EP1989282A1 - Agent nettoyant liquide inhibant le grisonnement - Google Patents

Agent nettoyant liquide inhibant le grisonnement

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Publication number
EP1989282A1
EP1989282A1 EP07722837A EP07722837A EP1989282A1 EP 1989282 A1 EP1989282 A1 EP 1989282A1 EP 07722837 A EP07722837 A EP 07722837A EP 07722837 A EP07722837 A EP 07722837A EP 1989282 A1 EP1989282 A1 EP 1989282A1
Authority
EP
European Patent Office
Prior art keywords
acid
methyl
composition according
agents
preferred
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
EP07722837A
Other languages
German (de)
English (en)
Other versions
EP1989282B1 (fr
Inventor
Josef Penninger
Nadine Warkotsch
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
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL07722837T priority Critical patent/PL1989282T3/pl
Publication of EP1989282A1 publication Critical patent/EP1989282A1/fr
Application granted granted Critical
Publication of EP1989282B1 publication Critical patent/EP1989282B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C11D3/16—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
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the invention relates to a liquid surfactant-containing detergent which contains a specific cellulose derivative as graying-inhibiting active ingredient.
  • 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 of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose 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 (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof are also contained 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 methyl-carboxymethylcellulose having a degree of methylation in the range of 0.01 to 0.3, in particular 0.05 to 0.2 , contains.
  • the agent methyl-carboxymethylcellulose having a degree of methylation in the range of 0.01 to 0.3, in particular 0.05 to 0.2 .
  • the degree of carboxymethylation which accordingly indicates the average number of carboxymethyl groups per anhydroglycosyl monomer unit, is preferably in the range of 0.3 to 1, especially 0.4 to 0.8.
  • the average molar mass of the cellulose derivatives used according to the invention is preferably in the range from 80,000 D to 300,000 D, in particular from 100,000 D to 280,000 D and particularly preferably in the range from 150,000 D to 250,000 D.
  • the determination of the degree of polymerization or of the molecular weight of the cellulose ether can be carried out based on the determination of the intrinsic viscosity of sufficiently dilute aqueous solutions by means of a Ubbelohde capillary viscometer (eg capillary 0c). From this, the degree of polymerization and, taking into account the degrees of substitution, the corresponding molecular weight can be calculated.
  • suitable methyl-carboxymethylcellulose can be prepared in the usual way by reacting cellulose with methylating agents, such as chloromethane, and subsequent reaction with Carboxymethyl istsagenzien, such as chloroacetic acid, in the corresponding molar equivalents.
  • An agent according to the invention preferably contains 0.1% by weight to 2% by weight, in particular 0.3% by weight to 1.5% by weight, of said methylcarboxymethylcellulose.
  • the invention also relates to the use of said low methylated methyl carboxymethylcellulose in aqueous liquid detergents to improve the grayness inhibition in the washing of textile fabrics with the aqueous liquid detergent.
  • the detergent according to the invention contains, in addition to said cellulose ether derivative and surfactants described in more detail below, 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 partially exchanged for a water-soluble solvent component.
  • 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 in the specified concentration range with water.
  • the solvents are preferably selected from ethanol, n- or i-propanol, 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, Ci 2- i 4 alcohols containing 3 EO, 7 EO or 4 EO, Cg.n alcohol containing 7 EO, C 3-I5 - alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci 2-I8 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2- i 4 alcohol with 3 EO and Ci 2- ig-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 tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing 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 any 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), R 1
  • 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'-OR 2
  • R-CO-N- [Z] in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 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 oxyalkyl radical having 1 to 8 carbon atoms
  • C is M - alkyl or phenyl radicals
  • [Z] is preferred 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.
  • a sugar for example 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 by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • 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.
  • Suitable surfactants of the sulfonate type are preferably Cg.n- alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxy-alkane sulfonates, and the disulfonates obtained, for example, from C 2 i 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation receives products into consideration.
