EP2956534A1 - Détergent inhibant le grisonnement - Google Patents

Détergent inhibant le grisonnement

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Publication number
EP2956534A1
EP2956534A1 EP14703080.3A EP14703080A EP2956534A1 EP 2956534 A1 EP2956534 A1 EP 2956534A1 EP 14703080 A EP14703080 A EP 14703080A EP 2956534 A1 EP2956534 A1 EP 2956534A1
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EP
European Patent Office
Prior art keywords
acid
composition according
agents
preferred
weight
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
EP14703080.3A
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German (de)
English (en)
Other versions
EP2956534B1 (fr
Inventor
Mareile Job
Birgit GLÜSEN
Christian Kropf
Bent Rogge
Michael STROTZ
Thomas Heinze
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2956534A1 publication Critical patent/EP2956534A1/fr
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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
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3454—Organic compounds containing sulfur containing sulfone groups, e.g. vinyl sulfones

Definitions

  • the invention relates to a liquid detergent containing as graying-inhibiting active ingredient a particular cellulose derivative.
  • Graying inhibitors have the task of keeping the fabric removed from the fiber during washing of the fiber suspended in the liquor and thus prevent the re-raising of the dirt on the textile.
  • water-soluble colloids are usually suitable organic nature, for example, glue, gelatin, or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methyl-carboxymethylcellulose and mixtures thereof are also present in amounts of normally 0.1 to 5% by weight, based on the detergent used.
  • cellulose ethers have a good graying-inhibiting effect, their use in water-based liquid detergents is so narrow that in practice they can not be incorporated into them. In addition to their graying inhibitor effect relevant only when used in the washing process, these cellulose ethers have a comparatively low solubility in surfactant-containing systems and a strongly thickening effect on aqueous systems.
  • the invention relates to an aqueous liquid detergent containing surfactant and optionally further conventional ingredients of detergents and cleaners, wherein the agent sulfoethyl cellulose having a degree of substitution of 0.3 to 0.9, in particular from 0.4 to 0.7 and / or containing their salt.
  • the agent sulfoethyl cellulose having a degree of substitution of 0.3 to 0.9, in particular from 0.4 to 0.7 and / or containing their salt.
  • the average molecular weight (weight average) of the cellulose derivatives used according to the invention is preferably in the range from 5,000 g / mol to 3,000,000 g / mol, in particular from 20,000 g / mol to 2,000,000 g / mol, particularly preferably in the range of 70,000 g / mol to 1 500 000 g / mol and even more preferably in the range of 150 000 g / mol to 1 000 000 g / mol.
  • the determination of the degree of polymerization or the molecular weight of the cellulose ether can be carried out, for example, based on the determination of the intrinsic viscosity of sufficiently dilute aqueous solutions using a Ubbelohde capillary viscometer. From this, the degree of polymerization and, taking into account the degrees of substitution, the corresponding molecular weight can be calculated. Alternatively, the molecular weight can be determined by size exclusion chromatography.
  • the sulfoethylcellulose suitable according to the invention can be prepared in the customary way by reacting cellulose with chloroethylsulfonic acid or ethylene sulfonic acid in the corresponding molar equivalents.
  • Suitable salts of sulfoethyl cellulose are, in particular, the alkali metal salts, such as the sodium and potassium salts, but also the ammonium salts of sulfoethyl cellulose.
  • An agent according to the invention preferably contains from 0.1% by weight to 5% by weight, in particular from 0.5% by weight to 3% by weight, of the said sulfoethylcellulose and / or its salts.
  • the invention also relates to the use of said sulfoethyl cellulose and / or its salts in aqueous liquid detergents for improving the grayness inhibition in the washing of textile fabrics with the aqueous liquid detergent.
  • the detergent according to the invention contains water in amounts, based on the total agent, of preferably up to about 85% by weight and in particular from 40% by weight to 75% by weight, which, if desired, may also be partly exchanged for a water-soluble solvent component or a water-soluble solvent component may additionally be present.
  • Non-aqueous solvents that can be used in the liquid agents, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range.
  • the solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol, butanediol, glycerol, diethylene glycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl 3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these.
  • the liquid detergents contain surfactant, wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. Preference is given to the presence of anionic surfactants, mixtures of anionic and nonionic surfactants being particularly advantageous from an application point of view.
