EP1032645A1 - Detergents liquides tres visqueux et faiblement concentres - Google Patents

Detergents liquides tres visqueux et faiblement concentres

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Publication number
EP1032645A1
EP1032645A1 EP98964403A EP98964403A EP1032645A1 EP 1032645 A1 EP1032645 A1 EP 1032645A1 EP 98964403 A EP98964403 A EP 98964403A EP 98964403 A EP98964403 A EP 98964403A EP 1032645 A1 EP1032645 A1 EP 1032645A1
Authority
EP
European Patent Office
Prior art keywords
weight
agents
liquid detergent
aqueous liquid
detergent 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
EP98964403A
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German (de)
English (en)
Other versions
EP1032645B1 (fr
Inventor
Dieter Legel
Josef Penninger
Theodor Völkel
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
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Henkel AG and Co KGaA
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Publication of EP1032645A1 publication Critical patent/EP1032645A1/fr
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • 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 present invention relates to low-concentration, higher-viscosity liquid detergents which, due to the use of a thickening system, are stable in storage and viscosity under a wide variety of climatic conditions, are not subject to phase separation and have color stability even when exposed to light.
  • Liquid detergents with viscosities between 500 to 20,000 mPas, preferably from 2,000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase are described in European patent application EP-A 691 399 (Colgate). These compositions contain 10 to 45% by weight of surfactant (s), at least one builder and 0.01 to 5% by weight of a mercapto-terminated polymer with an average molecular weight of between 1500 and 50,000 gmol "1 .
  • Liquid, aqueous detergent concentrates which maintain or increase their viscosity when diluted with water are described in EP-A 724 013 (Colgate). This effect is achieved through the use of two surfactants with different resistance to electrolytes and the addition of a dissolved electrolyte, whereby the concentrate has a viscosity of less than 2500 mPas and, when diluted with water, loses its micellar structure in favor of the formation of a lamellar phase.
  • WO96 / 01305 (Unilever) describes an aqueous detergent and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion which has particle sizes of 10 to 100 nm.
  • the agent contains 20 to 70 wt .-% water, 15 to 40 wt .-% of a surfactant system, the at least one nonionic surfactant from the group of alkoxylated alcohols and not more than 20 wt .-% anions, cations, ampho- or zwitterionic Contains surfactants, 5 to 30 wt .-% solvent and 5 to 20 wt .-% water-insoluble oil.
  • liquid detergents with the property profile mentioned can be produced if a thickening system comprising polyurethanes or modified polyacrylates, a boron compound and complexing agents is incorporated into the detergents.
  • the invention therefore relates to aqueous, highly viscous liquid detergents containing surfactant (s) and further customary ingredients of detergents and cleaning agents, the agents as a thickening system, in each case based on the total agent
  • the first component of the thickening system is a polyurethane or a modified polyacrylate, which, based on the total agent, is used in amounts of 0.2 to 5% by weight.
  • Polyurethanes are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula I.
  • R stands for a low molecular weight or polymeric diol residue, R for an ahphatic or aromatic group and n for a natural number.
  • R 1 is preferably a linear or branched C 2- ⁇ -alk (en) yl group, but can also be a radical of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from the above formula I in that the R 1 further -O-CO-NH groups are bound.
  • TDI 2,4- or 2,6-toluenediisocyanate
  • MDI C 6 H -CH 2 -C 6 H 4
  • polyurethane-based thickeners are, for example, Acrysol ® PM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel ® L75-N (non-ionic PU dispersion, 50% in water, Borchers), Coatex ® BR-100-P (PUR dispersion, 50% in water / butyl glycol, Dimed), Nopco ® DSX-1514 (PUR dispersion, 40% in water / butyl trigylcol, Henkel-Nopco), thickener QR 1001 (20% PUR emulsion in water / digylcol ether, Rohm & Haas) and Rilanit ® VPW-3116 (PUR dispersion, 43% in water, Henkel) available.
  • Acrysol ® PM 12 V mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas
  • Preferred liquid detergents contain 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.5 to 1.5% by weight of a polyurethane.
  • Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula II
  • R represents H or a branched or unbranched C 1- alk (en) yl radical
  • X represents NR or O
  • R 4 represents an optionally alkoxylated branched or unbranched, possibly substituted C 8-22 alk (en) yl radical
  • R 5 is H or R 4 and n is a natural number.
  • modified polyacrylates are generally esters or amides of acrylic acid or an ⁇ -substituted acrylic acid. Preferred among these polymers are those in which R 3 represents H or a methyl group.
  • the two hydrocarbon radicals which are bonded to the N atom being independent of one another can be selected from optionally alkoxylated branched or unbranched C 8-22 alk (en) yl radicals.
  • the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of alkoxylation.
  • Formula II only provides formulas for idealized homopolymers. However, copolymers in which the proportion of monomer units which satisfy the formula II is at least 30% by weight can also be used in the context of the present invention. For example, copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO " groups can also be used.
  • Modified polyacrylates to be preferably used in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula IIa
  • R 4 represents a preferably unbranched, saturated or unsaturated C 8-22 alk (en) yl radical
  • R 6 and R 7 independently of one another are H or CH 3
  • the degree of polymerization n is a natural number
  • the degree of alkoxylation a is a natural number is between 2 and 30, preferably between 10 and 20.
  • Products of the formula IIa are commercially strength, for example, under the name Acusol ® 820 (Rohm & Haas) in the form of 30 wt .-% dispersions in water available.
  • Acusol ® 820 Rohm & Haas
  • R 4 is a stearyl radical
  • R 6 is a hydrogen atom
  • R 7 is H or CH
  • the degree of ethoxylation a is 20.
  • Preferred liquid detergents contain, based on the total detergent, 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.5 to 1.5% by weight of a modified polyacrylate of the formula II.
  • the second component of the thickening system in the agents according to the invention is a boron compound which is used in amounts of 0.5 to 7% by weight.
  • boron compounds which can be used in the context of the present invention are boric acid, boron oxide, alkali borates such as ammonium, sodium and potassium ortho, meta and pyroborates, borax in its various hydration stages and polyborates such as alkali metal pentaborates .
  • Organic boron compounds such as esters of boric acid can also be used.
  • Preferred liquid detergents contain 0.5 to 4% by weight, preferably 0.75 to 3% by weight and in particular 1 to 2% by weight of boric acid or sodium tetraborate.
  • the liquid detergents according to the invention contain 1 to 8% by weight of a complexing agent.
  • complexing agent means low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid, or gluconic acid or salts thereof.
  • liquid detergents contain, as component c) of the thickening system, citric acid or sodium citrate, with liquid detergents which are preferably 2.0 to 7.5% by weight, preferably 3.0 to 6.0% by weight and in particular 4 , Contain 0 to 5.0% by weight sodium citrate.
  • the liquid detergents according to the invention contain surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants being used. Mixtures of anionic and nonionic surfactants are preferred from an application point of view, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants.
  • the total surfactant content of the moldings is, as described above, preferably below 30% by weight, based on the total liquid detergent.