  • alkanesulfonates consisting of Ci-I 2 8 - are obtained, for example alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
  • 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 glycerol esters are the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulf ⁇ er 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) yl sulfates are the alkali and especially the sodium salts of the Schwefelhoffreraumester C 2 -C 8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 0 -C 20 - oxo 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, petrochemical-based straight-chain alkyl radical which has an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • Ci 6 alkyl sulphates and C I2 -C 5 - - From the washing the Ci 2 are alkyl sulfates and C 14 -C 15 - Alkyl sulfates.
  • 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 Schwefelklasted Acidmonoester of the above alcohol alkoxylates such as ethoxylated with 1 to 6 moles of ethylene oxide chain or branched C 7-2I - alcohols, such as 2-methyl-branched C ⁇ i 1 alcohols containing on average 3.5 mol ethylene oxide (EO) or Ci 2- i 8 fatty alcohols with 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 acid esters and the 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- i 8 fatty alcohol radicals or mixtures thereof.
  • 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) erucic 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 carboxymethyl cellulose ether even 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 may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di-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 compositions 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 the high molecular weight crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene Homopolymers of acrylic acid (INCI name according to "International Dictionary of Cosmetic Ingredients" of "The Cosmetic, Toiletry and Fragrance Association (CTFA)”: Carbomer), which are also referred to as Carboxyvinylpolymere.
  • 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 (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci -4 alkanols formed, esters (INCI Acrylates Copolymer), which include for instance 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® as well as from the company Degussa (Goldschmidt) under the trade name Tego® polymer, eg the anionic non-associating polymers Aculyn 22, Aculyn 28, Aculyn 33 (cross-linked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852- 37-3); (ii) cross-linked), A
  • Preferred liquid detergents contain the polyacrylate in an amount of up to 5 wt .-%, in particular from 0.1 wt .-% to 2.5 wt .-%. It is advantageous if the polyacrylate is a copolymer of an unsaturated mono- or dicarboxylic acids and one or more C 1 -C 30 -alkyl esters of (meth) acrylic acid.
  • the viscosity of the liquid detergent and cleaning agent (for example, Brookfield viscometer LVT-II / min at 20 rpm and 2O 0 C, spindle 3) can be measured using standard methods 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 grayness inhibitors, optical brighteners, Anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • silicates aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances may be mentioned.
  • 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 1.9 to 4 and y 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 ⁇ -
  • 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” also "X-ray amorphous" Understood.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred 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 the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by SASOL under the brand name VEGOBOND AX ® and by the formula
  • 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 S - fatty alcohols having 2 to 5 ethylene oxide groups , Ci 2 -C] 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 18 to 22% by weight, in particular 20 to 22% by weight. % of bound water.
  • phosphates As builders, if such use is not to be avoided for ecological reasons.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. 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 peroxocarboxylic 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 and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts are 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 as well as Co, Fe, Cu and Ru-amine complexes can also be used as bleach catalysts.
  • Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. 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 the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • Bacillus subtilis Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus licheniformis Bacillus licheniformis
  • Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • 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 protease, 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.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ß-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the Cellulases the desired activities are set.
