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EP1863895B1 - Produit nettoyant ou detergent transparent a limite d'ecoulement - Google Patents

Produit nettoyant ou detergent transparent a limite d'ecoulement Download PDF

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Publication number
EP1863895B1
EP1863895B1 EP06707517A EP06707517A EP1863895B1 EP 1863895 B1 EP1863895 B1 EP 1863895B1 EP 06707517 A EP06707517 A EP 06707517A EP 06707517 A EP06707517 A EP 06707517A EP 1863895 B1 EP1863895 B1 EP 1863895B1
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EP
European Patent Office
Prior art keywords
cleaning agent
clear
washing
acid
propanediol
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EP06707517A
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German (de)
English (en)
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EP1863895A1 (fr
Inventor
Hermann Jonke
Bernhard Orlich
Piotr Malecki
Thomas Plantenberg
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D3/2068—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
    • 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

Definitions

  • the invention relates to a clear, liquid washing and cleaning agent with yield point, containing surfactant (s) and other conventional ingredients of detergents and cleaners.
  • liquid detergents and cleaning agents which, even after storage and transport, develop optimally at the time of use. This implies that the ingredients of the liquid detergent and cleaning agent have previously neither sedimented, decomposed or volatilized.
  • a concept for the incorporation of sensitive, chemically or physically incompatible as well as volatile components consists in the use of particles and in particular microcapsules in which these ingredients are trapped stable storage and transport.
  • liquid aqueous cleaning agents containing at least 2 wt .-% triethanolamine lauryl sulfate, a total of 8 to 50 wt .-% surfactant and 0.1 to 5 wt .-% suspended phase, for example, spheroidal capsules having a diameter of 0.1 to 5 mm contained, and have a pH of 5.5 to 11.
  • a homogeneous distribution of the suspended phase is achieved by using water-soluble acrylic acid polymers such as Carbopol 941.
  • the application contains no information as to whether the liquid aqueous cleaning agents have yield points.
  • the WO 97/12027 discloses liquid detergents having a pH of 5 to 9 (at 10% dilution), containing 10 to 40% by weight of anionic surfactants, 1 to 10% by weight of amine oxides, less than 10% by weight of solvent, and of 0 contain up to 10 wt .-% electrolyte.
  • the liquid has one Viscosity of 100 to 4000 cps at a shear rate of 20 s -1 and is able to suspend particles up to a size of 200 microns.
  • One way to suspend particles in a liquid is to use structured liquids.
  • structured liquids A distinction is made between internal and external structuring.
  • External structuring can be achieved, for example, by using structuring gums such as, for example, xanthan gum, guar gum, locust bean gum, gellan gum, wellan gum or carrageenan or of polyacrylate thickeners.
  • liquid detergents in which the particles are suspended are transparent or at least translucent.
  • structuring gums often leads to cloudy composition.
  • liquid detergents which are capable of suspending particles having a size of 300 to 5000 microns, comprising at least 15 wt .-% of surfactant and 0.01 to 5 wt .-% of a polymeric gum.
  • the application contains no information as to whether the liquid detergents have yield points.
  • EP 1 466 959 A1 are flow-containing formulations having high levels of anionic surfactants, which have no polymeric thickener, but an anionic and cationic surfactants in a specific, effective for generating a yield point ratio.
  • a clear, liquid washing and cleaning agent containing surfactant (s) and other conventional ingredients of detergents and cleaners, wherein the agent comprises a polyacrylate and a solvent component comprising a mixture of dipropylene glycol and 1,2-propanediol and wherein the ratio of dipropylene glycol to 1,2-propanediol is 3: 1 to 1: 3.
  • the ratio of dipropylene glycol to 1,2-propanediol is 1: 1.
  • the amount of the solvent component is 0.5 to 15% by weight, and preferably 2 to 9% by weight.
  • the amount of polyacrylate is 0.1 to 10 wt .-% and preferably 2 to 5 wt .-%.
