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EP2265703A1 - Produit détergent ou nettoyant protégeant la couleur - Google Patents

Produit détergent ou nettoyant protégeant la couleur

Info

Publication number
EP2265703A1
EP2265703A1 EP09731692A EP09731692A EP2265703A1 EP 2265703 A1 EP2265703 A1 EP 2265703A1 EP 09731692 A EP09731692 A EP 09731692A EP 09731692 A EP09731692 A EP 09731692A EP 2265703 A1 EP2265703 A1 EP 2265703A1
Authority
EP
European Patent Office
Prior art keywords
average particle
particle diameter
polyamide particles
porous polyamide
acid
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.)
Granted
Application number
EP09731692A
Other languages
German (de)
English (en)
Other versions
EP2265703B1 (fr
EP2265703B9 (fr
Inventor
Birgit GLÜSEN
Thomas Eiting
Stefan Van Der Burgh
Matthias Sunder
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL09731692T priority Critical patent/PL2265703T3/pl
Publication of EP2265703A1 publication Critical patent/EP2265703A1/fr
Publication of EP2265703B1 publication Critical patent/EP2265703B1/fr
Application granted granted Critical
Publication of EP2265703B9 publication Critical patent/EP2265703B9/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to the use of porous polyamide particles as active substances which inhibit the transfer of dye during washing and / or cleaning of textiles as well as detergents or cleaners containing such compounds.
  • Detergents and cleaners contain in addition to the indispensable for the washing and cleaning process ingredients such as surfactants and builder materials usually further ingredients that can be summarized under the term washing aids and the so different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and Include enzymes.
  • Such auxiliaries also include substances which are intended to prevent dyed textile fabrics from causing a changed color impression after washing.
  • This color impression change washed, ie cleaner, textiles can be based on the one hand, that dye components are removed by the washing or cleaning process from the textile ("fading"), on the other hand may be deposited by differently colored textiles dyes on the textile ("discoloration" ).
  • the discoloration aspect may also play a role in undyed laundry items when washed together with colored laundry items.
  • detergents In order to avoid these unwanted side effects of removing dirt from textiles by treatment with usually surfactant-containing aqueous systems, detergents, especially if they are provided as so-called color or colored laundry detergents for colored textiles, contain active ingredients that prevent the detachment of dyes from the textile or At least the deposition of detached, located in the wash liquor to avoid dyes on textiles.
  • many of the commonly used - usually water-soluble - polymers have such a high affinity for dyes that they draw them more from the dyed fiber, so that it comes in their use to color loss.
  • some conventional dye transfer inhibitors show performance only with some classes of dyes and can not prevent the transfer of other dye classes.
  • porous polyamide particles lead to unexpectedly high color transfer inhibition when used in detergents. Particularly pronounced is the prevention of dyeing of white or other colored fabrics by washed out of textiles dyes. It is conceivable that the polymer particles take up dye molecules detached from the dyed fabrics because of their large surface, which in particularly preferred cases may be dendritic or have a fractal geometry, do not release them again and prevent the deposition of the dyes on white or other-colored textiles.
  • the invention relates to the use of porous polyamide particles, which
  • oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more
  • the preparation of such porous polyamide particles can generally be accomplished by mixing a solution of polyamide in a suitable solvent with a liquid phase in which polyamides are insoluble.
  • the liquid phase is water-based, whereby it can be achieved by suitable further solvents that when mixing the liquids first of all a clear solution is formed, from which the polyamide particles precipitate.
  • mixing ratios of polyamide solution to liquid phase of from 1 to 999 to 300 to 700, preferably from 2 to 998 to 250 to 750, have proven useful in the production.
  • Polyamide solutions can be provided, for example, with the solvents o-cresol, m-cresol, p-cresol, chlorophenol, phenol or mixtures thereof.
  • Formic acid has also proven itself.
  • the liquid phase in which polyamides are insoluble is preferably miscible with the aforementioned solvents and, moreover, water-miscible.
  • Preferred liquid phases are aliphatic alcohols, aliphatic ketones and mixtures of these. Methanol, ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and mixtures of these have proven particularly useful.
  • liquid phase from which precipitate the polyamide particles.
  • the liquid phase may contain high molecular weight polyalkylene glycols, e.g. PEG or PPG, in amounts of, for example, 0.5 to 10 wt .-% (based on the liquid phase).
  • the order of mixing is not critical to the manufacturing process. In preferred method
  • a polyamide solution is added to a previously prepared mixture of aliphatic alcohols and / or ketones and water or
  • the formation of the porous polyamide particles by precipitation usually takes place in periods of 1 second to 2 hours and can be assisted by stirring.
  • the mixing of the liquid and formation of the particles at temperatures of from 5 to 7O 0 C is carried out, particularly preferably at 15 to 6O 0 C.