  • the bleach activators, catalysts and / or enzymes may be adsorbed and / or coated on carriers to protect them from premature decomposition.
  • the proportion of the 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. From a manufacturing point of view, 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 the alkylarylsulfonates or alkylarylsulfonic 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.
  • dyestuffs In order to improve the aesthetic impression of the liquid agents, they can be colored with suitable dyes.
  • Preferred dyestuffs 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 of the agent and against light and no pronounced substantivity to textile fibers so as 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 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 are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylimidones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, 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 cleaning agents 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, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.
  • 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 of oxidizing bleaches.
  • 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) dimethylbenzyl ammonium chlorides, which are suitable as antistatic agents for textile fabrics or as an additive to detergents, in which case additionally a finishing effect is achieved.
  • the treated fabrics can be used in the liquid detergents and cleaners, for example, silicone derivatives. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties.
  • Preferred 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 having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and urocanic acid.
  • 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 present in preferred liquid agents in amounts of from 0.01% to 2.5% by weight, preferably from
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • AMP aminotri (methylenephosphonic acid)
  • DTPMP diethylenetriamine penta (methylenephosphonic acid)
  • DETPMP diethylenetriamine penta
  • PBS-AM 2-phosphonobutane-l, 2,4-tricarboxylic acid
  • the liquid detergents are preferably clear, ie they have no sediment and are transparent or at least translucent.
  • the liquid detergents and cleaners without addition of a dye preferably have a transmission of the visible light (410 to 800 nm) of at least 30%, preferably at least 50% and especially preferably at least 75%.
  • a liquid washing and cleaning agent may also contain particles dispersed therein whose diameter along their greatest spatial extent is, for example, 0.01 ⁇ m to 10,000 ⁇ m.
  • 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 chloride. 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 largest spatial extent, depending on the components contained in their interior and the application between 0.01 microns (not visually recognizable as a capsule) and 10,000 microns. Preference is given to visible microcapsules having a diameter in the range from 100 ⁇ m to 7000 ⁇ m, in particular from 400 ⁇ m to 5000 ⁇ m.
  • the microcapsules are accessible by methods known in the art, with coacervation and interfacial polymerization being the most important.
  • microcapsules all surfactant-stable microcapsules available on the market can be used, for example the commercial products (in each case the shell material is indicated in parentheses) Hallcrest Microcapsules (gelatin, gum Arabicum), Coletica thalaspheres (marine collagen), Lipotec Millicapseln (alginic acid, agar-agar), Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified Agar Agar) and Kuhs Probiol Nanospheres (phospholipids).
  • Hallcrest Microcapsules gelatin, gum Arabicum
  • Coletica thalaspheres marine collagen
  • Lipotec Millicapseln alginic acid, agar-agar
  • Induchem Unispheres lacto
  • particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckies".
  • a preferred matrix-forming material is alginate.
  • For producing alginate-based speckles is an aqueous alginate solution which also contains the entrapped active ingredient or active ingredients to be entrapped, and then dripped cured 3+ ions precipitation bath containing ions in a Ca 2+ or Al.
  • 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 wash - And detergent, such as the fatty acid soaps, can go out, wash 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 wash - And detergent, such as the fatty acid soaps, can go out, wash 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 prior 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 incubated at room temperature and at 40 ° C. over a period of time. are stable for at least 4 weeks, and preferably for at least 6 weeks, without raising or sedimenting the means.
  • 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, is added.
  • 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 inventive detergents M1 and M2.
  • Washing device Launderometer, Fa. Atlas
  • Table 2 gives the percent improvement in grayness inhibition that results from the use of the low methylated carboxymethylcelluloses (compared to an otherwise equal composition lacking this agent).

