EP2173842A2 - Détergent doté d'un polymère à base de polyester favorisant le détachement des salissures - Google Patents

Détergent doté d'un polymère à base de polyester favorisant le détachement des salissures

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Publication number
EP2173842A2
EP2173842A2 EP08775291A EP08775291A EP2173842A2 EP 2173842 A2 EP2173842 A2 EP 2173842A2 EP 08775291 A EP08775291 A EP 08775291A EP 08775291 A EP08775291 A EP 08775291A EP 2173842 A2 EP2173842 A2 EP 2173842A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
weight
acid
washing
amounts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP08775291A
Other languages
German (de)
English (en)
Inventor
Birgit Burg
Michael Dreja
Ingrid Kraus
Maher Korakli
Konstantin Benda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2173842A2 publication Critical patent/EP2173842A2/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • the present invention relates to a washing or cleaning agent which contains at least one anionic surfactant based on oleochemicals and a polyester-based soil release polymer, as well as its use in manual or automatic textile laundering.
  • polyester-based soil release polymer in detergents or cleaners containing ester sulfonate for reducing textile graying in textile laundering.
  • it relates to a textile washing process using the aforementioned detergent or cleaning agent at a washing temperature ⁇ 4O 0 C.
  • the primary degradation must be at least 80%, the complete biodegradation (after 28 days) should be at least 60%.
  • primary stain removal performance
  • secondary prevention of graying
  • alkylbenzenesulfonates which are based on petrochemical raw materials and also offer at the same dosage equal to a lower cleaning performance, preferably stain removal performance, especially on greasy soils.
  • the concrete object of the present invention is to provide a washing or cleaning agent whose surfactant content protects the petrochemical resources. This object is solved by the subject matter of the invention.
  • the present invention is a detergent or cleaning agent containing at least one anionic surfactant based on oleochemical and a polyester-based soil release polymer.
  • fatty chemical base means that the surfactant in question, eg the anionic surfactant, is based essentially (ie at least partially, better by majority or even completely) on such raw materials which are predominantly made from vegetable oils, but also from animal oils and / or Important vegetable fats and oils include rapeseed oil, sunflower oil, linseed oil, coconut oil, coconut oil, palm oil, palm kernel oil, soybean oil, peanut oil, castor oil, etc. Important animal fats include beef tallow and lard.
  • Anionic surfactants on essentially (ie at least by proportion, better majority or even completely) oleochemical base are in particular the ester sulfonates, preferably the methyl ester sulfonates (MES), and the fatty alcohol sulfates ( FAS).
  • ester sulfonates preferably the methyl ester sulfonates (MES), and the fatty alcohol sulfates ( FAS).
  • ester sulfonates (based on a substantially oleochemical base) can be used with very particular preference.
  • Estersulfonates are well-known to the person skilled in the art for detergents and cleaners, so that the description can be kept short at this point.
  • Preferably usable ester sulfonates contain in the molecule a terminal ester and a sulfonate function, usually adjacent in the ⁇ -position.
  • These ⁇ -Estersulfonate can eg by Reaction of alkyl esters with conventional sulfonating agents, preferably air-diluted, dry sulfur trioxide (SO3), at 8O 0 C and subsequent neutralization can be obtained.
  • SO3 dry sulfur trioxide
  • esters based on coconut oil C12 / 14 chain
  • palm kernel oil palm kernel sulfofatty acid ester
  • taigmethyl ester C16 / 18 chain
  • Particularly preferred ester sulfonates can be described by the formula:
  • R is, on average, a C 6 -C 22 alkyl radical. It may preferably be a Ci 0 - Cis-alkyl radical, Ci 2 -Ci 4 -alkyl radical, Ci 4 -C 6 -alkyl radical, Ci 2 -Ci 5 -alkyl radical, C 8 -Ci 0 -alkyl radical, Ci 6 -Ci 8 -Alkyl radical, Ci 6 -alkyl radical, Ci 2 -i 6 -alkyl radicals or Ci 2 -Ci 8 -alkyl radical. Most preferably, however, C 6 -C 8 are - alkyl groups, Ci 2 _i 6 alkyl, C 6 alkyl or C 2 -C 8 alkyl.
  • R 1 is, on average, a C 1 -C 6 -alkyl radical, particularly preferably a methyl radical.
  • n is the number 1 or 2, preferably 1.
  • M n + is the counterion, where M is preferably Na, K, Ca, Mg, H, monoethanolammonium, diethanolammonium, triethanolammonium or a mixture thereof. In this case, n + is either 1+ or 2+, depending on the type of M. As counterion, Na + , K + or Mg + is preferred.
  • fatty alcohol sulfates (based on a substantially oleochemical base) can be used particularly preferably according to the invention.
  • Fatty alcohol sulfates are well known to those skilled in detergents and cleaners as such.
  • Preferred fatty alcohol sulfates can be described by the formula (II), R 2 O-SO 3 X. They are available, for example, by reaction of preferably saturated fatty alcohols with concentrated sulfuric acid, gaseous sulfur trioxide, chlorosulfonic acid or sulfamic acid.
  • R 2 O-SO 3 X R 2 is a particularly linear (or branched) aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • fatty alcohol sulfates based on C 12 / i 4 -, C 12 / C 16 i ⁇ - and / i ⁇ - fatty alcohols, and preferably in the form of their sodium salts.
  • branched primary alcohols are oxo alcohols, as they are accessible, for example, by reacting carbon monoxide and hydrogen to alpha-olefins by the shop process.
  • Alkyl sulfates based on oxo alcohols are therefore not anionic surfactants based on oleochemicals.
  • Detergents or cleaning compositions according to the invention which contain ester sulfonate and / or fatty alcohol sulfates (as anionic surfactants based on a substantially oleochemical base) and a polyester-based soil release polymer are particularly preferred according to the invention.
  • the anionic surfactants based on petrochemical raw material namely in particular alkanesulfonates, preferably secondary alkanesulfonates (SAS) and alkylbenzenesulfonates, such as preferably linear alkylbenzenesulfonates, and ⁇ -olefinsulfonates are to be distinguished from anionic surfactants.
  • alkanesulfonates preferably secondary alkanesulfonates (SAS) and alkylbenzenesulfonates, such as preferably linear alkylbenzenesulfonates, and ⁇ -olefinsulfonates
  • SAS secondary alkanesulfonates
  • alkylbenzenesulfonates such as preferably linear alkylbenzenesulfonates
  • ⁇ -olefinsulfonates are to be distinguished from anionic surfactants.
  • the total amount of anionic surfactants based on petrochemical raw material is advantageously ⁇ 20% by weight, preferably ⁇ 15% by weight, more preferably ⁇ 10% by weight, more preferably ⁇ 5% by weight and in particular ⁇ 1% by weight, based on the total mean.
  • anionic surfactant based on petrochemical raw material is contained in the agent according to the invention.
  • the washing or cleaning agent according to the invention should contain alkylbenzenesulfonates, which is possible but less preferred according to the invention, then at most in quantities of ⁇ 20% by weight, e.g. in amounts of from 0.01% by weight to ⁇ 15% by weight, but preferably in amounts of ⁇ 10% by weight, ⁇ 5% by weight or even ⁇ 1% by weight, based on the total washing or detergent.
  • no alkylbenzenesulfonate is contained in the composition according to the invention.
  • Alkylbenzenesulfonates have the following general formula: ⁇ ⁇ - ⁇ #!
  • R is an alkyl radical (usually C8-C12) and M 1 is a monovalent cation, preferably sodium.
  • washing or cleaning agent according to the invention should contain alkanesulfonates, which is possible, but is less preferred according to the invention, then at most in amounts of ⁇ 15% by weight, e.g. 0.01 wt .-% to ⁇ 10 wt .-%, but preferably in amounts ⁇ 5 wt .-% or ⁇ 1 wt .-%, based on the total detergent or cleaning agent.
  • no alkanesulfonate is contained in the composition according to the invention.
  • Alkanesulfonate is the collective name for compounds of the general formula R-SO 2 -OM, where R is a - usually secondary - alkyl radical and M is a monovalent cation, preferably sodium. If the washing or cleaning agent according to the invention should contain ⁇ -olefinsulfonates, which is possible, but less preferred according to the invention, if appropriate in quantities
  • ⁇ 15% by weight e.g. 0.01 wt .-% to ⁇ 10 wt .-%, but preferably in amounts ⁇ 5 wt .-% or ⁇ 1
  • no ⁇ -olefin sulfonate is present in the composition according to the invention.
  • technical ⁇ -olefin sulfonates consist of hydroxyalkanesulfonates and alkene sulfonates in a ratio of 2: 1.
  • Fatty alcohol ether sulfates can be obtained substantially on a oleochemical basis, namely by reacting fatty alcohols on (substantially) oleochemical raw material basis with alkylene oxide (preferably ethylene oxide) to fatty alcohol alkoxylates and subsequent reaction with e.g. Sulfur trioxide and neutralization to fatty alcohol ether sulfates.
  • alkylene oxide preferably ethylene oxide
  • Sulfur trioxide and neutralization to fatty alcohol ether sulfates.
  • the necessary alkylene oxide preferably ethylene oxide
  • it may also be recovered from the biomass, for example by reacting bioethanol (e.g., from sugar beet) to ethylene and then oxidizing to ethylene oxide. This is just for a reasonably cheap biomass offer, e.g.
