Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
• • 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
• • 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
  • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

• the invention relates to the use of hydrophobically modified polyalkyleneimines as color transfer inhibitors.
• color transfer inhibitors are often used. These are often polymers which contain monomers having nitrogen-heterocyclic radicals in copolymerized form.
• copolymers described in these documents are characterized in part by a good inhibition of color transfer in washing processes. However, they generally have low compatibility with the other commonly used detergent ingredients. Thus, there is the danger of incompatibilities, for example in the form of turbidity or phase separations, especially in liquid detergents.
• the DE 2025829 describes reaction products of fatty acid glycidyl esters with polyethyleneimines and their use as fabric softeners.
• the DE 2046304 describes reaction products of fatty acids or fatty acid esters with polyethyleneimines and their use as fabric softeners.
• the DE 2165900 describes reaction products of alkylglycidyl ethers with polyethylenimines and their use as grayness inhibitors.
• the WO 2002/095122 describes the use of hydrophobically modified polyethyleneimines as anti-caking additives for detergent formulations.
• hydrophobically modified poly-C 2 -C 4 -alkyleneimines are surprisingly achieved.
• the invention therefore relates to the use of hydrophobically modified poly-C 2 -C 4 -alkyleneimines, in particular hydrophobically modified polyethyleneimines, as color transfer inhibitors in detergent compositions for textiles.
• hydrophobically modified poly-C 2 -C 4 -alkyleneimines is meant here and below poly-C 2 -C 4 -alkyleneimines in which the hydrogen atoms of the primary and secondary amino groups are partially or completely replaced by linear or branched aliphatic, saturated or unsaturated hydrocarbon radicals. Radicals such as alkyl, alkenyl, alkadienyl or hydroxyalkyl radicals are replaced.
• the hydrocarbon radicals generally have at least 8, eg 8 to 30 C atoms, preferably 10 to 22 C atoms, in particular 10 to 18 C atoms.
• the hydrocarbon radical may also form an aldimine or ketimine group with the nitrogen of the poly-C 2 -C 4 -alkyleneimine or be linked to 2-nitrogen atoms of the poly-C 2 -C 4 -alkyleneimine via the carbon atom of a cyclic amidine group.
• hydrophobically modified poly-C 2 -C 4 -alkyleneimines in which the hydrocarbon radical is linked directly or via a carbonyl group to a nitrogen atom of the poly-C 2 -C 4 -alkyleneimine, the latter being particularly preferred.
• the hydrocarbon radicals are preferably linear.
• the hydrocarbon radicals are preferably saturated.
• the hydrocarbon radicals in the preferred hydrophobically modified poly-C 2 -C 4 -alkyleneimines are in the form of C 8 -C 30 -alkyl, C 8 -C 30 -alkylcarbonyl, C 8 -C 30 -alkenyl, C 8 - C 30 -alkenylcarbonyl, C 8 -C 30 -alkadienyl, C 8 -C 30 -alkadienyl-carbonyl and / or hydroxy-C 8 -C 30 -alkyl groups, in particular in the form of C 10 -C 22 -alkyl- C 10 -C 22 -alkylcarbonyl, C 10 -C 22 -alkenyl, C 10 -C 22 -alkenylcarbonyl, C 10 -C 22 -alkadienyl, C 10 -C 22 -alkadienylcarbonyl- and / or hydroxy-C C 10 -C 22 -al
• the hydrocarbon radicals are in the form of C 8 -C 30 -alkylcarbonyl or C 8 -C 30 -alkenyl-carbonyl groups, in particular in the form of C 10 -C 22 -alkylcarbonyl or C 10 -C 22 -alkenylcarbonyl groups and especially in the form of C 10 -C 18 -alkylcarbonyl or C 10 -C 18 -alkenylcarbonyl groups, the alkyl and alkenyl radicals of the abovementioned groups preferably being linear.
• the proportion of hydrocarbon radicals preferably 25 to 95 wt .-%, in particular 30 to 90 wt .-% and especially 40 to 80 wt .-%, based on the total weight of the hydrophobically modified poly-C 2 -C 4 -alkyleneimine from ,
• the weight-average molecular weight Mw of hydrophobically modified poly-C 2 -C 4 -alkyleneimines suitable according to the invention is typically in the range from 1000 to 1,000,000 daltons.
• the hydrophobically modified poly-C 2 -C 4 -alkylenimin has a number average molecular weight in the range of 3000 to 300,000 daltons and in particular in the range of 6000 to 200,000 daltons.