Abstract

L'invention concerne un agent nettoyant liquide aqueux, contenant un tensioactif, ainsi qu'éventuellement d'autres composants courants des agents de nettoyage et de lavage, ledit agent contenant de la méthylcarboxyméthylcellulose avec un degré de méthylation compris entre 0,01 et 0,3.
EP07722837.7A 2006-02-28 2007-02-16 Agent nettoyant liquide inhibant le grisonnement Active EP1989282B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL07722837T PL1989282T3 (pl) 2006-02-28 2007-02-16 Ciekły środek piorący zapobiegający szarzeniu

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006009578A DE102006009578A1 (de) 2006-02-28 2006-02-28 Vergrauungsinhibierendes Flüssigwaschmittel
PCT/EP2007/001341 WO2007098862A1 (fr) 2006-02-28 2007-02-16 Agent nettoyant liquide inhibant le grisonnement

Publications (2)

Publication Number Publication Date
EP1989282A1 true EP1989282A1 (fr) 2008-11-12
EP1989282B1 EP1989282B1 (fr) 2013-04-24

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EP07722837.7A Active EP1989282B1 (fr) 2006-02-28 2007-02-16 Agent nettoyant liquide inhibant le grisonnement

Country Status (7)

Country Link
US (1) US7883549B2 (fr)
EP (1) EP1989282B1 (fr)
JP (1) JP2009528410A (fr)
DE (1) DE102006009578A1 (fr)
ES (1) ES2409088T3 (fr)
PL (1) PL1989282T3 (fr)
WO (1) WO2007098862A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2135933B1 (fr) * 2008-06-20 2013-04-03 The Procter and Gamble Company Composition de lavage
ATE550415T1 (de) * 2008-06-20 2012-04-15 Procter & Gamble Waschzusammensetzung
JP2012508304A (ja) * 2008-11-14 2012-04-05 ザ プロクター アンド ギャンブル カンパニー ポリマー及び酵素を含む組成物
DE102009027811A1 (de) * 2009-07-17 2011-01-20 Henkel Ag & Co. Kgaa Flüssiges Wasch-oder Reinigungsmittel mit vergrauungsinhibierendem Polysaccarid
DE102009027812A1 (de) 2009-07-17 2011-01-20 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit vergrauungsinhibierendem Polymer
US8206511B2 (en) * 2009-10-06 2012-06-26 Ecolab Usa Inc. Daily cleaner with slip-resistant and gloss-enhancing properties
US9920281B2 (en) 2009-11-12 2018-03-20 Ecolab Usa Inc. Soil resistant surface treatment
BR112013014595B1 (pt) 2010-12-13 2021-01-26 Ecolab Usa Inc. composição de limpeza, método para limpar uma superfície dura de piso e kit
DE102013226421A1 (de) * 2013-12-18 2015-06-18 Henkel Ag & Co. Kgaa Waschmittel enthaltend Alkylcarbonsäureester
DE102016210743A1 (de) 2016-06-16 2017-12-21 Henkel Ag & Co. Kgaa Konzentrierte Flüssigwaschmittel enthaltend Polymere
WO2018124989A1 (fr) 2016-12-29 2018-07-05 Hayat Kimya San. A. Ş. Détergent à lessive liquide
WO2018169268A1 (fr) * 2017-03-14 2018-09-20 최영철 Balle de nettoyage de dispositif médical tubulaire et son procédé de fabrication
TW201928037A (zh) * 2017-12-06 2019-07-16 日商花王股份有限公司 纖維製品用液體洗淨劑組合物
DE102022200269A1 (de) 2022-01-13 2023-07-13 Henkel Ag & Co. Kgaa Saccharosederivate als vergrauungsinhibierende Wirkstoffe

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2994665A (en) * 1959-04-15 1961-08-01 Lever Brothers Ltd Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents
US4127495A (en) * 1978-01-19 1978-11-28 Hercules Incorporated Non-built liquid detergents
DE69313298T2 (de) * 1992-11-30 1998-03-26 Procter & Gamble Hochschäumende waschmittelzusammensetzungen mit speziell ausgewählten seifen
BR9408124A (pt) * 1993-11-22 1997-08-05 Colgate Palmolive Co Composição em microemulsão composição de limpeza para superficies duras para todos os fins detergente líquido para serviços leves e composição detergente líquida
DE19752165A1 (de) * 1997-11-26 1999-05-27 Henkel Kgaa Stabile höherviskose Flüssigwaschmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007098862A1 *

Also Published As

Publication number Publication date
DE102006009578A1 (de) 2007-09-06
WO2007098862A1 (fr) 2007-09-07
ES2409088T3 (es) 2013-06-24
JP2009528410A (ja) 2009-08-06
US7883549B2 (en) 2011-02-08
US20080313819A1 (en) 2008-12-25
EP1989282B1 (fr) 2013-04-24
PL1989282T3 (pl) 2013-09-30

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