WO2021078577A1 - Détergents anti-redéposition - Google Patents

Détergents anti-redéposition Download PDF

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Publication number
WO2021078577A1
WO2021078577A1 PCT/EP2020/078688 EP2020078688W WO2021078577A1 WO 2021078577 A1 WO2021078577 A1 WO 2021078577A1 EP 2020078688 W EP2020078688 W EP 2020078688W WO 2021078577 A1 WO2021078577 A1 WO 2021078577A1
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WIPO (PCT)
Prior art keywords
ethyl
mol
methyl
mixtures
range
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PCT/EP2020/078688
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German (de)
English (en)
Inventor
Nils Wedler
Antje Gebert-Schwarzwaelder
Christian Kropf
Regina Palkovits
Peter HAUSOUL
Janice Mahnke
Carsten Stobbe
Laura FALENSKI
Original Assignee
Henkel Ag & Co. Kgaa
Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen
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Application filed by Henkel Ag & Co. Kgaa, Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen filed Critical Henkel Ag & Co. Kgaa
Publication of WO2021078577A1 publication Critical patent/WO2021078577A1/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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the invention relates to liquid detergents which contain, as graying-inhibiting active ingredient, a certain copolymer with a monomer obtainable partly from renewable raw materials.
  • the task of graying inhibitors is to keep the dirt detached from the fibers when washing textiles suspended in the liquor and thus to prevent the dirt from being drawn back onto the textile.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatine, or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. It is also possible to use soluble starch preparations and other starch products than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methylhydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures are often used in amounts of normally 0.1 to 5% by weight, based on the detergent .
  • liquid detergents containing water and, in particular, anionic surfactants in the concentrations desired for the graying-inhibiting effect, products that are no longer flowable and pourable are generally obtained which can only be handled by the user through additional effort, for example making them water-soluble or tearable, water-insoluble, packaged individual dosing portions, or the cellulose ethers are, especially after storage, not completely dissolved in the water-containing liquid detergent or not evenly dispersed in it, which, in addition to being perceived as poor aesthetics, also leads to uneven dosage of the graying inhibitor active ingredient when using this containing agent leads.
  • the international patent application WO 2006/117056 A1 discloses the use of celluloses which have sulfoalkyl groups bonded via ether, ester or amide functions to prevent redeposition when washing textiles.
  • the international patent application WO 2014/124872 A1 discloses liquid detergents containing surfactants which contain sulfoethyl cellulose with a degree of substitution of 0.3 to 0.9 as the graying-inhibiting active ingredient.
  • the preferred number average molecular weight of the poly (propyleneoxy) propyl group is in the range from 300 g / mol to 400 g / mol.
  • the preferred number of carbon atoms in the radicals R 3 , R 6 and R 10 is, independently of one another, in each case in the range from 1 to 6.
  • copolymers of the general formula (I) whose number average molecular weight is in the range from 3,000 g / mol to 200,000 g / mol are preferred. Also preferred are those copolymers of the general formula (I) in which the proportion of m to the sum of m and n is in the range from 25% to 90% and the proportion of n to the sum of m and n is in the range of 10% up to 75%.
  • copolymers suitable according to the invention can be prepared by radical polymerization of primary 2-hydroxyalkyl-tetrahydrofuran-3,4-diol (meth) acrylic acid esters or 2-aminoalkyl-tetrahydrofuran-3,4-diol (meth) acrylic acid amides with (meth) acrylic acid or their Ci-io-alkyl esters or amides are prepared, it being possible for lower molecular weights to be enforced by added chain transfer agents.
  • the parts marked with the indices m and n can occur in blocks or randomly distributed in the copolymer essential to the invention, the random copolymers being preferred for the sake of simpler producibility.
  • R 3 is a methylene group
  • the copolymers suitable according to the invention contain, with the exception of parts originating from radical initiator or termination compounds, preferably no parts originating from monomers other than those which lead to the parts marked with the indices m and n.
  • An agent according to the invention preferably contains 0.01% by weight to 10% by weight, in particular 0.1% by weight to 5% by weight, of said copolymer of the general formula (I).
  • the invention also relates to the use of the above-mentioned copolymer of the general formula (I) in aqueous liquid detergents to improve the inhibition of graying when washing flat textile structures with the aqueous liquid detergent.
  • the detergent according to the invention contains water in amounts - based on the total detergent - of preferably up to 90% by weight and in particular from 30% by weight to 60% by weight, with this can, if desired, also be partially exchanged for a non-aqueous, water-soluble solvent or a non-aqueous, water-soluble solvent component can also be present.
