WO2008128827A1 - Systèmes liquides contenant un matériau photocatalytique - Google Patents

Systèmes liquides contenant un matériau photocatalytique Download PDF

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Publication number
WO2008128827A1
WO2008128827A1 PCT/EP2008/053000 EP2008053000W WO2008128827A1 WO 2008128827 A1 WO2008128827 A1 WO 2008128827A1 EP 2008053000 W EP2008053000 W EP 2008053000W WO 2008128827 A1 WO2008128827 A1 WO 2008128827A1
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Prior art keywords
textiles
photocatalytic material
preferred
oil
liquid system
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PCT/EP2008/053000
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German (de)
English (en)
Inventor
Sascha Schrecker
Georg Meine
Original Assignee
Henkel Ag & Co. Kgaa
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Publication of WO2008128827A1 publication Critical patent/WO2008128827A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the present invention relates to a liquid system, in particular a dispersion containing water, photocatalytic material and cationic surfactant, and a method for producing this liquid system. It further relates to a liquid washing or cleaning agent obtainable by mixing a liquid washing or cleaning agent matrix with the described liquid system. It also relates to methods of applying photocatalytic material to textiles and hard surfaces. Furthermore, it relates to methods for cleaning textiles and hard surfaces.
  • photocatalytic materials to control soil and / or unwanted microorganisms is desirable because the photocatalytic material may utilize electromagnetic radiation of a suitable wavelength range to degrade or deactivate debris and / or unwanted microorganisms by photocatalytic or photochemical reaction.
  • suitable photocatalytic material is very finely divided substances, for example in the size range of at least ⁇ 500 nm.
  • the incorporation of such photocatalytic material into liquid preparations, e.g. Detergents and cleaners can cause problems.
  • This object is achieved by the subject matter of the invention, namely a liquid system, in particular a dispersion containing water, photocatalytic material and cationic surfactant.
  • Such liquid systems are distinguished by good stability and can also be processed well in industrial processes, both continuously and batchwise, thus making it possible to provide liquid, storage and transport-stable detergents or cleaners which contain photocatalytic material and which need not be shaken before use by the consumer. Due to their excellent spreadability, the liquid systems, especially dispersions, can be very homogeneously incorporated into other liquid matrices, e.g. liquid detergents or cleaning agents are incorporated. The resulting products are very stable.
  • liquid systems according to the invention in particular dispersions, can also already be used as such as detergents or cleaners, since they have a general cleaning capability due to the photocatalytic material contained.
  • the contained photocatalytic material which is preferably finely divided, that is preferably has a mean particle diameter ⁇ 500 nm (particle diameter along the largest spatial extent), uses electromagnetic radiation of a suitable wavelength range, by virtue of which a general cleaning performance is provided, by virtue of which e.g. Soils or microbes by photocatalytic or photochemical reaction, e.g. by oxidation or reduction, degradable, deactivatable or reducible.
  • the photocatalytic material is in particular a daylight-active material, in particular a daylight-active bleach, thus uses the electromagnetic radiation of daylight.
  • a daylight-active material in particular a daylight-active bleach
  • the presence of preferably oxygen and / or water is required.
  • the dissolved oxygen present in water or the water contained in the air (air humidity) is sufficient.
  • the photocatalytic activity of the photocatalytic material advantageously relates to natural or artificial light having wavelengths in the range of 10-1200 nm, preferably 300-1200 nm, in particular between 380 and 800 nm.
  • UV light (10-380 nm) is very suitable.
  • the photocatalytic material can exert its effect in several ways, explained below using the example of the textile treatment.
  • the effect in the textile treatment bath is called. If you e.g. the textiles to be treated are placed in a tub which contains a wash liquor into which a liquid system according to the invention, in particular dispersion (or a liquid agent into which the liquid system has been incorporated, eg a washing or cleaning agent) has been added, and then this textile treatment bath For example, exposing light, eg in the sun, then the photocatalytic material in the textile treatment bath develops a general cleaning performance.
  • a viewing window porthole
  • the photocatalytic material applied to the textiles to be dried as part of the textile treatment can develop a general cleaning performance in conjunction with light irradiation, for example by sunlight when drying on a line outdoors. Such is also possible in the textile drying in an automatic clothes dryer with internal light source.
  • the effect after drying of the textile should be mentioned.
  • the dried textiles are not really dry in the true sense, but contain a residual moisture, which is in balance with the ambient humidity (room humidity, body moisture). These conditions are sufficient to develop a general cleaning performance, caused by the deposited on the textiles photocatalytic material under light irradiation, for example by sunlight. This latter effect is particularly advantageous because the treated garments are provided with a long-term protection, so that the clothing is equipped with a self-cleaning ability.
  • This self-cleaning ability is e.g. advantageous to counteract the development of fetid odors which may be present on clothing e.g. make swift after sweaty activities (such as sports activities).
  • This self-cleaning ability is e.g. advantageous to prevent or at least complicate the colonization of microbes on textiles.
  • This self-cleaning ability is e.g. advantageous to ward off or complicate the mounting and sticking of particular colored stains on fibers.
  • the rewashing ability of fabric soils treated with a liquid system according to the invention, in particular a dispersion (or a liquid agent into which the liquid system has been incorporated, for example detergents or cleaners), e.g. washed were, relieved.
  • quick action is the top priority, because the fresher a stain is, the easier it is to remove.
  • a drying of stains or other contaminants, such as blood, coffee, tea, pen, fruit, red wine or tar stains, especially over several days should usually be avoided so that it does not come to a possibly irreversible fiber adhesion.
  • the present invention brings relief here because textiles treated with a liquid system according to the invention, in particular a dispersion (or a liquid agent into which the liquid system has been incorporated, eg detergents or cleaners), have demonstrated the fiber adhesion of stains or others Dirt was so weakened that they could easily be washed out again.
  • the photocatalytically active material is thus advantageous in order to improve the Wiederauswaschberry of colored stains.
  • the photocatalytically active material is able namely under the action of light, the structure of particular colored stains (dyes) z. B by oxidation to destroy.
  • the conjugated double bonds which are responsible for the absorption of visible light in the dyes and thus for the coloring, are cleaved or hydroxylated.
  • the dye loses its coloring properties and also its strong fiber adhesion. At the same time the water solubility is increased. This prevents a colored stain from "eating into” the textile and destroying it permanently.
  • a liquid system according to the invention in particular a dispersion, (or a liquid agent in which the liquid system has been incorporated, for example washing or cleaning agents) in the textile treatment also enables a uniform coating of the photocatalytic material on the textiles to be treated.
  • cationic surfactant especially in the form of esterquat
  • dispersions leads to a very good and uniform application behavior of the photocatalytic material to the textiles to be treated.
  • the cationic surfactant, in particular esterquat also leads to an increased adhesion of the photocatalytic material to the textiles and thus prolongs its duration of action. Overall, this makes it possible to improve the cleaning performance.
  • the liquid system according to the invention in particular dispersion (or a liquid agent into which the liquid system has been incorporated, for example detergents or cleaners), furthermore makes possible a very textile-sparing textile treatment, e.g. Stain treatment.
  • a liquid system according to the invention in particular dispersion, (or a liquid agent in which the liquid system has been incorporated, for example washing or cleaning agents), as already mentioned, is that it contributes to the reduction, elimination or neutralization of fetid odors.
  • the fetid odor can be advantageously reduced so that a previously existing odor nuisance is no longer present.
  • the development of fetid odors can be prevented for a longer period of time.
  • This is also a great advantage since, overall, a general cleaning performance can be combined with the elimination of harmful microbes in one treatment step and, in addition, a blocking or prevention of foul odors with long-term effect is provided. This goes beyond the function of previous means, such as detergents or cleaning agents, significantly.
  • Noxa is understood to mean factors that can damage the human organism, or at least impair people's well-being. These are in particular the just mentioned factors, especially microbiological factors such as viruses, bacteria, fungi, etc.