  • the group of fatty alcohol ether sulfates is added to the anionic surfactants on (substantially) oleochemical raw material base, regardless of the origin of the alkylene oxide, since in any case the fatty alcohol component is accessible from a oleochemical source.
  • fatty alcohol ether sulfates are included in the composition of the invention in amounts of e.g. 0-20 wt .-%, advantageously in amounts of 0.01 wt .-% to 15 wt .-%, preferably in amounts of 1 wt .-% to 10 wt .-%, based on the total washing or cleaning agent , contain.
  • the polyester-based soil-release polymer in the detergent or cleaner according to the invention in amounts of 0.01 to 2 wt .-%, preferably 0.05 to 1, 5 wt .-%, advantageously 0, 1 to 1 wt .-%, in particular 0.15 to 0.8 wt .-%, based on the total agent included.
  • amount of soil-release polymer to do so contributes to achieving particularly good results in terms of primary and secondary washing performance in textile washing. It is also possible to use> 2% by weight of the polyester-based soil-release polymer in the washing or cleaning agent according to the invention.
  • ester sulfonate preferably methyl ester sulfonate (MES)
  • MES methyl ester sulfonate
  • alkylbenzenesulfonate preferably linear alkylbenzenesulfonate (LAS)
  • LAS linear alkylbenzenesulfonate
  • ester sulfonate preferably MES and alkylbenzenesulfonate, preferably LAS
  • the proportion of the ester sulfonate is not less than that of the alkylbenzenesulfonate, better even this outweighs.
  • the amount ratio of ester sulfonate to alkylbenzenesulfonate is therefore in a preferred embodiment preferably at least 1: 1, preferably at least 1, 1: 1, in particular at least 1.2: 1.
  • the ratio of ester sulfonate to alkylbenzenesulfonate can also be, for example, 2: 1 or 3: 1, for example in the range between 1: 1 and 20: 1, or in the range between 1.1: 1 and 10: 1.
  • the washing or cleaning agent according to the invention it is also possible for the washing or cleaning agent according to the invention to have very little, e.g. less than 1 wt .-%, based on the total average of alkylbenzenesulfonate or completely free of alkylbenzenesulfonate.
  • the soil release polymer according to the invention comprises, in particular essentially consists of, the structural units I to III or I to IV,
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another each represent hydrogen or a C 1 -C 18 -n- or iso-alkyl group
  • R 7 is a linear or branched C 1 -C 3 o-alkyl group or a linear or branched C 2 -C 30 -
  • Alkenyl group for a cycloalkyl group having 5 to 9 carbon atoms, a C 6 -C 30 -aryl group or a C 6 -C 30 -arylalkyl group, and
  • Polyfunctional unit stands for a unit having 3 to 6 functional groups capable of esterification reaction, so again there is a preferred embodiment of the invention.
  • e is a number between 1 and 30, in particular between
  • polyesters can be obtained, for example, by polycondensation of terephthalic acid dialkyl ester, 5-sulfoisophthalic acid dialkyl ester, alkylene glycols, optionally polyalkylene glycols (at a, b and / or c> 1) and polyalkylene glycols end capped on one side (corresponding to unit III). It should be pointed out that for numbers a, b, c> 1 there is a polymeric skeleton and thus the coefficients as an average can assume any value in the given interval. This value reflects the number average molecular weight.
  • R 1 and R 2 are each H
  • polyethylene glycol-co-propylene glycol having number-average molecular weights of 100 to 2000 g / mol.
  • from 1 to 50 units (I) can be contained per polymer chain.
  • the preferred use amount of the structural unit ( III) that necessary to achieve the mean molecular weights described below.
  • the use of crosslinked or branched polyester structures is also possible according to the invention. This is expressed by the presence of a crosslinking polyfunctional structural unit (IV) having at least three to a maximum of 6 functional groups capable of esterification reaction.
  • a crosslinking polyfunctional structural unit (IV) having at least three to a maximum of 6 functional groups capable of esterification reaction.
  • acid, alcohol, ester, anhydride or epoxy groups can be named as functional groups. Different functionalities in one molecule are also possible.
  • citric acid, malic acid, tartaric acid and gallic acid particularly preferably 2,2-dihydroxymethylpropionic acid
  • polyhydric alcohols such as pentaerythrol, glycerol, sorbitol and / or trimethylolpropane can be used.
  • These may also be polybasic aliphatic or aromatic carboxylic acids, such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), or benzene-1,3,5-tricarboxylic acid ( Trimesithklare) act.
  • the proportion by weight of crosslinking monomers, based on the total weight of the polyester, can be, for example, up to 10% by weight, in particular up to 5% by weight and particularly preferably up to 3% by weight.
  • the polyesters containing the structural units (I), (II) and (III) and optionally (IV) generally have number average molecular weights in the range from 700 to 50,000 g / mol, wherein the number average molecular weight can be determined by size exclusion chromatography in aqueous solution using a calibration using narrowly distributed polyacrylic acid Na salt standards.
  • the number-average molecular weights are preferably in the range from 800 to 25,000 g / mol, in particular from 1,000 to 15,000 g / mol, particularly preferably from 1,200 to 12,000 g / mol.
  • solid polyesters which have softening points above 40 ° C. are preferably used as part of the particle of the second type; they preferably have a softening point between 50 and 200 0 C, particularly preferably between 8O 0 C and 15O 0 C and extremely preferably between 100 0 C and 12O 0 C.
  • the synthesis of the polyesters may be prepared by known methods, for example by the above-mentioned Components are first heated under normal pressure with addition of a catalyst and then builds up the necessary molecular weights in vacuo by distilling off superstoichiometric amounts of the glycols used.
  • Suitable for the reaction are the known transesterification and condensation catalysts, such as, for example, titanium tetraisopropylate, dibutyltin oxide, alkali metal or alkaline earth metal alcoholates or antimony trioxide / calcium acetate.
  • titanium tetraisopropylate such as, for example, titanium tetraisopropylate, dibutyltin oxide, alkali metal or alkaline earth metal alcoholates or antimony trioxide / calcium acetate.
  • Preferred polyesters are of solid consistency and can easily be ground into powder or compacted or agglomerated into granules of defined particle sizes.
  • the granulation can be carried out by solidifying the copolymers obtained as melt in the synthesis by cooling in a cool gas stream, for example air or nitrogen, or by application to a flaking roll or to a treadmill to form flakes or flakes.
  • This coarse material can optionally be further ground, for example, in the roll mill or in the screen mill, which can be followed by a sieving and a rounding as described above.
  • the granulation can also be carried out in such a way that the polyesters are ground to powder after solidification and then reacted by compaction or agglomeration and the above-described rounding into granules with defined particle sizes.
  • the washing or cleaning agent according to the invention additionally contains nonionic surfactant, for the purposes of the invention the use of nonionic surfactants based on renewable raw materials, preferably on (essentially) is preferred based on fat chemical raw material or on the basis of sugars.
  • Preferred nonionic surfactants based on renewable raw materials include in particular the sugar surfactants, such as preferably alkyl polyglucosides (APG), sugar esters, in particular sucrose esters and / or sugar amides, in particular glucamides, fatty acid sarcosinates, alkanolamides, protein-fatty acid condensates and fatty amines.
  • Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerolamides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides.
  • sugar surfactants which can be used in the context of the present invention are the alkyl polyglycosides, the sugar amides (in particular glucamides) and the sugar esters, such as preferably sucrose esters, but especially the alkyl polyglycosides.
  • Glucamides are N-alkylated, preferably N-methylated fatty acid amides obtained by reaction of
  • N-alkyl (N-methyl) glucosamine can be obtained with fatty acid methyl esters.
  • R 1 in this aforementioned formula (IV) is a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, for example, for an n-Ci 2 alkyl radical
  • R 2 is a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 6 to 22, preferably 6 to 18, especially 8 to 16, particularly preferably 8 to 14 carbon atoms, a C
  • the alkyl polyglycosides (APG) are preferably usable sugar surfactants and preferably satisfy the general formula (V), RO (AO) 3 [G] x , in which R is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar moiety and x for a number from 1 to 10 and AO for an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a for the average degree of alkoxylation from 0 to 20
  • the group (AO) 3 may also contain different alkyleneoxy, for example ethyleneoxy or propyleneoxy, where it is a to the average Automatalkoxyltechniksgrad, ie the sum of Ethoxyltechniks- and Propoxyltechniksgrad acts.
  • the alkyl radicals R 1 of the APG are linear unsaturated radicals having the stated number of
  • APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • alkyl glycosides having a mean degree of oligomerization x of 1.1 to 3.0 are used. From an application point of view, those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred.
  • the glycosidic sugar used is preferably xylose, but especially glucose.
  • the alkyl or alkenyl radical R (based on the abovementioned formula (V) RO (AO) 3 [G] x ) can be derived from primary alcohols having 8 to 18, preferably 8 to 14, carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, such as those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelene's oxosynthesis.
  • the alkyl or alkenyl radical R is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • lauryl alcohol myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • elaidyl alcohol petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.
  • alkyl polyglycosides are, for example C 8 and C -io- t2 - U - Alkyl polyglucoside with an average degree of 1, 4 or 1, 5, in particular C 8 -io- alkyl-1, 5-glucoside and C t2 - U - alkyl-1, 4-glucoside.
  • APG may be e.g. be described with the following formula (VI):
  • the average degree of oligomerization x is preferably 1, 2-1, 5.
