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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic 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
  • C11D1/66—Non-ionic compounds
  • C11D1/825—Mixtures of compounds all of which are non-ionic
• • 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
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof
• • 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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
  • C11D1/721—End blocked ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/75—Amino oxides

Definitions

• the invention relates to a washing or cleaning agent, in particular a hard surface cleaner, which in comparison to known agents has an increased emulsifying ability for fats and oils and the use of this agent for cleaning and care of hard surfaces such as the interiors of washing machines and dishwashers ,
• Cleaning or care products usually contain surfactants and have a wide range of uses and depending on a very different composition. After the pH, alkaline, neutral and acid cleaning or care products, according to the offer form liquid and solid cleaning or care products are distinguished. Especially from liquid cleaners or conditioners the consumer expects that he can use the agents both in the undiluted and in the - dilute aqueous state and in any case a satisfactory starches etc. Maintenance result receives.
• the surfactants and / or alkali carriers which can be replaced by acids depending on the application, optionally also solvents such as glycol ethers and lower alcohols.
• the formulations also contain builders, depending on the type, also bleaching agents, enzymes, as well as perfume oils and dyes. The cleaning success depends to a great extent on the - also geographically very different - type of dirt and the properties of the surfaces to be cleaned.
• cleaning or care products are used as general-purpose or special agents (car care products, oven cleaners, descaling agents, window cleaners, stain removers, floor care products, glass ceramic hob cleaners, stoves, leather care products, metal cleaning agents, furniture care products, pipe cleaners, sanitary cleaners, abrasives, carpet care products or toilet cleaners) assembled.
• Technical cleaning or care products are mainly used in the beverage, food, cosmetic and pharmaceutical industries, but also in the metal industry for metal degreasing.
• the product group also includes cleaning or care products for car washes, tank truck and aircraft cleaning or care products.
• the group of cleaning or care products includes, for example, the dishwashing detergents and agents for cleaning or care of washing machine or dishwasher interior.
• cleaning agent sprays for removing lime deposits on bathroom tiles or for degreasing metal objects such as extractor hoods.
• Means that provide good cleaning or care results without significant mechanical treatment offer in addition to the convenience for the user also the ability to clean surfaces whose mechanical treatment with the means is not or only to a small extent possible. Examples of mechanically poorly cleaned surfaces are corners and angled surfaces, the inner surface of pipes and funnels, sharp-edged or intertwined surfaces, meshes, hose connections, but also surfaces which, due to their nature, must not be subjected to mechanical stress.
• appliances such as washing machines or dishwashers, coffee machines or kettles are incomplete from the inside and only with great effort by mechanical action, for example, by a rag or a brush to clean, so that even for these applications cleaning or care products that perform well without significant mechanical treatment, are desired.
• the effect of the cleaning or care products should be so great that not only the large surfaces of the The inside of the machine, which is exposed to the direct and intensive operating pressure of the cleaning fleet and thus experiences a mechanical load, but also angled areas, hose connections, door seals and all low-flow zones are optimally cleaned and / or maintained in these machines.
• the commercial alkaline or acidic dishwashing, cleaning or rinsing agents are not or insufficiently suitable for cleaning the so-called "problem areas" of dishwashers or washing machines, since they are metered into the cleaning or rinse cycle of the machines, but with the polluted areas either commercially available cleaning agents for hard surfaces are not suitable for this particular application, since they generally contain strong foaming surfactants, the residues of which, for example, in dishwashers can lead to disturbances of various types and also meet the requirements of Cleaning and care properties are not equal.
• the object of the present invention was to provide a washing or cleaning agent which overcomes the above-mentioned problems.
• this agent should have an increased emulsifying ability for fats and oils and thus improved performance in the area of fat removal.
• a washing or cleaning agent which a) 0.1 to 4 wt .-% of a nonionic surfactant (A) of the general formula R 1 O [CH 2 CH (R 2 ) O] X R 3 , in which one
• R 1 and R 3 are independently H or a linear or branched, saturated or mono- or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 26 carbon atoms, wherein at least one of R 1 and R 3 is not H ;
• R 2 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or
• x is values between 1 and 140, where each R 2 can be different; and b) 0.01 to 4 wt .-% of a nonionic surfactant (B) from the group of C 8 -C 22 amine oxides.
• Cleaning or care compositions according to the invention which comprise a combination of the two nonionic surfactants A and B, exhibit a significantly increased emulsifying capacity for fats and oils compared with conventional compositions which comprise other surfactants or only one of the two surfactants.
