Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • 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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to the use of soil release agents Comb polymers in detergents and cleaning agents.
• the majority of the soil release polymers are Polyester based on terephthalic acid, polyalkylene glycols and monomers Glycols.
• the main polymer chain of the comb polymers according to the invention preferably consists of polymeric aliphatic, cycloaliphatic or aromatic polycarboxylic acids or their derivatives such as, for example, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride and polynorbornene acid or their esters with aliphatic, cycloaliphatic or aromatic alcohols with C 1 -C 22 .
• the number average molecular weights of these polycarboxylic acids can be between 1,000 and 2,000,000 g / mol, the range from 2,000 to 100,000 g / mol being preferred.
• the polymer main chain can consist of a polymer aliphatic, cycloaliphatic or aromatic polyalcohol, for example Polyvinyl alcohol or polynorbornyl alcohol.
• the number average molecular weights these polyalcohols can be between 1,000 and 2,000,000 g / mol, the Range of 2,000 to 100,000 g / mol is preferred.
• Component b) may be considered polyalcohols aromatic, aliphatic or substituted by a sulfo group cycloaliphatic nature as defined above, for example ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,4-butanediol, sodium 1,2-dihydroxypropoxyethanesulfonate, Glycerin, pentaerythritol.
• Component c) consists of at least difunctional aromatic, aliphatic and / or cycloaliphatic C 2 -C 10 dicarboxylic acids, such as terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, 2,6-naphthalenedicarboxylic acid and optionally one or more sulfonated aromatic, aliphatic or cycloaliphatic C 3 -C 10 dicarboxylic acids, for example sulfosuccinic acid or 5-sulfoisophthalic acid or mixtures thereof.
• dicarboxylic acids such as terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, 2,6-naphthalenedicarboxylic acid and optionally one or more sulfonated aromatic, aliphatic or cycloaliphatic C 3 -C 10 dicar
• the sulfo group in the sulfo-containing components is preferably in the form of an alkali, alkaline earth or ammonium, mono-, di-, tri- or tetra-alkyl or -hydroxyalkyl-ammonium salt, an alkyl group 1 to 22 C atoms and the other alkyl groups as well as the hydroxyalkyl group can contain 1 to 4 C atoms.
• component e) are sulfonated mono- or polyethylene glycols of the formula H (OCH 2 CH 2 ) d SO 3 M, where d is a number from 1 to 10, preferably from 1 to 4 and M is an alkali or alkaline earth metalation.
• the comb polymers according to the invention can alternatively also be free from components according to d). In this case, the side chains of the comb polymer terminate with a hydrogen atom.
• the comb polymers preferably consist of 0.5 to 10% by weight of the component a), 15 to 45 wt .-% of component b), 30 to 70 wt .-% of component c) and 10 to 30% by weight of component d).
• the number average molecular weights of the comb polymers can be advantageous between 2,000 and 2,000,000 g / mol, particularly advantageously between 2,000 and 100,000 g / mol, the range of 2,000-30,000 g / mol being preferred Is used, very particularly advantageously from 5,000 - 15,000 g / mol.
• the invention also relates to the use of these comb polymers in Detergents and cleaning agents, especially to increase their cleaning performance against oily and greasy soiling.
• Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof.
• Suitable cations are alkali metals such as sodium or potassium or alkaline earth metals such as. As calcium or magnesium and ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures thereof.
• the following types of anionic surfactants are of particular interest: Alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkane sulfonates and soaps as described below.
• Alkyl ester sulfonates include linear esters of C 8 -C 20 carboxylic acids (ie fatty acids) which are sulfonated using gaseous SO 3 , as described in "The Journal of the American Oil Chemists Society” 52 (1975), pp. 323-329. Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but can also be synthetic in nature.
• Preferred alkyl ester sulfonates, especially for detergent applications are compounds of the formula wherein R 1 is a C 8 -C 20 hydrocarbon radical, preferably alkyl, and R is a C 1 -C 6 hydrocarbon radical, preferably alkyl.
• M stands for a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine.
• R 1 is preferably C 10 -C 16 alkyl and R is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R 1 is C 10 -C 16 alkyl are particularly preferred.
• alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, in which R is a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with a C 10 -C 20 alkyl component, particularly preferably a C 12 -C 18 alkyl or Is hydroxyalkyl.