  • the alkyl radical is preferably in the range C8-C16 (thus n in the aforementioned formula is preferably 7-15).
  • Sugar esters are also preferred nonionic surfactants.
  • Sugar esters are esters of sugar alcohols, in particular sucrose (ie sucrose esters) with organic or inorganic acids, in particular with fatty acids (derivatives), for example obtainable by reactions of sucrose with fatty acid esters in solution or melt or from alkali-catalyzed transesterifications with triglycerides.
  • Monoesters of short-chain fatty acids may be preferred, e.g. Monoester of lauric acid.
  • sucrose esters are e.g. by the following illustrative formulas VIII-X:
  • n in these formulas VIII-X is preferably in the range from 1 to 20.
  • the abovementioned formulas are intended primarily to illustrate, because not least because of the existing hydroxy functions, the sucrose esters are generally complex mixtures.
  • Fettkladsarcosinate are preferably usable nonionic surfactants.
  • the fatty acid sarcosinates are the condensation products of fatty acids with N-methylglycine.
  • Fatty acid sarcosinates can be prepared by reacting N-methylglycine with fatty acid chloride. Particularly preferred are e.g. Fatty acid sarcosinates based on C12 to C18 fatty acids. Fatty acid sarcosinates are characterized by a pronounced foaming power, while they also show a low sensitivity to water hardness and high skin tolerance.
  • Preferred fatty acid sarcosinates can be described by the following general formula (XI):
  • R is a linear or branched, saturated or unsaturated alkyl radical having preferably 8 to 22 carbon atoms.
  • fatty acid alkanolamides can preferably be used according to the invention.
  • Fatty acid alkanolamides may be e.g. by reaction of alkanolamines with fatty acids, fatty acid methyl esters or fatty acid glycerides.
  • Preferred fatty acid alkanolamides can be described by the following formula (XII):
  • R 1 -CO is a fatty acid radical, in particular a stearic, coconut oil or olefin radical.
  • alkanolamine di-, monoethanolamine or aminopropanols can be used, whereby the meaning of R 2 and n in the above-mentioned formula be determined.
  • fatty amines can be used in the invention. Fatty amines are for example obtainable by a process starting from fatty alcohols, which are reacted at 210-260 0 C in the presence of dehydrogenation catalysts with ammonia or short chain alkyl or dialkylamines.
  • the salts of fatty amines are cationic emulsifiers. These are included in the term fatty amine.
  • quaternary ammonium compounds can be obtained. These are included in the term fatty amine.
  • oxidation of the fatty amines for example with hydrogen peroxide, amine oxides can be obtained. These are included in the term fatty amine.
  • the amine oxides which can be used in the context of the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • Preferred amine oxides having the following formula (XIII), R 6 R 7 R 8 N + -O ", are described in which R 6 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 8 -i 8 alkyl radical, in particular a saturated C 10 -i 6 -alkyl radical, for example a saturated C 12 -i 4 -alkyl radical which, in the alkylamidoamine oxides, has a carbonylamidoalkylene group -CO-NH- (CH 2 ) Z - and in the alkoxyalkylaminoxides via an oxaalkylene group -O- (CH 2 ) Z - is bonded to the nitrogen atom N, where z is in each case a number from 1 to 10,
  • R 7, R, 8, independently, a CI_ 4 alkyl optionally hydroxysubstituted such as a hydroxyethyl group, in particular a methyl radical.
  • a preferred amine oxide is, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide).
  • protein-fatty acid condensates can be used in the invention. Protein-fatty acid condensates can be obtained, for example, by acylating protein hydrolysates, for example with fatty acids, fatty acid methyl esters, but preferably fatty acid chlorides or substituted maleic anhydrides. Particularly preferred protein-fatty acid condensates can be described by the following formula:
  • N is preferably 1-13.
  • Very well known are, for example, the Lamepon® types, Gluadin® types, Hostapon® KCG or the Amisoft® types.
  • Alkoxylated fatty alcohols can be obtained essentially on a oleochemical basis, namely by reacting corresponding fatty alcohols with alkylene oxide, preferably ethylene oxide.
  • alkylene oxide preferably ethylene oxide.
  • the necessary alkylene oxide can also be obtained via biomass, but usually comes from petrochemical sources.
  • the alkoxylated fatty alcohols are added to the surfactants on (essentially) oleochemical raw material basis, regardless of the origin of the alkylene oxide, since in any case the fatty alcohol is accessible from the oleochemical source.
  • alcohol ethoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, palm kernel, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 12 - C 4 alcohols containing 3 EO EO to 6, C 9 -C i-alcohols containing 7 EO, C 3 -C 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci 4 -Ci 5 -AIkOhOIe with 4 EO, 5 EO, 7 EO or 9 EO, Ci 2 -Ci 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -Ci 4- alcohol with 3 EO and Ci 2 -C- 8- alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • the washing or cleaning agent according to the invention contains nonionic surfactant, in particular on a oleochemical basis, in quantities of 0.01-20% by weight, preferably 0.1-15% by weight, in particular 1-10% by weight. -%, relative to the total budget.
  • nonionic surfactants based on renewable raw materials, ie preferably a fat-chemical base.
  • % By weight, preferably in amounts of from 0.01 to 15% by weight, in particular in amounts of from 1 to 10% by weight. %, based on the total washing or cleaning agent, so that corresponds to a preferred embodiment of the invention.
  • alkoxylated fatty alcohol for example ⁇ 5 wt .-%, preferably ⁇ 3 wt .-%, in particular ⁇ 2 wt .-% or even ⁇ 1 wt .-%, based on the total agent , It is even possible that no alkoxylated fatty alcohol is contained at all.
  • the total amount of surfactants present in the washing or cleaning agent according to the invention is in principle variable.
  • a total amount of e.g. However, 5-50% by weight, preferably 10 -35% by weight, in particular 15-30% by weight, of surfactants in the washing or cleaning agent according to the invention has proven to be very advantageous as far as the detergency in textile washing is concerned and therefore corresponds to a preferred embodiment of the invention.
  • the washing or cleaning agent according to the invention comprises enzymes, preferably amylase, protease, mannanase, tannase, carbonic anhydrase, pectinase, lipase and / or cellulase, advantageously in amounts of 0.01-5%. Wt .-%, based on the total agent. Below, enzymes are picked up again.
  • the washing or cleaning agent according to the invention is characterized in that it
  • ester sulfonate preferably MES, in particular in amounts of 1-20% by weight
  • Alkylbenzenesulfonate preferably LAS, in particular in amounts of 0-20% by weight, for example> 0.01-5% by weight, and also
  • nonionic surfactant advantageously in amounts of 0-15% by weight, preferably 0.01-10% by weight, in particular 0.1-5% by weight, and also
  • (D) enzymes advantageously in amounts of 0-5 wt .-%, wt .-% in each case based on the total agent, and optionally conventional further constituents of detergents or cleaning agents.
  • the washing or cleaning agent according to the invention contains at least 50 wt .-%, preferably> 60 wt .-%,> 70 wt .-%,> 80 wt .-% or> 90 wt .-%, advantageously > 95 wt .-%, more preferably> 99 wt .-% and in particular even 100 wt .-% surfactants on (essentially) oleochemical raw material basis, wt .-% based on the total amount of surfactant contained.
  • the washing or cleaning agent according to the invention contains a zeolite-containing builder system, preferably comprising zeolite in amounts of eg 1-50 wt .-%, advantageously> 5 wt .-%, more preferably> 10 wt .-%, further advantageous > 15% by weight, in particular> 20 wt .-%, based on the total agent.
  • the washing or cleaning agent according to the invention contains a soluble builder system, preferably comprising soda, silicate, citrate and / or polycarboxylates, in particular in a total amount of 2.5 to 60 wt .-%, based on the total agent.
  • the washing or cleaning agent according to the invention contains a phosphate-containing builder system, wherein phosphate is preferably present in amounts of 1-40 wt .-%, in particular 5-30 wt .-%, based on the total agent.
  • the present invention detergent or cleaning agent has a pH> 7.5, as measured in a 5% solution of the composition in water at 2O 0 C.
  • Another object of the invention is the use of an inventive, preferably esterulfonat ambiencen washing or cleaning agent in the manual or automatic textile laundry, in particular for reducing the Textilvergauung in the textile laundry.
  • Another object of the invention is the use of a polyester-based soil release polymer, in particular a polyester-based soil release polymer as defined above, in estersulfonat ambiencen detergents or cleaning agents, to reduce Textilvergrauung in the textile laundry.
  • Another object of the invention is the use of a polyester-based soil-release polymer, in particular a polyester-based soil release polymer as defined above, in esterulfonat ambiencen detergents or cleaning agents, to increase the primary washing performance.
  • Another object of the invention is a textile washing process using a washing or cleaning agent according to the invention, wherein the washing temperature ⁇ 4O 0 C, preferably ⁇ 3O 0 C. It is of course possible to work even at higher washing temperatures, for example at 6O 0 C or even higher. There are however, especially at low wash temperatures eg ⁇ 4O 0 C, preferably allows ⁇ 3O 0 C very good cleaning results.
  • anionic surfactants for example, those of the sulfonate type and sulfates can be used. Suitable anionic surfactants have already been mentioned. In general, surfactants based on oleochemicals are always to be preferred in the context of the invention.
  • Suitable anionic surfactants are e.g. also sulfated fatty acid glycerol esters.