  • tea, fruit, red wine, deep brown humic acid e.g. from coffee, tea, cocoa, green chlorophyll, for example, from green grasses, technical dyes from cosmetics, inks, colored pencils, colored metabolites and / or excretions from molds or other Mirkoflora or microbial growth or microbes.
  • the liquid system according to the invention in particular dispersion (or a liquid agent, in particular washing or cleaning agent in which the liquid system has been incorporated, for example detergents or cleaners) also counteracts the current washing habits of consumers.
  • the use of a liquid system according to the invention, in particular dispersion allows the consumer the consequent washing at T ⁇ 4O 0 C, with improved hygienic effect.
  • a liquid system according to the invention in particular dispersion, preferably makes possible the advantages of a hygiene rinser and a softener in a supply form and thus facilitates the textile care and treatment for the consumer, since instead of two different aftertreatment means, only one, namely the liquid system according to the invention, in particular dispersion, ( or a liquid textile treatment agent containing the liquid system according to the invention) must use if he considers a softening and hygienic aftertreatment of his laundry necessary.
  • the softness performance is advantageously provided by the cationic surfactant.
  • a liquid system according to the invention in particular dispersion, (or a liquid agent in which the liquid system has been incorporated, for example washing or cleaning agents)
  • a liquid system according to the invention, in particular dispersion, (or a liquid agent in which the liquid system has been incorporated, for example washing or cleaning agents) in the treatment, especially cleaning, hard surfaces also a uniform coating of the photocatalytic material on the treated textiles.
  • cationic surfactant especially in the form of esterquat
  • the cationic surfactant, especially esterquat also results in increased adhesion of the photocatalytic material to the hard surfaces, thus prolonging its duration of action. Overall, this makes it possible to improve the cleaning performance.
  • the liquid system according to the invention in particular a dispersion, contains a) 50-95% by weight, preferably 60-90% by weight of water, b) 0.01-50% by weight, preferably 15-25% by weight % photocatalytic material, c) 1-15% by weight, preferably 2-10% by weight of cationic surfactant.
  • the liquid systems according to the invention contain cation surfactant as a mandatory constituent.
  • Cationic surfactants are known to the person skilled in the art. These are surface-active compounds, as a rule from an optionally substituted hydrocarbon skeleton, with one or more cationic (positively charged) groups which preferentially dissociate in aqueous solution, advantageously adsorb at interfaces and preferably aggregate above the critical micelle concentration to positively charged micelles.
  • cationic surfactants are in particular quaternary ammonium compounds having one or two hydrophobic alkyl radicals.
  • cationic surfactants having two hydrophobic groups which are linked via ester bonds with a quaternized di (tri) ethanolamine or an analogous compound
  • esterquats are particularly preferred according to the invention.
  • Other examples of cationic surfactants are e.g. quaternary phosphonium salts, tertiary sulfonium salts, imidazolinium salts or N-alkylpyridinium salts.
  • Cationic surfactants can also be obtained by protonation of primary fatty amines or fatty amine N-oxides.
  • quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines are most preferred according to the invention.
  • quaternary ammonium compounds are shown, for example, in the formulas (I) and (II):
  • R is an acyclic alkyl radical having 12 to 24 carbon atoms
  • R 1 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical
  • R 2 and R 3 are either R or R 1 or are an aromatic radical
  • X ⁇ represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these.
  • Examples of cationic compounds of the formula (I) are monotaltrimethylammonium chloride, monostearyltrimethylammonium chloride, didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
  • R 4 is an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and / or optionally with substituents
  • R 5 is H, OH or O (CO) R 7 , R 6 , independently of R 5, is H, OH or O (CO) R 8 , where R 7 and R 8 are each independently an alipha- Table alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, m, n and p may each independently have the value 1, 2 or 3 have.
  • X can be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these anions.
  • R 5 represents the group 0 (CO) R 7 .
  • R 5 is the group 0 (CO) R 7 and R 4 and R 7 are alk (en) yl radicals having 16 to 18 carbon atoms.
  • R 6 is also OH.
  • Examples of compounds of the formula (I) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulfate, bis (palmitoyloxyethyl) hydroxyethyl methyl ammonium methosulfate, 1, 2-bis [tallowloxy] -3-trimethylammonium propane chloride or methyl N, N-bis (stearoyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulphate.
  • the acyl groups are preferred whose corresponding fatty acids have an iodine number between 1 and 100, preferably between 5 and 80, more preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular equal to or greater than 60:40.
  • Stepan under the tradename Stepantex ® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ® Cognis products, known under Rewoquat ® products from Degussa or those known under Tetranyl® products of Kao.
  • Further preferred compounds are the diester quats of the formula (III) which are obtainable under the name Rewoquat® W 222 LM or CR 3099.
  • R 21 and R 22 are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • ester group 0 (CO) R where R is a long-chain alk (en) yl radical
  • softening compounds which have the following groups: RO (CO), N (CO) R or RN (CO), where of these groups, N (CO) R groups are preferred.
  • Suitable cationic surfactants are, for example, also quaternary imidazolinium compounds of the formula (IV)
  • R 9 is H or a saturated alkyl radical having 1 to 4 carbon atoms
  • R 10 and R 11 independently of one another may each be an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms
  • R 10 may alternatively also be 0 (CO) R 20 where R 20 is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X - is an anion.
  • q can take integer values between 1 and 4.
  • R 12, R 13 and R 14 independently represents a C- ⁇ _ 4 alkyl, alkenyl or hydroxyalkyl group
  • R 15 and R 16 are each independently selected a C. 8 28 alkyl
  • X "is an anion and r is a number between 0 and 5.
  • a preferred example of a cationic deposition aid according to formula (V) is 2,3-bis [tallowacyloxy] -3-trimethylammonium propane chloride.
  • cationic surfactants which can be used according to the invention are the quaternized protein hydrolyzates or protonated amines.
  • cationic polymers can also be used according to the invention as cationic surfactant.
  • Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also referred to as Merquats.
  • polymers Polymer JR, LR and KG series from Amerchol
  • polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups bonded via allyldimethylammonium chloride
  • cationic cellulose derivatives such as cationic Guar, such as guar hydroxypropyl triammonium chloride, and similar quaternized guar derivatives (eg Cosmedia Guar from Cognis or the Jaguar series from Rhodia), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), eg the commercial product Glucquat® 100, according to CTFA nomenclature a "Lauryl Methyl Gluceth- 10 hydroxypropyl dimonium chlorides, copolymers of PVP and dimethylamine methacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers.
  • cationic surfactants are polyquaternized polymers (e.g., Luviquat® Care from BASF) and also chitin-based cationic biopolymers and their derivatives, for example, the polymer available under the trade name Chitosan® (manufactured by Cognis).
  • polyquaternized polymers e.g., Luviquat® Care from BASF
  • Chitosan® manufactured by Cognis
  • Some of the cited cationic polymers additionally have skin and / or textile care properties, which is advantageous.
  • cationic surfactants are compounds of the formula (VI),
  • R 17 can be an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5.
  • R 18 and R 19 are each independently H, C- ⁇ _ 4 alkyl or hydroxyalkyl and X " is an anion.
  • Suitable cationic surfactants include protonated or quaternized polyamines.
  • Particularly preferred cationic surfactants are alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or ido group.
  • alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or ido group.
  • Very particular preference is given to N-methyl-N- (2-hydroxyethyl) -N, N- (ditallowacyloxyethyl) ammonium methosulphate or bis (palmitoyloxyethyl) -hydroxyethylmethylammonium methosulphate.
  • a preferred embodiment of the invention is when the cationic surfactant, contained in the liquid system, in particular dispersion has a melting temperature> 3O 0 C, and preferably is an esterquat.
  • the photocatalytic material comprises titanium dioxide, in particular a modified titanium dioxide, preferably a carbon-modified titanium dioxide.