  • washing and cleaning agent is aqueous.
  • Aqueous detergents and cleaners can be inexpensively and easily manufactured in existing systems.
  • the washing and cleaning agent contains dispersed particles, particularly preferably microcapsules or speckles, whose diameter along their greatest spatial extent is 0.01 to 10,000 ⁇ m.
  • microcapsules or speckles sensitive, chemically or physically incompatible and volatile components of the aqueous liquid detergent and cleaning agent can be trapped stable storage and transport and dispersed homogeneously in the aqueous liquid detergent and cleaning agent. This ensures, among other things, that the washing and cleaning agent is available to the consumer at the time of use with full vigilance and cleaning power.
  • the washing and cleaning agent contains between 2 and 20 wt .-%, preferably between 3 and 10 wt .-% and most preferably between 4 and 8 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 when using a thickening system of polyacrylate and a solvent component comprising dipropylene glycol in the presence of high amounts of fatty acid soap clear, stable and thickened liquid detergents and cleaning agents are obtained with yield point. Typically, the use of high levels ( ⁇ 2% by weight) of fatty acid soap in such systems results in cloudy and / or unstable products.
  • the invention also relates to the use of a clear, liquid washing and cleaning agent according to the invention for cleaning textile fabrics or hard surfaces.
  • the invention further relates to a process for the preparation of a clear, liquid washing and cleaning agent containing surfactant (s) and other conventional ingredients of detergents and cleaners, comprising a polyacrylate as thickener and a solvent component comprising a mixture of dipropylene glycol and 1, 2-propanediol, wherein the ratio of dipropylene glycol to 1,2-propanediol is 3: 1 to 1: 3, is used.
  • surfactant s
  • solvent component comprising a mixture of dipropylene glycol and 1, 2-propanediol, wherein the ratio of dipropylene glycol to 1,2-propanediol is 3: 1 to 1: 3, is used.
  • the invention also relates to the use of a polyacrylate and a solvent component comprising a mixture of dipropylene glycol and 1,2-propanediol wherein the ratio of dipropylene glycol to 1,2-propanediol is 3: 1 to 1: 3 to produce a clear, liquid wash and cleaning agent with yield point.
  • washing and cleaning agents according to the invention are described in detail below, inter alia, by way of examples.
  • the washing and cleaning agent contains as thickener a polyacrylate.
  • the polyacrylates include polyacrylate or polymethacrylate thickeners, such as, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to "International Dictionary of Cosmetic Ingredients", The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from Noveon under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight approx 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000).
  • Polygel® for example Polygel DA
  • Carbopol® for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight approx 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000).
  • acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C 1-4 -alkanols (INCI acrylates copolymer), such as 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, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (cross-linked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852 -37-3); (i) Copo
  • Preferred liquid washing and cleaning agents contain the polyacrylate in an amount of 0.1 to 10 wt .-% and preferably 2 to 5 wt .-%.
  • 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 washing and cleaning agent contains a solvent component comprising dipropylene glycol and 1,2-propanediol.
  • the solvent component is dipropylene glycol and 1,2-propanediol.
  • the ratio of dipropylene glycol to 1,2-propanediol is between 3: 1 and 1: 3 and is most preferably 1: 1.
  • the amount of the solvent component based on the total amount of the washing and cleaning agent is 0.5 to 15 wt .-% and preferably 2 to 9 wt .-%.
  • the liquid detergents and cleaners contain surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.
  • the total surfactant content of the liquid washing and caremittei is preferably below 40 wt .-% and more preferably below 35 wt.%, Based on the total liquid detergent and cleaning agent.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture may contain, as they are usually present in Oxoalkcholresten.