  • Non-aqueous solvents that can be used in the liquid agents originate, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided 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, ethylene glycol mono-n-butyl 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 amount of the non-aqueous, water-soluble solvent component based on the total amount of the detergent and cleaning agent is preferably up to 15% by weight, in particular 0.5% by weight to 10% by weight.
  • the content of water that has not been exchanged for non-aqueous solvents is not more than 15% by weight, in particular 1% by weight to 8% by weight.
  • the liquid detergents contain surfactant, it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants.
  • anionic surfactants is preferred, 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 ranging from 10% by weight to 60% by weight, in particular 15% by weight to 50% by weight, in each case based on the total liquid agent.
  • the nonionic surfactants used are preferably alcohol alkoxylates, i.e. alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2- Position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, Ci 2 -i 4 alcohols with 3 EO, 4 EO or 7 EO, Cg-n alcohol with 7 EO, Ci3-i5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO , Ci2-is 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 Ci2-is alcohol with 7 EO.
  • the stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be a whole number or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples are 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 here, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • Mixed alkoxylated nonionic surfactants can also be used in which EO and PO units are not distributed in blocks, but rather statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • alkyl glycosides in particular of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms, can also be used as nonionic surfactants and G is the symbol that stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular 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 can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the alcohol alkoxylates, in particular not more than half that.
  • polyhydroxy fatty acid amides of the formula (II), in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are 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 (III),
  • R-CO-N- [Z] in which R stands for a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms, R 1 for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R 2 for one linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, Ci- 4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by 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 such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
  • the content of nonionic surfactants in the liquid detergents is preferably 5% by weight to 30% by weight, in particular 7% by weight to 20% by weight and particularly preferably 9% by weight to 15% by weight, each 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 and sulfate type can be used.
  • Surfactants of the sulfonate type are preferably Cg 13 -alkylbenzenesulphonates, olefinsulphonates, ie mixtures of alkene and hydroxyalkanesulphonates and disulphonates, such as those obtained, for example, from Ci2-is monoolefins with terminal or internal double bonds by sulphonation gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from Ci2-is-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the production 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 of glycerol.
  • 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) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of the Ci2-Ci8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cio-C2o-oxo alcohols and those Semi-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior similar to that of the appropriate compounds based on oleochemical raw materials. From the point of view of washing technology, the Ci2-Ci6-alkyl sulfates and Ci2-Cis-alkyl sulfates as well as Cn-Cis-alkyl sulfates are preferred.
  • the Schwefelklasted Acidmonoester of the above alcohol alkoxylates for example with 1 to 6 moles of ethylene ethoxylated linear or branched C7 2i alcohols such as 2-methyl-branched Cg-n-alcohols containing on average 3.5 mol ethylene oxide (EO) or Ci2 -is 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 represent the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Cs-is fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants (see description below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Preferred anionic surfactants are soaps.
  • 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, are suitable.
  • the detergent contains 2% by weight to 20% by weight, in particular 3% by weight to 15% by weight and particularly preferably 5% by weight to 10% by weight fatty acid soap.
  • Fatty acid soaps are an important component for the detergency of a liquid, especially aqueous, detergent and cleaning agent.
  • the anionic surfactants can 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 in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of anionic surfactants in preferred liquid detergents is 5% by weight to 35% by weight, in particular 8% by weight to 30% by weight and particularly preferably 10% by weight to 25% by weight, based in each case on the entire remedy. It is particularly preferred that the amount of fatty acid soap is at least 2% by weight, particularly preferably at least 3% by weight and in particular from 4% by weight to 10% by weight.
  • the agents contain at least 2, in particular 3, different anionic surfactants selected from alkylbenzenesulfonate, ether sulfate and fatty acid soap.
  • the detergent can contain a polyacrylate which acts as a co-builder and optionally also as a thickener.
  • the polyacrylates include polyacrylate or polymethacrylate thickeners, such as 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 the “International Dictionary of Cosmetic Ingredients” of “The Cosmetic Toiletry and Fragrance Association (CTFA) ”: Carbomer), which are also referred to as carboxyvinyl polymers.
  • CTFA Cosmetic Toiletry and Fragrance Association
  • Such polyacrylic acids are available 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 approx.
  • Preferred liquid detergents contain the polyacrylate in an amount of 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 acid and one or more Ci-C3o-alkyl esters of (meth) acrylic acid.