  • the photocatalytic material in particular the (preferably modified) titanium dioxide, according to a preferred embodiment of the invention in the liquid system according to the invention, in particular the dispersion, in amounts of advantageously 0.01 to 50 wt .-%, more preferably 1 to 30 Wt .-%, more preferably 15 to 25 wt .-%, wt .-% based on the total liquid system.
  • the titanium dioxide (preferably modified) is a carbon-modified titanium dioxide.
  • titanium dioxides for example nitrogen-modified titanium dioxide or e.g. Titanium dioxide doped with rhodium and / or platinum ions.
  • the carbon content of the advantageously carbon-modified titanium dioxide may in a preferred embodiment in the range of 0.01 to 10 wt .-%, preferably from 0.05 to 5.0 wt .-%, advantageously from 0.3 to 1, 5 wt. %, in particular from 0.4 to 0.8% by weight.
  • the TiO 2 content of the carbon-modified titanium dioxide is, for example, more than 95% by weight, 96% by weight, 97% by weight, 98% by weight or 99% by weight, based on the total with carbon modified titanium dioxide.
  • the modified titanium dioxide may advantageously additionally contain nitrogen.
  • the specific surface of the titanium dioxide preferably of the modified titanium dioxide, according to BET (BET advantageously determined according to DIN ISO 9277: 2003-05, preferably also simplified according to DIN 66132: 1975-07) preferably 50 to 500 m 2 / g, advantageously 100 to 400 m 2 / g, in a further advantageous manner 200 to 350 m 2 / g, in particular 250 to 300 m 2 / g, so is also a preferred embodiment.
  • the carbon-modified titanium dioxide can be obtained according to a preferred embodiment, for example, by intimately mixing a titanium compound having a specific surface area of preferably at least 50 m 2 / g according to BET, with an organic carbon compound and the mixture at a temperature of up to is thermally treated to 35O 0 C.
  • the carbonaceous substance which can be used in this case can, according to a preferred embodiment, be a carbon compound which contains at least one functional group, preferably selected from OH, CHO, COOH, NHx, SHx.
  • the carbon compound may be a compound selected from ethylene glycol, glycerol, succinic acid, pentaerythritol, carbohydrates, sugars, starch, alkyl polyglucosides, organoammonium hydroxides or mixtures thereof. It is also possible for carbon black or activated carbon to be used as the carbonaceous substance.
  • the carbonaceous substance which is advantageously mixed with the titanium compound to arrive after the thermal treatment to the modified titanium dioxide, a decomposition temperature of at most 400 0 C preferably ⁇ 35O 0 C and particularly preferably ⁇ 300 0 C. having.
  • the titanium compound which is preferably used for producing the modified titanium dioxide and intimately mixed with an organic carbon compound according to the aforementioned preferred embodiment may be an amorphous, partially crystalline or crystalline titanium oxide or hydrous titanium oxide or a titanium hydrate or a titanium oxyhydrate, which in turn corresponds to a preferred embodiment ,
  • the thermal treatment of the mixture of the titanium compound and the carbon compound can, according to a preferred embodiment, advantageously be carried out in a continuously operated calcining unit, preferably a rotary kiln.
  • the modified titanium dioxide can be obtained, in particular in the context of what has been described above, preferably by adding a titanium dioxide (eg having a particle size in the range from 2 to 500 nm or eg 3 to 150 nm or eg 4 to 100 nm or eg 5 to 75 nm or, for example, 10 to 30 nm or, for example, 200 to 400 nm), such as commercially available in powder or slurry form, and from this produces a suspension in a liquid, such as preferably water.
  • a titanium dioxide eg having a particle size in the range from 2 to 500 nm or eg 3 to 150 nm or eg 4 to 100 nm or eg 5 to 75 nm or, for example, 10 to 30 nm or, for example, 200 to
  • a carbonaceous substance is then advantageously added to the suspension.
  • Mixing can be assisted by the use of ultrasound.
  • the mixing process (eg stirring) may preferably last several hours, preferably 2, 4, 6, 8, 10 or 12 hours or even longer.
  • the amount of the carbon compound is advantageously 1-40% by weight, accordingly, the amount of the titanium compound is preferably 60-99% by weight.
  • the liquid is removed, for example by filtration, evaporation in vacuo or decantation, and the residue is preferably dried (eg, preferably at temperatures of 70-200 0 C, advantageously over several hours, for example at least 12 hours) and then calcined, for example a temperature of at least 26O 0 C, preferably for example at 300 0 C, preferably over a period of several hours, preferably 1-4 hours, in particular 3 hours.
  • the calcination may advantageously take place in a closed vessel.
  • the calcination temperature for example 300 0 C, is reached within one hour (slow heating to 300 0 C).
  • a color change of the powder from white to dark brown to beige or slightly yellowish-brownish is preferably observed. Too long a heating leads to inactive, colorless powders. The expert can estimate this with a few routine experiments.
  • the calcination may e.g. advantageously take place until after a color change of the powder from white to dark brown another color change takes place on beige or slightly yellowish-brownish.
  • a maximum temperature of 35O 0 C should preferably not be exceeded.
  • decomposition of the organic carbon compound occurs on the surface of the titanium compound, so that it is preferable to form a modified titanium dioxide containing preferably 0.005-4% by weight of carbon.
  • the product is advantageously deagglomerated by known methods, for example in a pin mill, jet mill or counter-jet mill.
  • the grain fineness to be achieved depends on the grain size of the starting titanium compound.
  • the particle size or specific surface area of the product is only slightly lower, but of the same order of magnitude as that of the educt.
  • the desired grain fineness of the photocatalyst depends on the field of application of the photocatalyst. It is usually in the range as in TiO 2 - pigments, but may also be below or above.
  • the photocatalytic material, preferably modified titanium dioxide, contained in the liquid system according to the invention, in particular dispersion, may advantageously have a particle size in the range between 2 and 500 nm, eg 3 to 150 nm or eg 4 to 100 nm or eg 5 to 75 nm or for example 10 up to 30 nm or eg 200 to 400 nm.
  • the particle size of the photocatalytic material, preferably modified titanium dioxide can preferably in the range of 100-500 nm, advantageously 200-400 nm. It may also be preferred that the particle size is very small, eg in the range of 2-150 nm, preferably
  • Very small particles e.g. with a particle size of in particular 2, 3, 4, 5 or 10 nm are preferably included, these can also form together agglomerates, which are then correspondingly larger, e.g. up to 600 nm or up to 500 nm or up to 400 nm or up to 300 nm in size, etc.
  • the particle size may e.g. advantageously at values such as 5 nm, 10 nm, 15 nm, 20 nm, 25 nm,
  • Titanium dioxide ie of very small particle size titanium dioxide, e.g. between 2 and
  • the particle size can then be e.g. advantageously at
  • the bulk density of the preferably modified titanium dioxide is preferably in the range from 100 to 800 g / l, advantageously from 200 to 600 g / l, in particular from 300 to 500 g / l.
  • the bulk density may be 350 g / l, 400 g / l or 500 g / l.
  • the (preferably modified) titanium dioxide is present in the anatase crystal modification.
  • the modified titanium dioxide described above is characterized by a very good photocatalytic activity, in particular with the use of daylight.
  • visible to the human eye radiation of the visible region of the spectrum with wavelengths between 380 and 800 nm are used very well for the purposes of degradation, deactivation or reduction of impurities from the described modified titanium dioxide.
  • UV light (10-380 nm) can also be used.
  • liquid system according to the invention in particular the dispersion, comprises further ingredients.
  • ingredients which can usually be used in detergents and cleaners. Such are z.T. described in more detail below.
  • Another object of the invention is a process for the preparation of a liquid system according to the invention, in particular a dispersion in which first a predispersion Cationic surfactant and water, preferably produced under low shear energy, and then the photocatalytic material is distributed in this predispersion.
  • the dispersed cationic surfactant acts as a carrier system for the photocatalytic material, so that the photocatalytic material can be incorporated very uniformly into the liquid by the stated method.