  • alcohol ethoxylates with linear residues of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -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 homologous distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants 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.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 C 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 ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (2) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group 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 (3), 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 and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is at least substituted 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 is the liquid detergents and cleaners preferably 5 to 30 wt .-%, preferably 7 to 20 wt .-% and in particular 9 to 15 wt.%, Each based on the total agent.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning 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.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 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.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • 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 8-18 fatty alcohol radicals or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Particularly 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 anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of preferred liquid detergents and cleaners to anionic surfactants is 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-%, each based on the total agent. It is particularly preferred that the amount of fatty acid soap is at least 2% by weight and more preferably at least 3% by weight and most preferably at least 4% by weight.
  • the viscosity of the liquid detergents and cleaning agents can be measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 1500 to 5000 mPas.
  • Preferred agents have viscosities of 2000 to 4000 mPas, with values around 3500 mPas being particularly preferred.
  • the liquid detergents and cleaners may contain other ingredients that further improve the performance and / or aesthetic properties of the liquid detergent and cleaning agent.
  • preferred agents comprise one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, additional nonaqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, 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.
  • Suitable builders which may be present in the liquid detergents and cleaners are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 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 ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • 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 are washed out in electron diffraction experiments or even provide sharp diffraction maxima. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic 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 particularly preferred.
  • 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 C 12 -C 18 fatty alcohols with. 2 to 5 ethylene oxide groups, C 12 -C 14 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 are possible, unless such use should not be avoided for environmental 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.
  • bleach activators can be incorporated into the detergents and cleaners.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-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 can also be incorporated into the liquid detergents and cleaners.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline 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 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 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 celloblohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes may be adsorbed to carriers to protect against premature degradation.
  • the proportion of the enzymes, enzyme liquid formulations, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt.%, Preferably 0.12 to about 2.5 wt.%.
  • 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 agents is usually 0.5 to 5 wt .-%.
  • the clear, liquid detergents and cleaners are particularly preferably aqueous, ie they have a water content of greater than 5% by weight, preferably greater than 15% by weight and more preferably greater than 25% by weight.
  • non-aqueous solvents that can be used in the liquid detergents and cleaners, for example, from the group 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, glycol, butanediol, glycerol, diglycol, butyldiglycol, 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, di-isopropylene 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 solvents.
  • aqueous liquid detergents and cleaners can be used in aqueous liquid detergents and cleaners, in amounts of between 0.5 and 8% by weight, but preferably below 5% by weight and in particular below 3% by weight. These amounts are independent of the amount of solvent component in aqueous detergents and cleaners.
  • pH adjusters In order to bring the pH of the liquid detergents and cleaners into the desired range, the use of 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. Usually, 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 detergents and cleaners may comprise from 0.01% to 20% by weight of a hydrotrope, more preferably from 0.05% to 10%, and most preferably from 0.1% to 5% by weight.
  • dyes In order to improve the aesthetic impression of the liquid washing and cleaning agents, they can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • Suitable foam inhibitors which can be used in the liquid detergents and cleaners are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable anti-redeposition agents which are also referred to as "soil repellents" are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on nonionic cellulose ethers and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.
  • 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 graying and yellowing of the treated textile fabrics. These substances are absorbed by the fiber and cause lightening and fake bleaching by turning invisible ultraviolet radiation into visible longer wavelength Converting light, wherein the ultraviolet light absorbed from the sunlight is emitted as a faint bluish fluorescence and with the yellow color of the grayed or yellowed laundry results in 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, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.
  • the optical brighteners are usually used in amounts of between 0.03 and 0.3 wt .-%, based on the finished composition.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • 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 in amounts of from 0.1 to 5% by weight, based on the compositions.
  • compositions may contain synthetic crease inhibitors.
  • synthetic products based on fatty acids, fatty acid esters, fatty acid amides, -alkylolestern, -alkylolamiden or fatty alcohols which are usually reacted with ethylene oxide, or products based on lecithin or modified, phosphoric acid ester.