  • the viscosity of the liquid detergents and cleaning agents can be measured using customary standard methods (for example Brookfield LVT-II viscometer at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 150 mPas to 5000 mPas.
  • Preferred agents have viscosities of 500 mPas to 4000 mPas, with values of 1000 mPas to 3500 mPas being particularly preferred.
  • liquid detergents can contain other ingredients that further improve their application and / or aesthetic properties.
  • preferred agents contain one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, additional anti-redeposition agents or graying inhibitors, optical brighteners, anti-wrinkle agents, Dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellent and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • Builders that can be contained in the liquid agents include, in particular, silicates, aluminum silicates (especially 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 0 2x + i H2O, 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 are 2.3 or 4 are.
  • Preferred crystalline sheet silicates of the formula given are those in which M stands for sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 Os.yH 2 O are preferred.
  • the delay in dissolution compared with conventional amorphous sodium silicates can be brought about in various ways, for example by surface treatment, compounding, compaction / compression 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, as are typical for crystalline substances, but rather one or more maxima of the scattered X-ray radiation that have a width of several degree units of the diffraction angle.
  • Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compressed / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and / or P.
  • the zeolite P, zeolite MAP ® (commercially available from Crosfield) is especially preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable and are commercially available and, for example, a co-crystallizate of zeolite X and zeolite A (approx.
  • the zeolite can be used as a spray-dried powder or as an undried, stabilized suspension that is still moist from its manufacture.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups, Ci 2 -Ci 4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 mhi (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates As builder substances, provided that such use is not to be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and, in particular, tripolyphosphates are particularly suitable.
  • bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids that provide H2O2, such as perbenzoates, peroxophthalates, diperazelic acid, phthaloimino peracid or diperdodecanedioic acid. If present, these are preferably used in wrapped form in order to protect them against disintegration during storage.
  • bleach activators can be incorporated into the detergents and cleaning agents.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances are suitable carry the O- and / or N-acyl groups with the stated number of carbon atoms 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), are preferred, N-acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetine, Diacetoxy-2,5-dihydrofuran.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5
  • bleach catalysts can also be incorporated into the liquid detergents and cleaning agents.
  • These substances are bleach-intensifying transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen 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.
  • Particularly suitable enzymes are those from the class of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to maintain the color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or to inhibit color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to maintain the color and increase the
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used.
  • enzyme mixtures for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or of cellulase and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic acting enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically acting enzymes of particular interest.
  • lipolytically acting enzymes are the known cutinases.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • the cellulases used are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures of these. Because there are different types of cellulase differentiate by their CMCase and Avicelase activities, the desired activities can be set through targeted mixtures of the cellulases.
  • the bleach activators, catalysts and / or enzymes can be adsorbed and / or coated on carrier substances in order to protect them against premature decomposition.
  • the proportion of enzymes, liquid enzyme formulations, enzyme mixtures or enzyme granules can be, for example, about 0.1% by weight to 5% by weight, preferably 0.12% by weight to about 2.5% by weight, based in each case on the total agent , amount.
  • a wide number of the most varied salts can be used as electrolytes from the group of inorganic salts.
  • 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 MgCl2 in the agents is preferred.
  • the proportion of electrolytes in the agents is usually not more than 8% by weight, in particular 0.5% by weight to 5% by weight.
  • pH adjusting agents In order to bring the pH value of the liquid agent into the desired range, the use of pH adjusting agents may be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for technical or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 10% by weight of the formulation as a whole.
  • hydrotropes include the sulfonated hydrotropes such as, for example, the alkylarylsulfonates or alkylarylsulfonic acids.
  • Preferred hydrotropes are selected from xylene, toluene, cumene, naphthalene sulfonate or sulfonic acid and mixtures thereof.
  • Counter ions are preferably selected from sodium, calcium and ammonium.
  • the liquid agents can optionally comprise up to 20% by weight of a hydrotrope, in particular 0.05% by weight to 10% by weight.
  • dyes 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 the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, as well as no pronounced substantivity to textile fibers in order not to stain them.
  • Foam inhibitors which can be used in the liquid detergents and cleaning agents are, for example, soaps, paraffins or silicone oils, which can optionally also have been applied to carrier materials.