  • the cationic surfactant in molten form is preferably added at temperatures> 4O 0 C, wherein the water comprises in the addition of the cationic surfactant preferably at room temperature.
  • liquid systems according to the invention are distinguished by the fact that they can be further processed without problems, in particular, they can be homogeneously mixed into other liquids or diluted with other liquids.
  • the further processing products are stable in transport and storage.
  • liquid systems according to the invention in particular dispersions, into liquid detergent or makesffenmatrices is advantageous and corresponds to a preferred embodiment of the invention.
  • a further subject of the invention is therefore a liquid washing or cleaning agent obtainable by mixing a liquid washing or cleaning agent matrix with a liquid system according to the invention, in particular a dispersion.
  • the liquid detergent or cleaning agent matrix may contain the customary components which are customarily contained in conventional liquid detergents or cleaners. Particularly advantageous is e.g. the incorporation of the liquid system according to the invention in wool detergent
  • a humectant is contained in the resulting washing or cleaning agent.
  • This can already be contained in the liquid system according to the invention, in particular the dispersion, and / or constituent of the liquid washing or Be detergent matrix, to which the liquid system according to the invention, in particular the dispersion, is added.
  • a liquid washing or cleaning agent according to the invention comprises a humectant, preferably glycerol, dimers and trimers of glycerol, ethylene glycol, propylene glycol, sugar alcohols, preferably glucitol, xylitol, mannitol, alkyl polyglucosides, fatty acid glucamides, sucrose esters, Sorbitans, polysorbates, polydextrose, polyethylene glycol, preferably having average molecular weights of from 200 to 8000, propanediols, butanediols, triethylene glycol, hydrogenated glucose syrup and / or mixtures of the abovementioned, preferably in amounts of from 0.01 to 10% by weight, advantageously 0.1 to 5 wt .-%, in particular 0.5 to 2 wt .-%, wt .-% in each case based on the total agent.
  • a humectant preferably glycerol, dimers and trimers of
  • the detergent comprises at least one, preferably organic, humectant
  • further improved deposition and action of the finely divided photoactive material on the substrates to be treated preferably textiles, hard surfaces
  • a particularly suitable humectant is glycerin as well as its dimers and trimers and / or mixtures thereof.
  • a liquid washing or cleaning agent according to the invention contains a) photocatalytic material b) cationic surfactant, preferably in amounts of> 0.1% by weight, advantageously 1 to 40% by weight, in particular 3 to 30% by weight .-% c) optionally fragrances, preferably in amounts of> 0.01 wt .-%, advantageously 0.05 to 10 wt .-%, in particular 0.1 to 5 wt .-%, d) water, preferably in amounts> 50% by weight, advantageously> 60% by weight, in particular> 70% by weight e) optionally solvents, preferably monohydric alcohols, in particular 2-propanol, advantageously in amounts of from 0.05 to 5% by weight, in particular 0.1 to 4 wt .-%, in particular 0.3 to 3 wt .-%, f) optionally humectants g) optionally emulsifiers, preferably nonionic surfactants, advantageously in amounts of 0 to
  • MgCl 2 or NaCl 0.01 to 5 wt .-%, in particular 0.05 to 2 wt .-%, j) optionally skin care active ingredients, preferably in an amount of 0 to 15 wt .-%, advantageously 0.1 to 10 Wt .-%, in particular 0.5 to 5 wt .-%, j) optionally thickener, eg polyacrylate-based, preferably in amounts of 0.01 to 3 wt .-%, in particular 0.1 to 1 wt .-%,
  • skin care products or skin-care active substances are also contained in the washing or cleaning agent according to the invention, in particular in amounts of> 0.01% by weight, based on the total washing or cleaning agent.
  • Skin care agents may in particular be those which give the skin a sensory benefit, e.g. by delivering lipids and / or moisturizing factors.
  • Skin care agents may e.g. Proteins, amino acids, lecithins, lipids, phosphatides, plant extracts, vitamins; Likewise, fatty alcohols, fatty acids, fatty acid esters, waxes, petrolatum, paraffins can act as skin care agents.
  • Skin-care active substances are all those active substances which give the skin a sensory and / or cosmetic advantage.
  • Skin-care active substances are preferably selected from the following substances: a) waxes such as, for example, carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others.
  • Hydrophobic plant extracts c) Hydrocarbons such as squalene and / or squalanes
  • Hydrocarbons such as squalene and / or squalanes
  • Higher fatty acids preferably those having at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or polyunsaturated fatty acids and other.
  • Higher fatty alcohols preferably those having at least 12 carbon atoms, for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and others.
  • esters preferably such as cetyloctanoates, lauryl lactates, myristyl lactates, cetyl lactates, isopropyl myristates, myristyl myristates, isopropyl palmitates, isopropyl adipates, butyl stearates, Decyloleates, cholesterol isostearates, glycerol monostearates, glycerol distearates,
  • Glycerol tristearates alkyl lactates, alkyl citrates and / or alkyl tartrates and others, g) lipids such as cholesterol, ceramides and / or sucrose esters and other h) vitamins such as vitamins A and E, vitamin C esters, including vitamin
  • Preferred skin care active substances are preferably also essential oils, in particular selected from the group of Angelica fine - Angelica archangelica, Anis - Pimpinella anisum, Benzoin siam - Styrax tokinensis, Cabreuva - Myrocarpus fastigiatus, Cajeput - Melaleuca leucadendron, Cistrose - Cistrus ladaniferus, Copaiba - Balsam - Copaifera reticulata, Costus root - Saussurea discolor, Edeltann needle - Abies alba, Elemi - Canarium luzonicum, Fennel - Foeniculum dulce Spruce needle - Picea abies, Geranium - Pelargonium graveolens, Ho- leaves - Cinnamonum camphora, Immortelle Helichrysum ang., Ginger Extra - Zingiber off., St.
  • essential oils in particular selected from the group of Angelica fine - Angelica ar
  • Preferred skin-care active ingredients are preferably also skin-protecting oils, in particular selected from the group algae oil Oleum Phaeophyceae, aloe vera oil aloe vera brasiliana, apricot kernel oil Prunus armeniaca, arnica oil Arnica montana, avocado oil Persea americana, borage oil Borago officinalis, calendula oil Calendula officinalis, camellia oil Camellia oleifera, safflower oil Carthamus tinctorius, peanut oil Arachis hypogaea, hemp oil Cannabis sativa, hazelnut oil Corylus avellana /, St.
  • skin-protecting oils in particular selected from the group algae oil Oleum Phaeophyceae, aloe vera oil aloe vera brasiliana, apricot kernel oil Prunus armeniaca, arnica oil Arnica montana, avocado oil Persea americana, borage oil Borago officinalis
  • the use of skin-protecting oils corresponds to a preferred embodiment of the invention.
  • the optional skin care actives may be applied to the textile during a textile treatment with an agent of the invention and then transferred from the textile to the skin in turn when the fabric is in contact with the skin, e.g. while wearing clothes.
  • skin-care active ingredients in the washing or cleaning agents according to the invention are beneficial to the skin of the consumer.
  • detergents or cleaners according to the invention which optionally contain skin-care active substances
  • the skin-care active ingredients of the skin of the consumer are of immediate advantage, namely when the hand is in contact with the wash liquor.
  • the use of skin-care active ingredients is purely optional.
  • the washing or cleaning agents according to the invention in particular textile treatment agents, e.g. Aftertreatment agents, preferably fabric softeners, may also preferably contain nonionic softening components, especially polyoxyalkylene glycol alkanoates, polybutylenes, long-chain fatty acids, ethoxylated fatty acid ethanolamides, alkyl polyglucosides, in particular sorbitan mono, di- and triesters, and fatty acid esters of polycarboxylic acids. But also a softening clay (eg bentonite) can be included.
  • nonionic softening components especially polyoxyalkylene glycol alkanoates, polybutylenes, long-chain fatty acids, ethoxylated fatty acid ethanolamides, alkyl polyglucosides, in particular sorbitan mono, di- and triesters, and fatty acid esters of polycarboxylic acids.
