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
  • C11D3/02—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
  • C11D3/50—Perfumes
• • 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
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
• • 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
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/507—Compounds releasing perfumes by thermal or chemical activation

Definitions

• the present invention is in the field of detergents or cleaners.
• the invention relates in particular to detergents or cleaners which comprise reaction products of metal oxides and fragrances. It further relates to a process for the preparation of detergents or cleaners and a washing or cleaning process, a process for fixing odoriferous substances on hard and / or textile surfaces and furthermore a process for targeted release of fragrance on hard and / or textile surfaces.
• detergents or cleaners In connection with the use of detergents or cleaners, the consumers generally not only strive for a primary effect, which consists in a washing or cleaning performance, but usually an additional effect is expected, which usually in the generation of a fragrance the target substrates, such as Textiles, exists.
• detergents or cleaners are usually perfumed.
• fragrances can be incorporated directly into the respective agents.
• techniques are used which protect the fragrances.
• encapsulated fragrances can be used.
• perfume precursors have become established.
• the functional principle of fragrance precursor compounds is usually based on converting fragrances into compounds which do not produce a direct fragrance impression, but which are able to release the original fragrance to a certain stimulus, for example the action of heat or acid, and thus become fragrant.
• oxazolidine-based fragrance precursors are known. Such are in the German publication DE 10 2006 003 092 A1 described.
• the fragrance precursors described there are bicyclic oxazolidine derivatives of fragrance ketones or aldehydes, such as, for example, decanal, which on hydrolysis are able to liberate the fragrant aldehydes or ketones.
• Known fragrance precursors are, for example, the silicic acid esters. Such are in the German publication DE198 41 147 A1 described. These silicic acid esters contain the radicals of perfume alcohols, such as, for example, octan-1-ol, and are suitable for scenting detergents and cleaners, since they release the fragrant alcohols during the hydrolysis.
• JP2004180979A describes an antibacterial deodorant comprising colloidal particles of inorganic oxide, in particular TiO 2 , with negative surface charge, to which metallic components, such as in particular silver or zinc, adhere, mixed with fragrances.
• metallic components such as in particular silver or zinc
• washing or cleaning agents are not described there.
• DE10212121A1 describes a process for the preparation of nano-zinc oxide dispersions which have a content of halogenated constituents of less than 5 wt .-%. A connection with fragrances is not produced.
• WO 2008/077239 A2 describes nanocapsules with core-shell structure, wherein the shell comprises at least one metal oxide.
• the core material may include fragrances.
• WO 2009/103651 A2 describes personal care compositions comprising cationic nanoparticles, on the surface organic substituents are bonded, having at least one cationic group. Detergents or cleaning agents are not described.
• compositions which include polymeric networks wherein the polymers are microporous or nanoporous.
• the compositions may contain perfumes.
• nanoparticles which contain cores of an inorganic material, at least one intermediate layer comprising silane groups and at least one outer layer comprising polyoxyalkylene monoamines.
• WO 2010/076803 A2 there is described a topical multicomponent system in which at least one component comprises an active agent which is coated with a metal oxide. Detergents or cleaning agents are not described.
• the object of the present invention was to provide a washing or cleaning agent which allows the generation of a fragrance on the substrates treated therewith.
• Frragrances is the name for chemical compounds with odor, which in humans trigger a preferably pleasant sense of smell and therefore find the perfuming or scenting of technical and sanitary articles, soaps, personal care products, detergents, cleaning agents and the like.
• perfume and perfume are to be understood in the context of this invention synonymous.
• Metal oxides are chemical compounds of a metal with oxygen.
• reaction products of fragrances with metal oxides are referred to in the context of this invention, those products which result in the mixing or in bringing the starting materials, ie the fragrances and the metal oxides, in particular in solution or suspension, by their interaction. In particular, this can lead to the formation of coordination compounds. Likewise adsorption or accumulation of the fragrances on the surface of the metal oxides can occur. Due to the interaction between the fragrances and the metal oxides results in a modification of the fragrances, which surprisingly leads to significant advantages in the scenting of objects, especially textiles, compared with fragrances, which were not brought into interaction with metal oxides. These advantages will be described later in more detail.
