrimethylammonium bromide, RHODAQUAT® TFR marketed by the company RHODIA, said cationic surfactants, when they are present, may represent up to 10%, preferably from 1 to 5% by dry weight of the total mass of said composition.
  • zwitterionic surfactants include aliphatic quaternary ammonium derivatives, especially 3- (N, N-dimethyl-N-hexadecylammonio) propane-1-sulfonate and 3- (N, N-dimethyl-N-hexadecyl) -ammonio) 2-hydroxypropane 1-sulfonate.
  • amphoteric surfactants include betaines, sulfobetaines and carboxylates and sulfonates of fatty acids and imidazole.
  • the following surfactants are preferred:
  • alkyldimethylbetaines alkylamidopropyldimethylbetaines, alkyldimethylsulfobetaines or alkylamidopropyldimethylsulfobetaines, such as the MIRATAINE CBS sold by the company Rhodia, the condensation products of fatty acids and of protein hydrolysates;
  • alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms.
  • amphoteric derivatives of alkylpolyamines such as AMPHIONIC XL® marketed by RHODIA, AMPHOLAC 7T / X® and AMPHOLAC 7C / X® marketed by BEROL NOBEL.
  • Hand dishwashing compositions may further include foam modifying additives, including foam improvers, density, and / or whiteness, agents which increase the shelf life of the foam. foam and / or increasing the amount of foam.
  • foam toners foam enhancers or "foam boosters” in English.
  • It may for example be aliphatic alcohols (AA), preferably linear ,, for example C 8 -C 22, preferably C 2 -C 8, especially -C 2 -C 6, or mixtures thereof which are described in WO 2006/035154. It may also be (co) polymers, for example described in WO 00/71651, WO
  • the composition further comprises water and / or at least one solvent compatible with water.
  • Water-compatible solvent is understood to mean any solvent which, when mixed with water, forms, at ambient temperature, a single, transparent phase.
  • the water and / or the solvent can represent up to 99.5% of the total mass of said composition; the minimum amount of water and / or solvent compatible with water is usually 1%.
  • said solvent can represent up to 80% of the weight of said mixture.
  • Said solvent is preferably chosen from C 2 -C 8 aliphatic mono or polyalcohols, and their ethers. Examples of solvents that may be mentioned include ethanol, propanol, isopropanol, butanol, 2-butoxyethanol, diethylene glycol, 1-butoxyethanol-2-propanol and diethylene monobutyl ether.
  • Said composition may further comprise at least one polymer for controlling the viscosity and / or the stability of the foams, such as polyacrylic acids or their water-soluble salts having a molecular weight of weight of 1000 to 5,000,000 g / mol, ethylene oxide-propylene oxide block copolymers with a molecular weight of up to 30,000 g / mol, polyethylene glycols having a molecular weight of at least 400 g / mol mol, biopolymers having a molecular weight of at least 10,000 g / mol; when present, said polymer may represent from 0.01 to 10% of the dry mass of the concentrated liquid composition.
  • concentrated composition is meant any composition that can be diluted during use.
  • polymers capable of controlling the viscosity and / or the stability of the foams mention may be made of
  • Polyacrylic acids or their salts such as CARBOPOL from B. F. Goodrich, in particular CARBOPOL 941, CARBOPOL 801, CARBOPOL 907, CARBOPOL 910, CARBOPOL 934 and CARBOPOL 940.
  • Block copolymers of ethylene oxide-propylene oxide such as
  • ANTAROX from Rhodia in particular ANTAROX F-88
  • Biopolymers such as guar, arabic, xanthan, rheozan, welan, carragenans, cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropylguar)
  • bleaching agents builders, hydrotropic agents, moisturizing agents, fragrances, biocides, preservatives and other usual additives, depending on the purpose of the composition.
  • hydrotropic agents such as short C 2 -C 8 alcohols, in particular ethanol, diols and glycols such as diethylene glycol, dipropylene glycol,
  • moisturizing or humectant agents for the skin such as glycerol, urea or skin-protecting agents, such as proteins or protein hydrolysates, cationic polymers such as cationic guar derivatives (Jaguar C13S®, Jaguar C162®, HICARE 1000® marketed by RHODIA.
  • compositions can be diluted at the time of their use, they can be diluted 10 to 50 000 times their volume according to their destination.
  • Their concentration of surfactant, after dilution, can generally reach from 0.0001 to 10%, preferably from 0.001 to 5%, especially from
  • the dishwashing composition can be used in the usual manner.
  • Step e) Dry
  • Dishwashing processes may vary by individual.
  • Step a) may correspond to the constitution of a dishwashing bath.
  • the dilution ratio can typically be 100 to 2000. This is sometimes referred to as a "full sink” process.
  • the copolymer concentration of the invention may especially be from 0.00025% to 0.01%, preferably from 0.0001% to
  • the dilution ratio can be adapted for this purpose. In particular, it may be prescribed by any means of communication related to the product, for example on the label, in a advertising, via a consumer service, a website. Some dilution can be made when applying the composition to a suitable application and / or rubbing means comprising water such as a sponge soaked with water or an aqueous composition, or a nonwoven pad . In such an embodiment, the copolymer concentration of the invention (after dilution) can in particular be from 1 to 100.
  • Step b) may in particular be performed by quenching the dishware object in a dishwashing bath.
  • the composition is applied directly to the dishware object, for example by pressure on a flexible or semi-flexible container comprising the composition or with the aid of a pump, or by simple gravity.
  • the composition is applied to an application means such as a sponge, a pad, a brush or the fingers of the person operating the dishes, possibly protected by gloves, and the means of application is put in contact of the dishware object.
  • an application means such as a sponge, a pad, a brush or the fingers of the person operating the dishes, possibly protected by gloves, and the means of application is put in contact of the dishware object.
  • the direct application type process may be preferred and provide a more significant drying improvement.
  • it can be prescribed by any means of communication related to the product, for example on the label, in an advertisement, via a consumer service, a website.
  • the friction step c) can be carried out in a conventional manner by circular movements and / or reciprocating movements of the friction means on the dishware object.
  • the friction means may be for example a sponge, a pad, a brush or the fingers of the person operating the dishes, possibly protected by gloves. It can also act on the means of application of step b). It is possible to operate the contacting while rubbing, step b) and step c) are then merged.
  • Step d) is generally recommended. It can be operated in a conventional manner, for example by quenching in clean water (the dishware is then removed), or by passing under a jet of water.
  • Step e) can be operated in a conventional manner. During this step, simply let the dishes dry, if necessary on a drainer or a cloth or other device promoting the evacuation and / or absorption of water.
  • a drainer or a cloth or other device promoting the evacuation and / or absorption of water.
  • Example 1.1 Copolymer of 90 mol% of vinylpyrrolidone and 10 mol% of SPE
  • a condenser and a temperature regulation by a bath of oil are added 32.2g of water.
  • the temperature of the reaction medium is brought to 75 ° C.
  • 0.1 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride dissolved in 0.6 g of water are added.
  • a solution containing 82.1 g of n-vinylpyrrolidone, 22.9 g of SPE and 195 g of water and another solution containing 1 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride and 20 g of water are then added simultaneously to 4h and 5h respectively. At the end of these additions the stirring and the temperature are maintained over 4 hours. The reaction medium is then cooled to room temperature.
  • Example 2 Formulation in a dishwashing liquid by hand and evaluation of the drying rate
  • a kitchen glass is washed by hand using the formulation to be evaluated, rinsed and soaked in a basin of water, at 40 ° C. In order to facilitate the visualization of traces of persistent water after total drying of the glass, this dipping is carried out in water with very high hardness. For convenience, we use Contrex® brand commercial mineral water.
  • the glass loaded with water, at the outlet of the basin, is placed on a support placed on a scale.
  • a metal support rod (2) whose upper end is slightly beveled, is placed on the scale (4).
  • a large funnel 3 turned over, covers the scale without touching the tray. The stem passes through the tube of the funnel.
  • the kitchen glass (1) will be placed upside down on the end of the support rod. The only point of contact is on the bottom of the glass, inside. The end being beveled, the glass leans so as to facilitate the flow of water at one point. Water flows on the funnel.
  • the scale measures the mass loss of the glass. The acquisition of the measurements is done automatically (connection of the scale on a computer by an RS232 port), by a Microsoft® Excel routine. In general, one reading per second is carried out for a period of about 200 seconds.
  • Figure 2 shows a diagram of the device.
  • the edges of the glass should not touch the funnel so as not to distort the weighing.
  • Example 2.1 washing of the glass with a commercial formulation: Palmoliver® sensitive skin
  • a drinking glass is washed according to the protocol described above with a commercial dishwashing formulation: Palmolive® sensitive skin, marketed in France by Colgate-Palmolive.
  • the mass of water remaining on the glass is recorded as a function of time according to the protocol above.
  • a dishwashing liquid formulation is prepared as follows:
  • Example 2.1 The experiment conducted in Example 2.1 is then repeated and the following drying profile is obtained:
  • Figure 1 shows a photograph with:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP08786305A 2007-07-26 2008-07-22 Copolymer für verbesserte trocknung Withdrawn EP2176309A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0705449A FR2919292B1 (fr) 2007-07-26 2007-07-26 Copolymere pour un sechage ameliore.
PCT/EP2008/059569 WO2009013283A2 (fr) 2007-07-26 2008-07-22 Copolymere pour un sechage ameliore