  • a softening clay eg bentonite
  • washing or cleaning agent according to the invention is contained in an opaque packaging. This corresponds to a preferred embodiment of the invention. Also preferred are disposable portions, for example in the form of pouches. The same applies to the liquid systems according to the invention, in particular dispersions, as such, these too are preferably contained in an opaque packaging.
  • the washing or cleaning agents according to the invention and liquid systems, in particular dispersions can also be provided in the dosage form "spray".
  • the washing or cleaning agents according to the invention can also be used as 2-phases. Be provided systems, the phases are arranged horizontally, so one above the other.
  • Another object of the invention is a process for the preparation of a preferably storage-stable liquid detergent or cleaning agent containing photocatalytic material and other conventional ingredients of detergents or cleaning agents, in which a liquid system according to the invention, in particular dispersion, as described above, with a liquid wash or detergent matrix is mixed.
  • Another object of the invention is a method for applying photocatalytic
  • Liquid system in particular a dispersion, and / or an inventive washing or
  • the contacting takes place in a textile treatment bath containing a liquid system according to the invention, in particular dispersion, and / or an inventive
  • the photocatalytic material advantageously absorbs excellent and good adhesion to the textiles, probably due to the contained
  • Another object of the invention is a process for cleaning, care, equipment, softening and / or conditioning of textiles by contacting these textiles with a liquid system according to the invention, in particular dispersion, or a detergent or cleaner, at and / or followed by exposure of the Textiles to light with wavelengths in the range of 10-1200 nm.
  • the contacting of the textiles with a liquid system according to the invention in particular dispersion, or a washing or cleaning agent in a textile treatment bath.
  • the photocatalytic material also advantageously attracts excellent and good adhesion to the textiles, probably due to the cationic surfactant contained. If the method according to the invention is directed to the elimination, deactivation or reduction of microorganisms, in particular bacteria and germs, in textiles using light having wavelengths in the range of 10-1200 nm, a preferred embodiment of the invention is provided.
  • the method according to the invention is directed to the prophylactic treatment of textiles in the form of an anticipatory defense and inhibition of stains and stains with the use of light having wavelengths in the range of 10-1200 nm, then a preferred embodiment of the invention is provided.
  • the method of the present invention is directed to finishing textiles with photocatalytic material to facilitate the removal of colored stains (colored stains) from textiles using light having wavelengths in the range of 10-1200 nm
  • a preferred embodiment of the invention is provided.
  • the method according to the invention is directed to equipment of textiles with photocatalytic material for reducing the fiber adhesion of dirt, preferably colored spots, to textiles using light with wavelengths in the range of 10-1200 nm, then a preferred embodiment of the invention is provided.
  • the method according to the invention is directed to the equipment of textiles with photocatalytic material for increasing the water solubility of dirt, preferably colored spots, on textiles using light having wavelengths in the range of 10-1200 nm, then a preferred embodiment of the invention is provided.
  • the method according to the invention is directed to the equipment of textiles with photocatalytic material for furnishing the textiles with a self-cleaning capability, using light having wavelengths in the range of 10-1200 nm, then a preferred embodiment of the invention is provided.
  • Is the method according to the invention directed to the removal or reduction of stains and stains on textiles, in particular due to: red to blue anthocyanin dyes, such as cyanidin, for example from cherries or blueberries, red betanidine from the red beet, orange-red carotenoids such as lycopene, beta-carotene, for example from tomatoes or carrots, yellow curcuma dyes, such as curcumin, eg from curry and mustard , brown tannins, eg from tea, fruit, red wine deep brown humic acid, eg from coffee, tea, cocoa, green chlorophyll, eg, from green grasses, technical dyes from cosmetics, inks, colored pencils colored metabolic products and / or excretory products of mold or other Mirkoflora or microbial growth or microbes, using light with wavelengths in the range of 10-1200 nm.
  • red to blue anthocyanin dyes such as cyanidin, for example from cherries or blueberries, red
  • the inventive method is carried out using an automatic washing machine, preferably an automatic washing machine with light source, wherein the liquid system according to the invention, in particular dispersion, and / or an inventive detergent or cleaning agent is added in particular in the final rinse.
  • the photocatalytic material advantageously attracts excellent and well adhering to the textiles, probably due to the cationic surfactant contained.
  • the method according to the invention is a manual process which is carried out in an open tub, in particular hand washing and / or soaking, wherein the tub is lighted after the textiles to be treated have penetrated with the wash liquor exposed to wavelengths in the range of 10-1200 nm, in particular sunlight, preferably for a period of> 5 minutes.
  • the photocatalytic material advantageously attracts excellent and well adhering to the textiles, probably due to the cationic surfactant contained.
  • the inventive method is carried out using an automatic clothes dryer, preferably an automatic clothes dryer with light source, wherein the liquid system according to the invention, in particular dispersion, and / or a detergent or cleaning agent according to the invention in the tumble dryer is added to the textile material to be dried , for example by spraying.
  • the photocatalytic material advantageously attracts excellent and well adhering to the textiles, probably due to the cationic surfactant contained. All the methods described above are particularly effective utilizing light in the visible range (380-800 nm) and / or in the UV range (10-380 nm). It corresponds, therefore, based on all the aforementioned methods, in each case a preferred embodiment, when light in the wavelength range 380-800 nm and / or in the range 10-380 is used.
  • Another object of the invention is a method for applying photocatalytic material to hard surfaces by contacting these hard surfaces with a liquid system according to the invention, in particular dispersion, and / or a detergent or cleaning agent according to the invention.
  • Another object of the invention is a method for cleaning hard surfaces, comprising:
  • hard surfaces are surfaces of the interior, wet rooms, and / or outdoor, preferably
  • kitchen furnishings and utensils such as, preferably, ovens, glass ceramic hobs, hobs, kitchen furniture, kitchen fittings, porcelain items, ceramics, grills (including garden barbecues)
  • structure and property such as preferably masonry, wallpapered, painted, painted walls and / or ceilings, bricks, bricks, plaster, floor slabs, joints, preferably cement and silicone joints, laminate, plastic surfaces, garage doors, plasterboard
  • outdoor furnishings and garden accessories preferably garden furniture, stair treads, swimming pools, walkway fixtures of wood and stone, e.g. Path plates, garden sheds, wooden fences, ornamental and fruit trees, so is a preferred embodiment of the invention.
  • the hard surface treated with a liquid system according to the invention in particular a dispersion, and / or a washing or cleaning agent according to the invention is subjected to a mechanical treatment after completion of the light exposure, such as preferably brushing, Suction or abrasion, in particular spraying, preferably by means of high-pressure cleaner, so there is a preferred embodiment of the invention.
  • liquid system according to the invention in particular dispersion, and / or the washing or cleaning agent according to the invention by brushing, rubbing, spraying, wiping or in particular by spraying, preferably by means of high-pressure cleaner, so is a preferred embodiment of the invention.
  • the inventive method for cleaning hard surfaces allows, in each case according to a preferred embodiment,
  • the method is directed to the defense against or inhibition of algae, moss, lichens, fungi, especially molds, spores, bacteria and other microflora and other microbial growth on hard surfaces, by treating these surfaces with washing or cleaning agents according to the invention and / or followed by exposure of the substrate to light having wavelengths in the range of 10-1200 nm, a preferred embodiment of the invention is provided.
  • Another object of the invention is the use of a liquid system according to the invention, in particular dispersion, and / or a washing or cleaning agent according to the invention for the removal of mold stains and / or foxing of hard surfaces such as preferably tile surfaces, cement and silicone joints, papered, painted, painted Walls and / or ceilings, wood, shower curtains, sanitary ware using light with wavelengths in the range 10-1200 nm.