  • the total surfactant content of the liquid agent is preferably in the range from 10% by weight to 60% by weight, in particular from 15% by weight to 50% by weight, in each case based on the total liquid agent.
  • the nonionic surfactants used are preferably alcohol alkoxylates, ie 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 is linear or preferably 2- Position may be methyl branched or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of native 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.
  • Preferred ethoxylated alcohols include, for example, C 1 2 -i4 alcohols containing 3 EO, 7 EO or 4 EO, with 7 EO, C 13 . 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -i 8-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -i4-alcohol with 3 EO and Ci 2 -i 8-alcohol with 7 EO.
  • the stated degrees of ethoxylation represent statistical averages, 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • nonionic surfactants and alkyl glycosides in particular of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which 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 between 1 and 10; preferably x is 1, 2 to 1, 4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • 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.
  • the amount of these nonionic surfactants is preferably not more than that of the alcohol alkoxylates, especially not more than half thereof.
  • nonionic surfactants are polyhydroxy fatty acid amides of the formula (I)
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms
  • Ci_ 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substit for example glucose,
  • the content of nonionic surfactants in the liquid detergents is preferably 5 wt .-% to 30 wt .-%, in particular 7 wt .-% to 20 wt .-% and particularly preferably 9 wt .-% to 15 wt .-%, in each case based on the total mean.
  • the nonionic surfactant is selected from alcohol alkoxylate and alkyl polyglycoside and mixtures thereof.
  • anionic surfactants for example, those of the sulfonate type and sulfates can be used.
  • the surfactants of the sulfonate type are preferably C 9 . 13- Alkylbenzol- sulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from Ci 2 -8 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation gets into consideration.
  • alkanesulfonates the 2 -18-alkanes are recovered for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization from Ci.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • Fatty acid glycerines are to be understood as meaning the mono-, di- and triesters and mixtures thereof, such as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myrilecyl, cetyl or stearyl alcohol or the C 10 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • 2,3-alkyl sulfates which may for example be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the above-mentioned alcohol alkoxylates for example the straight-chain or branched C 7 ethoxylated with 1 to 6 mol of ethylene oxide.
  • 2 i-alcohols such as 2-methyl-branched Cg-n-alcohols having on average 3.5 mol of ethylene oxide (EO) or Ci 2 _i 8 -fatty alcohols having 1 to 4 EO, are suitable. These are often referred to as ether sulfates.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic 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 . 18- fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • 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 alk (en) yl chain or salts thereof.
  • Preferred anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the detergent contains 2 wt .-% to 20 wt .-%, in particular 3 wt .-% to 15 wt .-% and particularly preferably 5 wt .-% to 10 wt .-% fatty acid soap.
  • Fatty acid soaps are an important ingredient for the detergency of a liquid, especially aqueous, detergent and cleaning agent. Surprisingly, it has been shown that clear and stable liquid detergents are obtained when using the low-methylated carboxymethylcellulose also in the presence of high amounts of fatty acid soap. Typically, the use of high levels (> 2% by weight) of fatty acid soap in such systems results in cloudy and / or unstable products.
  • the anionic surfactants, including soaps 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.
  • the content of preferred liquid detergents to anionic surfactants is 5 wt .-% to 35 wt .-%, in particular 8 wt .-% to 30 wt .-% and particularly preferably 10 wt .-% to 25 wt .-%, each based on the entire remedy. It is particularly preferred that the amount of fatty acid soap is at least 2% by weight, more preferably at least 3% by weight and in particular from 4% by weight to 10% by weight. In a further preferred embodiment, the agents contain at least 2, in particular 3, different anionic surfactants selected from alkylbenzenesulfonate, ether sulfate and fatty acid soap.
  • the detergent may contain a polyacrylate acting as a cobuilder and optionally also as a thickener.
  • the polyacrylates include polyacrylate or polymethacrylate thickeners, such as, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to "International Dictionary of Cosmetic Ingredients", The Cosmetic, Toiletry and Fragrance Association (CTFA): Carbomer), also referred to as carboxyvinyl polymers.
  • CFA Cosmetic, Toiletry and Fragrance Association
  • Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from Noveon under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight approx 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000).