  • the polyamide particles can be easily separated from the solvent mixture by decantation, filtration or centrifugation. This is preferably followed by washing with methanol and / or acetone and drying in vacuo.
  • Very particularly preferred processes for the preparation use a solution of polyamide 11 and / or polyamide 12 in phenol, which contains 0.1 to 50 wt .-% Polymaid (e) based on their weight.
  • a liquid phase in such preferred method a mixture of ethanol (preferably 50 to 90% by weight, based on the liquid phase), ethylene glycol (preferably 1 to 10 wt .-%, based on the liquid phase) and glycerol (preferably 1 to 12% by weight, based on the liquid phase).
  • the polyamide solution in phenol preferably 30 to 70 wt .-%, based on the mixture
  • the liquid phase preferably 40 to 65 wt .-%, based on the mixture
  • polyethylene glycol and / or polypropylene glycol having molecular weights> 1000 daltons preferably 0.5 to 10 wt .-%, based on the mixture
  • This mixture which ideally has a viscosity below 200 Pas is stirred at 20 to 8O 0 C, preferably at 25 to 65 0 C for 30 to 60 minutes.
  • the spherical porous polyamide particles produced by the processes described above, which are used in preferred embodiments of the invention, usually have number-average particle diameters of from 0.1 .mu.m to 100 .mu.m, preferably from 0.3 .mu.m to 50 .mu.m, in particular from 0.5 .mu.m to 25 ⁇ m.
  • the ratio of volume-average particle diameter (Dv) to number-average particle diameter (Dn), which is also called particle size distribution index (PDI Dv / Dn), is preferably in the range of 1, 0 to 1, 3.
  • the porous polyamide particles have a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more.
  • Particularly preferred particles according to the invention have a specific surface area according to BET (according to DIN 66131) of 5 m 2 / g to 80 m 2 / g, preferably from 6 m 2 / g to 60 m 2 / g and in particular from 7.5 m 2 / g to 50 m 2 / g ,
  • Very particularly preferred embodiments of the invention are characterized in that the porous polyamide particles have a BET specific surface area
  • the porous polyamide particles have an average pore diameter of 0.01 ⁇ m to 0.20 ⁇ m, particularly 0.02 ⁇ m to 0.1 ⁇ m, and a crystallinity (DSC measurement) of 40% or greater.
  • the standard enthalpy (or specific heat of fusion) of the porous polyamide particles is measured by DSC.
  • the sample is heated under nitrogen atmosphere from room temperature (2O 0 C), starting with a temperature increase rate of 5 ° C / min.
  • the standard enthalpy is calculated from the area of the heat absorption peak between 120 ° C. and 230 ° C.
  • the crystallinity of the porous polyamide particles is the quotient of the measured specific heat of fusion and the standard enthalpy of crystalline polyamide, the latter for polyamide 12 being about 209 J / g.
  • agents according to the invention are preferred in which the porous polyamide particles have an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more, preferably 170 ml / 100 g or more.
  • oil absorption capacity boiling linseed oil
  • porous polyamide particles are also disclosed, for example, in Japanese Patent Laid-Open Publication No. 2002-80629.
  • the porous polyamide particles are spherical.
  • the porous polyamide particles can be added separately to the washing solution as part of a manual or mechanical washing or cleaning process, are preferably brought into contact with the textile as part of a pretreatment agent in a step upstream of the actual washing process or are furthermore preferably used as a constituent of a washing or cleaning agent introduced into the washing solution.
  • the porous polyamide particles also develop their positive effect when they are used in the final rinse, in which usually textile softening active ingredients are used.
  • Their use in a laundry pre-treatment step is also possible, in which case the particulate polymer preferably remains on the textile to be subsequently washed or passes together with it into the wash liquor.
  • Another object of the invention is therefore a color protective laundry, laundry pretreatment, Wäschenach treating or cleaning agent containing a dye transfer inhibitor in the form of above defined porous polyamide particles in addition to conventional ingredients compatible with this ingredient.
  • An agent according to the invention preferably contains from 0.05% by weight to 20% by weight, in particular from 0.1% by weight to 5% by weight, of such porous polyamide particles.
  • the mentioned active ingredients contribute to both previously mentioned aspects of color constancy, that is to say they reduce both discoloration and fading, although the effect of preventing staining, especially when washing white textiles, is most pronounced.
  • Another object of the invention is therefore the use of porous polyamide particles as defined above to avoid the change in the color impression of textiles in their washing in particular surfactant-containing aqueous solutions. By changing the color impression is by no means the difference between dirty and clean textile to understand, but the color difference between each clean textile before and after the washing process.
  • Another object of the invention is a process for washing dyed textiles in surfactant-containing aqueous solutions, which is characterized in that one uses a surfactant-containing aqueous solution containing above-defined porous polyamide particles. In such a method, it is possible to wash white or undyed textiles together with the dyed textile without the white or undyed textile being dyed.