  • a liquid system according to the invention in particular dispersion, and / or a washing or cleaning agent according to the invention for the removal of mold stains and / or foxing of hard surfaces such as preferably tile surfaces, cement and silicone joints, papered, painted, painted Walls and / or ceilings, wood, shower curtains, sanitary ware using light with wavelengths in the range 10-1200 nm.
  • a liquid system according to the invention in particular a dispersion, and / or a detergent or cleaning agent according to the invention directed to the removal or reduction of colored stains and stains on hard surfaces, which are based on: red to blue anthocyanin, such as cyanidin, for example Cherries or blueberries, red betanidine from beetroot, orange-red carotenoids such as lycopene, beta-carotene, for example from tomatoes or carrots, yellow curcuma dyes, such as curcumin, eg from curry and mustard, brown tannins, eg from tea, fruit, red wine deep brown humic acid, eg from coffee, tea, cocoa, green chlorophyll, for example, from green grasses, technical dyes from cosmetics, inks, colored pencils colored metabolites and / or excretory products of molds or other Mirkoflora or microbial growth or microbes, using light with wavelengths in the range of 10-1200 nm, so is
  • a liquid system according to the invention in particular a dispersion, and / or a washing or cleaning agent according to the invention directed to the removal of color graffiti from sprayed objects, such as preferably house walls, railway vehicles and traffic structures such as underpasses and highway bridges using light Wavelengths in the range of 10-1200 nm, so is a preferred embodiment of the invention.
  • a liquid system according to the invention in particular a dispersion, and / or a detergent or cleaning agent according to the invention is directed to a prophylactic treatment of hard surfaces in the form of an anticipatory defense and inhibition of stains and stains, especially mold stains and / or foxing using light with wavelengths in the range of 10-1200 nm, so is a preferred embodiment of the invention.
  • liquid system according to the invention in particular dispersion, and / or a washing or cleaning agent according to the invention directed to the denaturation or growth inhibition of molds, mold spores and lichens or other Mirkoflora or other microbial growth or microbes on hard surfaces using light with wavelengths in the Range of 10-1200 nm, so is a preferred embodiment of the invention.
  • All the above-mentioned uses and methods are particularly preferred using light having wavelengths in the range 10-380 nm and / or 380-800 nm.
  • the detergents or cleaners according to the invention may contain further optional ingredients.
  • the optional components of the washing or cleaning agent according to the invention are described in detail. % By weight information always refers to the entire detergent or cleaning agent, unless otherwise specified. It is also possible that the liquid systems according to the invention, in particular dispersions, contain optional constituents, in particular those which are described below.
  • the detergents or cleaners according to the invention may preferably contain surfactant (s), it being possible in particular to use anionic, nonionic, cationic and / or amphoteric surfactants.
  • the total surfactant content of the washing or cleaning agent according to the invention is preferably below 40% by weight and more preferably below 35% by weight, based on the total liquid washing or cleaning agent. If the washing or cleaning agent according to the invention contains nonionic surfactants, then a preferred embodiment is present.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -i 4 -alcohols with 3 EO, 4 EO or 7 EO, Cg-n-alcohol with 7 EO, C 3 _i 5 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -i 8 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • nonionic surfactants which can be 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 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • 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),
  • RCO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R ⁇ is hydrogen
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (3), R 1 -OR 2
  • 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 oxy-alkyl radical having 1 to 8 carbon atoms
  • Ci_ 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof 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 sub- 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.
  • nonionic surfactants leads to a particularly good cleaning performance and corresponds to a preferred embodiment of the invention.
  • the content of nonionic surfactants may preferably be used in the washing or cleaning compositions according to the invention, e.g. 5 to 30 wt .-%, preferably 7 to 20 wt .-% and in particular 9 to 15 wt .-% amount, each based on the total agent.
  • washing or cleaning agent according to the invention is free of nonionic surfactant, that is less than 5 wt .-%, 3 wt .-%, 2 wt .-% or 1 wt .-% of nonionic surfactant contains, in particular no, so 0 wt .-% nonionic surfactant contains.
  • anionic surfactants for example, those of the sulfonate type and sulfates can be used.
  • Suitable surfactants of the sulfonate type are preferably C 9 .i 3 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, as are known for example from C 1 2-18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-i 8 alkanes, for example by sulfochlorination or sulfoxidation and 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 of 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) yl sulfates are the alkali and especially the sodium salts of the Schwefelklareschester C 2 -C 8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristic stylet, cetyl or stearyl alcohol or the d 0 -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.
  • sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with 1 to 6 moles of ethylene oxide are suitable.
  • 2 i-alcohols such as 2-methyl-branched Cg-n-alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -i 8 -fatty alcohols having 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 8 -i 8 -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.
  • Particularly preferred anionic surfactants are soaps.
  • Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of preferred liquid washing or cleaning agents to anionic surfactants may be 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-%, each based on the total agent. It may be particularly preferred that the amount of fatty acid soap is at least 2% by weight and more preferably at least 3% by weight and especially preferably at least 4% by weight.
  • Another, more preferred embodiment is when the detergent or cleaner according to the invention is free of anionic surfactant, that is, less than 5 wt .-%, 3 wt .-%, 2 wt .-% or 1 wt .-% of anionic surfactant contains, in particular no, so 0 wt .-% anionic surfactant contains.
  • the viscosity of the inventive detergent or cleaning agent can be measured using standard methods (for example Brookfield viscometer LVT-II at 20 U / min and 2O 0 C, spindle 3) and is preferably in the range of 500 to 5000 mPas.
  • Preferred agents have viscosities of from 1000 to 4000 mPas, with values between 1500 and 3500 mPas being particularly preferred. Also values ⁇ 500 mPas are possible, eg those> 100 mPAs.
  • the washing or cleaning agents according to the invention may contain further optional ingredients, which are e.g. further improve the performance and / or aesthetic properties of the washing or cleaning agent according to the invention, e.g. from the group of builders, bleaches, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents Active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • further optional ingredients e.g. further improve the performance and / or aesthetic properties of the washing or cleaning agent according to the invention, e.g. from the group of builders, bleaches, bleach activators, enzymes, electrolytes, nona
  • washing or cleaning agent according to the invention contains builders, then a preferred embodiment is present.
  • Suitable builders which may be present in the washing or cleaning agents according to the invention 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 + I H 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Preferred crystalline sheet silicates of given formula are those in which M is sodium and x takes the value 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 YH 2 O are preferred.
  • the washing or cleaning agent according to the invention may also contain, for example, only small amounts, for example ⁇ 3% by weight, ⁇ 2% by weight or ⁇ 1% by weight, in particular no crystalline, layered sodium silicates, So 0 wt .-%, included.
  • 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 to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compacting / compacting or by overdrying.
  • the term "amorphous" is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses.
  • the washing or cleaning agent according to the invention may also contain only small amounts, for example ⁇ 3% by weight, ⁇ 2% by weight or ⁇ 1% by weight, especially not at all, ie 0% by weight .-%, containing amorphous sodium silicate.
  • the optionally usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • 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),
  • 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 may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 2 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , Ci 2 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the washing or cleaning agent according to the invention may also contain only small amounts, for example ⁇ 3% by weight, ⁇ 2% by weight or ⁇ 1% by weight, especially not at all, ie 0% by weight .-%, containing zeolite.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • the compounds serving as bleaches in water H 2 O 2 sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further usable 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.
  • the washing or cleaning agent according to the invention may also contain, for example, only small amounts, for example ⁇ 3% by weight, ⁇ 2% by weight or ⁇ 1% by weight, in particular none, ie 0% by weight. -%, containing the aforementioned bleaching agent.
  • bleach activators can be incorporated into the detergents or 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), 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 Isononanoyloxybenzolsulfonat (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacety
  • the washing or cleaning agent according to the invention may also contain only small amounts, for example ⁇ 3% by weight, ⁇ 2% by weight or ⁇ 1% by weight, in particular none, ie 0% by weight. -%, bleach activators included.