  • Fatty acid glycerine 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 mol fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Sulfated fatty acid glycerol esters may be present in the composition according to the invention, for example in amounts of> 0.01% by weight, based on the total agent.
  • the agent according to the invention is free of sulfated fatty acid glycerol ester, ie it contains ⁇ 5% by weight, preferably ⁇ 3% by weight, advantageously ⁇ 1% by weight, but in particular no sulfated fatty acid glycerol esters, by weight. % in each case based on the total mean.
  • Alk (en) yl sulfates are for example the alkali and especially the sodium salts of the Schwefelhoffreschester C 2 -C 8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or d 0 -C 2 o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths can be used. It is also possible, for example, to use alk (en) ylsulfates of the stated chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous decomposition behavior to the adequate compounds based on oleochemical raw materials. From the washing are the C 2 -C 6 alkyl sulfates and C 2 -C 5 alkyl sulfates and C 4 -C 5 - Alkyl sulfates.
  • the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C 7 - 2 i-alcohols such as 2-methyl-branched C 9 .n-alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci 2 -i 8 fatty alcohols with 1 to 4 EO, can be used, for example. Due to their high foaming behavior, they are preferably used only in relatively small amounts, for example in amounts of from 1 to 5% by weight, in detergents in particular.
  • the agents according to the invention may preferably be free of sulfuric acid monoester.
  • Ethercarboxylic acids may optionally be present in the composition according to the invention, for example in amounts of> 0.01% by weight, based on the total agent.
  • the agent according to the invention is free of ether carboxylic acids, ie it contains ⁇ 5% by weight, preferably ⁇ 3% by weight, advantageously ⁇ 1% by weight, but in particular no ethercarboxylic acids, by weight in each case based on the total mean.
  • Useful anionic surfactants are, for example, the partial esters of di- or polyhydroxyalkanes, mono- and disaccharides, polyethylene glycols with the ene-adducts of maleic anhydride to at least monounsaturated carboxylic acids having a chain length of 10 to 25 carbon atoms with an acid number of 10 to 140.
  • Usable anionic surfactants are, for example, the sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates.
  • the sulfosuccinates are the salts of the mono- and di-esters of sulfosuccinic acid HOOCCH (SO 3 H) CH 2 COOH, while the sulfosuccinamates are the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides are the salts of the diamides of sulfosuccinic acid ,
  • the salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or ammonium salts , most preferably sodium salts.
  • one or both carboxyl groups of the sulfosuccinic acid are preferably with one or two identical or different unbranched or branched, saturated or unsaturated saturated, acyclic or cyclic, optionally alkoxylated alcohols with 4 to 22, preferably 6 to 20, especially 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified.
  • esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation from 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4.
  • the monoesters are preferred in the context of the present invention over the diesters.
  • a particularly preferred sulfosuccinate is sulphonated bernsteinklarylpolyglykolester-di-sodium salt (lauryl EO sulfosuccinate, di-sodium salt; INCI Disodium Laureth Sulfosuccinate) which succinatgehalt for example as Tego ® sulfosuccinate F 30 (Goldschmidt) with a sulfo of 30 wt .-% is commercially available.
  • one or both form carboxyl groups of the sulfosuccinic acid preferably with a primary or secondary amine having one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals having 4 to 22 , preferably 6 to 20, in particular 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms, a carboxylic acid amide.
  • Particular preference is given to unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals.
  • Suitable examples include the following according to INCI sulfosuccinates and sulfosuccinamates, which are described in the International Cosmetic Ingredient Dictionary and Handbook: Ammonium Dinonyl Sulfosuccinate, Ammonium Lauryl Sulfosuccinate, Diammonium Dimethicone Copolyol Sulfosuccinate, Diammonium Lauramido MEA Sulfosuccinate, Diammonium Lauryl Sulfosuccinate, Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Dioctyl Sodium Sulfosuccinate, Disodium Cete
  • the total content of the washing or cleaning agent according to the invention of anionic surfactants can vary within wide ranges.
  • an agent according to the invention may contain very large amounts of anionic surfactant, preferably up to an order of magnitude of up to 40, 50 or 60% by weight or more.
  • an agent according to the invention may contain only very small amounts of anionic surfactant, for example less than 15 or 10% by weight or less than 5% by weight or even less.
  • anionic surfactants are advantageously present in the compositions according to the invention in amounts of 1 to 40% by weight and in particular 5 to 30% by weight, with concentrations above 10% by weight and even above 15% by weight finding particular preference can.
  • the washing or cleaning agent according to the invention contains anionic surfactants, preferably in amounts of at least 0.1% by weight, based on the total washing or cleaning agent.
  • soaps can be included in the washing or cleaning agent according to the invention.
  • Particularly 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 of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the content of the agent on soaps, independently of the anionic surfactants is preferably not more than 3% by weight and in particular 0.5 to 2.5% by weight, based on the total agent.
  • the agent according to the invention is free of soap.
  • the anionic surfactants and soaps 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. Preferably, they are in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • Anionic surfactants and soaps can also be prepared in situ by e.g. into the spray-dried composition, the anionic surfactant acids and optionally fatty acids are introduced, which are then neutralized by the alkali carriers in the spray-drying composition.
  • nonionic surfactants may also be included in the detergents or cleaners according to the invention.
  • their content may be up to 2 or 3 or 5 wt .-%. It may also contain greater amounts of nonionic surfactant, for example up to 10 wt .-% or 15 wt .-% or 20 wt .-%, 30 wt .-%, 40 wt .-%, 50 wt .-% or even beyond, if appropriate.
  • Useful lower limits may be values of 0.01, 0.1, 1, 2, 3 or 4 wt .-%, wt .-% in each case based on the total mean.
  • the washing or cleaning agent according to the invention contains nonionic surfactants, preferably in amounts of at least 0.1% by weight, based on the total washing or cleaning agent.
  • the agent according to the invention is free of nonionic surfactant.
  • nonionic surfactants known from the prior art may be present in the compositions according to the invention, although those based on oleochemicals are preferred.
  • the washing or cleaning agents according to the invention may preferably also contain cationic surfactants.
  • Suitable cationic surfactants are, for example, surface-active quaternary compounds, in particular having an ammonium, sulfonium, phosphonium, iodonium or arsonium group.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • Particularly preferred cationic surfactants are the quaternary, partially antimicrobial ammonium compounds (QAV, INCI Quaternary Ammonium Compounds) according to the general formula (R ') (R ") (R'") (R IV ) N + X " , in which R 1 to R ⁇ v identical or different C ⁇ -alkyl radicals 1 C 7 - 28 aralkyl radicals or heterocyclic radicals, wherein two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or Imidazoliniumver and X ⁇ are halide ions, sulfate ions, hydroxide ions or similar anions
  • at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecy
  • Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (mp-dichlorobenzyl-dimethyl-C 1-4 -alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyl-dodecyl-bis- (2-hydroxyethyl) -ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No.
  • benzetonium chloride N, N-dimethyl-N- [2- [2- [p- (1, 1, 3, 3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0
  • dialkyldimethylammonium chlorides such as di-n-decyl-dimethylammonium chloride (CAS No. 7173-51-5-5) , Didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 1-cetylpyridinium chloride (CAS No.
  • Preferred QUATS are the benzalkonium chlorides containing C 8 -C 8 alkyl radicals, in particular C 2 - C 4-benzyl--Aklyl dimethylannnno-niunnchlorid.
  • a particularly preferred QAC Kokospentaethoxymethyl- ammoniunnnethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat ® CPEM).
  • cationic surfactants including quaternary ammonium compounds, are described in particular in connection with avivating substances. These may also be contained in the compositions according to the invention.
  • the washing or cleaning agents according to the invention may contain one or more cationic surfactants, advantageously in amounts, based on the total composition, of from 0 to 30% by weight, more preferably greater than 0 to 20% by weight, preferably from 0.01 to 10 Wt .-%, in particular 0.1 to 5 wt .-%. Suitable minimum values may also be 0.5, 1, 2 or 3 wt .-%.
  • the washing or cleaning agent according to the invention contains cationic surfactants, preferably in amounts of at least 0.01% by weight, based on the total washing or cleaning agent.
  • the agent according to the invention is free of cationic surfactant.
  • the detergents or cleaners according to the invention may also contain amphoteric surfactants. These will be described in more detail below.
  • the washing or cleaning agents according to the invention may contain one or more amphoteric surfactants, advantageously in amounts, based on the total composition, of from 0 to 30% by weight, more preferably from 0 to 20% by weight, preferably from 0.01 to 10% by weight .-%, in particular 0.1 to 5 wt .-%.
  • the agent according to the invention is free of amphoteric surfactants.
  • ingredients of the washing or cleaning agents according to the invention may be inorganic and organic builders.
  • Inorganic builders include water-insoluble or non-water-soluble ingredients such as aluminosilicates and especially zeolites.
  • the washing or cleaning agent according to the invention contains no phosphate.
  • a phosphate-containing agent is possible. It may be advantageously provided that the washing or cleaning agent according to the invention has a zeolite content of at least 10 wt .-%, z. B. at least 15 wt .-% or at least 20% by weight or at least 30 wt .-% or even beyond, for example at least 50 wt .-%, based on the total washing or cleaning agent.