• the cleaning or care agent according to the invention is preferably used in the treatment of hard surfaces and is particularly suitable for the cleaning or care of washing machines or dishwashers, especially for dishwashers.
• compositions of the invention contain as a first ingredient 0.1 to 4 wt .-% of a nonionic surfactant (A) of the general formula R 1 O [CH 2 CH (R 2 ) O] X R 3 , in which R 1 and R 3 independently of one another for H or a linear or branched, saturated or on or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 26 carbon atoms, wherein at least one of R 1 and R 3 is not H; R 2 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical; and x is between 1 and 140, wherein each R 2 can be different.
• A nonionic surfactant of the general formula R 1 O [CH 2 CH (R 2 ) O] X R 3 , in which R 1 and R 3 independently of one another for H or a linear or branched, saturated or on or polyun
• the detergents or cleaners contain nonionic surfactants from the group of alkoxylated alcohols.
• 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 natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -i ⁇ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 - H -AikOhOl with 3 EO and Ci 2 -i 8 -alcohol with 5 EO.
• the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of 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.
• ethoxylated nonionic surfactants selected from C 6-20 be. 20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were obtained used.
• a particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (Ci. 6 2 o alcohol), preferably a C 18 alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide. Of these, the so-called "narrow ranks ethoxylates" are particularly preferred.
• nonionic surfactants (A) which have a melting point above room temperature.
• Suitable nonionic surfactants (A) which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.
• Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
• the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
• such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
• Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
• the alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants.
• Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
• surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
• surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
• nonionic surfactants of the general formula R 1 O [CH 2 CH 2 OCH 2 CH (R 2 ) O] x [CH 2 CH 2 O] y [CH 2 CH (R 3 ) O] z H, in which 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
• Nonionic surfactants of the general formula R 1 O [CH 2 CH 2 O yCH 2 CH (CH 3 ) O] x H are preferred in particular, in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 .
• the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
• the radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
• Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as usually present in oxo alcohol radicals.
• nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
• alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
• R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
• nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
• These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
• detergents or cleaners which comprise as nonionic surfactant (A) a surfactant of the general formula R 1 O [CH 2 CH (R 2 ) O] X H, in which R 1 represents a linear or branched aliphatic hydrocarbon radical having from 4 to 20 carbon atoms, preferably from 12 to 20 carbon atoms and especially from 12 to 18 carbon atoms;
• A nonionic surfactant
• R 1 represents a linear or branched aliphatic hydrocarbon radical having from 4 to 20 carbon atoms, preferably from 12 to 20 carbon atoms and especially from 12 to 18 carbon atoms;
• R 2 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-butyl radical, in particular H or a methyl radical, where each R 2 may be different; and x represents values between 1 and 140, preferably between 1 and 120 and in particular between 1 and 90.
• laundry detergents or cleaning agents which comprise as nonionic surfactant (A) a surfactant of the general formula R 1 O [CH 2 CH (R 2 ) O] .sub.x CH 2 CH (OH) R 3 are furthermore preferred
• R 1 and R 3 are independently a linear or branched, saturated or mono- or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 24 carbon atoms;
• R 2 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical;
• x for values between 1 and 140, where each R 2 can be different;
• the group of these preferred surfactants (A) include, for example, surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A" O) z -R 2 , in which R 1 and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 -alkyl or -alkenyl radical; A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 - CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and
• end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 24 carbon atoms, where x is between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
• surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 OJ y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched Hydrocarbon radical having 2 to 24 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15
• each R 3 in the above formula may be different if x ⁇ 2.
• the alkylene oxide unit in the square bracket may be varied.
• the value 3 for x has been selected here by way of example and can be quite large where the range of variation increases with increasing x values and includes, for example, a large number of (EO) groups combined with a small number (PO) groups, or vice versa
• laundry detergents or cleaning agents which comprise as nonionic surfactant (A) a surfactant of the general formula R 1 O [CH 2 CH (R 2 ) O] .sub.x CH 2 CH (OH) R 3 are furthermore preferred
• R 1 and R 3 independently of one another are a linear or branched, saturated or mono- or polyunsaturated, functionalized or non-functional hydrocarbon radical having 2 to 24 carbon atoms
• R 2 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl
• x is between 1 and 140, where each R 2 may be different
• the proportion by weight of the nonionic surfactant (A) is preferably between 0.1 and 3% by weight, preferably between 0.2 and 2.5% by weight and in particular between 0.4 and 2.0% by weight.