• the reaction products are obtainable, in particular, by dissolving or dispersing the metal oxides and fragrances together, if appropriate by supplying thermal energy.
• the metal oxide as a solution or dispersion is introduced and the fragrances or perfume oils are added later, so that the reaction products only in the target product, e.g. a liquid detergent.
• a reaction product of fragrances and metal oxides in a separate step, and then to convert this separately prepared reaction product to the target product, e.g. to be added to a detergent.
• a solution or dispersion of the starting materials is preferably first prepared, and this mixture is advantageously stirred for a period of at least 1 minute at room temperature (21 ° C).
• thermal energy may also be supplied, e.g. by heating to 60 ° C.
• the particle size of the metal oxides used is basically freely selectable. However, it is preferred for the metal oxides to have particle sizes ⁇ 1000 ⁇ m, advantageously ⁇ 500 ⁇ m, moreover advantageously ⁇ 100 ⁇ m, preferably ⁇ 1 ⁇ m, in particular ⁇ 0.1 ⁇ m. A possible lower limit of the particle size may e.g. at 1 nm or 10 nm.
• particle size here means the largest elongation of the individual particle.
• the determination of the particle size can be carried out by the skilled person in many ways.
• the determination of the particle size can preferably be carried out by optical methods depending on the particle size with the aid of light microscopy or electron microscopy.
• metal oxide nanoparticles ie particles of metal oxides whose dimensions are in the range of 1 nm to 100 nm, in order to arrive by their reaction with fragrances to the reaction products of the invention.
• metal oxide nanoparticles such as zinc oxide nanoparticles, iron oxide nanoparticles, tin oxide nanoparticles, zirconia nanoparticles, or alumina nanoparticles.
• the metal oxide nanoparticles are usually produced in a sol-gel process.
• the starting materials usually metal alkoxides, are initially introduced in homogeneously dissolved form in an aqueous medium.
• the metal alcoholates hydrolyse with elimination of alcohol.
• the resulting molecules then polycondensate with elimination of water, so that, with a suitable choice of the reaction conditions, inorganic sol particles with sizes in the nanometer range are formed.
• the sol-gel synthesis method is described in detail in the literature, see eg Schmidt, Chem. Republicer Zeit, (2001) 35 (3), 176 ,
• the washing or cleaning agent according to the invention makes it possible to produce a fragrance on the substrates treated therewith.
• the invention goes hand in hand with some further advantages.
• a significant advantage is that the invention allows a fragrant effect by rewetting.
• objects treated with the washing or cleaning agent according to the invention e.g. Textiles, after which they surprisingly exude a particularly intense fragrance when they are moistened again.
• This effect is beneficial for many processes of daily life.
• a towel washed with the detergent of the invention unfolds on drying e.g. of crockery or the human body, by the absorbed moisture a fragrance effect.
• appropriate underwear e.g. Undershirt, by the body moisture a renewed fragrance effect are triggered.
• This effect ie a re-flow of fragrance after rewetting, does not occur when using ordinary detergents or cleansers, i. It is usually not expected that a towel exudes fragrance as soon as it is moistened again.
• Another advantage lies in the improvement of the absorption of fragrances from aqueous, preferably surfactant-containing solutions on the treated objects, in particular textiles. This not only affects the fragrances introduced via the reaction products according to the invention, but also benefits the other fragrances which are not introduced into the system via the reaction products according to the invention. This allows for improved efficiency in fragrance use.
• Another advantage lies in the improved fixation of fragrances on soft and hard surfaces, such as textiles, skin and hair or hard surfaces. With improved fixation here is meant an improved, so strong adhesion of the already scented on the objects fragrances.
• Bad-smell components are volatile compounds with kakosmophoren groups, z. As amine derivatives and sulfur derivatives.
• the present invention can afford not only a targeted release of fragrances, but also a recording and thus reduction of malodors.
• the metal oxides are selected from ZnO, CeO 2 and / or SnO 2 . These result in particularly advantageous scent benefits, especially with regard to the described fragrance release by rewetting.
• the usable fragrances which relate to the reaction products of the invention, are freely selectable.
• Preferred fragrances are those which can function as Elektronenpardonatoren, ie those molecules which can provide a lone pair of electrons for binding with a Lewis acid.