  • an agent according to the invention may, in addition to the abovementioned dye-transfer-inhibiting active ingredient, additionally comprise a known dye transfer inhibitor, then preferably in amounts of from 0.01% by weight to 5% by weight, in particular from 0.1% by weight to 1% by weight.
  • a known dye transfer inhibitor which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
  • polyvinylpyrrolidones having molecular weights of from 15,000 to 50,000 and also polyvinylpyrrolidones having molecular weights of more than 1,000,000, in particular from 1,500,000 to 4,000,000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyl oxazolidones, polyamine N-oxide Polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids.
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which gives off hydrogen peroxide in water.
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine
  • Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10,000 to for use in agents according to the invention 60,000, in particular in the range of 25,000 to 50,000.
  • those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.
  • the detergents according to the invention may be solid or liquid and may be in the form of homogeneous solutions or suspensions, in particular in the form of pulverulent solids, may contain, in principle, all known and conventional ingredients in addition to the porous polyamide particles used according to the invention.
  • the agents according to the invention may in particular be builders, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolyte, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, foam reg ulcers and dyes and fragrances.
  • porous polyamide particles to a water-insoluble cloth or to introduce them, optionally with other conventional ingredients, in a particularly well-sealed bag made of water-insoluble but water-permeable material and as an additive, if desired several times, in particular 2 times, 3 times or 4 times to use in the washing process.
  • the porous polyamide particles or the agents containing them may be packed in portions in a water-soluble material, e.g. a polyvinyl alcohol film, are introduced into the washing process.
  • compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alkyl with 3 EO or 4 EO, C 9 -C 11 -AlkOhOIe with 7 EO, cis-Cis alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -Ci 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -Ci 4- alcohol with 3 EO and Ci 2 -Ci 8 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • agents for use in mechanical processes usually extremely low-foam compounds are used. These include preferably Ci ⁇ -C-alkylphenol-polypropyleneglycol ethers with in each case at to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1, 2 to 1, 4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 1 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 Carbon atoms
  • R 5 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein dC 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain with at least two hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy-fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • nonionic surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants not only such "dimer”, but also corresponding to "trimeric” surfactants understood.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates.
  • End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality.
  • the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.
  • Schwefelcher of linear or branched C ethoxylated with 1 to 6 mol ethylene oxide 7 -C 2 i-alcohols such as 2-methyl-branched C 9 -C i-alcohols containing on average 3.5 mol ethylene oxide (EO) or C 2 -Ci 8 fatty alcohols with 1 to 4 EO.
  • EO ethylene oxide
  • C 2 -Ci 8 fatty alcohols with 1 to 4 EO.
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue other than derived ethoxylated fatty alcohols, which are considered by themselves nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the Al k (en) yl chain or salts thereof.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides).
  • sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants are particularly soaps into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Surfactants are present in detergents according to the invention in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides or dextrins polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also contain polymerized small amounts of polymerizable substances
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, although less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an alkylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical ,
  • Such polymers generally have a molecular weight between 1,000 and 200,000.
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 weight percent aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • alkali metal silicates alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding properties which can be determined according to the specifications of German Patent DE 24 12 837, are generally in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 of less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, known as the modulus, an integer of 1, 9 to 22, in particular 1, 9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred.