• M is hydrogen or a cation, e.g. an alkali metal cation (e.g. sodium, potassium, lithium) or ammonium or substituted ammonium, e.g. B.
• alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
• Alkyl chains with C 12 -C 16 are preferred for low washing temperatures (eg below approx. 50 ° C) and alkyl chains with C 16 -C 18 for higher washing temperatures (eg above approx. 50 ° C).
• Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, in which R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 alkyl or hydroxyalkyl radical, particularly preferably C 12 -C 18 represents alkyl or hydroxyalkyl.
• A is an ethoxy or propoxy unit
• m is a number greater than 0, preferably between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as, for .
• substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
• alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
• Examples include C 12 to C 18 fatty alcohol ether sulfates, the content of EO being 1, 2, 2.5, 3 or 4 mol per mol of the fatty alcohol ether sulfate, and in which M is sodium or potassium.
• the alkyl group can either be saturated or unsaturated, branched or linear and optionally with a hydroxyl group be substituted.
• the sulfo group can be at any position on the C chain, with the primary methyl groups at the beginning and end of the chain none Possess sulfonate groups.
• the preferred secondary alkanesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably about 10 to about 20 Carbon atoms and particularly preferably about 13 to 17 carbon atoms.
• the Cation is, for example, sodium, potassium, ammonium, mono-, di- or Triethanolammonium, calcium or magnesium, and mixtures thereof. sodium is preferred as the cation.
• primary alkanesulfonates can also be used in the washing and cleaning agents according to the invention are used.
• the preferred alkyl chains and cations correspond to those of the secondary alkane sulfonates.
• the production of primary alkanesulfonic acid, from which the corresponding sulfonates which are effective as surfactants are obtained, is described, for example, in EP 854 136-A1.
• alkenyl or alkylbenzenesulfonates are alkenyl or alkylbenzenesulfonates.
• the Alkenyl or alkyl group can be branched or linear and optionally with a Hydroxyl group may be substituted.
• the preferred alkyl benzene sulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or Triethanolammonium, calcium or magnesium and mixtures thereof.
• Magnesium is preferred as the cation for surfactant systems Standard washing applications, however, sodium.
• Alkenylbenzenesulfonates are alkenyl or alkylbenzenesulfonates.
• anionic surfactants also includes olefin sulfonates which are obtained by sulfonating C 12 -C 24 , preferably C 14 -C 16 ⁇ -olefins with sulfur trioxide and subsequent neutralization. Due to the manufacturing process, these olefin sulfonates can contain smaller amounts of hydroxyalkanesulfonates and alkane disulfonates. Special mixtures of ⁇ -olefin sulfonates are described in US 3,332,880.
• Suitable anionic surfactants are carboxylates, e.g. Fatty acid soaps and comparable surfactants.
• the soaps can be saturated or unsaturated and can have various substituents, such as hydroxyl groups or ⁇ -sulfonate groups contain.
• Linear saturated or unsaturated are preferred Hydrocarbon residues as a hydrophobic portion with about 6 to about 30, preferably about 10 up to approx. 18 carbon atoms.
• Suitable anionic surfactants are salts of acylaminocarboxylic acids, the acyl sarcosinates formed in the alkaline medium by reaction of fatty acid chlorides with sodium sarcosinate; Fatty acid-protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; Salts of alkylsulfamidocarboxylic acids; Salts of alkyl and alkylaryl ether carboxylic acids; C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB-1,082,179; Alkylglycerol sulfates, oleylglycerol sulfates, alkylphenol ether sulfates, primary paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, is
• nonionic surfactants Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.
• These compounds include the condensation products of alkyl phenols with a C 6 to C 20 alkyl group, which can be either linear or branched, with alkene oxides. Compounds with about 5 to 25 mol of alkene oxide per mol of alkylphenol are preferred.
• Commercially available surfactants of this type are, for example, Igepal® CO-630, Triton® X-45, X-114, X-100 and X-102, and the ®Arkopal-N brands from Clariant GmbH. These surfactants are referred to as alkylphenol alkoxylates, for example alkylphenol ethoxylates.
• nonionic surfactants of this type are Tergitol® 15-S-9 (condensation product of a linear secondary C 11 -C 15 alcohol with 9 mol ethylene oxide), Tergitol® 24-L-NMW (condensation product of a linear primary C 12 -C 14 -alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution).
