EP1863895A1 - Produit nettoyant ou detergent transparent a limite d'ecoulement - Google Patents

Produit nettoyant ou detergent transparent a limite d'ecoulement

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Publication number
EP1863895A1
EP1863895A1 EP06707517A EP06707517A EP1863895A1 EP 1863895 A1 EP1863895 A1 EP 1863895A1 EP 06707517 A EP06707517 A EP 06707517A EP 06707517 A EP06707517 A EP 06707517A EP 1863895 A1 EP1863895 A1 EP 1863895A1
Authority
EP
European Patent Office
Prior art keywords
cleaning agent
clear
liquid
washing
agent according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06707517A
Other languages
German (de)
English (en)
Other versions
EP1863895B1 (fr
Inventor
Hermann Jonke
Bernhard Orlich
Piotr Malecki
Thomas Plantenberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
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Priority to PL06707517T priority Critical patent/PL1863895T3/pl
Publication of EP1863895A1 publication Critical patent/EP1863895A1/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
    • 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 compositions which contain at least 2% by weight of triethanolamine lauryl sulfate, a total of 8 to 50% by weight of surfactant and 0.1 to 5% by weight of suspended phase, for example containing spheroidal capsules with a diameter of 0.1 to 5 mm, and having 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.
  • 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. % Solvent and from 0 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 are described, 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.
  • liquid detergents described in WO 00/36078 have only small amounts of fatty acid soaps ( ⁇ 1.42% by weight).
  • EP 1 466 959 A1 describes flow-limiting formulations containing large amounts of anionic surfactants which have no polymeric thickener but instead an anionic and cationic surfactant in a specific ratio which is effective to produce a flow limit. It is an object of the present invention to provide a clear liquid flow-type detergent and cleaner which is stable in storage and transport and capable of homogeneously dispersing particles.
  • a clear, liquid washing and cleaning agent containing surfactant (s) and other conventional ingredients of detergents and cleaning agents, wherein the agent contains a polyacrylate and a solvent component comprising dipropylene glycol.
  • the solvent component comprises a mixture of dipropylene glycol and 1,2-propanediol
  • the ratio of dipropylene glycol to 1,2-propanediol be 3: 1 to 1: 3. It is particularly preferred that 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, in particular 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.
  • 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 washing and cleaning agents are obtained with yield point.
  • 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 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, in which a polyacrylate and a solvent component comprising dipropylene glycol is used.
  • the invention also relates to the use of a polyacrylate and a solvent component comprising dipropylene glycol for the preparation of a clear, liquid, liquid-phase detergent and cleaner.
  • a polyacrylate and a solvent component comprising dipropylene glycol for the preparation of a clear, liquid, liquid-phase detergent and cleaner.
  • 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 the company 3V Sigma under the trade name Polygel®, for example Polygel DA, and from Noveon under the trade name Carbopol®, eg Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 ( Molecular weight about 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000).
  • Polygel® for example Polygel DA
  • Carbopol® eg Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 ( Molecular weight about 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000).
  • acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C - ⁇ - alkanols formed esters (INCI acrylates copolymer), which include about the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and the example of Rohm & Haas under the trade name Aculyn ® and Acusol® as well as from the company Degussa (Goldschmidt) under the trade name Tego® polymer are available, eg the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (cross-linked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii)
  • Carbopol® eg the hydrophobic Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C 10 30 alkyl acrylate crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473).
  • Preferred liquid 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 acid and one or more C 1 -C 30 -alkyl esters of (meth) acrylic acid.
  • the washing and cleaning agent contains a solvent component comprising di propylene glycol.
  • the solvent component comprises dipropylene glycol and 1,2-propanediol.
  • the solvent component consists of dipropylene pylene glycol and 1,2-propanediol.
  • the ratio of dipropylene glycol to 1,2-propanediol is advantageously between 3: 1 and 1: 3 and most preferably 1: 1.
  • the amount of the solvent component based on the total amount of the detergent 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 cleaning agent is preferably below 40% by weight and more preferably below 35% by weight, 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 an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 C 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 -i 4 -alcohols with 3 EO, 4 EO or 7 EO, C 9 . ir alcohol containing 7 EO, C. 13 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -i 8 -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 C 12 .i 8 -alcohol with 7 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • 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.
  • surfactants are polyhydroxy fatty acid amides of the formula (2),
  • 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-CO-N- [Z] (3) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, where C 1 -C 4 -alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain with min. at least two hydroxyl groups is substituted, 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.
  • surfactants of the sulfonate type preferably come here C 9 .i 3 -alkylbenzenesulfonates t olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as for example, from Ci 2 -i 8 -Monoolefine ⁇ i with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or suifoxidation with subsequent hydrolysis or neutralization.
  • esters of .alpha.-sulfo fatty acids esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-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 in the preparation by esterification of a monoglycerol with 1 to 3 mol fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myrilecyl, cetyl or stearyl alcohol or the C 10 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 6 -alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates 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.
  • 2 i-alcohols such as 2-methyl-branched Cg-n-alcohols having on average 3.5 mol of ethylene oxide (EO) or Ci 2 .i 8 -Fettalkohole 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 esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C a . 18- fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants preferred '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 detergent and cleaning agent (for example, Brookfield viscometer LVT-II at 20 U / min and 2O 0 C, spindle 3) can be measured using standard methods and is preferably in the range of 1500 to 5000 mPas. Preferred agents have viscosities of 2000 to 4000 mPas, with values around 3500 mPas being particularly preferred.
  • the solvent component and the / surfactant (s), the liquid detergent and cleaning agent can contain further ingredients that improve the performance and / or aesthetic properties of the liquid washing and cleaning agent.