  • Suitable additional anti-redeposition agents which are also referred to as “soil repellents”, are, for example, the polymers known from the prior art of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • Optical brighteners can be added to the liquid detergents and cleaning agents in order to remove yellowing of the treated textile fabrics. These substances are absorbed by the fiber and cause a lightening effect by converting ultraviolet radiation, invisible to the human eye, into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a faint bluish fluorescence and, with the yellow tone of yellowed laundry, results in pure white.
  • Suitable compounds originate from the substance classes of the 4,4 'diamino-2,2-stilbenedisulfonic acids (flavonic), 4,4'-biphenylene -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles.
  • 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.
  • the agents can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid esters or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • the liquid washing and cleaning agents can contain antimicrobial active ingredients.
  • antimicrobial active ingredients bacteriostatics and bactericides, fungistats and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely with the agents according to the invention.
  • the agents can contain antioxidants.
  • Class include, for example, substituted phenols, hydroquinones, catechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • antioxidants are used, the agents according to the invention are naturally free from oxidizing bleaching agents.
  • Antistatic agents increase the surface conductivity and thus enable the charges that have formed to flow off better.
  • External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give the surfaces a more or less hygroscopic film. These mostly surface-active antistatic agents can be divided 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 additives to detergents, with an additional softening effect being achieved.
  • silicone derivatives can be used in the liquid detergents and cleaning agents. These also improve the rinsing behavior of the agents through their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which can 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 at 25 ° C. in the range between 100 and 100,000 mPas, it being possible to use the silicones in amounts between 0.2 and 5% by weight, based on the total agent.
  • the liquid washing and cleaning agents can also contain UV absorbers which are absorbed onto the treated textile fabrics and improve the light resistance of the fibers.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position which are effective by radiationless deactivation.
  • Substituted benzotriazoles, acrylates substituted by phenyl in the 3-position (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and urocanic acid are also suitable.
  • substances can be used that complex heavy metals.
  • Suitable heavy metal complexing agents are, for example, the alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) as well as 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 used in preferred liquid agents in amounts from 0.01% by weight to 2.5% by weight, preferably from 0.02% by weight to 2% by weight and in particular from 0.03 wt .-% to 1.5 wt .-% are included.
  • These preferred compounds include, in particular, organophosphonates such as, for example, 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic 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, for example, 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (D
  • a liquid detergent and cleaning agent can also contain particles dispersed therein, the diameter of which along their greatest spatial extent is, for example, 100 ⁇ m to 10,000 ⁇ m.
  • particles can be microcapsules or speckles as well as granules, compounds and scented pearls, 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 made of polymer (s) solid phases, during the manufacture 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 powders.
  • multi-core aggregates also called microspheres, are known, the two or more cores Single or multi-core microcapsules can also be enclosed by an additional second, third, etc. shell.
  • Single-core microcapsules with a continuous shell are preferred.
  • the shell can be made of natural, semi-synthetic or synthetic mat materials exist.
  • coating materials are, for example, gum arabic, agar-agar, agarose, maltodextrins, alginic acid or their salts, e.g. 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 casing materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose and carboxymethyl cellulose, and starch derivatives, in particular starch ethers and esters.
  • Synthetic shell materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
  • the microcapsules can contain, for example, optical brighteners, surfactants, complexing agents, bleaches, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial active ingredients, antiredeposition agents, pH adjusters, electrolytes, foam inhibitors and / or UV absorbers are located.
  • the microcapsules can contain, for example, vitamins, proteins, preservatives, detergency boosters or pearlescent agents.
  • the fillings of the microcapsules can be solids or liquids in the form of solutions or emulsions or suspensions.
  • the microcapsules can have any shape within the scope of production, but they are preferably approximately spherical. Their diameter along their greatest spatial extent can, depending on the components contained in their interior and the application, be between 0.01 ⁇ m (visually not recognizable as a capsule) and 10,000 ⁇ m. Visible microcapsules with a diameter in the range from 100 ⁇ m to 7,000 ⁇ m, in particular from 400 ⁇ m to 5,000 ⁇ m, are preferred.
  • the microcapsules can be obtained by methods known in the art, the coacervation and the interfacial polymerization being of the greatest importance.
  • microcapsules All surfactant-stable microcapsules available on the market can be used as microcapsules, for example the commercial products (the shell material is indicated in each case in brackets) Hallcrest Microcapsules (gelatine, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec Millicapsules (alginic acid, agar-agar) , Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar) and Kuh's Probiol Nanospheres (phospholipids).
  • Hallcrest Microcapsules gelatine, gum arabic
  • Coletica Thalaspheres maritime collagen
  • Lipotec Millicapsules alginic acid, agar-agar
  • particles which do not have a core-shell structure but in which the active ingredient is distributed in a matrix made of a matrix-forming material.