• the molecular weights given here refer to those indicated by dynamic light scattering, to dilute ones aqueous solutions at 25 ° C measured molecular weights corresponding to the weight average molecular weight.
• hydrophobically modified poly-C 2 -C 4 -alkyleneimines used according to the invention may be linear or branched, based on the poly-C 2 -C 4 -alkylenimine on which they are based; C 2 -C 4 -alkylenimin part are branched.
• linear poly-C 2 -C 4 -alkyleneimines are composed exclusively of repeating units of the formula A in which Q is C 2 -C 4 -alkylene
• at least 5%, especially at least 10, and more preferably at least 15%, eg 5 to 40% and especially 15 to 35% of the nitrogen atoms of the underlying poly-C 2 -C 4 -alkyleneimine are tertiary nitrogen atoms.
• the hydrophobically modified polyols have C 2 -C 4 -alkyleneimines have a core-shell-like structure wherein the poly-C 2 -C 4 -alkyleneimine moieties form the core and the hydrophobic moieties form the shell.
• hydrophobically modified poly-C 2 -C 4 -alkyleneimines can be uncrosslinked or crosslinked, and quaternized in addition to the hydrophobic modification and / or by reaction with alkylene oxides, di-C 1 -C 4 alkylcarbonates, C 2 -C 4 alkylene carbonates or C 1 -C 4 carboxylic acids modified.
• hydrophobically modified poly-C 2 -C 4 -alkyleneimines are preferably uncrosslinked.
• the hydrophobically modified poly-C 2 -C 4 -alkyleneimines have no further modification in addition to the hydrophobic modification.
• the hydrophobically modified poly-C 2 -C 4 -alkyleneimines are quaternized in addition to the hydrophobic modification.
• Such quaternized hydrophobically modified poly-C 2 -C 4 -alkyleneimines preferably have no further modification.
• the degree of quaternization ie the number of quaternized nitrogen atoms bzeogen on the total amount of the nitrogen atom of the hydrophobically modified poly-C 2 -C 4 -alkyleneimine, is preferably not more than 80 mol%, in particular not more than 50 mol%, for example 1 to 80 mol%, in particular 5 to 50 mol%, based on the nitrogen atoms of the poly-C 2 -C 4 -alkyleneimine.
• hydrophobically modified poly-C 2 -C 4 -alkyleneimines used according to the invention are in part known from the cited prior art or can be prepared analogously to the methods described therein.
• hydrophobically modified poly-C 2 -C 4 -alkyleneimines are prepared by polymer-analogous reaction of unmodified poly-C 2 -C 4 -alkyleneimines with a hydrophobicizing agent.
• one embodiment of the invention relates to the use of a hydrophobically modified poly-C 2 -C 4 -alkylenimine obtainable by a process which comprises reacting a non-modified poly-C 2 -C 4 -alkylenimine, in particular an unmodified one , branched poly-C 2 -C 4 -alkyleneimine, and especially an unmodified, branched polyethyleneimine, with a hydrophobing agent.
• Preferred hydrophobizing agents are long-chain, linear or branched carboxylic acids having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the alkyl or alkenyl radical and their amide-forming derivatives, in particular linear saturated carboxylic acids having 10 to 22 C atoms, in particular 10 to 18 C atoms in the alkyl radical.
• Preferred water repellents are also alkyl epoxides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms.
• the unmodified poly-C 2 -C 4 -alkyleneimines which are based on the hydrophobically modified poly-C 2 -C 4 -alkyleneimines used according to the invention, include homopolymers of ethyleneimine (aziridine) and its higher homologues propyleneimine (methylaziridine) and butyleneimines (1, 2-dimethylaziridine, 1,1-dimethylaziridine and 1-ethylaziridine), copolymers of ethyleneimine with its higher homologues and the graft polymers of polyamidoamines or polyvinylamines with ethyleneimine and / or its higher homologues.
• graft polymers of C 2 -C 4 -alkyleneimines such as ethyleneimine on polyamidoamines or on polyvinylamines.
• Such graft polymers generally have a weight fraction of C 2 -C 4 -alkyleneimines of at least 10% by weight, in particular at least 30% by weight, for example 10 to 90% by weight, in particular from 10 to 85% by weight, based on the total weight of the unmodified poly C 2 -C 4 -alkyleneimine.