• the fragrances which relate to the reaction products of the invention are selected from dihydromyrcenol (CAS number: 18479-58-8), acylated (CAS number: 5413-60-5), propidyl (CAS number : 17511-60-3), triplal (CAS number: 68039-49-6), hexyl acetate, 2-tert-butylcyclohexylacetate, 4-tert-butylcyclohexyl acetate, linalyl acetate, terpinyl acetate (CAS number 8007-35-0), ethylene brassylate ( CAS number: 105-95-3), Applelide (CAS number: 478695-70-4), Lilial, Cyclamenaldehyde (CAS number: 103-95-7), Cyclogalbanat (CAS number: 68901-15-5), Allylamylglycolate (CAS number: 67634-00-8), ethyl 2-methylbutyrate (CAS number: 7452
• the metal oxide used according to the invention is doped with metal nanoparticles with dimensions ⁇ 100 nm, preferably ⁇ 10 nm, in particular gold, silver, platinum, palladium and / or iron nanoparticles.
• Metal nanoparticles can usually be generated via the reduction process.
• metal salts as starting materials initially lie in homogeneously dissolved form in aqueous or organic media in front. Thereafter, the finest metal nuclei are formed by admixing a reducing agent.
• the nanoparticles are usually stabilized by suitable ligands to avoid aggregation of the nanoparticles.
• the doping of the metal oxide used according to the invention with metal nanoparticles is preferably carried out by mixing the metal nanoparticles with the metal oxide to be doped, in particular in aqueous or organic media.
• the amount of the metal oxide introduced into the washing or cleaning agent via the reaction product according to the invention is basically optional.
• the amount of metal oxide present preferably introduced via the reaction product according to the invention into the washing or cleaning agent, is 0.00001 to 10% by weight, preferably 0.01 to 1% by weight, based on the total washing or cleaning agent is a preferred embodiment of the invention.
• the amount of fragrances contained in the washing or cleaning agent according to the invention is basically optional and is preferably oriented to the intended use of the agent concerned. According to a preferred embodiment of the invention, the amount of the fragrances contained 0.00001 to 80 wt .-%, preferably 0.01 to 15 wt .-%, based on the total washing or cleaning agent.
• the washing or cleaning agent according to the invention contains 0.0001 to 95 wt .-%, preferably 0.01 to 40 wt .-% surfactants.
• Particularly high surfactant contents can be e.g. be implemented in toilet soaps (bar soaps).
• the reaction product according to the invention is first prepared according to a preferred embodiment and then incorporated into the detergent or cleaning agent matrix.
• the metal oxide product may first be incorporated into the product and then the perfume oil or its individual components added. However, this is less preferred since this type of reaction is less effective and also involves side reactions.
• Another object of the invention is a process for the preparation of a detergent or cleaner, which comprises a reaction product of fragrances with metal oxides and this reaction product combined with the detergent or cleaning agent matrix.
• a reaction product the statements made above apply.
• Another object of the invention is a washing or cleaning process in which hard and / or textile surfaces are brought into contact with a treatment liquid which contains a washing or cleaning agent according to the invention.
• the advantage of this method is, inter alia, that the surfaces treated in this way develop a pleasant fragrance after rewetting, so that a targeted release of fragrance is made possible.
• Another object of the invention is a method for fixing fragrances on hard and / or textile surfaces, wherein the surface with an aqueous, preferably surfactant-containing treatment liquid comprising reaction products of fragrances with metal oxides, as defined above, over a period of 5 seconds Treated for 300 minutes at a temperature below 95 ° C.
• washing or cleaning agent in the context of the invention also includes the aftertreatment agents. These include, in particular, the fabric softeners, the hygiene rinse and the dryer sheets (so-called dryer sheets), but also the textile fresheners and ironing water.
• the corresponding agents preferably contain the usual ingredients for the product category in question.
• a hygiene rinse usually contains active ingredients that, depending on the individual case, can kill a wide range of organisms from viruses, bacteria, fungi.
• agents such as alkylbenzyldimethylammonium chloride, are known in the art.
• fabric softeners contain softening active ingredients, usually cationic surfactants, preferably esterquats, ie quaternary ammonium compounds having two hydrophobic radicals, each containing an ester group as a so-called predetermined breaking point for easier biodegradation.