  • 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.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • External antistatic agents are, for example, lauryl (or stearyl) dimethylbenzylammonium chlorides, which are suitable as antistatic agents for textile fabrics or as an additive to laundry detergents, wherein additionally a finishing effect is achieved.
  • silicone derivatives can be used in the liquid detergents and cleaners. 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 the body's own urocanic acid.
  • Suitable heavy metal complexing agents For example, the alkali metal salts of ethylenediamine tetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediamine tetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which in preferred liquid detergents and cleaners in amounts of from 0.01 to 2.5 wt .-%, preferably 0.02 to 2 wt .-% and in particular from 0.03 to 1 , 5 wt .-% are included.
  • These preferred compounds include, in particular, organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts.
  • organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP
  • the resulting liquid detergents and cleaners are clear, that is they have no sediment and are preferably 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 detergent and cleaning agent may contain dispersed particles whose diameter along their greatest spatial extent is from 0.01 to 10,000 ⁇ m.
  • 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.
  • einkemigen microcapsules and polynuclear 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.
  • Natural filling materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, Lecithins, gelatin, albumin, shellac, polysaccharides such as starch or dextran, sucrose and waxes.
  • Semi-synthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and also starch derivatives, in particular starch ethers and esters.
  • Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
  • active ingredients for example, optical brighteners, surfactants, complexing agents, bleaching agents, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, grayness inhibitors, anti redeposition agents, pH adjusters, electrolytes, foam inhibitors and UV absorbers are located.
  • the microcapsules may contain, for example, cationic surfactants, 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 (the shell material is indicated in parentheses) Hallcrest microcapsules (gelatin, gum arabic), Coletica thalaspheres (marine collagen), Lipotec millicapsules (alginic acid, agar-agar) , Also 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 arabic
  • Coletica thalaspheres marine collagen
  • Lipotec millicapsules alginic acid, agar-agar
  • unispheres lactose, microcrystalline
  • 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 "speckles”.
  • a preferred matrix-forming material is alginate.
  • 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 again with water to remove excess complexing agent.
  • matrix-forming materials can be used instead of alginate.
  • matrix-forming materials include polyethylene glycol, polyvinylpyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, ficoll®, starch, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hyaluronic acid, Carboxymethylcellulose, carboxymethylcellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials.
  • the matrix formation in these materials takes place for example via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the art as well as the production of particles with these matrix-forming materials.
  • the particles can be stably dispersed in the aqueous liquid detergent and cleaner.
  • Stable means that the compositions are stable at room temperature and at 40 ° C for a period of at least 4 weeks, and preferably at least 6 weeks, without the medium creaming or sedimenting.
  • the release of the active ingredients from the microcapsules or speckles is usually carried out during the application of the agents containing them by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action.
  • the liquid detergents and cleaners contain identical or different particles in amounts of from 0.01 to 10% by weight, in particular from 0.2 to 8% by weight and very preferably from 0.5 to 5% by weight. -%.
  • the detergents and cleaning agents according to the invention can be used for cleaning textile surface fabrics and / or hard surfaces.
  • the acidic components such as the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc. and the nonionic surfactants are presented.
  • the solvent component is preferably also added at this time, but the addition may also be made at a later time.
  • To these components is added the polyacrylate.
  • a base such as NaOH, KOH, triethanolamine or monoethanolamine is added followed by the fatty acid, if any.
  • the remaining ingredients and the remaining solvents of the aqueous liquid detergent and cleaner are added to the mixture and the pH is adjusted to about 8.5.
  • the particles to be dispersed can be added and distributed homogeneously in the aqueous liquid washing and cleaning agent by mixing.
  • Table 1 shows washing and cleaning agents E1 to E4 according to the invention and a comparative example V1 and V2 .
  • the washing and cleaning agents E1 to E4 obtained were clear, had a viscosity of 3,000 mPas and a yield point ⁇ 0.6 Pa.
  • the pH of the liquid detergents and cleaners was 8.5. All information is given in weight percent, in each case based on the total mean.