• Preferred agents according to the invention contain only one nonionic surfactant (A)
• compositions according to the invention contain nonionic surfactants (B) from the group of C 8 -C 22 amine oxides as being particularly advantageous with respect to their emulsifying ability and fat dissolving power have been found to amine oxides with two short-chain alkyl radicals.
• nonionic surfactant (B) comprises a surfactant of the general formula R 1 R 2 R 3 NO, in which
• R 1 and R 2 independently represent a methyl, ethyl or propoyl radical
• R 3 for a linear or branched carbon radical having 10 to 22, preferably having 12 to 18 carbon atoms are therefore preferred according to the invention.
• the weight fraction of the nonionic surfactant (B) is preferably between 0.01 and 3 wt .-%, preferably between 0.02 and 2 wt .-% and in particular between 0.05 and 1 wt .-%.
• the two nonionic surfactants (A) and (B) in any proportion in the compositions according to the invention, such agents have proved to be particularly advantageous in terms of emulsifiability and cleaning performance in which the weight ratio of the surfactants (A) and ( B) is between 30: 1 and 1: 1, preferably between 20: 1 and 2: 1 and in particular between 15: 1 and 4: 1.
• the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
• compositions according to the invention may contain further nonionic surfactants, it being possible for the proportion by weight of the further nonionic surfactants to vary within wide ranges.
• the proportion of additionally used nonionic surfactants is preferably below 6% by weight, more preferably below 4% by weight, preferably below 3% by weight, more preferably below 2% by weight and in particular below 1% by weight.
• the weight fraction of the nonionic surfactants (A) and (B), based on the total weight of all nonionic surfactants present in the composition is at least 60% by weight, preferably at least 80% by weight at least 90 wt .-%, most preferably at least 95 wt .-% and in particular at least 98 wt .-% is.
• agents according to the invention whose nonionic surfactants can be assigned exclusively to the nonionic surfactants of groups (A) and (B).
• the sum of the weight fractions of all nonionic surfactants present in the composition is preferably between 0.2 and 10% by weight, more preferably between 0.2 and 8% by weight, very particularly preferably between 0.2 and 6% by weight in compositions according to the invention. -% and in particular between 0.2 and 4 wt .-%.
• the alkyl glycosides have proved to be detrimental to the inventive effect of the claimed detergents or cleaners.
• Preferred detergents or cleaners therefore contain less than 1% by weight, preferably less than 0.5% by weight and in particular no alkyl glycosides.
• surfactants are polyhydroxy fatty acid amides of the formula
• R is an aliphatic acyl radical having 6 to 22 carbon atoms
• R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
• [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
• R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
• R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N Alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• compositions of the invention may further contain a thickening agent.
• thickeners also called thickeners
• the effect of the thickener is based on various effects such as swelling, gelation, association of micelles, solvation, formation of network structures and / or hydrogen bonds and their interaction.
• the molecular structure and relative molecular weight of the hydrocolloids determine the degree of thickening.
• the compositions according to the invention contain inorganic thickeners such as silica, clays, phyllosilicates, preferably smectites, in particular montmorillonite or hectorite; low molecular weight organic thickeners such as metal soaps, hydrogenated castor oil, modified fatty derivatives or polyamides.
• inorganic thickeners such as silica, clays, phyllosilicates, preferably smectites, in particular montmorillonite or hectorite
• low molecular weight organic thickeners such as metal soaps, hydrogenated castor oil, modified fatty derivatives or polyamides.
• Polyvinyl alcohols, polyacrylic and polymethacrylic acids and their salts, polyacrylamides, polyvinylpyrrolidone, polyethylene glycols, styrene-maleic anhydride copolymers and salts thereof are used in particular from the large group of organic fully synthetic thickeners. Particular preference is given to the copo
• Associative thickeners differ from the modified natural substances listed below and the organic fully synthetic thickeners in that they contain not only hydrophilic groups but also hydrophobic end or side groups in the molecule. This associative thickener surfactant character and are capable of forming micelles. Representatives of this group are preferably contained in the agents according to the invention. It is noteworthy that associative thickeners thicken finely divided dispersions more than coarse-grained ones because of their larger total surface area. One differentiates
• hydrophobically modified polyacrylates which contain nonionic hydrophilic and hydrophobic groups incorporated in an anionic acrylate thickener molecule by copolymerization;
• - hydrophobically modified cellulose ethers prepared by reaction of hydroxyethyl cellulose during the etherification or subsequently with long-chain Alkylepoxiden or halides;
• Hydrophobically modified polyacrylamides prepared by copolymerization of acrylamide with alkyl-modified acrylamide and optionally acrylic acid;
• hydrophobically modified polyethers and associative polyurethane thickeners consisting of hydrophilic, relatively high molecular weight polyether segments linked via urethane groups, capped with at least two terminal, hydrophobic molecule groups.