  • preferred agents comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, additional non-aqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents.
  • 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 + IH 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.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 -VH 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 even lead to particularly good builder properties if the silicate particles are used in electron diffraction experiments. provide washy or even 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.
  • Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by SASOL under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used as a spray-dried powder or else as an undried, stabilized suspension which is still moist from its production.
  • the zeolite is used as a suspension, this may contain minor additions of nonionic surfactants as stabilizers', for example 1 to 3 wt .-%, based on zeolite, of ethoxylated Ci 2 -Ci 8 -Fettalkoholen with 2 to 5 ethylene oxide groups, C 2 -C 14 fatty alcohols containing 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.
  • 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 may be incorporated in the detergents and cleaning agents.
  • 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), 1- acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2, 5-diacetoxy-2,5-dihydrofuran.
  • TAED 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 salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Suitable enzymes are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. Cellulases and other glycosyl hydrolases can also contribute to color retention and softness of the fabric by removing pilling and microfibulae. Oxireductases can also be used for bleaching or inhibiting color transfer.
  • 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.
  • Cellulases used are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the 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 .-%.
  • electrolyte ⁇ 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 Haiogenide and sulfates. From a production 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, 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 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 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 alkylaryl sulfonates or alkylaryl sulfonic acids.
  • Preferred hydrotropes are selected from xylene, toluene, cumene, naphthalenesulfonate or sulfonic acid and mixtures thereof. Counterions are preferably selected from sodium, calcium and ammonium.
  • the liquid 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, in each case to the nonionic cellulose ethers and to the polymers of phthalic acid and / or terephthalic acid or their derivatives known in the art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof sulfonated derivatives of phthalic and terephthalic acid polymers.
  • Optical brighteners can be added to liquid detergents to remove graying and yellowing of the treated fabrics, which will be absorbed by the fiber and cause brightening and fake bleaching by causing invisible ultraviolet radiation in the fabric visible longer wave 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 (flavone acids), 4,4'-distyrylbiphenyls, methylene belliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, Benzoxazole, Benzisoxazol- and benzimidazole systems and substituted by heterocycles 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, used.
  • 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 cleaners may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, 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, with an additional finishing effect being achieved.
  • the treated fabrics can be used in the liquid detergents and cleaners, for example, silicone derivatives.
  • silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
  • the liquid detergents and cleaners may also contain UV absorbers that wick onto the treated fabrics and improve the lightfastness of the fibers.
  • Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of the benzophenone having substituents in the 2- and / or 4-position. 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 metals Talikomplexsentner are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which in preferred liquid detergents and cleaners in amounts of 0.01 to 2.5 wt .-%, preferably 0.02 to 2% by weight 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 (methylene phosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane -1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
  • organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylene phosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane
  • the 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.
  • multinuclear aggregates also called microspheres, are known, which contain two or more cores distributed in the continuous shell material.
  • Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath.
  • the shell may be made of natural, semi-synthetic or synthetic materials. Natural shell materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, Lecithins, gelatin, albumin, shellac, polysaccharides such as starch or dextran, sucrose and waxes.
  • Natural shell materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, Lecithins, gelatin, albumin, shellac, polysaccharides such as starch or dextran, sucrose and waxes.
  • Semi-synthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and also starch derivatives, in particular starch ethers and esters.
  • Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
  • the microcapsules may include, for example, optical brighteners, surfactants, complexing agents, bleaching agents, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, graying inhibitors, antiredeposition 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 7,000 ⁇ m, in particular from 400 ⁇ m to 5,000 ⁇ 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
  • Unicerin C30 lactose, microcrystalline cellulose
  • particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material are also referred to as "speckies".
  • a preferred matrix-forming material is alginate.
  • an aqueous alginate solution which also contains the active ingredient to be enclosed or the active ingredients to be enclosed, is dripped off and then cured in a precipitation bath containing Ca 2+ ions or Al 3+ ions.
  • the alginate-based speckles are subsequently washed with water and then washed in an aqueous solution with a complexing agent to free Ca 2+ ions or free Al 3+ ions, which undesirable interactions with ingredients of the liquid 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, polyvinyl pyrrolidone, polymethacrylate, polylysine, poloxarene, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, Ficoll®, starch, hydroxyethyl cellulose, 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 for 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, for example, the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, fatty alcohol ether sulfates, etc. and the nonionic surfactants are initially charged.
  • 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. Subsequently, 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 E5 according to the invention and a comparative example V1.
  • the washing and cleaning agents E1 to E5 obtained were clear, had a viscosity of around 3,000 mPas and a yield point of> 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.
  • Dequest ® 2010 hydroxyethylidene-1, 1-diphosphonic acid, tetra-sodium salt (ex Solutia)
  • Dequest ® 2066 diethylenetriaminepenta (methylenephosphonic acid), Hepta-Na salt (ex Solutia)
  • the flow limits were determined on an AR 1000-N rheometer from Texas Instruments at a temperature of 25 ° C.
  • the four detergents and cleaning agents E1 to E5 were stable at room temperature and at 4O 0 C for 8 weeks.