  • Such particles are also known as “speckles”.
  • a preferred matrix-forming material is alginate.
  • an aqueous alginate solution which also contains the active ingredient or ingredients to be included, is dripped and then hardened in a precipitation bath containing Ca 2+ ions or Al 3+ ions.
  • the alginate-based speckles are then washed with water and then washed in an aqueous solution with a complexing agent in order to remove free Ca 2+ ions or free Al 3+ ions, which undesired interactions with ingredients of the liquid detergent, for example the fatty acid soaps, can be washed out.
  • the alginate-based speckles are then washed with water in order to remove excess complexing agents.
  • other 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, hydroxy cellulose, hydroxypropyl cellulose, hydroxyproethyl Hyaluronic acid, carboxymethyl cellulose, carboxymethyl cellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials.
  • the matrix formation takes place, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the prior art, as is the production of particles with these matrix-forming materials.
  • the particles can be dispersed stably in the aqueous liquid detergents and cleaning agents. Stable means that the agents are stable at room temperature and at 40 ° C. over a period of at least 4 weeks and preferably for at least 6 weeks without the agents creaming or sedimenting.
  • the liquid detergents contain the same or different particles in amounts of 0.01 to 10% by weight, in particular 0.2 to 8% by weight and extremely preferably 0.5 to 5% by weight.
  • Aqueous detergents and cleaning agents can be produced inexpensively and easily in conventional mixing and filling systems.
  • 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 point in time, but the addition can also take place at a later point in time.
  • the complexing agent is added to these components.
  • a base such as NaOH, KOH, triethanolamine or monoethanolamine, followed by the fatty acid, if present, is then added.
  • the remaining ingredients and optionally the remaining solvents of the aqueous liquid agent are then added to the mixture and the pH is adjusted to the desired value.
  • the particles to be dispersed can be added and homogeneously distributed in the aqueous liquid agent by mixing. Examples
  • Example 2 Composition of and graying tests with detergents containing the copolymers
  • household washing machines Moele W1935
  • the dosage of the detergent was 50 ml, washing was carried out at a temperature of 40 ° C. in the normal program.
  • 1 GRAYING SWATCH II and 5 SBL2004 cloths both obtained from wfk Testabric GmbH, were added as dirt. This has been replicated five times.
  • the laundry was then measured colorimetrically and the brightness value (Y value) was determined (in each case the arithmetic mean of 5 measuring points) and compared with the values for the unwashed laundry.
  • Y value the brightness value
  • Table 2 shows the DDU values (differences between the brightness differences before and after washing between V1 and E1).
  • the detergent with the copolymer essential to the invention inhibited the graying of the various textiles better than the detergent without the polymer.

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

Abstract

L'invention concerne un détergent liquide aqueux contenant un tensioactif et éventuellement d'autres constituants classiques, le détergent contenant un copolymère contenant des entités qui peuvent être obtenues à partir de matières premières renouvelables et qui sont liées, par l'intermédiaire de liaisons ester ou amide, à une chaîne principale pouvant être obtenue par la polymérisation de monomères à insaturation éthylénique.
PCT/EP2020/078688 2019-10-21 2020-10-13 Détergents anti-redéposition WO2021078577A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367049A2 (fr) * 1988-10-31 1990-05-09 BASF Aktiengesellschaft Utilisation de copolymères estérifiés partiellement pour compositions détergentes liquides
DE102009027812A1 (de) * 2009-07-17 2011-01-20 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit vergrauungsinhibierendem Polymer
DE102013226151A1 (de) * 2013-12-17 2015-06-18 Henkel Ag & Co. Kgaa Vergrauungsinhibierende Waschmittel
DE102017010656A1 (de) * 2017-11-17 2019-05-23 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel mit polymerem Wirkstoff

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0367049A2 (fr) * 1988-10-31 1990-05-09 BASF Aktiengesellschaft Utilisation de copolymères estérifiés partiellement pour compositions détergentes liquides
DE102009027812A1 (de) * 2009-07-17 2011-01-20 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit vergrauungsinhibierendem Polymer
DE102013226151A1 (de) * 2013-12-17 2015-06-18 Henkel Ag & Co. Kgaa Vergrauungsinhibierende Waschmittel
DE102017010656A1 (de) * 2017-11-17 2019-05-23 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel mit polymerem Wirkstoff

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