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EP2176309A2 true EP2176309A2 (de) 2010-04-21

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US (1) US20110137001A1 (de)
EP (1) EP2176309A2 (de)
FR (1) FR2919292B1 (de)
WO (1) WO2009013283A2 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2272942B1 (de) * 2009-07-08 2014-06-04 The Procter and Gamble Company Reinigungszusammensetzung für harte Oberflächen
JP2017510694A (ja) * 2014-03-19 2017-04-13 ザ プロクター アンド ギャンブル カンパニー 液体洗剤組成物
EP3290503A3 (de) 2016-09-01 2018-05-30 The Procter & Gamble Company Reinigungszusammensetzung zum automatischen geschirrspülen

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Publication number Priority date Publication date Assignee Title
US4607076A (en) * 1985-01-02 1986-08-19 Exxon Research And Engineering Co. Betaine copolymers-viscosifiers for water and brine
US5232622A (en) * 1990-06-20 1993-08-03 Rohm And Haas Company Chlorine-free machine dishwashing
FR2894585B1 (fr) * 2005-12-14 2012-04-27 Rhodia Recherches Et Tech Copolymere comprenant des unites zwitterioniques et d'autres unites, composition comprenant le copolymere, et utilisation

Non-Patent Citations (1)

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Title
See references of WO2009013283A2 *

Also Published As

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US20110137001A1 (en) 2011-06-09
FR2919292A1 (fr) 2009-01-30
WO2009013283A3 (fr) 2009-08-20
WO2009013283A2 (fr) 2009-01-29
FR2919292B1 (fr) 2012-10-05

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