  • bleach catalysts can also be incorporated into the detergents or cleaners according to the invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or - carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • the washing or cleaning agent according to the invention may e.g. but also small amounts, e.g. ⁇ 3 wt .-%, ⁇ 2 wt .-% or ⁇ 1 wt .-%, in particular no, so 0 wt .-%, bleach catalysts.
  • a washing or cleaning agent according to the invention may contain a thickening agent.
  • the thickener may include, for example, a polyacrylate thickener, xanthan gum, gellan gum, guar gum, alginate, carrageenan, carboxymethyl cellulose, bentonites, wellan gum, locust bean gum, agar, tragacanth, gum arabic, pectins, polyoses, starch, dextrins, gelatin and casein include.
  • modified natural substances such as modified starches and celluloses, examples which may be mentioned here include carboxymethylcellulose and other cellulose ethers, hydroxyethyl and -propylcellulose and core flour ethers, can be used as thickeners.
  • polyacrylic and polymethacrylic thickeners include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers.
  • CFA Cosmetic, Toiletry and Fragrance Association
  • Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from BF Goodrich under the trade name Carbopol®, for example 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® for example 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 (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably C-.
  • 4- 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 which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol® and from Degussa (Goldschmidt) under the trade name Tego® Polymer, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (cross-linked), Acusol 810, Acusol 820, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, which are crosslinked with an allyl ether of sucrose or of pentaerythritol copolymers of C
  • Carbopol® for example, the hydrophobized Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / Ci O - 3O Alkyl Acrylate Crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473).
  • xanthan gum a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
  • a fatty alcohol is also suitable as thickener.
  • Fatty alcohols may be branched or unbranched, of native origin or of petrochemical origin.
  • Preferred fatty alcohols have a C chain length of 10 to 20 C atoms, preferably 12 to 18. Preference is given to using mixtures of different C chain lengths, such as tallow fatty alcohol or coconut oil fatty alcohol. Examples are Lorol ® Special (C 12 - M -ROH) or Lorol® Technical (C 12-18 -ROH) (both ex Cognis).
  • Preferred laundry detergents or cleaners according to the invention advantageously contain from 0.01 to 3% by weight, and preferably from 0.1 to 1% by weight, of thickening agent, based on the total textile treatment agent. The amount of thickener used depends on the type of thickener and the desired degree of thickening.
  • 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. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
  • hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • Bacillus subtilis Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus licheniformis Bacillus licheniformis
  • Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • 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. It is particularly advantageous if the washing or cleaning agents according to the invention contain mannanase, in particular incorporated in micro-chips and / or speckles.
  • the enzymes may be adsorbed to carriers to protect against premature degradation.
  • the proportion of enzymes, enzyme liquid formulations, enzyme mixtures or enzyme granules may for example be about 0.1 to 5 wt .-%, preferably 0.12 to about 2.5 wt .-% amount.
  • the washing or cleaning agent according to the invention may also contain, for example, only small amounts, in particular none, ie 0% by weight, of enzymes.
  • electrolytes from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl 2 in the compositions is preferred.
  • the proportion of electrolytes in the agents may, for example, usually be 0.5 to 5% by weight.
  • Optional nonaqueous solvents which can be used in the detergents or cleaners according to the invention are derived, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • 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, di-propylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, e
  • nonaqueous solvents can be used in detergents or cleaners according to the invention, e.g. in amounts between 0.5 and 8 wt .-%, but preferably below 5 wt .-% and in particular below 3 wt .-% are used.
  • pH adjusters In order to bring the pH value of the detergents or cleaners according to the invention into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 10% by weight of the total formulation.
  • hydrotropes include the sulfonated hydrotropes such as, for example, the alkylarylsulfonates or alkylarylsulfonic acids.
  • Preferred hydrotropes are selected from xylene, toluene, cumene, naphthalenesulfonate or sulfonic acid and mixtures thereof. Counterions are preferably selected from sodium, calcium and ammonia. elected.
  • the detergents or cleaners of the invention 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 washing or cleaning agents according to the invention, 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 detergents or cleaners according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable anti-redeposition agents which are also referred to as "soil repellents" are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on nonionic cellulose ethers and the polymers of phthalic acid and / or terephthalic acid known from the prior art or of derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof, particularly preferred of these are the sulphonated derivatives the phthalic and terephthalic acid polymers.
  • Optical brighteners may be added to the detergents or cleaners of the present invention to eliminate graying and yellowing of the treated fabrics
  • the fabrics soak onto the fiber and cause lightening and fake bleaching by causing invisible ultraviolet radiation convert visible light of longer wavelength, the absorbed from sunlight ultraviolet light is radiated as a pale blue fluorescence and the yellow shade of the grayed or yellowed laundry pure white.
  • Suitable compounds originate for example from the substance classes of the 4,4-diamino-2, 2 stilbenedisulfonic acids (flavonic), 4,4 'biphenylene -Distyryl-, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles.
  • the optical brighteners can usually be used in amounts, for example, 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 are usually suitable organic nature, such as glue, gelatin, salts of Ether sulfonic acids of starch 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, for example in amounts of from 0.1 to 5% by weight, based on the compositions used.
  • the compositions may contain synthetic crease inhibitors.
  • detergents or cleaners according to the invention may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats 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.
  • compositions 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 detergents, wherein additionally a finishing effect is achieved.
  • 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 detergents or cleaners according to the invention may optionally also contain UV absorbers which are absorbed by the treated textile fabrics and improve the light fastness of the fibers.
  • UV absorbers which are absorbed by the treated textile fabrics and improve the light fastness of the fibers.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates which are present in preferred detergents or cleaners according to the invention, for example in amounts of from 0.01 to 2.5% by weight, 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, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane.
  • organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane.
  • PBS-AM 2,4-tricarboxylic acid
  • Preferred complexing agents are tertiary amines, in particular tertiary alkanolamines (amino alcohols).
  • the alkanolamines have both amino and hydroxy and / or ether groups as functional groups.
  • Particularly preferred tertiary alkanolamines are tri-ethanolamine and tetra-2-hydroxypropyl-ethylenediamine (N, N, N ', N'-tetrakis (2-hydroxy-propyl) ethylenediamine).
  • Particularly preferred combinations of tertiary amines with Zinkricinoleat and one or more ethoxylated fatty alcohols as nonionic solubilizers and optionally solvents are described in the prior art.
  • a particularly preferred complexing agent is etidronic acid (1-hydroxyethylidene-1, 1-diphosphonic acid, 1-hydroxyethyl-1, 1-diphosphonic acid, HEDP, acetophosphonic acid, INCI Etidronic Acid) including their salts.
  • the washing or cleaning agent according to the invention accordingly contains etidronic acid and / or one or more of its salts as complexing agent.
  • the resulting detergents or cleaners according to the invention are preferably clear, ie they have no sediment and are preferably transparent or at least translucent.
  • the detergents or cleaners according to the invention preferably have a transmission of the visible light (410 to 800 nm) of at least 30%, preferably at least 50% and particularly preferably at least 75%, without the addition of a dye.
  • the washing or cleaning agent optionally contains one or more perfumes (perfume oils, fragrances) e.g. in an amount of usually up to 10% by weight, preferably 0.01 to 5% by weight, in particular 0.05 to 3% by weight, particularly preferably 0.1 to 2% by weight and very preferably 0, 4 to 0.8% by weight.
  • perfumes perfume oils, fragrances
  • the amount of perfume used depends on the type of application.
  • perfume oils fragments, fragrances
  • individual fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures as are available from plant sources.
  • perfume oil is meant preferably self-contained perfume compositions which are commonly used for product scenting and are fragrant in particular at the human discretion. This will be explained with an example. If an expert wants to To make a cleanser fragrant, he usually adds to it not only a (well) smelling substance but a collective (well) smelling substance. Such a collective usually consists of a plurality of individual fragrances, e.g. more than 10 or 15, preferably up to 100 or more. These fragrances cooperatively form a desired fragrant, harmonious odor image.