• the unmodified poly-C 2 -C 4 -alkyleneimines are branched poly-C 2 -C 4 -alkyleneimines, preferably polyethyleneimines, in particular branched polyethyleneimines and especially homopolymers of ethyleneimine, which are in particular branched.
• the unmodified poly-C 2 -C 4 -alkyleneimine used for the preparation is preferably branched, with the above-mentioned degree of branching being for hydrophobically modified poly-C 2 -C 4 -alkyleneimines.
• the unmodified poly-C 2 -C 4 -alkyleneimine used for the preparation preferably has a number-average molecular weight in the range from 1000 to 200 000 daltons, in particular in the range from 2000 to 100 000 daltons.
• reaction of the unmodified poly-C 2 -C 4 -alkylenimine with the hydrophobing agent can be carried out in analogy to known methods of the prior art.
• the reaction conditions naturally depend on the nature and functionality of the hydrophobing agent.
• the reaction can be carried out in bulk or in solution.
• the reaction is carried out in a suitable solvent for the reaction.
• suitable solvents are hydrocarbons, especially aromatic hydrocarbons, e.g. Alkylbenzenes such as xylenes, toluene, cumene, tert-butylbenzene and the like.
• the reaction can be carried out in the presence of catalysts, which improves the reactivity of the hydrophobing agent over the poly-C 2 -C 4 -alkylenimin.
• the type of catalyst depends in a conventional manner on the nature and reactivity of the hydrophobing agent.
• the catalysts are Lewis or Bronsted acids. Often, for example in the case of carboxylic acids, one can do without the use of catalysts.
• the reaction water, alcohols or hydrogen chloride
• the water formed will preferably be removed from the reaction mixture via an entraining agent.
• Typical entrainers are hydrocarbons, in particular alkylaromatics such as toluene or xylenes.
• the reaction is then preferably carried out in an organic solvent suitable as an entraining agent.
• the hydrophobing agent in an amount that corresponds to the desired functionalization, which also includes the water repellent can use in excess.
• the molar ratio of hydrophobizing agent to nitrogen atoms in the unmodified polyalkyleneimine is the same as that previously stated for the functionalization of the hydrophobicized polyalkyleneimine.
• the hydrophobizing agent calculated as the parts of the hydrophobizing agent remaining in the product (that is, the amount of hydrophobing agent less any low molecular weight products such as water), in an amount of 0.35 to 20 parts by weight, in particular in an amount of 0.5 to 10 Parts by weight, per part by weight of unmodified poly-C 2 -C 4 -alkylenimin.
• the hydrophobically modified poly-C 2 -C 4 -alkyleneimines are quaternized. Accordingly, the preparation of the hydrophobically modified poly-C 2 -C 4 -alkyleneimines additionally comprises a quaternization. The quaternization can take place before or in particular after the hydrophobicization.
• alkylating agents such as alkyl halides, which generally have 1 to 10 carbon atoms in the alkyl radical, or dialkyl sulfates, which generally contain alkyl radicals having 1 to 10 carbon atoms used.
• alkylating agents from these groups are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and dimethyl sulfate and diethyl sulfate.
• alkylating agents are, for example, benzyl halides, in particular benzyl chloride and benzyl bromide; Chloroacetic acid; Fluorschwefelklaremethylester; diazomethane; Oxonium compounds such as trimethyloxonium tetrafluoroborate; Alkylene oxides, such as ethylene oxide, propylene oxide and glycidol, which are used in the presence of acids; cationic epichlorohydrins.
• Preferred quaternizing agents are methyl chloride, dimethyl sulfate and diethyl sulfate.
• the secondary or in particular the tertiary nitrogen atoms of the underlying poly-C 2 -C 4 -alkylenimin part are converted into quaternary nitrogen atoms, ergo ammonium groups, whereby the hydrophobically modified poly-C 2 -C 4 -alkylenimin imparted a positive overall charge becomes.
• the hydrophobically modified poly-C 2 -C 4 -alkyleneimines are generally water-soluble or water-dispersible and can be used in solid and liquid detergents and in laundry after-treatment agents. They are distinguished in particular by high compatibility with conventional detergent ingredients, in particular with the constituents of liquid detergent formulations, especially those which have a low content of anionic surfactants.
• the incorporation into the respective detergent or laundry aftertreatment agent formulation is carried out in a manner known per se, the hydrophobically modified polyalkyleneimines frequently being used in liquid, ie dissolved or dispersed form.