  • Soluble builders may preferably comprise the washing or cleaning agent of the invention in amounts, e.g. 50 wt .-%, advantageously from 0.1 wt .-% to 40 wt .-%, preferably 5 wt .-% to 30 wt .-% and particularly preferably 10 wt .-% to 20 wt .-%, based on the total weight of the agent, with sodium carbonate as the soluble builder being particularly preferred.
  • the agent according to the invention contains less than 10% by weight, for example less than 5% by weight, of soluble builder.
  • the agent according to the invention is free of soluble builder.
  • Useful finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • VEGOBOND AX ® a product of Condea Augusta SpA
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 2 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups, C 2 -C 14 fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of preferably less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • zeolites are faujasite-type zeolites. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which are characterized by the double-six-membered subunit D6R. In addition to the faujasite types mentioned, the zeolite structural group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogs.
  • Faujasite-type zeolites are composed of ⁇ -cages linked by tetrahedral D6R subunits, with the ⁇ -cages resembling the carbon atoms in the diamond.
  • the three-dimensional network of the faujasite-type zeolites suitable according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell also contains 8 cavities with a diameter of approximately 13 A and can be represented by the formula Na 86 [(AlO 2 ) 86 (SiO 2) io 6] 264 H 2 O describe.
  • the network of zeolite X in this case contains a void volume of about 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume).
  • zeolite type zeolite denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • zeolite Y and faujasite and mixtures of these compounds are also suitable according to the invention, with pure zeolite X being preferred.
  • Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which need not necessarily belong to the zeolite structure group 4, are also suitable according to the invention, with preferably at least 50% by weight of the faujasite-type zeolites being suitable.
  • the suitable aluminum silicates are commercially available and the methods for their preparation are described in standard monographs.
  • zeolite A-LSX which corresponds to a co-crystals of zeolite X and zeolite A and in its anhydrous form has the formula (M 2 / n O + M 1 ⁇ n O) Al 2 O 3 ZSiO 2 , wherein M and M 'may be alkali or alkaline earth metals and z is a number from 2.1 to 2.6.
  • VEGOBOND AX by the company CONDEA Augusta SpA
  • Y-type zeolites are also commercially available and can be obtained, for example, by the formulas Na 56 [(AIO 2 ) 56 (SiO 2 ) 136 ] x H 2 O, K 56 [(AIO 2 ) 56 (SiO 2 ) 136 ] x H 2 O, where x is numbers greater than 0 to 276, describe. These zeolites have pore sizes of 8.0 ⁇ .
  • the particle sizes of the suitable zeolites are advantageously in the range from 0.1 ⁇ m to 100 ⁇ m, preferably from 0.5 ⁇ m to 50 ⁇ m and in particular from 1 ⁇ m to 30 ⁇ m, in each case measured by standard particle size determination methods.
  • the washing or cleaning agent according to the invention is free of zeolite.
  • all inorganic constituents contained preferably be water-soluble.
  • builders other than the zeolites mentioned are therefore used.
  • 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, terephthalic aldehyde 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 '-di-succinate (EDDS) is preferably used in form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are, for example, 3 to 15 wt .-%, based on the total detergent or cleaning agent.
  • 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.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene lenphosponate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable, especially if the washing or cleaning agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • phosphates in particular pentasodium triphosphate, if appropriate also pyrophosphates and orthophosphates, which act primarily as precipitants for calcium salts.
  • Phosphates are predominantly used in automatic dishwasher detergents, but in some cases also in detergents.
  • NaH 2 PO 4 Sodium dihydrogen phosphate, NaH 2 PO 4 , exists as a dihydrate (density 1, 91 like '3 , melting point 60 °) and monohydrate (density 2.04 like ' 3 ). Both salts are white, very soluble in water powders, which lose the water of crystallization on heating and at 200 0 C in the weak acid diphosphate (disodium hydrogendiphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate or potassium phosphate monobasic, KDP), KH 2 PO 4 , is a white salt of density 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) J and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like “3 , water loss at 95 °), 7 moles (density 1, 68 like '3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1, 52 like "3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° C and goes on stronger heating in the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous white salt that is readily soluble in water.
  • trisodium phosphate is readily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of Disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 '3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 '3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like ' 3 , melting point 94 ° with loss of water). Both substances are colorless crystals which are soluble in water with an alkaline reaction.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% '3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Condensation of the NaH 2 PO 4 or of the KH 2 PO 4 gives rise to relatively high molecular weight sodium and potassium phosphates, in which cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium or potassium polyphosphates, can be distinguished.
  • cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium or potassium polyphosphates can be distinguished.
  • hot or cold phosphates Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; After two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphos-phat, K 5 P 3 Oi 0 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
  • sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and sodium potassium trihydrate Polyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
  • carbonates and silicates are used as inorganic builder substances.
  • NaMSi x O 2x + -TyH 2 O where M is sodium or hydrogen, x is a number from 1, 6 to 4, preferably 1, 9 to 4.0 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • crystalline silicates are preferably subsequently added to the direct or post-treated spray-drying product.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both .beta.- and ⁇ -sodium Na 2 Si 2 O 5 ⁇ yH 2 O preferred.
  • SKS® is a ⁇ -sodium having the formula Na 2 Si 2 0 5 yH 2
  • SKS-7 ® is predominantly a beta-sodium disilicate. Reaction with acids (eg citric acid or carbonic acid) results from the ⁇ -sodium disilicate
  • phyllosilicates of the general empirical formula x Na 2 O • y SiO 2 • z P 2 O 5 in which the ratio x to y corresponds to a number 0.35 to 0.6, the ratio x to z to a number from 1.75 to 1200 and the ratio y to z corresponds to a number from 4 to 2800 known.
  • the solubility of the layered silicates can also be increased by using particularly finely divided layered silicates.
  • compounds from the crystalline layer silicates with other ingredients can be used.
  • compounds with cellulose derivatives which have advantages in the disintegrating action, and compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.
  • the preferred builder substances also include amorphous sodium silicates having a modulus Na 2 O: SiO 2 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 have secondary washing properties.
  • amorphous is also understood to mean "X-ray amorphous”. This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle.
  • Particularly preferred inorganic water-soluble builders are alkali metal carbonates and alkali metal bicarbonates, with sodium and potassium carbonate, and especially sodium carbonate, being among the preferred embodiments.
  • the content of alkali metal carbonates in particular zeolite-free agents can vary within a very wide range and is preferably 1 to 50 wt .-%, advantageously 5 to 40 wt .-%, in particular 8 to 30 wt .-%, wherein usually the content of alkali metal - Carbonates is higher than on (X-ray) amorphous silicates.
  • the washing or cleaning agent according to the invention is free of alkali metal carbonates.
  • Useful organic builders are, for example, usable in the form of their alkali and especially sodium polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an application for environmental reasons is not objectionable , as well as mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus, for example in the granules according to the invention, also serve to establish a lower and milder pH of detergents or cleaners.
  • an acidifying component for example in the granules according to the invention, also serve to establish a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 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 means of gel permeation chromatography (GPC), a UV detector being used. 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 molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • the detergents or cleaners according to the invention may also contain polymers. Suitable polymers include in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • 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 content of detergents or cleaning agents on organic builders may vary within a wide range. Preferred are levels of e.g. 2 to 20 wt .-%, wherein in particular contents of not more than 10 wt .-% find particular approval. According to another preferred embodiment, the washing or cleaning agent according to the invention is free of organic builders.
  • the detergents or cleaners according to the invention may contain components from the classes of the grayness inhibitors (soil carriers), the neutral salts and / or the fabric-softening auxiliaries (for example cationic surfactants), which is preferred.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of preferably from 0.1 to 5% by weight. %, based on the detergents or cleaning agents used.
  • a typical example of a suitable representative of neutral salts is sodium sulfate. It can be used in amounts of, for example, from 0 to 60% by weight, preferably from 2 to 45% by weight.
  • Suitable plasticizers are, for example, swellable phyllosilicates of the type of corresponding montmorillonites, for example, bentonite, as well as cationic surfactants.
  • the content of water in the washing or cleaning agent is preferably from 0 to less than 30% by weight and in particular from 0.5 to less than 20% by weight, with values of not more than 15% by weight, not more than 10 Wt .-%, at most 5 wt .-%, at most 3 wt .-% or at most 2 wt .-% special preference. Not included in this case was the possibly existing aluminosilicates such as zeolite adhering water.
  • nonionic surfactants which may optionally be contained in the washing or cleaning agent, are described in more detail. These nonionic surfactants may e.g. be applied to the particulate detergent or cleaning agent in a post-treatment step. Of course, all nonionic surfactants may advantageously be contained directly in the washing or cleaning agent according to the invention.
  • nonionic surfactants e.g. alkoxylated, advantageously ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and preferably on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical is linear (or may be methyl branched in the 2-position or linear and methyl-branched radicals in the mixture, as they are usually present in oxo-alcohol radicals).
  • EO ethylene oxide
  • employable alcohol ethoxylates include e.g. a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • NRE narrow rank ethoxylates
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • usable nonionic surfactants are, for example, one or more of ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, straight (or branched), saturated or unsaturated C 10 - 22 - alcohols with a degree of alkoxylation up to 30, preferably ethoxylated C 10 -i 8 -fatty alcohols having a degree of ethoxylation of less than 30, preferably 1 to 20, in particular 1 to 12, particularly preferably 1 to 8, most preferably 2 to 5, for example Ci 2 -i 4 -Fettalkoholethoxylate with 2, 3 or 4 EO or a mixture of the Ci 2 -i 4 -Fettalkoholethoxylate with 3 and 4 EO in the weight ratio of 1 to 1 or Isotridecylalkoholethoxylat with 5, 8 or 12 EO.