  • Polygel® for example Polygel DA
  • Carbopol® for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight approx 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000).
  • acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci_ 4 -alkanols formed ester (INCI acrylates copolymer), which include about the copolymers of methacrylic acid Butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol ® and by the company Degussa (Goldschmidt) under the trade name Tego® polymer are available, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3 ); (ii)
  • alkanols, esters (INCI acrylates / C10-30 alkyl acrylate crosspolymer) and which are available, for example, from Noveon under the trade name Carbopol®, for example the hydrophobic Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C 10-30 alkyl acrylate crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473).
  • Preferred liquid detergents contain the polyacrylate in an amount up to 5% by weight, in particular from 0.1% by weight to 2.5% by weight. It is advantageous if the polyacrylate is a copolymer of an unsaturated mono- or dicarboxylic acids and one or more Cp C 30 -alkyl esters of (meth) acrylic acid.
  • the viscosity of the liquid detergents and cleaning agents can be measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 150 mPas to 5000 mPas.
  • Preferred agents have viscosities from 500 mPas to 4000 mPas, with values from 1000 mPas to 3500 mPas being particularly preferred.
  • liquid detergents may contain other ingredients that further improve their performance and / or aesthetic properties.
  • preferred agents comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, additional antiredeposition agents or graying inhibitors, optical agents Brighteners, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatics, ironing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • Suitable builders which may be present in the liquid agents are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + i H 2 O, where M is sodium or hydrogen, x is a number from 1 to 9 and 4 is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not produce sharp X-ray reflections, which are typical for crystalline substances, but at most a or multiple maxima of the scattered X-radiation having a width of several degrees of the diffraction angle. However, it may even lead to particularly good buil- ding properties if the silicate particles produce fuzzy or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred.
  • Such so-called X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses.
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and / or P.
  • the zeolite P, zeolite MAP ® (Crosfield commercial product) is most preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P.
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated Ci 2 -Ci 8 fatty alcohols having 2 to 5 ethylene oxide groups , Ci 2 -Ci 4 - fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain from 18 to 22% by weight, in particular from 20 to 22% by weight, of bound water.
  • phosphates As builders, if such use is not to be avoided for ecological reasons.
  • H 2 0 2-providing compounds which have umperborattetrahydrat sodium and sodium perborate monohydrate are particularly important.
  • Further useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate peracids. hydrates and H 2 0 2 supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, Phthaloiminopertica Acid or Diperdodecandiklare. If present, they are preferably used in encased form to protect against disintegration upon storage.
  • bleach activators can be incorporated into the detergents and cleaners.
  • 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-dioxo-hexahydro-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 and 2, 5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacety
  • bleach catalysts can also be incorporated into the liquid detergents and cleaners.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Suitable enzymes are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
  • hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protein ase, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellulases used are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the bleach activators, catalysts and / or enzymes may be adsorbed and / or coated on carriers to protect them from premature decomposition.
  • the proportion of enzymes, enzyme liquid formulations, enzyme mixtures or enzyme granules may, for example, about 0, 1 wt .-% to 5 wt .-%, preferably 0.12 wt .-% to about 2.5 wt .-%, each based on the total agent , amount.
  • electrolytes from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates.
  • the use of NaCl or MgCl 2 in the compositions is preferred.
  • the proportion of electrolytes in the compositions is usually not more than 8% by weight, in particular from 0.5% by weight to 5% by weight.
  • pH adjusters may be indicated.
  • Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited.
  • the amount of these adjusting agents does not exceed 10% by weight of the total formulation.
  • hydrotropes include the sulfonated hydrotropes, such as, for example, the alkylaryl sulfonates or alkylaryl sulfonic acids.