  • the flow limits were determined on an AR 1000-N rheometer from Texas Instruments at a temperature of 25 ° C.
  • the four detergents E1 to E4 were stable at room temperature and at 40 ° C for 8 weeks.

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Claims (12)

  1. Agent de lavage et de nettoyage limpide, liquide, présentant une limite d'écoulement, contenant un ou plusieurs tensioactifs ainsi que d'autres constituants usuels des agents de lavage et de nettoyage, l'agent contenant un polyacrylate comme épaississant et un composant de type solvant, comprenant un mélange de dipropylèneglycol et de 1,2-propanediol, et le rapport dipropylèneglycol à 1,2-propanediol valant 3:1 à 1:3.
  2. Agent de lavage et de nettoyage limpide, liquide selon la revendication 1, caractérisé en ce que le rapport dipropylèneglycol à 1,2-propanediol vaut 1:1.
  3. Agent de lavage et de nettoyage limpide, liquide selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que la quantité de composant de type solvant est de 0,5 à 15% en poids et de préférence de 2 à 9% en poids.
  4. Agent de lavage et de nettoyage limpide, liquide selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la quantité de polyacrylate est de 0,1 à 10% en poids et de préférence de 2 à 5% en poids.
  5. Agent de lavage et de nettoyage limpide, liquide selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le polyacrylate est un copolymère d'un acide monocarboxylique ou dicarboxylique insaturé et d'un ou de plusieurs esters C1-C30-alkyliques de l'acide (méth)acrylique.
  6. Agent de lavage et de nettoyage limpide, liquide selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'agent de lavage et de nettoyage est aqueux.
  7. Agent de lavage et de nettoyage limpide, liquide selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'agent de lavage et de nettoyage contient des particules dispersées dont le diamètre, le long de leur plus grande extension dans l'espace, est de 0,01 à 10 000 µm.
  8. Agent de lavage et de nettoyage limpide, liquide selon la revendication 7, caractérisé en ce que les particules dispersées sont des microcapsules ou des mouchetures (Spechles).
  9. Agent de lavage et de nettoyage limpide, liquide selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'agent de lavage et de nettoyage contient entre 2 et 20% en poids, de préférence entre 3 et 10% en poids et de manière tout particulièrement préférée entre 4 et 8% en poids de savons d'acide gras.
  10. Utilisation de l'agent de lavage et de nettoyage limpide, liquide selon les revendications 1 à 9 pour le nettoyage de structures planes textiles ou de surfaces dures.
  11. Procédé de préparation d'un agent de lavage et de nettoyage limpide, liquide, contenant un ou plusieurs agents tensioactifs ainsi que d'autres constituants usuels des agents de lavage et de nettoyage, dans lequel on utilise un polyacrylate comme épaississant et un composant de type solvant, comprenant un mélange de dipropylèneglycol et de 1,2-propanediol, le rapport de dipropylèneglycol à 1,2-propanediol valant 3:1 à 1:3.
  12. Utilisation d'un polyacrylate et d'un composant de type solvant, comprenant un mélange de dipropylèneglycol et de 1,2-propanediol, le rapport de dipropylèneglycol à 1,2-propanediol valant 3:1 à 1:3 pour la préparation d'un agent de lavage et de nettoyage limpide, liquide, présentant une limite d'écoulement.