  • EO ethylene oxide
  • PO propylene oxide
  • nonionic surfactants which can be used are, for example, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, particularly preferred are C 12 -C 18 fatty acid methyl esters having an average of 3 to 15 EO, in particular an average of 5 to 12 EO, can also be used, for example.
  • Nonionic surfactants of the amine oxide type mentioned above for example N-cocoalkyl N, N-dimethylamine oxide and N-tallow alkyl N, N-dihydroxyethyl amine oxide, and the fatty acid alkanolamides may also be suitable.
  • alkoxylated amines advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines having preferably 1 to 18 C atoms per alkyl chain and on average 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of amine.
  • EO ethylene oxide
  • PO propylene oxide
  • the detergents or cleaners according to the invention may also contain foam inhibitors, for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • suitable foam-inhibiting paraffin oils which may also be present in admixture with paraffin waxes, are generally complex mixtures without a sharp melting point.
  • the melting range is usually determined by differential thermal analysis (DTA) and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling.
  • DTA differential thermal analysis
  • Paraffins with fewer than 17 carbon atoms are not useful in accordance with the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit that can be significantly measured by conventional analytical methods, for example gas chromatography.
  • paraffins are used, which solidify in the range of 2O 0 C to 7O 0 C.
  • paraffin wax mixtures may contain different proportions of liquid paraffin oils.
  • the liquid fraction at 4O 0 C is as high as possible, even without being 100% at this temperature.
  • Preferred paraffin wax mixtures have at 4O 0 C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 6O 0 C, a liquid content of at least 90 wt .-%. This has the consequence that the paraffins, preferably down to at least 6O 0 C are flowable and pumpable at temperatures down to at least 7O 0 C.
  • paraffins contain as far as possible no volatile components.
  • Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 1 10 0 C and atmospheric pressure vaporizable fractions.
  • Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® from DEA Mineralöl AG.
  • the paraffin oils may contain at room temperature solid bisamides derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil.
  • suitable diamines are ethylenediamine 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
  • the washing or cleaning agent may preferably comprise UV absorbers which advantageously are applied to the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of other formulation constituents. Under UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back.
  • Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • the biphenyl and especially stilbene derivatives commercially available as Tinosorb ® FD or Tinosorb ® FR available ex Ciba.
  • 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3- (4-methylbenzylidene) camphor may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid iso-amyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicy
  • UV-A filter in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1, 3-dione and enamine compounds.
  • the UV-A and UV-B filters can also be used in mixtures.
  • insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • silicates (talc) barium sulfate or zinc stearate can be used.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and in particular from 15 to 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
  • the pigments can also be surface-treated, ie hydro-philated or hydrophobed.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck).
  • Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the relevant prior art.
  • the UV absorbers can advantageously be present in quantities of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight, in the washing or cleaning agent. They can also be subsequently added to the washing or cleaning agent, for example together with other substances.
  • the detergents or cleaners according to the invention may preferably also be in the form of tablets or shaped articles.
  • tablette or “shaped bodies” are dimensionally stable, solid bodies, irrespective of the manner of their preparation. Such bodies can be prepared for example by crystallization, molding, injection molding, reactive or thermal sintering, (co) - extrusion, Verprillung, pastillation, or compaction processes such as calendering or tableting.
  • the preparation of the "tablets" or “shaped bodies” by tabletting is particularly preferred in the context of the present application.
  • the tablet is thus preferably made of compressed, particulate material.
  • Detergents or cleaning agents according to the invention may preferably contain disintegration aids.
  • Suitable swellable disintegration aids are, for example, bentonites or other swellable silicates. It is also possible to use synthetic polymers, in particular the superabsorbents or cross-linked polyvinylpyrrolidone used in the hygiene sector.
  • polymers based on starch and / or cellulose are used as swellable disintegration aids.
  • These base substances can be processed alone or in mixture with other natural and / or synthetic polymers to swellable disintegrating agents.
  • a cellulosic material or pure cellulose can be converted by pressure transfer into secondary particles by granulation, compaction or other application, which swell on contact with water and thus serve as a disintegrant.
  • Wood pulp which has been obtained by thermal or chemical-thermal processes from wood or wood chips (sawdust, sawmill waste) has proven to be suitable as a cellulosic material.
  • This cellulose material from the TMP process thermo-mechanical pulp
  • CTMP process chemothermomechanical pulp
  • pure cellulose can also be used in a completely analogous manner, although it is more expensive from the raw material base.
  • Both microcrystalline and amorphous fine-particle cellulose can be used here and mixtures thereof are used.
  • the primary fiber length of the cellulose or cellulose used in the cellulose-containing material should be less than 200 .mu.m, preference being given to primary fiber lengths of less than 100 .mu.m, in particular less than 50 .mu.m.
  • the secondary particles ideally have a particle size distribution in which preferably more than 90 wt .-% of the particles have sizes above 200 microns.
  • a certain proportion of dust can contribute to an improved storage stability of the tablets produced therewith.
  • compositions according to the invention may contain conditioning or conditioning substances or components.
  • conditioning is preferably to be understood as meaning the avivating treatment of textiles, fabrics and fabrics. Conditioning gives the textiles positive properties, such as improved softness, increased gloss and color brilliance, improved fragrance impression, reduction of felting, ironing relief by reducing the sliding properties, reducing the creasing behavior and the static charge and a color transfer inhibition in dyed textiles ,
  • compositions according to the invention may comprise plasticizer components.
  • plasticizer components examples include quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in agents for Textilavivage.
  • softening compounds which will also be described in more detail below, can be present in all inventive compositions, in particular in compositions with the desired softening effect.
  • Suitable examples are quaternary ammonium compounds of the formulas (A) and (B),
  • R and R 1 is an acyclic alkyl radical having 12 to 24 carbon atoms
  • R 2 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical
  • R 3 is either R, R 1 or R 2 or is a aromatic residue stands.
  • X ⁇ represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these.
  • Examples of cationic compounds of the formula (A) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
  • Ester quats are so-called ester quats. Esterquats are characterized by excellent biodegradability.
  • R 4 is an aliphatic alkyl radical having 12 to 22 Carbon atoms having 0, 1, 2 or 3 double bonds
  • R 5 is H, OH or O (CO) R 7
  • R 6 is, independently of R 5, H, OH or O (CO) R 8
  • R 7 and R 8 are each independently an aliphatic alk ( en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • m, n and p may each independently have the value 1, 2 or 3 have.
  • X " can be either halide genome, methosulfate, methophosphate or phosphate ion and mixtures of these, preference being given to compounds which, for R 5, are the group O (CO) R 7 and for R 4 and R 7 are alkyl radicals having from 16 to Particular preference is given to compounds in which R 6 is OH.
  • Examples of compounds of the formula (IV) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammo ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methoxide or methyl N, N bis (acyl oxyethyl) N- (2-hydroxyethyl) ammonium methosulfate are quaternized compounds of the formula (IV) which have unsaturated alkyl chains, the acyl groups are preferred whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in wt .-%) of greater than 30: 70, preferably greater than 50: 50 and in particular larger than 70: 30.
  • Stepan Commercial examples are sold by Stepan under the tradename Stepantex ® methylhydroxy- alkyldi-alkoyloxyalkylammoniummethosulfate or those known under Dehyquart ® Cognis products known under or Rewoquat ® manufactured by Goldschmidt-Witco. Further preferred compounds are the diester quats of the formula (C) which are obtainable under the name Rewoquat® W 222 LM or CR 3099 and, in addition to the softness, also provide stability and color protection.
  • R 9 is H or a saturated alkyl radical having 1 to 4 carbon atoms
  • R 10 and R 11 independently of one another may each be an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms
  • R 10 may alternatively also be 0 (CO)
  • R 20 is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms
  • Z is an NH group or oxygen
  • X "is an anion q can have integer values between 1 and 4.
  • Further suitable quaternary compounds are Formula (E) described, R13 H
  • R14 CH 2 - 0 (C0) R 16 wherein R 12, R 13 and R 14 independently represent a d ⁇ alkyl, alkenyl or hydroxyalkyl group, R 15 and R 16 each selected independently a C 8-28 alkyl group and r is a number between 0 and 5.
  • short-chain, water-soluble, quaternary ammonium compounds such as trihydroxyethylmethylammonium nethanesulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylamino-niunnochlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldi-methylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.
  • quaternary ammonium compounds such as trihydroxyethylmethylammonium nethanesulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylamino-niunnochlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride,
  • protonated alkylamine compounds which have plasticizing effect, as well as the non-quaternized, protonated precursors of cationic emulsifiers are suitable.
  • cationic compounds which can be used according to the invention are the quaternized protein hydrolysates.
  • Suitable cationic polymers include the polyquaternium polymers as referred to in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, also referred to as Merquats, Polyquaternium-10 polymers (Ucare Polymer IR 400, Amerchol), polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups bonded via allyl dimethyl ammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyltriammonium - trimethylammonium chloride, and similar quaternized guar derivatives (eg Cosmedia guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), for example the commercial product Glucquat ® 100, according to CTFA nomenclature a "lauryl methyl
  • Polyquaternized polymers for example, Luviquat Care by BASF.