• R is -NH-C- (O-CH 2 -CH 2 ) X JOC-NH-Fr-NH-C- (O-CH 2 -CH 2 ) X -IOC-NH-R 1
• Preferred thickening agents come from the groups of organic natural thickening agents such as starch, gelatin and casein and the modified natural substances, in particular the polysaccharides.
• Important representatives of the latter group are (hydroxy) ethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose, succinoglycan, xanthan gum, guar gum, locust bean gum, tragacanth, as well as derivatives and mixtures of these thickeners.
• the thickener contained in the agents of the invention is selected from polysaccharides, preferably from cellulose compounds, xanthan gum and guar gum, and from acrylate thickeners, urethane thickeners and clays.
• xanthan gum and derivatives thereof are available under the names Keltrol® RD (CP Kelco), Kelzan® S (CP Kelco), Kelzan® T (CP Kelco), Rhodopol® T (Rhodia) and Rhodigel® X747 (Rhone Poulenc).
• Keltrol® RD CP Kelco
• Kelzan® S CP Kelco
• Kelzan® T CP Kelco
• Rhodopol® T Rhodia
• Rhodigel® X747 Rhone Poulenc
• the xanthan gum content makes at least 20 wt .-%, preferably at least 40 wt .-%, preferably at least 60 wt .-%, particularly preferably at least 80 wt .-% and in particular at least 90 wt .-%, especially 99 wt .-% of the total thickener contained in the agent.
• washing or cleaning agent 0.05 to 1 wt .-%, preferably 0.1 to 0.9 wt .-%, particularly preferably 0.15 to 0.8 wt .-%, preferably 0.2 to 0.7% by weight, preferably 0.25 to 0.6% by weight, very particularly preferably 0.3 to 0.5% by weight and in particular 0.3 to 0.4% by weight Contain thickener.
• the weight ratio of surfactant (A) to thickener is preferably between 50: 1 and 1:10.
• this ratio is between 22: 1 and 1: 2, preferably between 18: 1 and 1: 1, 5, more preferably between 14: 1 and 1: 1, more preferably between 10: 1 and 1, 5: 1 and in particular between 6: 1 and 2: 1.
• the weight ratio between surfactant (B) and thickener is preferably between 40: 1 and 1: 30. This ratio is preferably between 10: 1 and 1: 8, preferably between 7.5: 1 and 1: 6, more preferably between 5: 1 and 1: 4 and in particular between 2.5: 1 and 1: 2.
• Preferred washing or cleaning agents are characterized in that they are between 10 and 90 wt .-%, preferably between 13 and 70 wt .-%, particularly preferably between 16 and 50 wt .-%, most preferably between 19 and 40 wt. % and in particular between 22 and 30 wt .-% of one or more inorganic or organic acid (s).
• the resulting acidic detergents or cleaners according to the invention are also suitable, in addition to the removal of greasy or oily contaminants, also for the removal of limescale and calcareous soils.
• Preferred detergents or cleaners are characterized in that a 1% strength by weight solution of the composition in water (20 ° C.) has a pH of less than 6.0, preferably less than 5.0, particularly preferably less than 4.5, completely particularly preferably less than 4.0 and in particular less than 3.5.
• the undiluted liquid composition preferably has a pH of less than 6, preferably less than 5, more preferably less than 4, more preferably less than 3 and in particular less than 2.5.
• Suitable acids are organic mono- or polybasic, optionally substituted by hydroxyl groups, optionally unsaturated carboxylic acids having 2 to 6 carbon atoms in the molecule.
• the acid has a dissociation constant of less than 10 "6.
• Aliphatic acids Preferred are formic acid, acetic acid, adipic acid, succinic acid, tartaric acid, malic acid, glutaric acid, sorbic acid, maleic acid, malonic acid, lactic acid, glycolic acid, propionic acid, oxalic acid and in particular citric acid.
• lactobionic acid and gluconic acid are also preferred, and preferred inorganic acids are boric acid, sulfamic acid, phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid, and cyanuric acid is also suitable.
• the inventive agents may simultaneously contain one, two, three, four or more organic and / or inorganic acids (acid mixtures).
• the detergents or cleaners contain one or two acids.