  • Preferred hydrotropes are selected from xylene, toluene, cumene, naphthalenesulfonate or sulfonic acid and mixtures thereof.
  • Counterions are preferably selected from sodium, calcium and ammonium.
  • the liquid agents may comprise up to 20% by weight of a hydrotrope, in particular from 0.05% to 10% by weight.
  • liquid agents In order to improve the aesthetic impression of the liquid agents, they can be colored with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to a person skilled in the art, have a high storage stability and insensitivity to the other ingredients. agents and light and no pronounced substantivity to textile fibers in order not to stain them.
  • Suitable foam inhibitors which can be used in the liquid detergents and cleaning agents are, for example, soaps, paraffins or silicone oils, which may also have been applied to support materials.
  • Suitable additional antiredeposition agents which are also referred to as "soil repellents" are, for example, the polymers of phthalic acid and / or terephthalic acid known from the prior art or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners can be added to the liquid detergents and cleaners to eliminate yellowing of the treated fabrics. These fabrics attract and cause lightening by converting ultraviolet radiation invisible to the human eye into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence and turning the yellowish yellowed laundry to pure white.
  • Suitable compounds originate from the substance classes of the 4,4 'diamino-2,2-stilbenedisulfonic acids (flavonic), 4,4' biphenylene -Distyryl-, imides Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, Benzoxazole, benzisoxazole and benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • Optical brighteners are normally used in amounts of up to 0.5% by weight, in particular from 0.03% by weight to 0.3% by weight, based on the finished composition.
  • compositions may contain synthetic crease inhibitors.
  • the liquid detergents and cleaners may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfur fonates, halophenols and Phenolmercuriacetat, wherein the compounds of the invention can be completely dispensed with these compounds.
  • the agents may contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • the agents according to the invention are naturally free from oxidizing bleaching agents.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • External antistatic agents are, for example, lauryl (or stearyl) dimethylbenzylammonium chlorides, which are suitable as antistatic agents for textile fabrics or as an additive to laundry detergents, with an additional finishing effect being achieved.
  • silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
  • the liquid detergents and cleaners may also contain UV absorbers that wick onto the treated fabrics and improve the lightfastness of the fibers.
  • Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of the benzophenone having substituents in the 2- and / or 4-position.
  • Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which are preferred liquid agents in amounts of from 0.01% to 2.5%, preferably from 0.02% to 2%, by weight, and especially from 0.03 wt .-% to 1, 5 wt .-% are included.
  • These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylene phosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane -1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
  • organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylene phosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane
  • the liquid detergents are preferably clear, ie they have no sediment and are transparent or at least translucent.
  • the liquid detergents without addition of a dye preferably have a transmission of the visible light (410 to 800 nm) of at least 10%, in particular of at least 15% and particularly preferably of at least 25%.
  • a liquid washing and cleaning agent but also particles dispersed therein, the diameter along its greatest spatial extent, for example, 100 ⁇ to 10,000 ⁇ contain.
  • Such particles may be microcapsules or speckles as well as granules, compounds and fragrance beads, with microcapsules or speckles being preferred.
  • microcapsule is understood to mean aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s). These are usually finely dispersed liquid or solid phases coated with film-forming polymers, during the production of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization.
  • the microscopic capsules can be dried like powder.
  • multinuclear aggregates also called microspheres, are known, which contain two or more cores distributed in the continuous shell material.
  • Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath.
  • the shell may be made of natural, semi-synthetic or synthetic materials.
  • shell materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran , Sucrose and waxes.
  • Semi-synthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and also starch derivatives, in particular starch ethers and esters.
  • Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
  • active ingredients for example, optical brighteners, surfactants, complexing agents, bleaching agents, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, anti redeposition agents, pH adjusters, electrolytes, foam inhibitors and / or UV absorbers are located.