  • 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 radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-1 alcohols with 3 EO, 4 EO or 7 EO, C 9 n alcohol with 7 EO, C ⁇ 3-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ⁇ 2- ⁇ s- alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12- ⁇ alcohol with 3 EO and C 12- 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this 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.
  • mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x, the the distribution of monoglycosides and oligoglycosides indicates any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula III,
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 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 IV,
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms
  • Ci- 4- alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propxylated derivatives of this residue.
  • [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, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the content of nonionic surfactants in preferred liquid detergents is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the total composition.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C 9- thereby ⁇ 3 -Alkylbenzolsul- sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfide, obtained, for example, from C 12 ⁇ 8 monoolefins with terminal or internal Double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 2 - 8 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 0 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 2 -C 16 alkyl sulfates and C] 2 -C 15 alkyl sulfates and C 14 -C 5 alkyl sulfates are preferred for reasons of washing technology.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • Alcohols such as 2 -methyl-branched C 9 n -alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 1-5 fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 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 which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8- ⁇ 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of preferred liquid detergents in anionic surfactants is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition.
  • the viscosity of the agents according to the invention can be measured using customary standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 500 to 5000 mPas.
  • Preferred agents have viscosities of 1000 to 4000 mPas, values between 1300 and 3000 mPas being particularly preferred.
  • the agents according to the invention can contain further ingredients which further improve the technical and / or aesthetic properties of the liquid detergent.
  • preferred agents contain, in addition to the thickening system and surfactant (s), one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, Hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids and anti-swelling agents, and anti-phobic agents, anti-phobic agents, and anti-phobic agents.
  • surfactant one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, Hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors,
  • the builders that can be contained in the liquid detergents according to the invention include, 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 + ⁇ '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.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 -yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the dissolution delay compared to conventional amorphous sodium silicates can be done in various ways, for example by surface treatment, compounding, compacting / compression or by Overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 2 -C 8 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 1 - fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; Measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphate, 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 detergent tablets.
  • Compounds which, under perhydrolysis conditions, give ahphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraacet
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of
  • Enzymatic substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or Enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.12 to about 2% by weight.
  • a wide number of different salts can be used as electrolytes from the group of inorganic salts.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl 2 in the agents according to the invention is preferred.
  • the proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
  • Non-aqueous solvents which can be used in the agents according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol -methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, l-butoxyethoxy-2-propanol , 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixture
  • pH adjusting agents In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not for application-related or ecological reasons or for reasons of Prohibits consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a long shelf life and are insensitive. Compared to the other ingredients of the agents and against light and no pronounced substantivity towards textile fibers, so as not to stain them.
  • Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable anti-deposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose 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 the nonionic cellulose ethers and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry.
  • Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids ( Flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles.
  • the optical brighteners are usually in amounts 0.05 and 0.3 wt .-%, based on the finished agent used.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfur acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, are preferably used
  • the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • the agents according to the invention can contain antimicrobial active ingredients.
  • antimicrobial active ingredients Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenolmercuriacetate, these compounds also being dispensed with entirely in the agents according to the invention can.
  • the agents can contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • antistatic agents which are additionally added to the agents according to the invention. Enlarge antistatic agents the surface conductivity and thus enable an improved flow of charges formed.
  • External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • External antistatic agents are described, for example, in patent applications FR 1,156,513, GB 873 214 and GB 839 407.
  • the lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.
  • silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylsiloxanes, in which the alkyl groups have one to five carbon atoms and are partially or completely fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 mPas, the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.
  • the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • 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 urocanoic acid are also suitable.
  • Suitable heavy metal complexing agents are, for example, the alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which are used in preferred liquid detergents in amounts of 0.01 to 1.5% by weight, preferably 0.02 to 1% by weight and in particular 0.03 to 0.5% by weight. -% are included.
  • These preferred compounds include in particular organophosphonates such as, for example, l-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
  • organophosphonates such as, for example, l-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphono
  • Particularly preferred liquid detergents contain, as component c) of the thickening system, l-hydroxyethane-l, l-diphosphonic acid in the form of their ammonium or alkali metal salts.
  • the agents according to the invention are prepared by simply mixing the constituents in stirred kettles, water, non-aqueous solvents and surfactant (s) advantageously being introduced and the further constituents being added in portions. A separate heating during production is not necessary, if it is desired, the temperature of the mixture should not exceed 80 ° C.
  • liquid detergents E1 and E2 according to the invention and the comparative examples VI to V4, the composition of which is given in Table 1, were prepared by mixing the individual constituents.