• Preferred washing or cleaning agents are characterized in that they contain citric acid and at least one further acid, wherein the weight fraction of citric acid in the acid mixture of two or more acids at least 50 wt .-%, preferably at least 60 wt .-%, preferably at least 70 Wt .-%, particularly preferably at least 80 wt .-%, more preferably at least 90 wt .-% and in particular at least 95 wt .-%, based on the acids contained, is.
• this acid is preferably citric acid or acetic acid.
• the content of the agent in this one acid is then preferably between 15 and 60 wt .-%, more preferably between 18 and 50 wt .-%, most preferably between 21 and 40 wt .-% and in particular between 24 and 30 wt. -%.
• inventive cleaning or care agents additionally contain at least one surfactant from the group of anionic, cationic and amphoteric surfactants.
• anionic surfactants for example, those of the sulfonate type and sulfates are used.
• the surfactants of the sulfonate type are preferably C 9 . 13- Alkylbenzolsulfonate, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C 12 -i 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, in consideration.
• alkanesulfonates which are obtained from C 12 -is-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• esters of ⁇ -sulfo fatty acids for example, the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettcicren suitable.
• sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of C 1 -C 20 -oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 4 -C 15 - alkyl sulfates are preferred.
• 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
• 21 -alcohols such as 2-methyl-branched C 9 _n-alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. They are used in the cleaning or care products due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and 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 by themselves are nonionic surfactants.
• Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
• alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• anionic surfactants are particularly soaps into consideration. Suitable are saturated 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 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 agents according to the invention preferably contain at least one anionic surfactant from the group of alkylphenoxybenzene disulfonates, linear or branched alkylbenzenesulfonates, linear or branched alkylnaphthalene sulfonates, alkylsulfonates, olefinsulfonates, paraffin sulfonates, alkylarylsulfonates, soaps, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates or monoglycerol sulfates.
• anionic surfactant from the group of alkylphenoxybenzene disulfonates, linear or branched alkylbenzenesulfonates, linear or branched alkylnaphthalene sulfonates, alkylsulfonates, olefinsulfonates, paraffin sulfon
• the agent comprises an alkyl benzene sulphonate, preferably an alkyl benzene sulfonate having an alkyl chain length of C 2 -C 2O, in particular cumene sulfonate.
• the agent preferably contains an anionic surfactant which has hydrotropic properties (hydrotrope).
• anionic surfactant (s), preferably anionic surfactant (s) having hydrotropic properties are constituents of automatic dishwashing detergent, their content, based on the total weight of the compositions, is preferably between 2 and 10% by weight, preferably between 3 and 9% by weight. , most preferably between less than 4 and 8 wt .-% and in particular between 5 and 7 wt .-%. Automatic dishwashing detergents which contain only hydrotropic properties from the group of anionic surfactants are particularly preferred.
• cationic active substances for example, cationic compounds of the following formulas can be used:
• Betaines and / or amine oxides in the compositions according to the invention are preferably less than 10% by weight, preferably less than 8% by weight, more preferably less than 6% by weight, more preferably less than 4% by weight, completely more preferably less than 2% by weight, and especially not at all.
• the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1 Weight%. Agents which do not contain cationic and / or amphoteric surfactants are particularly preferred.
• the inventive agent may be in solid form such as powders, pellets, tablets, capsules, pearls, as well as in liquid form. If the agent is solid at room temperature, it is preferably completely at temperatures below 90 0 C, preferably below 80 0 C, preferably below 70 0 C, more preferably below 60 0 C and especially below 55 0 C completely or partially flowable / liquid. Under liquid is understood here also gel. "Liquid” therefore refers to any condition which is characterized at 20 0 C by a footed (flowable) state of aggregation.
• the agent is in the liquid state and has a viscosity above 50 mPas, preferably between 100 and 700 mPas, preferably between 200 and 600 mPas and in particular between 300 and 500 mPas.
• Suitable carriers of liquid agents are water, nonaqueous solvents and mixtures of these.
• Suitable organic carriers are alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers ), Ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (Nitrobenzene), halogenated hydrocarbons (dichlorome
• Such a solvent mixture is, for example, benzine, a mixture of various hydrocarbons suitable for dry cleaning, preferably containing C12 to C14 hydrocarbons above 60% by weight, more preferably above 80% by weight and in particular above 90% by weight, in each case based on the total weight of the mixture, preferably with a boiling range of 81 to 110 0 C.
• the proportion by weight of the organic solvents in the total weight of compositions according to the invention is preferably between 0.1 and 7% by weight, preferably between 0.1 and 5% by weight and in particular between 0.1 and 3% by weight.