• care products for spraying textiles in the household to absorb volatile, unpleasant-smelling molecules and to mask them with pleasant scents are referred to as textile fresheners.
• the most preferred agents include the detergents and the fabric softeners as well as the hard surface cleaners.
• Detergents or cleaning agents according to the invention preferably comprise, in addition to the reaction product according to the invention, at least one, preferably several, active components, in particular washing, care and / or cleaning active components, advantageously selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, acidifiers , Alkalizing agents, anti-wrinkling compounds, antibacterials, antioxidants, anti-redeposition agents, antistatics, builders, bleaches, bleach activators, bleach stabilizers, bleach catalysts, ironing aids, fragrances, anti-shrinkage agents, electrolytes, enzymes, colorants, dyes, color transfer inhibitors, fluorescers, fungicides , Germicides, odor-complexing substances, hydrotropes, rinse aid, complexing agents, preservatives, corrosion inhibitors, optical brighteners, pearlescers, pH adjusters, phobies and Impregnating agents, polymers, swelling and anti-slip agents,
• the surfactant content will be higher or lower.
• the surfactant content of, for example, detergents between e.g. 5 and 50% by weight, preferably between 10 and 30% by weight and in particular between 15 and 25% by weight
• automatic dishwashing detergents are usually between e.g. 0.1 and 10 wt .-%, preferably between 0.5 and 7.5 wt .-% and in particular between 1 and 5 wt .-% surfactants.
• the detergents or cleaners according to the invention may preferably comprise surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic surfactants.
• the optionally usable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates, of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms.
• the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
• Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
• alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
• suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
• ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides are also suitable.
• alkoxylates are those obtained by ethoxylation of linear primary alcohols, in particular by ethoxylation of corresponding linear primary alcohols having chain lengths of C14 and C15.
• alkoxylates are those obtained by ethoxylation of branched primary alcohols, in particular by ethoxylation of corresponding branched primary alcohols having 11 to 36 carbon atoms and an average of 0.7 to 3.0 branches per molecule, which branches comprise methyl and ethyl branches.
• Such alkoxylates are used in US 7,871,973 B1 described.
• Surfactants based on 2-propylheptanol are particularly suitable for washing at low temperatures, in particular sulfates derived therefrom, ethoxylates and ether sulfates.
• the ethoxylates based on 2-propylheptanol in particular in admixture with C16 / C18 fatty alcohol ethoxylates, are preferred.
• surfactants based on isotridecanol especially in particular the isotridecanol-based ethoxylates.
• alkyl polyglycosides which are suitable for optional incorporation into the compositions according to the invention are compounds of the general formula (G) n -OR 8 in which R 8 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
• the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose.
• the oligomers consisting of such glycosidically linked monomers are, in addition to the type of sugar contained in them by their number, the so-called Oligomermaschinesgrad, characterized.
• the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
• Preferred monomer building block is glucose because of its good availability.
• Nonionic surfactant is preferably present in detergents or cleaners according to the invention in amounts of from 0.1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight, based on the weight entire washing or cleaning agent.
• the detergents or cleaners may instead or additionally contain further optional surfactants, preferably anionic surfactants.
• anionic surfactants of the sulfate or sulfonate type in amounts of preferably not more than 30 wt .-%, in particular from 0.1 wt .-% to 18 wt .-%, in each case based on total washing or cleaning agent, optionally included .
• Suitable anionic surfactants which are particularly suitable for use in the detergents or cleaners according to the invention are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation call.
• alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
• a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
• alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases Such alkyl and / or alkenyl sulfates are optionally contained in the detergents or cleaners, preferably in amounts of from 0.1% to 20% by weight, in particular from 0.5% to 18% by weight.
• Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates.
• ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
• the sulfonate type anionic surfactants which can be used include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, especially those of fatty acids with 8 to 22 C-atoms, preferably 12 to 18 C-atoms, and linear alcohols having 1 to 6 C-atoms, preferably 1 to 4 C-atoms, derivative sulfonation products, as well as the formal saponification of these resulting sulfo fatty acids.
• Particularly preferred optional anionic surfactants are the alkylbenzenesulfonates, e.g. Sodium dodecylbenzenesulfonate.