EP06707517A 2005-04-01 2006-03-10 Produit nettoyant ou detergent transparent a limite d'ecoulement Active EP1863895B1 (fr)

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Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2016161B1 (fr) * 2006-05-08 2009-11-18 Ecolab Inc. Nettoyant acide pour surfaces métalliques
DK2308957T3 (da) * 2006-12-15 2013-05-13 Colgate Palmolive Co Flydende vaskemiddel-sammensætning
US8017566B2 (en) * 2009-11-13 2011-09-13 Conopco, Inc. Liquid personal cleansing composition
EP2336285B1 (fr) * 2009-12-18 2013-09-04 The Procter & Gamble Company Composition comprenant des microcapsules
JP5086450B2 (ja) * 2010-01-21 2012-11-28 三洋化成工業株式会社 磁気ディスク基板用洗浄剤
JP5832813B2 (ja) * 2011-08-11 2015-12-16 花王株式会社 液体洗浄剤組成物
WO2014200658A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase issue de promicromonospora vindobonensis
WO2014200657A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant destreptomyces xiamenensis
WO2014200656A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant de streptomyces umbrinus
WO2014204596A1 (fr) 2013-06-17 2014-12-24 Danisco Us Inc. Alpha-amylase issue d'un membre de la famille des bacillaceae
EP3060659B1 (fr) 2013-10-03 2019-05-29 Danisco US Inc. Alpha-amylases de exiguobacterium, methodes et utilisation
US20160186102A1 (en) 2013-10-03 2016-06-30 Danisco Us Inc. Alpha-amylases from exiguobacterium, and methods of use, thereof
EP3071691B1 (fr) 2013-11-20 2019-10-23 Danisco US Inc. Variants d'alpha-amylases ayant une sensibilité réduite au clivage protéasique, et leurs procédés d'utilisation
DE102014226456A1 (de) * 2014-12-18 2016-06-23 Henkel Ag & Co. Kgaa Waschmittelprodukt, umfassend flüssiges Waschmittel mit Fließgrenze in einer Verpackung mit Abgabevorrichtung
EP3101106B1 (fr) * 2015-06-05 2019-04-24 The Procter and Gamble Company Composition de detergent liquide compacte pour blanchisserie
DE102015217890A1 (de) 2015-09-17 2017-03-23 Henkel Ag & Co. Kgaa Transparente Flüssigkeiten, insbesondere Textilbehandlungsmittel, enthaltend Riechstoff und Mikrokapseln mit Geruchsmodulationsverbindung
EP3202878B1 (fr) * 2016-02-05 2020-05-13 The Procter and Gamble Company Article de dose unitaire soluble dans l'eau
WO2017173324A2 (fr) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions et procédés
WO2017173190A2 (fr) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions et procédés
WO2017216212A1 (fr) * 2016-06-16 2017-12-21 Henkel Ag & Co. Kgaa Détergents à lessive liquides isotropes concentrés contenant des polymères
WO2017216216A1 (fr) * 2016-06-16 2017-12-21 Henkel Ag & Co. Kgaa Détergents à lessive liquides isotropes concentrés contenant de polymères
DE102016217304A1 (de) 2016-09-12 2018-03-15 Henkel Ag & Co. Kgaa Wasserlöslicher Beutel mit einem Wasch- oder Reinigungsmittel und Makropartikeln
JP6445505B2 (ja) * 2016-10-07 2018-12-26 花王株式会社 機械洗浄前洗い用食器洗浄剤組成物
WO2018229035A1 (fr) * 2017-06-16 2018-12-20 Henkel Ag & Co. Kgaa Détergent ou produit de nettoyage liquide contenant un dérivé de glucosamine
JP7408497B2 (ja) * 2020-06-26 2024-01-05 Ｓａｎｅｉ株式会社 水栓装置
US20230348739A1 (en) * 2022-04-29 2023-11-02 N.J. Solar & Safety Film LLC / DBA National National Window Film Ultraviolet (uv) absorbing inks and films for glass