  • the microcapsules may contain, for example, vitamins, proteins, preservatives, detergency boosters or pearlescing agents.
  • the fillings of the microcapsules may be solids or liquids in the form of solutions or emulsions or suspensions.
  • the microcapsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their greatest spatial extent, depending on the components contained in their interior and the application between 0.01 ⁇ (visually not recognizable as a capsule) and 10,000 ⁇ lie. Preference is given to visible microcapsules having a diameter in the range from 100 ⁇ to 7,000 ⁇ , in particular from 400 ⁇ to 5,000 ⁇ .
  • the microcapsules are accessible by methods known in the art, with coacervation and interfacial polymerization being the most important.
  • Suitable microcapsules are any of the surfactant-stable microcapsules available on the market, for example the commercial products (the shell material is indicated in parentheses) Hallcrest microcapsules (gelatin, gum arabic), Coletica thalaspheres (marine collagen), Lipotec millicapsules (alginic acid, Agar-agar), Induchem Unisphe- res (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified Agar Agar) and Kuhs Probiol Nanosphere (phospholipids).
  • particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material are also referred to as "speckies".
  • a preferred matrix-forming material is alginate.
  • an aqueous alginate solution which also contains the active ingredient to be enclosed or the active ingredients to be enclosed, is dripped off and then cured in a precipitation bath containing Ca 2+ ions or Al 3+ ions.
  • the alginate-based speckles are subsequently washed with water and then washed in an aqueous solution with a complexing agent to free Ca 2+ ions or free Al 3+ ions, which undesirable interactions with ingredients of the liquid detergent , for example, the fatty acid soaps, can be washed out. Subsequently, the alginate-based speckles are washed with water to remove excess complexing agent.
  • a complexing agent to free Ca 2+ ions or free Al 3+ ions, which undesirable interactions with ingredients of the liquid detergent , for example, the fatty acid soaps, can be washed out.
  • the alginate-based speckles are washed with water to remove excess complexing agent.
  • matrix-forming materials can be used instead of alginate.
  • matrix-forming materials include polyethylene glycol, polyvinylpyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, Ficoll®, starch, hydroxyethylcellulose, hydroxypropylcellulose, Hydroxypropylmethylcellulose, hyaluronic acid, carboxymethylcellulose, carboxymethylcellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials.
  • the matrix formation in these materials takes place for example via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the art as well as the production of particles with these matrix-forming materials.
  • the particles can be stably dispersed in the aqueous liquid detergent and cleaner. Stable means that the compositions are stable at room temperature and at 40 ° C for a period of at least 4 weeks, and preferably at least 6 weeks, without the medium creaming or sedimenting.
  • the release of the active ingredients from the microcapsules or speckles is usually carried out during the application of the agents containing them by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action.
  • the liquid detergents contain identical or different particles in amounts of 0.01 to 10 wt .-%, in particular 0.2 to 8 wt .-% and most preferably 0.5 to 5 wt .-%.
  • Aqueous detergents and cleaners can be inexpensively and easily produced in conventional mixing and bottling plants.
  • the acidic components such as, for example, the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, and the nonionic surfactants are preferably initially introduced.
  • the solvent component is preferably also added at this time, but the addition may also be made at a later time.
  • the complexing agent is added. Subsequently, a base such as NaOH, KOH, triethanolamine or monoethanolamine, followed by the fatty acid, if present.
  • the remaining ingredients and optionally the remaining solvents of the aqueous liquid agent are added to the mixture and the pH is adjusted to the desired value.
  • the particles to be dispersed can be added and distributed homogeneously in the aqueous liquid agent by mixing.
  • Table 1 shows the composition (ingredients in percent by weight, in each case based on the total agent) of the inventive detergent M1 and the non-inventive compositions V1, V2, V3 and V4 prepared for comparison.
  • the means M1 had a transmission of 18% at 550 nm, whereas the means V3 and V4 had transmissions of only 1% and 7% and the means V1 a transmission of 81% at the same wavelength of light.
  • the agents were tested in a Miele® W 1714 washing machine (cotton washing program, 40 ° C., water hardness 16 ° dH, gray carrier Greying Swatch, dosage 66 ml of the respective product per wash cycle).
  • the following materials were used in addition to filling laundry to a load of 3.5 kg (each 8 pieces of fabric in the size 20 x 40 cm): A 100% cotton, cotton fabric WFK 10A, without opt. brighteners
  • Table 2 shows the brightness change ( ⁇ value) of the materials after 3 washes with the respective agent.