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Abstract

L'invention concerne un produit nettoyant ou détergent liquide, qui contient un ou plusieurs agents tensioactifs, un polyacrylate comme agent épaississant, un constituant solvant comprenant du dipropylène glycol, ainsi que d'autres constituants courants des produits nettoyants et détergents. Les produits nettoyants ou détergents obtenus sont transparents, stables au transport et au stockage, présentent une limite d'écoulement et peuvent disperser des particules de manière stable pendant une longue durée.
EP06707517A 2005-04-01 2006-03-10 Produit nettoyant ou detergent transparent a limite d'ecoulement Active EP1863895B1 (fr)

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PL06707517T PL1863895T3 (pl) 2005-04-01 2006-03-10 Klarowny środek piorący i czyszczący z granicą płynięcia

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DE102005015328A DE102005015328A1 (de) 2005-04-01 2005-04-01 Klares Wasch- und Reinigungsmittel mit Fließgrenze
PCT/EP2006/002217 WO2006102978A1 (fr) 2005-04-01 2006-03-10 Produit nettoyant ou detergent transparent a limite d'ecoulement

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WO2006102978A1 (fr) 2006-10-05
PL1863895T3 (pl) 2013-03-29
DE102005015328A1 (de) 2006-10-05
EP1863895B1 (fr) 2012-10-24
US20090075857A1 (en) 2009-03-19
JP2008534718A (ja) 2008-08-28

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