  • cationic biopolymers based on chitin and derivatives thereof, for example, under the trade designation chitosan ® (manufacturer: Cognis) polymer obtainable.
  • cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimeth-icon), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also known as amodimers).
  • the alkylamidoamines may be in their quaternized or, as shown, their quaternized form.
  • R 17 can be an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5.
  • R 18 and R 19 are each independently H, d 1-4 alkyl or hydroxyalkyl.
  • Preferred compounds are fatty acid amidoamines, such as sold under the name Tego Amid ® S 18 stearylamidopropyldimethylamine available or the 3-tallowamidopropyl trimethylammo-nium methosulfate obtainable under the name Stepantex ® X 9124, which is a good conditioning effect by dye transfer-inhibiting effect and by to distinguish their good biodegradability.
  • alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate.
  • Suitable nonionic plasticizers are, in particular, polyoxyalkylene glycol alkanoates, polybutylenes, long-chain fatty acids, ethoxylated fatty acid ethanolamides, alkyl polyglycosides, in particular sorbitan mono-, di- and triester and fatty acid esters of polycarboxylic acids.
  • plasticizers may be used in amounts of from 0.01 to 80% by weight, usually from 0.1 to 70% by weight, preferably from 0.2 to 60% by weight and in particular from 0.5 to 40% by weight. %, in each case based on the total agent.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini Surfactants understood not only dimeric but also trimeric surfactants.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in the relevant prior art.
  • RCO is an aliphatic acyl group having 6 to 22 carbon atoms
  • R 23 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl group 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.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 24 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 25 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms
  • Ci_ 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof residue.
  • the detergents or cleaners according to the invention may preferably also contain amphoteric surfactants.
  • amphoteric surfactants In addition to numerous mono- to tri-alkylated amine oxides, the betaines represent an important class.
  • Betaines are known surfactants, which are predominantly produced by carboxyalkylation, preferably carboxymethylation of aminic compounds.
  • the starting materials are condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, wherein one mole of salt is formed per mole of betaine.
  • unsaturated carboxylic acids such as, for example, acrylic acid, is also possible.
  • suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (G),
  • R 26 are alkyl and / or alkenyl radicals having 6 to 22 carbon atoms
  • R 27 is hydrogen or alkyl radicals having 1 to 4 carbon atoms
  • R 28 is alkyl radicals having 1 to 4 carbon atoms
  • n is from 1 to 6
  • X 1 is an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, Decyldi- methylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C methylamine 12/14 -Kokosalkyldinne-, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethyl-methyl amine, oleyl dimethyl amine, C16 / i 8 -Talgalkyldimethylamin and their technical mixtures.
  • Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, acids , Behenic acid and erucic acid and technical mixtures thereof, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium
  • R 32 is an alkyl radical having 5 to 21 carbon atoms
  • R 33 is a hydroxyl group
  • an OCOR 32 or NHCOR 32 radical and m is 2 or 3.
  • These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethyl-ethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethyl-ethanolamine
  • Typical examples are condensation products of the above mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or C, in turn, 12 / i 4 coconut oil fatty acid, which are subsequently betainized with sodium chloroacetate.
  • Chelating agents also called sequestering agents, are ingredients that are capable of complexing and inactivating metal ions, for example, to prevent their adverse effects on the stability or appearance of the agents, for example clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. The complexation of the ions of heavy metals such as iron or copper retards the oxidative decomposition of the finished agents.
  • Suitable examples are the following complexing agents designated according to INCI, which are described in more detail, for example, in the International Cosmetic Ingredient Dictionary and Handbook: Aminotri. methylene phosphonic acid, beta-alanine diacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexane diamine tetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriamine pentamethylene phosphonic acid, dipotassium EDTA, disodium azacycloheptane diphosphonate, disodium EDTA, disodium pyrophosphate, EDTA , Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine
  • Preferred complexing agents are tertiary amines, in particular tertiary alkanolamines (amino alcohols).
  • the alkanolamines have both amino and hydroxy and / or ether groups as functional groups.
  • Particularly preferred tertiary alkanolamines are tri-ethanolamine and tetra-2-hydroxypropyl-ethylenediamine (N, N, N ', N'-tetrakis (2-hydroxy-propyl) ethylenediamine).
  • Particularly preferred combinations of tertiary amines with Zinkricinoleat and one or more ethoxylated fatty alcohols as nonionic solubilizers and optionally solvents are described in the prior art.
  • a particularly preferred complexing agent is etidronic acid (1-hydroxyethylidene-1, 1-diphosphonic acid, 1-hydroxyethyl-1, 1-diphosphonic acid, HEDP, acetophosphonic acid, INCI Etidronic Acid) including their salts.
  • the washing or cleaning agent according to the invention accordingly contains etidronic acid and / or one or more of its salts as complexing agent.
  • the washing or cleaning agent according to the invention contains a complexing agent combination of one or more tertiary amines and one or more further complexing agents, preferably one or more complexing acids or salts thereof, in particular triethanolamine and / or tetra-2-hydroxypropylethylenediamine and etidronic acid and / or or one or more of their salts.
  • the washing or cleaning agent according to the invention advantageously contains complexing agents in an amount of usually 0 to 20 wt .-%, preferably 0.1 to 15 wt .-%, in particular 0.5 to 10 wt .-%, particularly preferably 1 to 8 wt .-%, most preferably 1, 5 to 6 wt .-%, based on the total agent.
  • the washing or cleaning agent according to the invention optionally contains one or more enzymes, as already described above.
  • Suitable enzymes are in particular those from the classes of hydrolases such as proteases, carbonic anhydrases, tannases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other Glykosylhydrolasen and mixtures of these enzymes in question. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
  • hydrolases such as proteases, carbonic anhydrases, tannases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other Glykosylhydrolasen and mixtures of these enzymes in question. All of these hydrolases in the wash contribute to the removal of
  • enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenifor- mis, Streptomyceus griseus and Humicola insolens.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus lichenifor- mis Streptomyceus griseus
  • Humicola insolens preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • cellulases are preferably cellobiohydrolases, endoglucanases and ß-Glucosi-denen, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes may be adsorbed as a shaped body to carriers or embedded coated to protect against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 wt .-%, based on the total agent.
  • the washing or cleaning agents according to the invention may optionally contain bleaching agents.
  • bleaching agents include the compounds serving as bleaches, which yield H 2 O 2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particular Importance.
  • Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as persulfates or persulfuric acid.
  • peroxopyrophosphates citrate perhydrates
  • H 2 O 2 -producing peracidic salts or peracids such as persulfates or persulfuric acid.
  • urea peroxohyd rat percarbamide which can be described by the formula H 2 N-CO-NH 2 H 2 O 2 .
  • the means for cleaning hard surfaces for example in automatic dishwashing, they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents.
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid (Phthalimidoperoxyhexanoic acid, PAP), Carboxybenzamidoperoxycaproic acid, N -nonylamidoperadipic acid and N-nonenylamidopersuccinates, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyl-diperoxybutan-1, 4- diacid
  • Dyes can be used in the washing or cleaning agent according to the invention, wherein the amount of one or more dyes is to be chosen so small that remain after application of the agent no visible residues.
  • the agent according to the invention is free of dyes.
  • the washing or cleaning agent according to the invention may preferably contain one or more antimicrobial agents or preservatives in an amount of usually 0.0001 to 3 wt .-%, preferably 0.0001 to 2 wt .-%, in particular 0.0002 to 1 wt. %, more preferably 0.0002 to 0.2% by weight, most preferably 0.0003 to 0.1% by weight.
  • Antimicrobial agents or preservatives are differentiated depending on the antimicrobial spectrum and mechanism of action between bacteriostats and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercuriacetate.
  • the terms antimicrobial action and antimicrobial active substance have the usual meaning in the context of the teaching according to the invention.
  • Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formal, benzimidines , Isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-di-cyanobutane tan, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above.
  • the antimicrobial agent may be selected from ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydric acid, o- Phenylphenol, N-methylmorpholine-acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methyl-bis (6-bromo-4-chlorophenol), 4,4'-di-chloro -2'-hydroxydiphenyl ether (dichlosan), 2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N '- (1, 10-decanediyldi-i-pyridinyl-W-yliden
  • halogenated xylene and cresol derivatives such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial agents of plant origin (eg from spices or herbs), of animal and microbial origin.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and also essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group, comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound having an ammonium, sulfonium, phosphonium, iodonium or arsonium group, peroxo compounds and chlorine compounds.
  • substances of microbial origin so-called bacteriocins, can be used.
  • Glycine, glycine derivatives, formaldehyde, compounds which readily split off formaldehyde, formic acid and peroxides are also used.
  • quaternary ammonium compounds have been described above. Is particularly suitable, for example, benzalkonium chloride, etc. Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason, Variquat ® ex Witco / Sherex and Hyamine ® ex Lonza and as Bardac ® ex Lonza.
  • antimicrobial agents are N- (3-chloroallyl) - hexaminiumchlorid as Dowicide and Dowicil ® ® ex Dow, benzethonium chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,
  • silicone derivatives can be used in the formulations. These additionally improve the rinsing out of the wash-active formulations by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-C 1 H, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones at 25 0 C in the range between 100 and 100,000 mPas, wherein the silicones can be added in amounts between 0.2 and 5 wt .-%, based on the total agent.