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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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un détergent aqueux liquide comprenant un tensioactif ainsi qu'éventuellement d'autres ingrédients habituels, le détergent contenant de la sulfoéthylcellulose ayant un degré de substitution de 0,3 à 0,9 et/ou son sel.
EP14703080.3A 2013-02-12 2014-02-07 Détergent inhibant le grisonnement Active EP2956534B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013202269.7A DE102013202269A1 (de) 2013-02-12 2013-02-12 Vergrauungsinhibierende Waschmittel
PCT/EP2014/052398 WO2014124872A1 (fr) 2013-02-12 2014-02-07 Détergent inhibant le grisonnement

Publications (2)

Publication Number Publication Date
EP2956534A1 true EP2956534A1 (fr) 2015-12-23
EP2956534B1 EP2956534B1 (fr) 2023-05-31

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US (1) US9523064B2 (fr)
EP (1) EP2956534B1 (fr)
DE (1) DE102013202269A1 (fr)
WO (1) WO2014124872A1 (fr)

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WO2018172503A2 (fr) 2017-03-24 2018-09-27 Basf Se Détergent pour lessive liquide comprenant un saccharide ou un polysaccharide modifié
EP4134420A1 (fr) 2021-08-12 2023-02-15 The Procter & Gamble Company Composition détergente comprenant un tensioactif détergent et des polymères greffés biodégradables
EP4134421A1 (fr) 2021-08-12 2023-02-15 The Procter & Gamble Company Composition détergente comprenant un tensioactif détergent et un polymère greffé
CN118119692A (zh) 2021-10-14 2024-05-31 宝洁公司 包含阳离子去垢性聚合物和脂肪酶的织物和家庭护理产品
DE102022200126A1 (de) * 2022-01-07 2023-07-13 Henkel Ag & Co. Kgaa Fucoidane als vergrauungsinhibierende Wirkstoffe
DE102022200127A1 (de) 2022-01-07 2023-07-13 Henkel Ag & Co. Kgaa Ulvane als vergrauungsinhibierende Wirkstoffe
DE102022200269A1 (de) 2022-01-13 2023-07-13 Henkel Ag & Co. Kgaa Saccharosederivate als vergrauungsinhibierende Wirkstoffe
EP4321604A1 (fr) 2022-08-08 2024-02-14 The Procter & Gamble Company Tissu et composition de soins à domicile comprenant un tensioactif et un polyester
WO2024094802A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Tissu et composition d'entretien ménager
WO2024094785A1 (fr) 2022-11-04 2024-05-10 Clariant International Ltd Polyesters
WO2024094790A1 (fr) 2022-11-04 2024-05-10 Clariant International Ltd Polyesters
WO2024119298A1 (fr) 2022-12-05 2024-06-13 The Procter & Gamble Company Composition de soin textile et ménager comprenant un composé de carbonate de polyalkylène
WO2024129520A1 (fr) 2022-12-12 2024-06-20 The Procter & Gamble Company Composition de soin textile et ménager
EP4386074A1 (fr) 2022-12-16 2024-06-19 The Procter & Gamble Company Composition de soin pour le linge et le domicile

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GB800705A (en) * 1955-09-06 1958-09-03 Colgate Palmolive Co Liquid detergent compositions

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DE3742104A1 (de) * 1987-12-11 1989-06-22 Wolff Walsrode Ag Sulfoethylcellulose mit hervorragender loesungsqualitaet und verfahren zu ihrer herstellung
DE4113892A1 (de) 1991-04-27 1992-10-29 Wolff Walsrode Ag Wasserloesliche sulfoethylcelluloseether mit sehr guter loesungsqualitaet und verfahren zu ihrer herstellung
GB0508882D0 (en) 2005-04-29 2005-06-08 Unilever Plc Polymers for laundry applications
US7714124B2 (en) * 2006-03-27 2010-05-11 The Procter & Gamble Company Methods for modifying cellulosic polymers in ionic liquids

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GB800705A (en) * 1955-09-06 1958-09-03 Colgate Palmolive Co Liquid detergent compositions

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US9523064B2 (en) 2016-12-20
DE102013202269A1 (de) 2014-08-14
EP2956534B1 (fr) 2023-05-31
US20150368591A1 (en) 2015-12-24
WO2014124872A1 (fr) 2014-08-21

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