  • amorphous alkali silicates practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 XH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 XH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 XH 2 O, makatite).
  • Na-SKS eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite)
  • Na-SKS-2 Na 2 Si 14 O 29 XH 2 O, magadiite
  • Na-SKS-3 Na 2 Si 8 O 17 XH 2 O
  • Na-SKS-4 Na 2 Si 4 O 9 XH 2 O, makatite
  • Na-SKS-5 (X-Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 0 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 3H 2 O), Na-SKS-10 (NaHSi 2 O 5 3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 0 5) and Na SKS-13 (NaHSi 2 O 5)
  • Na-SKS-6 (5-Na 2 Si 2 O 5).
  • Builder substances are preferably present in the compositions according to the invention in amounts of up to 75% by weight, in particular 5% by weight to 50.
  • suitable peroxygen compounds are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration.
  • organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
  • an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • Bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters
  • TAED
  • the hydrophilic substituted acyl acetals and the acyl lactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-supplying bleach, in the usual amount range, preferably in amounts of 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on the total agent
  • percarboxylic acid as the sole bleaching agent, it is preferable that it be completely contained.
  • sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes may also be present as so-called bleach catalysts.
  • Suitable enzymes which can be used in the compositions are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof.
  • Particularly suitable are enzymatic active ingredients obtained from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, can this can be carried out by incorporation of the two or more separate or in a known manner separately prepared enzymes or by two or more together in a granule ready-made enzymes.
  • organic solvents which can be used in addition to water include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4C -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the classes of compounds mentioned ether.
  • Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,
  • Detergents according to the invention may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents.
  • optical brighteners for use as color detergents.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which are substituted for the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the type of substituted diphenylstyrene may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyls, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) - biphenyl. Mixtures of the aforementioned optical brightener can be used.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci 8 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally signed silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • dyes In order to improve the aesthetic impression of the agents, they can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and, in the case of use in laundry detergents, no pronounced substantivity to textile fibers, so as not to stain them.
  • compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later.
  • inventive compositions having an increased bulk density in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
  • compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
  • the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN.
  • a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or be angular, with intermediate forms are possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
  • Liquid or pasty compositions of the invention in the form of conventional solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients that can be added in bulk or as a solution in an automatic mixer.
  • a staining scale rating which is based on ISO 105-A04, was carried out.
  • two white fabrics A: 6x16 cm standard cotton fabric wfk, B: 6x16 cm standard polyamide fabric
  • a color generator (1: Acid Blue 113, 2: Disperse Red 60, 3: Disperse Blue 79)
  • the concentration of 3 g / l (Farbgeber 1) and 10 g / l (colorants 2 and 3) in the wash liquor
  • a color transfer inhibitor-free detergent composition dosage 5.0 g / l
  • adding I.) 1 g / l or (II.) 10 g / l porous polyamide particles in a Linitest device at 60 0 C, then rinsed with water and dried hanging at room temperature.
  • the degree of discoloration of the two tissues was determined spectrophotometrically.
  • the degree of discoloration of the two tissues was determined spectrophotometrically.
  • the degree of discoloration of the two tissues was
  • the degree of discoloration was then given in values from 1 (strong discoloration) to 5 (no discoloration).
  • compositions according to the invention have better dye transfer-inhibiting properties than the formulation without the dye transfer inhibiting active ingredient:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La protection de la couleur par les détergents et nettoyants, lors de leur utilisation pour le lavage ou le nettoyage de structures planes textiles teintes, devrait être améliorée. On y arrive pour l'essentiel en utilisant dans le détergent ou le produit nettoyant des particules poreuses de polyamide.
EP09731692.1A 2008-04-17 2009-04-09 Composition détergente protégeant la couleur Not-in-force EP2265703B9 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09731692T PL2265703T3 (pl) 2008-04-17 2009-04-09 Chroniący barwę środek piorący lub czyszczący