  • Anionic surfactants preferably ester sulfonate, in particular methyl ester sulfonate, in amounts of advantageously 1-35% by weight, preferably 5-25% by weight, in particular 10-20% by weight,
  • Nonionic surfactants such as, for example, alkylpolyglucoside, fatty acid glucamide, fatty alcohol ethoxylate, advantageously in amounts of 0.1-20% by weight, preferably 2-15% by weight, in particular 6-11% by weight
  • Builders such as zeolite, polycarboxylate, sodium citrate, for example in amounts of 5-60% by weight, preferably in amounts of 10-55% by weight, in particular 15-40% by weight,
  • Alkalis e.g. Sodium carbonate, advantageously in amounts of 1-30 wt .-%, preferably 2-25 wt .-%, in particular 5-20 wt .-%,
  • Bleaching agents e.g. Sodium perborate, sodium percarbonate advantageously in amounts of 5-25 wt .-%, preferably 10-20 wt .-%,
  • Corrosion inhibitors e.g. Sodium silicate, advantageously in amounts of 1-6 wt .-%, preferably 2-5 wt .-%, in particular 3-4 wt .-%,
  • Stabilizers e.g. Phosphonates, advantageously in amounts of 0-1% by weight,
  • Foam inhibitor e.g. Soap, silicone oils, paraffins advantageously in amounts of 0.1-4% by weight, preferably 0.2-3% by weight, in particular 1-2% by weight,
  • Enzymes e.g. Proteases, amylases, cellulases, lipases, tannases, pectinases, carbonic anhydrases, advantageously in amounts of 0.01-2 wt .-%, preferably 0.1-1 wt .-%, in particular 0.3-0.8 wt. %
  • - grayness inhibitor e.g. Carboxymethylcellulose, advantageously in amounts of 0-1% by weight,
  • Discoloration inhibitor e.g. Polyvinylpyrrolidone derivatives, advantageously in amounts of 0-2% by weight,
  • polyester-based soil-release polymer preferably in amounts of from 0.01 to 2% by weight
  • - Adjustment means such as Sodium sulfate, advantageously in amounts of 0-60 wt .-%.
  • Sodium sulfate advantageously in amounts of 0-60 wt .-%.
  • 1-40% by weight in particular 5-20% by weight,
  • Optical brighteners e.g. Stilbene derivative, biphenyl derivative, advantageously in amounts of 0.1-0.3% by weight, in particular 0.1-0.4% by weight,
  • the detergents or cleaners according to the invention may preferably also be perfumed with perfume oil (fragrances, perfumes).
  • Adhesive-resistant fragrances which can advantageously 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, Champacablütenöl, Edeltannenöl, Edeltannenzapfenöl, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil , Gurijar balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copa ⁇ va balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lemongrass oil, musk kernel oil, myrrh oil, clove oil, neroli oil, niaouli oil , Oliban
  • fragrances of natural or synthetic origin can be used in the context of the present invention advantageously as adherent fragrances or fragrance mixtures in the perfume oils.
  • 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, borneol, bornyl acetate, ⁇ -bromostyrene , n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl
  • more volatile fragrances which are advantageously used in the perfume oil in the present invention include, in particular, the lower-boiling fragrances natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • Usable fragrances are, for example, condensation products of amines and aldehydes.
  • Preferred examples of condensation products of amines and aldehydes are anisaldehyde-methyl anthranilate, aurantiol (hydroxycitronellalmethyl anthranilate), verdantiol (4-tert-butyl-alpha-methyldihydrocinnamaldehyde-methyl anthranilate), vertosin (2,4-dimethyl-3-cyclohexene carbaldehyde), hydroxycitronellalcyl anthranilate, hydroxycitronellinallylanthranilate, methyl N- (4- (4-hydroxy-4-methylpentyl) -3-cyclohexenylmethylidenes) anthranilate, methylnaphthyl ketone methyl anthranilate, methyl nonyl acetaldehyde methyl anthranilate, methyl N- (3,5,5
  • fragrances such as, for example, adoxal (2,6,10-trimethyl-9-undecene-1-al), amyl acetate, anisaldehyde (4-methoxy-benzaldehydes), bacdanol (2-ethyl-4- (2 , 2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol), benzaldehyde, benzophenone, benzyl acetate, benzyl salicylate, 3-hexen-1-ol, cetalox (dodecahydro-3A, 6 , 6,9A-tetramethyl-naphtho [2,1 B] -furan), cis-3-hexenylacetate, cis-3-hexenylsalicylate, citronellol, coumarin, cyclohe
  • fragrances such as, for example, adoxal (2,6,10-trimethyl-9-undecene-1-al), amyl
  • the washing or cleaning agent according to the invention contains certain minimum values of perfume oil, namely at least 0.01% by weight, advantageously at least 0.1% by weight, in a considerably advantageous manner at least 0.15% by weight more preferably at least 0.2 wt.%, more preferably at least 0.25 wt.%, even more advantageously at least 0.3 wt.%, most preferably at least 0.35 wt.% , in a particularly advantageous manner at least 0.4 wt .-%, in a particularly advantageous manner at least 0.45 wt .-%, in a significantly advantageous manner at least 0.5 wt .-%, in a very advantageous manner, at least 0.55 Wt .-%, in an extremely advantageous manner at least 0.6 wt .-%, most advantageously at least 0.65 wt .-%, most advantageously at least 0.7 wt .-%, in an exceptionally advantageous manner at least 0.75 Wt .-%, in an exceptionally advantageous manner, at least 0.8
  • the perfume oils contain less than 8, advantageously less than 7, more preferably less than 6, more preferably less than 5, more preferably less than 4, even more preferably less than 3, preferably less than 2, especially no fragrances from the list of amyl cinnamal, amyl cinnamyl alcohol, benzyl alcohol, benzyl salicylate, cinnamyl alcohol, cinnamal, citral, coumarin, eugenol, geraniol, hydroxycitronellal, hydroxymethylpentylcyclohexenecarboxaldehyde, isoeugenol, anisyl alcohol, benzyl benzoate, benzyl cinnamate, citronellol, farnesol, hexyl cinnamaldehyde, lilial, d Limes, linalool, methylh
  • Defoamer 1 3 wt .-% enzymes (amylase, protease, cellulase) +
  • Enzymes (amylase, protease, cellulase) + perfume 0.5% by weight
  • the detergent 2 differed from detergent 1 only in that in detergent 2 half of the LAS (C9-13-alkylbenzenesulfonate, Na-SaIz) was replaced by MES (C16-18-methyl ester sulfonate). The total amount of surfactant remained the same.
  • Defoamer 1 3 wt .-% enzymes (amylase, protease, cellulase) +
  • Detergent 3 differed from Detergent 1 only in that in Detergent 2 the total amount of LAS (C9-13-alkylbenzenesulfonate, Na-SaIz) was replaced by MES (C16-18-methyl ester sulfonate). The total amount of surfactant remained the same.
  • Detergent A (according to the invention):
  • Defoamer 1 3 wt .-% enzymes (amylase, protease, cellulase) +
  • Soil-Release Polymer * The soil-release polymer used was a polyester-based soil release polymer which met the conditions specified in claim 8.
  • Detergent A differed from Detergent 1 only in that in Detergent A half of the LAS (C9-13-alkylbenzenesulfonate, Na-SaIz) was replaced by MES (C16-18-methyl ester sulfonate). The total amount of surfactant remained the same. In addition, detergent A still contained 0.2% by weight of soil
  • Detergent B (according to the invention):
  • Defoamer 1 3 wt .-% enzymes (amylase, protease, cellulase) +
  • Soil-Release Polymer * The soil-release polymer used was a polyester-based soil release polymer which met the conditions specified in claim 8.
  • Detergent B differed from Detergent 1 only in that in Detergent B the total amount of LAS (C9-13-alkylbenzenesulfonate, Na-SaIz) was replaced by MES (C16-18-methyl ester sulfonate). The total amount of surfactant remained the same. In addition, detergent B still contained 0.2% by weight of soil-release polymer, the only difference to detergent 2.
  • LAS C9-13-alkylbenzenesulfonate
  • MES C16-18-methyl ester sulfonate

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Abstract

L'invention décrit comment configurer la substitution partielle voire totale d'alkylbenzène sulfonate à chaîne linéaire (LAS) par du méthylester sulfonate (MES) dans des détergents sans nuire à l'effet de lavage primaire et secondaire, lorsque l'on ajoute un polymère à base de polyester favorisant le détachement des salissures (SRP). La substitution réussie de tensio-actifs à base pétrochimique par des tensio-actifs à base lipochimique, sans que l'utilisateur ne doive se résigner à une baisse des performances de lavage des textiles, ouvre de nouvelles perspectives. Cela représente une étape supplémentaire sur la voie du développement durable dans le domaine des détergents.
EP08775291A 2007-08-10 2008-07-23 Détergent doté d'un polymère à base de polyester favorisant le détachement des salissures Ceased EP2173842A2 (fr)

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DE200710038029 DE102007038029A1 (de) 2007-08-10 2007-08-10 Wasch- oder Reinigungsmittel mit polyesterbasiertem Soil-Release-Polymer
PCT/EP2008/059619 WO2009021813A2 (fr) 2007-08-10 2008-07-23 Détergent doté d'un polymère à base de polyester favorisant le détachement des salissures

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WO2009021813A3 (fr) 2009-05-07

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