  • a usable perfume oil may contain individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramate, melusate and jasmecyclate.
  • DMBCA dimethylbenzylcarbinyl acetate
  • Benzyl ethyl ether and ambroxane to the aldehydes, for example, the linear alkanals having 8 - 18 carbon atoms, citral, citronellal, citronellyloxy-acetaldehyde, cyclamen aldehyde, lilial and bourgeonal, to the ketones such as the Jonone, ° c-
  • somethylionon and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • mixtures of different fragrances are preferably used, which together produce an attractive fragrance of the perfume oil formed.
  • the perfume oils may also contain natural fragrance mixtures, such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • a fragrance must be volatile, with molecular weight also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound.
  • odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note or body” and “base note “(end note or dry out) divided.
  • Adhesive-resistant fragrances which are advantageously usable in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, Bayöl, Champacablütenöl, Edeltannenöl, Edeltannenzapfenöl, Elemiöl, eucalyptus oil, fennel oil, spruce alder oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil , Gurjunbalsamöl, Helichrysumöl, Ho oil, ginger oil, iris oil, Kajeputöl, calamus oil, chamomile oil, camphor oil, Kanagaöl, cardamom oil, cassia oil, pine oil, Kopa ⁇ vabalsamöl, coriander oil, spearmint oil, caraway oil, cumin oil, lemongrass oil, musk oil, myrrh oil, clove oil, neroliol, niaouli oil , Olibanum
  • fragrances of natural or synthetic origin can be used in the context of the present invention advantageously as adherent fragrances or fragrance mixtures.
  • These compounds include the compounds listed below and mixtures thereof: ambrettolide, ⁇ -amyl cinnamaldehyde, anethole, Anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, borneol, bornyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, Geranyl formate,
  • the lower-boiling fragrances include natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • fragrances from the group of allyl alcohol esters, esters of secondary alcohols, esters of tertiary alcohols, allylic ketones, acetals, ketals, condensation products of amines and aldehydes and / or mixtures thereof may be included.
  • the washing or cleaning agent according to the invention contains certain minimum values of perfume oil (fragrances), namely at least 0.00001% by weight, advantageously at least 0.0001% by weight, considerably advantageously at least 0.001% by weight, more preferably at least 0.01% by weight, more preferably at least 0.1% by weight, even more advantageously at least 0.2% by weight, most preferably at least 0.3% by weight.
  • perfume oil fragments
  • % in a particularly advantageous manner at least 0.4% by weight, in a particularly advantageous manner at least 0.45% by weight, in a significantly advantageous manner at least 0.5% by weight, in a very advantageous manner at least 0, 55 wt .-%, in extreme advantageously at least 0.6% by weight, most advantageously at least 0.65% by weight, most advantageously at least 0.7% by weight, in an exceptionally advantageous manner at least 0.75% by weight, in exceptional advantageously at least 0.8 wt .-%, in an extremely advantageous manner, at least 0.85 wt .-%, in particular at least 0.9 wt .-% of perfume oil, based on the total washing or cleaning agent.
  • the perfume oils contain less than 8, advantageously less than 7, more preferably less than 6, more preferably less than 5, more preferably less than 4, even more preferably less than 3, preferably less than 2, especially no fragrances from the list Amylcinnamal, Amylcinnamylalkohol, Benzylalcohol, Benzylsalicylat, Cinnamylalkohol, Cinnamal, Citral, Cumarin, Eugenol, Geraniol, Hydroxycitronellal, Hydroxymethylpentylcyclohexencarboxaldehyde, Isoeugenol, Anisylalkohol, Benzylbenzoat, Benzylcinnamat, Citronellol, Farnesol, Hexylcinnamaldehyd, Lilial, d-Limonen, Linalool , Methylheptincarbonate, 3-methyl-4- (2,6,6-trimethyl-2-cyclohexen-1-yl)
  • the washing or cleaning agent according to the invention can be completely free of perfume oil (fragrances). However, it is much more preferred that fragrances are included.
  • liquid systems according to the invention in particular dispersions, contain optional constituents, in particular those which have been described above.

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Abstract

L'invention décrit des systèmes liquides contenant un matériau photocatalytique et un tensioactif cationique, en particulier des dispersions, leur fabrication ainsi que leur transformation en agents de lavage ou de nettoyage. Ces systèmes permettent le nettoyage, l'entretien, le finissage, l'avivage et/ou le conditionnement de textiles par exposition à de la lumière de longueurs d'onde comprises dans la plage allant de 10 à 1200 nm. Ils permettent, entre autres, une élimination, une désactivation ou une diminution des micro-organismes dans des textiles, dans une mesure ne présentant aucun risque pour la santé, ainsi qu'une réduction de l'adhérence de la saleté aux fibres. Ils peuvent en outre prévenir l'apparition de mauvaises odeurs sur les textiles et doter lesdits textiles d'un pouvoir autonettoyant. Ils permettent aussi le nettoyage de surfaces dures.
PCT/EP2008/053000 2007-04-23 2008-03-13 Systèmes liquides contenant un matériau photocatalytique WO2008128827A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200710019374 DE102007019374A1 (de) 2007-04-23 2007-04-23 Photokatalytisches Material enthaltende Flüssigsysteme
DE102007019374.4 2007-04-23

Publications (1)

Publication Number Publication Date
WO2008128827A1 true WO2008128827A1 (fr) 2008-10-30

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PCT/EP2008/053000 WO2008128827A1 (fr) 2007-04-23 2008-03-13 Systèmes liquides contenant un matériau photocatalytique

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DE (1) DE102007019374A1 (fr)
WO (1) WO2008128827A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2013107583A1 (fr) * 2012-01-19 2013-07-25 Unilever Plc Procédé et composition de traitement de tissu
US10212932B2 (en) 2016-07-28 2019-02-26 eXion labs Inc. Antimicrobial photoreactive composition comprising organic and inorganic multijunction composite

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FR2789591A1 (fr) * 1999-02-17 2000-08-18 Rhodia Chimie Sa Utilisation de dispersions filmogenes de dioxyde de titane pour la desinfection des surfaces dures, dispersions filmogenes de dioxyde de titane et procede de desinfection
GB2358638A (en) * 1999-12-22 2001-08-01 Reckitt & Colmann Prod Ltd Cleaning compositions
DE10105143A1 (de) * 2001-02-06 2002-08-08 Basf Ag Verfahren zur UV-Schutzausrüstung von textilem Material
JP2005082708A (ja) * 2003-09-09 2005-03-31 Soushin:Kk 洗浄剤
US20060287218A1 (en) * 2005-06-17 2006-12-21 Gsi Camden Products, Inc. Fungicidal composition
WO2008003632A1 (fr) * 2006-07-07 2008-01-10 Henkel Ag & Co. Kgaa Produit de traitement pour la peau désinfectant

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Publication number Priority date Publication date Assignee Title
FR2789591A1 (fr) * 1999-02-17 2000-08-18 Rhodia Chimie Sa Utilisation de dispersions filmogenes de dioxyde de titane pour la desinfection des surfaces dures, dispersions filmogenes de dioxyde de titane et procede de desinfection
GB2358638A (en) * 1999-12-22 2001-08-01 Reckitt & Colmann Prod Ltd Cleaning compositions
DE10105143A1 (de) * 2001-02-06 2002-08-08 Basf Ag Verfahren zur UV-Schutzausrüstung von textilem Material
JP2005082708A (ja) * 2003-09-09 2005-03-31 Soushin:Kk 洗浄剤
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WO2008003632A1 (fr) * 2006-07-07 2008-01-10 Henkel Ag & Co. Kgaa Produit de traitement pour la peau désinfectant

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013107583A1 (fr) * 2012-01-19 2013-07-25 Unilever Plc Procédé et composition de traitement de tissu
US10212932B2 (en) 2016-07-28 2019-02-26 eXion labs Inc. Antimicrobial photoreactive composition comprising organic and inorganic multijunction composite

Also Published As

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