• Preferred washing or cleaning agents are characterized in that they contain, based on the total weight of the washing or cleaning agent, between 10 and 95% by weight, preferably between 20 and 80% by weight, preferably between 30 and 80% by weight. and in particular between 40 and 70 wt .-% of a liquid carrier, said carrier is preferably selected from the group which further comprises the alcohols in addition to water, with a water / alcohol mixture and in particular a water / glycerol mixture particularly preferred become.
• the ratio between alcohol and water in the carrier is preferably between 10: 1 and 1: 100, preferably between 1: 1 and 1:90, particularly preferably between 1: 5 and 1:80, very particularly preferably between 1:10 and 1: 60 and especially between 1:15 and 1:40.
• composition according to the invention may contain abrasive, undissolved and / or dispersed constituents, be cloudy or translucent or clear.
• agents according to the invention described above preferably comprise further cleaning-active and / or care-active substances, preferably from the group of builders, polymers, bleaches, bleach activators, enzymes, corrosion inhibitors, disintegration aids, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
• the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
• crystalline layered silicates of general formula NaMSi x O 2x + I • y H 2 O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
• the crystalline layered silicates of the formula NaMSi x O 2x + 1 • y H 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
• silicates Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 • x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 • x H 2 O, Makatite).
• crystalline layer silicates are particularly suitable of the formula NaMSi x O 2x + 1 • y H 2 O, in which x stands for 2 h.
• x stands for 2 h.
• both are .beta.- and ⁇ -sodium Na 2 Si 2 O 5 ⁇ y H 2 O, and further in particular Na-SKS-5 (CC-Na 2 Si 2 O 5), Na-SKS-7 (B-Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 • H 2 O), Na-SKS-10 (NaHSi 2 O 5 • 3 H 2 O, kanemite), Na-SKS-11 ( t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 (5-Na 2 Si 2 O 5 ) are preferred.
• amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably dissolution-delayed and have secondary cleaning properties.
• the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
• amorphous is understood to mean that the silicates are not sharp in X-ray diffraction experiments Provide X-ray reflections, as they are typical for crystalline substances, but at best one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle, cause.
• X-ray-amorphous silicates are used whose silicate particles give washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
• the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
• Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
• the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts and also contribute to the cleaning performance.
• phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 Oi 0 (potassium tripolyphosphate).
• the sodium potassium tripolyphosphates are also preferably used according to the invention.
• alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
• alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
• a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
• a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
• organic cobuilders include polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates. These classes of substances are described below
• Useful organic framework substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
• these are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, Nit ⁇ lotriessigkla (NTA) 1 if such use is not objectionable for environmental reasons, as well as mixtures of these
• the free acids in addition to their builder effect typically also have the property of an acidifying component and thus serve to set a lower and milder pH value of detergents or cleaners
• citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are to be mentioned
• polymeric polycarboxylates are suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70000 g / mol
• the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard , which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which polystyrenesulfonic acids are used as standard. The molecular weights measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this specification
• Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of from 2000 to 20 000 g / mol. Because of their superior solubility, this group may in turn comprise the short-chain polyacrylates, the molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, have, be preferred
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid which have proven effective are 50 to 90% by weight of acrylic acid and 50 to 10 wt .-% maleic acid.
• Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
• the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
• biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
• copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• polymeric aminodicarboxylic acids their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.
• polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
• it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
• a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
• DE dextrose equivalent
• oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Ethylenediamine-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
• glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• the agents according to the invention preferably contain methylglycinediacetic acid (MGDA), ethylenediaminetetraacetic acid (EDTA) and / or nitrilotriacetic acid (NTA), their salts and mixtures of the acids and / or salts.
• MGDA methylglycinediacetic acid
• EDTA ethylenediaminetetraacetic acid
• NTA nitrilotriacetic acid
• cationic, anionic and amphoteric polymers can also be used in the compositions according to the invention in addition to nonionic polymers.
• “Cationic polymers” for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
• amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
• Suitable cationic or amphoteric polymers contain as monomer unit a compound of the general formula
• R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms;
• R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group;
• x and y independently represent integers between 1 and 3.
• X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
• a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate
• Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CHa) -CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
• cationic or amphoteric polymers contain a monomer unit of the general formula
• R1 HC CR 2 -C (O) -NH- (CH 2) -N + R3R4R5
• R 1, R 2, R 3, R 4 and R 5 are independently a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from - CH 3 , -CH 2 -CH 3 , -CH 2 - CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 - CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n is H and x is an integer between 1 and 6.