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

L'invention concerne des détergents liquides très visqueux et faiblement concentrés, dont la viscosité demeure stable au stockage dans les conditions climatiques les plus diverses, qui ne subissent aucune séparation de phases ou séparation d'agglomérés et dont les couleurs demeurent stables sous l'action de la lumière. Des détergents liquides présentant le profil de caractéristiques souhaité renferment 0,2 à 5 % en poids d'un polyuréthanne ou bien d'un polyacrylate modifié, 0,5 à 7 % en poids d'un composé de bore, ainsi qu'1 à 8 % en poids d'un complexant.
EP98964403A 1997-11-26 1998-11-17 Detergents liquides tres visqueux et faiblement concentres Expired - Lifetime EP1032645B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19752163A DE19752163A1 (de) 1997-11-26 1997-11-26 Niedrigkonzentrierte höherviskose Flüssigwaschmittel
DE19752163 1997-11-26
PCT/EP1998/007344 WO1999028430A1 (fr) 1997-11-26 1998-11-17 Detergents liquides tres visqueux et faiblement concentres

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EP1032645A1 true EP1032645A1 (fr) 2000-09-06
EP1032645B1 EP1032645B1 (fr) 2002-03-06

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US (1) US6342472B1 (fr)
EP (1) EP1032645B1 (fr)
JP (1) JP4361678B2 (fr)
KR (1) KR100567607B1 (fr)
AT (1) ATE214092T1 (fr)
DE (2) DE19752163A1 (fr)
ES (1) ES2173661T3 (fr)
HU (1) HU228345B1 (fr)
PL (1) PL187488B1 (fr)
WO (1) WO1999028430A1 (fr)

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WO2003035712A1 (fr) * 2001-10-22 2003-05-01 Henkel Kommanditgesellschaft Auf Aktien Polymeres a base d'urethanne facilitant l'elimination des taches sur les textiles en coton
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US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
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ATE214092T1 (de) 2002-03-15
JP4361678B2 (ja) 2009-11-11
ES2173661T3 (es) 2002-10-16
DE59803303D1 (de) 2002-04-11
HU228345B1 (en) 2013-03-28
US6342472B1 (en) 2002-01-29
PL340621A1 (en) 2001-02-12
HUP0100078A2 (hu) 2001-05-28
JP2001525453A (ja) 2001-12-11
EP1032645B1 (fr) 2002-03-06
KR20010032541A (ko) 2001-04-25
WO1999028430A1 (fr) 1999-06-10
HUP0100078A3 (en) 2002-11-28
DE19752163A1 (de) 1999-05-27
KR100567607B1 (ko) 2006-04-04
PL187488B1 (pl) 2004-07-30

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