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008019443A DE102008019443A1 (de) 2008-04-17 2008-04-17 Farbschützendes Wasch- oder Reinigungsmittel
PCT/EP2009/054278 WO2009127587A1 (fr) 2008-04-17 2009-04-09 Produit détergent ou nettoyant protégeant la couleur

Publications (3)

Publication Number Publication Date
EP2265703A1 true EP2265703A1 (fr) 2010-12-29
EP2265703B1 EP2265703B1 (fr) 2014-03-05
EP2265703B9 EP2265703B9 (fr) 2014-06-25

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EP09731692.1A Not-in-force EP2265703B9 (fr) 2008-04-17 2009-04-09 Composition détergente protégeant la couleur

Country Status (5)

Country Link
US (1) US20110034364A1 (fr)
EP (1) EP2265703B9 (fr)
DE (1) DE102008019443A1 (fr)
PL (1) PL2265703T3 (fr)
WO (1) WO2009127587A1 (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009004524A1 (de) * 2009-01-09 2010-07-15 Henkel Ag & Co. Kgaa Farbschützendes maschinelles Geschirrspülmittel
CN102817208B (zh) * 2011-06-09 2017-03-01 塞罗斯有限公司 洗涤用固体颗粒及其洗涤方法
CN106566735A (zh) * 2011-09-07 2017-04-19 塞罗斯有限公司 洗涤用固体颗粒及其洗涤方法
ES2575802T3 (es) 2012-02-13 2016-07-01 Henkel Ag & Co. Kgaa Agente de lavado o de limpieza protector del color
MX2014009702A (es) 2012-02-13 2014-09-12 Basf Se Detergente de proteccion de color o agente de limpieza.
WO2015112339A1 (fr) 2014-01-22 2015-07-30 The Procter & Gamble Company Composition de traitement de textile
WO2015112340A1 (fr) 2014-01-22 2015-07-30 The Procter & Gamble Company Procédé de traitement de surfaces textiles
WO2015112338A1 (fr) 2014-01-22 2015-07-30 The Procter & Gamble Company Procédé de traitement de surfaces textiles
EP3097175B1 (fr) 2014-01-22 2018-10-17 The Procter and Gamble Company Composition de traitement de textile
EP3256563A1 (fr) 2014-11-17 2017-12-20 The Procter and Gamble Company Compositions d'apport d'agent bénéfique
EP3088505B1 (fr) 2015-04-29 2020-06-03 The Procter and Gamble Company Procédé de traitement d'un textile
CN107820515A (zh) 2015-04-29 2018-03-20 宝洁公司 洗涤剂组合物
CN107548415A (zh) 2015-04-29 2018-01-05 宝洁公司 洗涤织物的方法
CN107532116B (zh) 2015-04-29 2021-05-07 宝洁公司 处理织物的方法
US10513671B2 (en) 2015-04-29 2019-12-24 The Procter & Gamble Company Method of treating a fabric
EP3328979B1 (fr) 2015-07-29 2019-06-12 Basf Se Particules de nettoyage et leur utilisation
MX2018006475A (es) 2015-11-26 2018-09-28 Procter & Gamble Composiciones detergentes liquidas que comprenden proteasa y lipasa encapsulada.
EP4112707A1 (fr) 2021-06-30 2023-01-04 The Procter & Gamble Company Traitement des tissus
CA3260784A1 (fr) 2022-07-11 2024-01-18 The Procter & Gamble Company Composition de détergent à lessive contenant un copolymère greffé et un agent bénéfique
WO2022214113A2 (fr) 2022-07-11 2022-10-13 The Procter & Gamble Company Composition de détergent de lessive contenant un copolymère greffé et un polymère inhibiteur de transfert de colorant
JP2024545006A (ja) 2022-07-11 2024-12-05 ザ プロクター アンド ギャンブル カンパニー グラフトコポリマー及び香料原料を含有する洗濯洗剤組成物
EP4306628A1 (fr) 2022-07-11 2024-01-17 The Procter & Gamble Company Composition de détergent pour le lavage du linge contenant deux copolymères greffés
CN119421941A (zh) 2022-07-11 2025-02-11 宝洁公司 包含聚环氧烷接枝共聚物和染料转移抑制剂聚合物的衣物洗涤剂组合物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
US4493783A (en) * 1981-04-20 1985-01-15 Alcon Laboratories, Inc. Cleaning agent for optical surfaces
DE3723873A1 (de) 1987-07-18 1989-01-26 Henkel Kgaa Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung
DE4328254A1 (de) * 1993-08-23 1995-03-02 Henkel Kgaa Verfärbungsinhibitoren für Waschmittel
DE4420880A1 (de) * 1994-06-15 1995-12-21 Wella Ag Festigendes Haarreinigungsmittel
TWI264309B (en) * 1999-07-08 2006-10-21 Kao Corp Personal cleansing sheet
JP2002080629A (ja) 2000-06-14 2002-03-19 Ube Ind Ltd ポリアミド多孔質球状粒子およびその製造方法
CN100457079C (zh) * 2002-11-14 2009-02-04 宇部兴产株式会社 化妆品组合物
MXPA05011846A (es) * 2003-05-07 2006-08-01 Ciba Holding Inc Composicion blanqueante y composicion detergente blanqueante.
JP5110429B2 (ja) * 2005-09-27 2012-12-26 宇部興産株式会社 ポリアミド多孔質球状粒子
KR20100125247A (ko) * 2008-02-15 2010-11-30 헨켈 아게 운트 코. 카게아아 다공성 폴리아미드 입자를 함유하는 세제 및 세정제

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009127587A1 *

Also Published As

Publication number Publication date
EP2265703B1 (fr) 2014-03-05
US20110034364A1 (en) 2011-02-10
EP2265703B9 (fr) 2014-06-25
WO2009127587A1 (fr) 2009-10-22
PL2265703T3 (pl) 2014-08-29
DE102008019443A1 (de) 2009-10-29

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