• the hydrophobically modified polyalkyleneimines can also be used in powder or granular form.
• the solid detergent formulations may be in powder, granule, extrudate or tablet form.
• the anionic surfactants are preferably added to the detergent in the form of salts.
• Suitable salts are e.g. Alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
• Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidbetaines, aminopropionates, aminoglycinates and amphoteric imidazolium compounds.
• the advantages of the hydrophobically modified polyalkyleneimines according to the invention are particularly evident in those detergent formulations which contain only a small proportion of anionic surfactants.
• the proportion of anionic surfactants based on the total amount of surfactant in the detergent or laundry aftertreatment agent formulation, is preferably not more than 50% by weight, in particular not more than 30% by weight, and especially not more than 10% by weight.
• the anionic surfactant does not constitute more than 8% by weight, in particular not more than 5% by weight, based on the total weight of the formulation.
• Suitable grayness inhibitors are, for example, carboxymethylcellulose and graft polymers of vinyl acetate on polyethylene glycol.
• Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.
• Suitable bleach activators are e.g. N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile methyl sulfate.
• TAED tetraacetylethylenediamine
• Enzymes preferably used in detergents are proteases, lipases, amylases, cellulases, oxidases and peroxidases.
• Suitable further color transfer inhibitors are, for example, homopolymers, copolymers and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.
• Selected colored fabric (EMPA 130, EMPA 132, EMPA 133 or EMPA 134) was washed in the presence of white cotton and polyester / polyester and polyester / cotton ballast fabrics and polyester with a detergent at 60 ° C with the addition of the LCST polymers. After the wash, the fabrics were rinsed, spun and dried. To determine the Farbübertragunsinhibierende effect, the staining of the white test tissue was determined photometrically (photometer: Elrepho ® 2000 Fa. Datacolor). From the remission values measured on the test fabric, after the in A. Kud, soaps, oils, fats, waxes, volume 119, pages 590-594 (1993 ) determines the color strength of the staining.
• the tinting strength for the test without test substance and the tinting strength of the test fabric before washing was the color transfer inhibiting effect of the test substance according to determined by the following formula in%.
• F ⁇ U ⁇ ⁇ l - effect % Dyer ⁇ a ⁇ ⁇ strength without polymer - Dyer ⁇ a ⁇ ⁇ strength with polymer Dyer ⁇ a ⁇ ⁇ strength without polymer - Dyer ⁇ a ⁇ ⁇ strength in front of the W ⁇ a ⁇ ⁇ cal x 100
• the washing conditions are given in Table 1.
• the composition of the detergent A used is shown in Table 2.
• the color transfer inhibition test results are shown in Table 3.
• Table 1 washing conditions Washing conditions main wash device Launder-o-meter of the company Atlas, Chicago, USA
• Dosage of polymer 0.05 g / l liquor colored fabric 1 g of EMPA 130 (CI Direct Red 83: 1) 1 g of EMPA 132 (CI Direct Black 22) 1 g of EMPA 133 (CI Direct Blue 71) 0.5 g EMPA 134 (CI Direct Orange 39) (all Federal Material Testing Institute, St.
• Test fabric 5 g cotton fabric 221 (bleached) ballast fabric 5 g blended fabric 768 (65:35 PES: BW) + 5 g polyester fabric 854 Composition detergent A (liquid detergent) ingredients [Wt .-%] C 13 C 15 oxo alcohol x 7 EO 12 C 6 -alcohol x 5 EO 5 citric acid 3 propylene glycol 10 ethanol 2 Diethylenetriamine-penta (methylenephosphonic acid) 1.0 water on 100 Adjust to pH 9 with sodium hydroxide solution.
• Polyethyleneimine A Mw 25,000 g / mol; Amine number: 20.14 mmol / g Ratio of primary: secondary: tertiary nitrogen atoms: 1.0: 1.1: 0.7, determined by means of 13 C-NMR.
• Polyethyleneimine B Mw 5000 g / mol; Amine number: 9.22 mmol / g Ratio of primary: secondary: tertiary nitrogen atoms: 1.0: 1.0: 0.7, determined by means of 13 C-NMR.
• Polymer 8 (666 g) was heated to 75 ° C. Dimethyl sulfate was then added (71.8 g, Dosimat 2.5 ml / min). Subsequently, the excess dimethyl sulfate was removed under reduced pressure. The product was obtained as a brown amorphous substance (407.5 g).

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• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

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