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942217A (en) * 1997-06-09 1999-08-24 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US6033679A (en) * 1998-04-27 2000-03-07 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US5958856A (en) * 1989-09-22 1999-09-28 Colgate-Palmolive Co Liquid crystal compositions containing a polyethylene abrasive
JPH04120012A (ja) * 1990-09-10 1992-04-21 Sakamoto Yakuhin Kogyo Kk 透明ゲル状洗浄料
US5240633A (en) * 1991-05-31 1993-08-31 Colgate-Palmolive Company Liquid automatic dishwashing composition containing enzymes
US5656257A (en) * 1995-04-28 1997-08-12 Electronics Hair Styling, Inc. Shampoo and conditioning composition
DE19539846C1 (de) * 1995-10-26 1996-11-21 Henkel Kgaa Esterquats
US5985817A (en) * 1997-02-24 1999-11-16 Reckitt & Colman South Africa Ltd. Pourable, thickened aqueous bleach and abrasive containing compositions
DE19714424A1 (de) * 1997-04-08 1998-10-15 Beiersdorf Ag Kosmetische und dermatologische waschaktive Zubereitungen, enthaltend Acrylatcopolymere, Alkylglucoside und Alkohole
AU4356997A (en) * 1997-06-09 1998-12-30 Procter & Gamble Company, The Malodor reducing composition containing amber and musk materials
ID28183A (id) * 1997-06-09 2001-05-10 Procter & Gamble Komposisi-komposisi pembersih makanan yang mengandung siklodekstrin
DE19743687C1 (de) * 1997-10-06 1998-11-26 Henkel Kgaa Detergensgemische und deren Verwendung
JP2001520304A (ja) * 1997-10-23 2001-10-30 ザ、プロクター、エンド、ギャンブル、カンパニー 脂肪酸、石鹸、界面活性剤系、およびそれらをベースにした消費製品
US5874395A (en) * 1997-12-29 1999-02-23 Colgate-Palmolive Company Liquid rinse cycle fabric softening compositions containing diacid polymeric fatty ester quaternary ammonium compounds
US6573233B1 (en) * 1998-08-25 2003-06-03 The Procter & Gamble Company Wrinkle and malodour reducing composition
US6533873B1 (en) * 1999-09-10 2003-03-18 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Suspending clear cleansing formulation
WO2002010503A1 (fr) * 2000-07-28 2002-02-07 Unilever N.V. Composition facilitant le repassage
DE10039100A1 (de) * 2000-08-07 2002-02-28 Henkel Kgaa Desodorierendes Textilbehandlungsmittel
DE10153554A1 (de) * 2001-07-07 2003-05-15 Henkel Kgaa Wäßrige "3in1"-Geschirrspülmittel II
US20030114335A1 (en) * 2001-12-11 2003-06-19 Goldschmidt Chemical Company Blend of imidazolinium quat and dialkyl dimethyl quat for use in high-solids fabric softeners with premium softening and viscosity properties
JP4173712B2 (ja) * 2002-04-12 2008-10-29 花王株式会社 洗浄剤組成物
US20050176614A1 (en) * 2002-10-16 2005-08-11 Heinz-Dieter Soldanski Transparent abrasive cleaning product, especially manual dishwashing liquid
DE10248313A1 (de) * 2002-10-16 2004-05-06 Henkel Kgaa Transparentes abrasives Reinigungsmittel, insbesondere Handgeschirrspülmittel
US6924261B2 (en) * 2002-11-01 2005-08-02 Colgate-Palmolive Co. Aqueous composition comprising oligomeric esterquats
DE10316001A1 (de) * 2003-04-07 2004-10-21 Goldschmidt Ag Wässrige Formulierungen enthaltend Kombinationen aus anionischen und kationischen Tensiden zur Erzeugung einer Fließgrenze
EP1502944B1 (fr) * 2003-08-01 2007-02-28 The Procter & Gamble Company Composition détergente aqueuse liquide comprenant des particules visibles

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ES2395042T3 (es) 2013-02-07
DE102005015328A1 (de) 2006-10-05
WO2006102978A1 (fr) 2006-10-05
US20090075857A1 (en) 2009-03-19
JP2008534718A (ja) 2008-08-28
EP1863895A1 (fr) 2007-12-12
PL1863895T3 (pl) 2013-03-29

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