• H 2 C C (CH 3 ) -C (O) -NH- (CH 2 ) X -N + (CH 3 ) 3
• MAPTAC Metalacrylamidopropyl trimethylammonium chloride
• amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
• anionic monomer units are derived for example from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
• Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
• Preferred usable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the
• Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
• amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
• amphoteric polymers are selected from the group of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethylcyclodially ammonium chloride / alkyl
• amphoteric polymers from the group of:
• the polymers are present in prefabricated form.
• the encapsulation of the polymers by means of water-soluble or water-dispersible polymers is suitable
• Coating compositions preferably by means of water-soluble or water-dispersible natural or synthetic polymers, the encapsulation of the polymers by means of water-insoluble, fusible
• Coating composition preferably by means of water-insoluble coating agent from the
• Tragermate ⁇ alien from the group of washing or cleaning-active substances, particularly preferably from the group of builders (scaffolds) or cobuilders
• Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionogenic or nonionogenic monomers are particularly preferably usable as sulfonic acid-containing polymers
• R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
• Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.
• Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds.
• the content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer.
• copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid,
• the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
• Particularly preferred polymers have certain structural units, which are described below. For example, copolymers which are structural units of the formula are preferred
• These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative.
• acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred.
• the corresponding copolymers contain the structural units of the formula
• Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
• maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula
• Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y is -O- (CH 2 ) n - where n is 0 to 4, -O- (C 6 H 4 ) -, - NH-C (CHs) 2 - or -NH-CH (CH 2 CH 3 ) -, are preferred.
• the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
• metal ions preferably alkali metal ions and in particular for sodium ions.
• partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
• the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
• terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
• the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
• Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol '1 , preferably from 4000 to 25,000 gmol "1 and in particular from 5000 to 15,000 gmol " 1 .
• the bleaching agents are a cleaning substance used with particular preference.
• sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
• Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
• bleaching agents from the group of organic bleaching agents can also be used.
• Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
• peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)] , o- Carboxybenzamidoperoxycaproic acid, N-Nonenylamidoperadipinklare and N-
• Nonenylamidopersuccinates and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid,
• chlorine or bromine releasing substances can be used as a bleaching agent and chlorine or bromine releasing substances.
• suitable chlorine or bromine releasing materials are for example heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
• DICA dichloroisocyanuric acid
• Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
• Bleach activators are used in detergents or cleaners, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 0 C and below.
• As bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
• Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
• polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholin
• bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.
• Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula
• R 1 is -H, -CH 3, a C 2-24 -alkyl or -alkenyl radical, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a d ⁇ -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C ⁇ -alkyl group and at least one further substituent on the aromatic ring
• R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -
• bleach catalysts can also be used.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
• Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are preferably used.
• Enzymes can be used to increase the cleaning performance of the agents according to the invention. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof.
• subtilisin type those of the subtilisin type are preferable.
• these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
• amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
• lipases or cutinases are also usable according to the invention.
• these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
• the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
• Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
• the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
• the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
• further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
• Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
• such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
• a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
• damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
• inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
• Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
• Corrosion inhibitors serve to protect the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. Can be used the known substances of the prior art.
• silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts.
• Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid.
• organic carboxylic acids such as acetic, glycolic, citric and succinic acid.
• cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
• active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
• oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds used.
• salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
• transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.
• redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.
• the metal salts or metal complexes used should be at least partially soluble in water.
• the counterions suitable for salt formation include all conventional mono-, di-, or tri-negatively charged inorganic anions, e.g. Oxide, sulfate, nitrate, fluoride, but also organic anions such as e.g. Stearate.
• metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 ,
• the inorganic redox-active substances are preferably coated, i. completely coated with a waterproof, but easily soluble in the cleaning temperatures material to prevent their premature decomposition or oxidation during storage.
• Preferred coating materials which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.
• the metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total agent.
• compositions according to the invention can be formulated in liquid or solid form, for example in the form of tablets.
• disintegration aids so-called tablet disintegrants
• tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.
• Preferred disintegrating agents are cellulosic disintegrating agents.
• Pure cellulose has the formal gross composition (C 6 H 10 Os) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
• Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
• Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
• Such chemically Modified celluloses include, for example, products of esterifications or etherifications in which hydroxy-hydrogen atoms have been substituted.
• Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
• the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
• CMC carboxymethylcellulose
• the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
• the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.
• the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
• the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
• microcrystalline cellulose As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used.
• This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and can be compacted, for example, into granules having an average particle size of 200 ⁇ m.
• gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
• the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
• the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas.
• Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
• Acidificationsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
• organic acidifying agents preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
• perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
• 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.
• 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 note” ) and “base note” (end note or dry out).
• the top note of a perfume does not consist solely of volatile compounds, while the base note is largely made up of less volatile, i. adherent fragrances.
• more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
• fixatives preventing them from evaporating too quickly.
• the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
• carrier materials for example, cyclodextrins have been proven, the Cyclodextrin-perfume complexes can additionally be coated with other excipients.
• Preferred dyes the selection of which presents no difficulty for the skilled person, have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic tableware do not stain them.
• the colorants When choosing the colorant, it must be noted that the colorants have high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For readily water-soluble colorants, it is typical to choose colorant concentrations in the range of a few 10 -2 to 10 -3 wt%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes is the appropriate concentration of the coloring agent in washing or cleaning agents, however, typically a few 10 '3 to 10 "4 wt .-%.
• Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofarads.
• a liquor containing the inventive agent, a standardized oily component and water in fixed amounts in a pump simulation test within 1 minute shows a phase separation of less than 15%, preferably less than 10%, more preferably less than 5%. , very particularly preferably less than 2.5%, more preferably less than 1.0% and in particular less than 0.2% or less than 40%, preferably less than 30%, more preferably within 5 minutes less than 20%, more preferably less than 10%, more preferably less than 5%, and most preferably less than 2.5%.
• Another object of the present application is therefore the use of a washing or cleaning agent according to the invention for the removal of greasy or oily stains.
• An additional subject of the present invention is the use of the agent according to the invention for cleaning and care of hard surfaces, preferably of washing machines or dishwashers, in particular for cleaning the interior of dishwashers.
• the agent is preferably introduced into the cutlery basket or directly into one of the baskets or the machine interior (interior floor).
• the compositions according to the invention are used either by introduction into the dosing drawer or into the washing drum.
• the consumer applies the agent directly from a storage bottle or a storage package on the surface to be cleaned.
• the consumer introduce the agent into the machine in a prefabricated dosage unit, such as a tablet, a pouch with a solid or liquid filling or a small bottle, without risking it to be exposed to skin contact with the agent.
• This dosing unit comprises, especially when using liquid agents for cleaning the interiors of washing machines or dishwashers between 100 to 400 ml, preferably between 200 to 300 ml.
• the inventive agent is released at the beginning of the consumer started washing or cleaning program of the washing machine or dishwasher in the machine interior.
• This may be possible by complete or partial dissolving or dispersing the packaging or also by melting individual or all parts of the packaging at temperatures of preferably less than 6O 0 C 1 more preferably less than 50 ° C and in particular less than 4O 0 C.
• the consumer can remove the closure part, for example, from a dosing unit such as a bottle filled with a solidified melt, a wax or a gel, and then introduce the dosing unit with the opening downwards into the machine interior.
• a dosing unit such as a bottle filled with a solidified melt, a wax or a gel
• the viscosity of the agent is reduced by the warm wash liquor and thus allows a rapid release of the liquid agent by flowing out of the package.
• At least 80% by weight, preferably at least 90% by weight and in particular at least 95% by weight of the agent used in a package are preferred within 15, preferably within 12, preferably within 9, more preferably within 6 and in particular released within 5 minutes after reaching the maximum liquor temperature in the washing machine or dishwasher interior.
• the agent has such a low viscosity that it flows out immediately after removal of the closure with a suitable inclination of the container and thus is available during the entire cleaning or care process.
• the maximum brine temperature is preferably greater than 30 0 C, preferably greater than 35 ° C, more preferably greater than 40 0 C, to preferably greater than 45 0 C, most preferably greater than 5O 0 C and in particular from 60 0 C to 70 ° C.
• This test is used to simulate the short-term energy input through a circulation pump in a household dishwasher.
• the energy for making the emulsion is introduced into the system at 800 rpm using a four-blade 30 mm diameter stirrer (IKA RW 20).
• IKA RW 20 a four-blade 30 mm diameter stirrer
• the stirrer is switched on for 30 seconds.
• the sample is transferred to a 100 mL graduated cylinder.
• a phase separation takes place in which settles an aqueous phase at the bottom of the cylinder.
• the volume of this newly forming phase is measured in milliliters as a function of time.
• the formulations 2 and 3 according to the invention have a significantly improved emulsifying ability compared to the comparative example, despite the small total amounts of nonionic surfactants. At the same time, these formulations also significantly improve performance when removing soiling containing grease or oil. This is especially true for the cleaning of hard surfaces.

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