• Anionic surfactant is preferably present in detergents or cleaners according to the invention in amounts of from 0.1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight, based on the weight entire washing or cleaning agent.
• soaps saturated fatty acid soaps, such as the salts of lauric, myristic, palmitic or stearic, as well as from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, derived soaps suitable are.
• those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
• soap is optionally contained in the detergent or cleaning agent according to the invention in amounts of from 0.1% by weight to 5% by weight. In particular, in liquid detergents or cleaners, however, higher amounts of soap of up to 20 wt .-% may optionally be included.
• Cationic surfactants can also be present optionally in the detergents or cleaners according to the invention, in particular in the laundry aftertreatment compositions according to the invention.
• cationic surfactants are quaternary ammonium compounds having preferably one or in particular two hydrophobic alkyl radicals.
• Particularly preferred are esterquats, ie quaternary ammonium compounds having two hydrophobic radicals, each containing an ester group as a so-called predetermined breaking point for easier biodegradation.
• esterquats are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulfate, bis (palmitoyloxyethyl) -hydroxyethyl-methyl-ammonium methosulfate, 1,2-bis [tallowacyloxy ] -3-trimethylammoniumpropane chloride, N, N-dimethyl-N, N-di (tallowacyloxyethyl) ammonium methosulphate or methyl N, N-bis (stearoyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulphate.
• the cationic surfactants are optionally contained in the compositions according to the invention in amounts of preferably 0.05 to 20% by weight, based on the total agent. Amounts of 0.1 to 5 wt.% Are particularly preferred.
• surfactants are present in detergents or cleaners according to the invention in a total amount of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
• surfactants are present in detergents or cleaners according to the invention in a total amount of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
• laundry aftertreatment agents Preferably, up to 30 wt .-%, in particular 5 wt .-% to 15 wt .-% of surfactants, among these, preferably at least partially cationic surfactants used.
• a washing or cleaning agent according to the invention may preferably comprise at least one builder, preferably a water-soluble and / or water-insoluble, organic and / or inorganic builder.
• the use of water-soluble builder is preferred.
• the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
• polycarboxylic acids in particular citric acid and sugar acids
• monomeric and polymeric aminopolycarboxylic acids in particular methylglycinediacetic acid, nitrilotriacetic acid and
• Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
• organic builder substances may be present in the detergents or cleaners according to the invention in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, detergents or cleaners according to the invention.
• Detergents or cleaning agents according to the invention e.g. Softener, may optionally also be free of organic builder.
• Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polyphosphates, preferably sodium triphosphate.
• Crystalline or amorphous alkali metal aluminosilicates in amounts of, for example, up to 50% by weight, preferably not more than 40% by weight and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable water-insoluble, water-dispersible inorganic builder materials.
• suitable water-insoluble, water-dispersible inorganic builder materials are particularly suitable water-insoluble, water-dispersible inorganic builder materials.
• the detergent grade crystalline sodium aluminosilicates especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used optionally in solid, particulate agents.
• Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
• the alkali metal silicates useful as builders in the detergents or cleaners according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 of less than 0.95, in particular of 1: 1.1 to 1:12 and may be amorphous or crystalline. Amorphous alkali silicates are preferred.
• water-insoluble builder materials such as zeolite
• Builders are optionally in the detergents or cleaning agents according to the invention in amounts of up to 60 wt .-%, in particular from 5 wt .-% to 40 wt .-%, optionally included.
• Aftertreatment agents according to the invention such as e.g. Softener, are preferably free of inorganic builder.
• organic peracids or peracid salts of organic acids such as phthalimide percaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate, are suitable as the optionally usable peroxygen compounds.
• organic peracids or peracid salts of organic acids such as phthalimide percaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate, are suitable as the optionally usable peroxygen compounds.
• solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
• alkali percarbonate alkali perborate monohydrate or, in particular, in liquid media, hydrogen peroxide in the form of aqueous solutions containing from 3% by weight to 10% by weight of hydrogen peroxide.
• a washing or cleaning agent according to the invention contains bleaches, such as preferably peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
• bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
• bleach activators it is possible to use optionally compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
• Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
• polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetyl oxy-2,5-dihydrofuran and eno
• TAED
• Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
• Combinations of conventional bleach activators can also be used.
• Such bleach activators may optionally be present in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, based on the total agent.
• Suitable enzymes which can optionally be used in the washing or cleaning agents are, in particular, those from the class of the proteases, cutinases, amylases, pullulanases, hemicellulases, cellulases, lipases, oxidases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
• the optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are optionally present in the detergents or cleaners according to the invention, preferably in amounts of not more than 5% by weight, in particular from 0.2% by weight to 2% by weight.
• the detergents or cleaning agents may optionally contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners.
• Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
• brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.
• the optionally usable foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffin waxes and mixtures thereof with silanated silica or bis-fatty acid alkylenediamides.
• mixtures of different foam inhibitors can be used, for example those of silicones, paraffins or waxes.
• the optional foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are bound to a granular, water-soluble or dispersible carrier substance.
• mixtures of paraffin waxes and bistearylethylenediamides are preferred.
• the detergents or cleaning agents may optionally also contain components which positively influence the oil and grease washability from textiles, so-called soil-release active ingredients. This effect is particularly evident when a textile is soiled, which has been previously washed several times with a detergent containing this oil and fat dissolving component was washed.
• the preferred oil and fat dissolving components include e.g.
• nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art known polymers of phthalic acid and / or terephthalic acid or derivatives thereof with monomeric and / or polymeric diols, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.
• the detergents or cleaners may optionally also contain color transfer inhibitors, preferably in amounts of from 0.1% by weight to 2% by weight, in particular from 0.1% by weight to 1% by weight, which in a preferred embodiment of the invention are polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide, or copolymers of these.
• polyvinylpyrrolidones N-vinylimidazole / N-vinylpyrrolidone copolymers
• polyvinyl oxazolidones copolymers based on vinyl monomers and carboxamides
• polyesters containing pyrrolidone groups and polyamides polyesters containing pyrrolidone groups and polyamides
• grafted polyamidoamines and polyethyleneimines polymers containing amide groups from secondary amines
• polyamine N-oxide Polymers polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids.
• the optionally applicable graying inhibitors have the ability to keep suspended from the textile fiber dirt suspended in the fleet.
• Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• water-soluble polyamides containing acidic groups are suitable for this purpose.
• starch derivatives can be used, for example aldehyde starches.
• 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 washing or cleaning agent, be used as optional grayness inhibitors.
• the organic solvents which are optionally usable in the washing or cleaning agents according to the invention especially if they are in liquid or pasty form, preferably include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 C-atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers.
• Such Water-miscible solvents may be present in the detergents or cleaners according to the invention preferably in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight, optionally.
• alcohols and / or organic solvents can be used with up to 50%.
• a liquid, hydrophobic compound selected from limonene, dioctyl ether, hexylhexylate, decamethylcyclopentasiloxane, C 11-13 isoparaffin and mixtures thereof, preferably in combination with fatty acid soap and / or unneutralized fatty acid.
• detergents or cleaning agents according to the invention acids, especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid , But also mineral acids, especially sulfuric acid, or bases, in particular ammonium or alkali hydroxides, optionally included.
• Such pH regulators may preferably not be more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the detergents or cleaners according to the invention.
• fragrances or fragrances or perfume oils all known substances and mixtures can be used.
• fragment (s) perfumes
• perfume oil (s) are used synonymously. This means, in particular, all those substances or mixtures thereof which are perceived by humans as odor, in particular perceived by humans as a pleasant odor, thus triggering a pleasant sense of smell.
• perfumes perfume oils or perfume oil ingredients can be used.
• perfume oils or fragrances can according to the invention individual fragrance compounds, eg.
• ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are e.g.
• the ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes z. B.
• the linear alkanals with 8-18 C-atoms citral, citronellal, citronellyloxy-acetaldehyde, cyclamen aldehyde, Lilial and Bourgeonal, to the ketones z.
• the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
• the hydrocarbons include mainly the terpenes such as limonene and pinene.
• mixtures of different fragrances are used, which together produce an attractive fragrance.
• perfume oils may also contain natural fragrance mixtures 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, neroli oil, orange peel oil and sandalwood oil.
• a fragrance In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most 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 perfume or 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).
• the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent fragrances.
• the base note consists for the most part of less volatile, ie adherent fragrances.
• more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
• the subsequent classification of the fragrances in "more volatile” or “adherent” fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.
• Adhesion-resistant fragrances which can be used 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, bay oil, bergamot oil, Champacablütenöl, Edel fir oil, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine needle oil, copalva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Musk Grain Oil, Myrrh Oil, Clove
• fragrances can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances.
• These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, Ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farn
• the more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
• Examples of more volatile fragrances are alkyl isothiocyanates (alkylmustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
• the preparation of solid compositions according to the invention in particular washing or cleaning agents, can be carried out in a manner known in principle, for example by spray-drying or granulation, e.g. optional peroxygen compound and optional bleach catalyst may be added later, if desired.
• the reaction product according to the invention is preferably introduced into the composition at the end of the preparation, preferably by spraying, in particular together with further fragrances or with a perfume oil.
• agents according to the invention e.g. Detergents or cleaning agents having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
• the preparation of liquid agents according to the invention e.g.
• Detergents or cleaning agents can also be carried out in a conventional manner, wherein the reaction product of the invention preferably at the end of the preparation in the means, e.g. Detergent or detergent is introduced, in particular together with other fragrances or with a perfume oil.
• the teaching according to the invention can be used to reduce the perfume fraction in the agents concerned, for example, laundry after-treatment agents, because the incorporation of the reaction product according to the invention allows a Particularly efficient perfuming can be ensured, resulting from the targeted fragrance release.
• the washing or cleaning agent according to the invention is solid, in particular particulate and contains in addition to the reaction product according to the invention 5 wt .-% to 55 wt .-% builders, 2.5 wt .-% to 20 wt .-% anionic surfactant .
• Adjusting agent in particular alkali metal sulphate, and up to 2% by weight, in particular from 0.4% by weight to 1.2% by weight, of enzyme, preferably particulate formulated enzyme, in particular protease, lipase, amylase, cellulase and / or oxidoreductase.
• This embodiment may optionally also be free of bleach and bleach activator.
• the washing or cleaning agent according to the invention is in liquid form, preferably in gel form.
• Preferred liquid detergents or cleaners have water contents of e.g. 10-95 wt .-%, preferably 20-80 wt .-% and in particular 30-70 wt .-%, based on the total agent.
• the water content may also be particularly low, e.g. ⁇ 30% by weight, preferably ⁇ 20% by weight, especially ⁇ 15% by weight, e.g. 0.1 to 10 wt .-%, wt .-%, each based on the total agent.
• the liquid agents may also contain non-aqueous solvents.
• a particularly preferred liquid washing or cleaning agent contains at least anionic surfactants in amounts of from 0.5% by weight to 20% by weight, nonionic surfactants in amounts of from 1% by weight to 25% by weight, Builders in amounts of 1 to 25 wt .-%, enzymes and water.
• a solution of 11.8 g of zinc acetate in 500 ml MeOH was reacted under stirring with a solution of 5.92 g KOH in 260 ml MeOH within one hour. For this, the mixture was heated to 60 ° C. The reaction solution first became cloudy upon heating to 60 ° C, before it cleared again after about 1.5 hours. After 2 hours, the heating was stopped and the resulting ZnO particles-containing transparent solution was then filled so that the solution could not draw water. The solution was still completely transparent after about 1 week and no precipitate formation.
• the resulting reaction products of fragrances with metal oxides were then applied to smelling strips of filter cardboard (240 g / m 2 , length 135 mm x width 6 mm) by immersion. Thereafter, the fresh odor impression emanating from the smelling strip was evaluated on a scale from 0 (corresponding to: without odor) to 10 (corresponding to a very strong odor). The olfactory impression was then checked after 24 hours on the now dry smelling strips. Thereafter, the odor impression (ie also after 24 hours) was checked, which resulted after moistening the olfactory strip with water. The review was carried out by a panel of 5 people with a good sense of smell, with the entire test being repeated twice. The values given are the average values of this review.

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• 2011
  • 2011-03-29 DE DE102011006315A patent/DE102011006315A1/de not_active Withdrawn
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