• Genapol® brands from Clariant GmbH also fall under this product class.
• the hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800.
• the attachment of ethylene oxide to this Hydrophobic part leads to an improvement in water solubility.
• the product is liquid up to a polyoxyethylene content of approx. 50% of the total weight of the Condensation product, which is a condensation with up to about 40 mol of ethylene oxide corresponds.
• the Pluronic® brands are commercially available examples of this product class from BASF and the ®Genapol PF brands from Clariant GmbH.
• the hydrophobic unit of these compounds consists of the reaction product of Ethylene diamine with excess propylene oxide and generally has Molecular weight from about 2500 to 3000. At this hydrophobic unit Ethylene oxide up to a content of approx. 40 to approx. 80% by weight of polyoxyethylene and a molecular weight of about 5000 to 11000 added.
• Ethylene oxide up to a content of approx. 40 to approx. 80% by weight of polyoxyethylene and a molecular weight of about 5000 to 11000 added.
• Commercially available Examples of this class of compounds are the ®Tetronic brands from BASF and the ®Genapol PN brands from Clariant GmbH.
• non-ionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each with an alkyl radical of about 10 to about 18 carbon atoms.
• Semipolar nonionic surfactants are also amine oxides of the formula
• R is an alkyl group with about 7 to about 21, preferably about 9 to about 17 carbon atoms and each radical R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 4 O) x H means, where x varies from about 1 to about 3.
• C 8 -C 20 amides, monoethanolamides, diethanolamides and isopropanolamides are preferred.
• Preferred amphoteric surfactants of this formula are monocarboxylates and Dicarboxylates. Examples include cocoamphocarboxypropionate, Cocoamidocarboxypropionic acid, Cocoamphocarboxyglycinat (or also as Cocoamphodiacetate) and Cocoamphoacetat.
• Suitable builders include the ether hydroxypolycarboxylates, Copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. Ethylenediaminetetraacetic acid and nitrilotriacetic acid, and also polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, Carboxymethyloxy succinic acid and its soluble salts.
• polyacetic acids such as e.g. Ethylenediaminetetraacetic acid and nitrilotriacetic acid
• polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic
• Citric acid and its soluble salts, especially the sodium salt are preferred polycarboxylic acid builders that also in granulated formulations, especially together with zeolites and / or Layered silicates can be used.
• auxiliaries include the substances mentioned in US Pat. No. 3,936,537, for example enzymes, in particular proteases, lipases and cellulases, Foam booster, foam brakes, anti-tarnish and / or anti-corrosion agents, Suspending agents, dyes, fillers, optical brighteners, disinfectants, Alkalis, hydrotropic compounds, antioxidants, enzyme stabilizers, perfumes, Solvents, solubilizers, redeposition inhibitors, dispersants, Color transfer inhibitors, e.g. B.
• enzymes in particular proteases, lipases and cellulases
• Foam booster foam brakes
• anti-tarnish and / or anti-corrosion agents Suspending agents, dyes, fillers, optical brighteners, disinfectants, Alkalis, hydrotropic compounds, antioxidants, enzyme stabilizers, perfumes, Solvents, solubilizers, redeposition inhibitors, dispersants, Color transfer inhibitors, e.g. B.
• the detergent and detergent compositions of the present invention can optionally contain one or more conventional bleaches, as well as activators or stabilizers, in particular peroxy acids, which are not compatible with the Comb polymers according to the invention react. In general, must be ensured be that the bleach used with the detergent ingredients are tolerated. Conventional test methods, such as determining the Bleaching activity of the formulated detergent depending on the Storage times can be used for this purpose.
• the peroxy acid can either be a free peroxy acid or a combination from an inorganic persalt, for example sodium perborate or Sodium percarbonate and an organic peroxyacid precursor that leads to a Peroxyacid is converted when the combination of persalt and Peroxyacid precursor is dissolved in water.
• the organic peroxyacid precursors are often referred to as bleach activators in the prior art. Examples of suitable organic peroxyacids are disclosed in US 4,374,035, U.S. 4,681,592, U.S. 4,634,551, U.S. 4,686,063, U.S. 4,606,838 and U.S. 4,671,891.
• peroxyacids preferred for use in this invention are peroxydodecanedioic acid (DPDA), the nonylamide of Peroxysuccinic acid (NAPSA), the nonyl amide of peroxyadipic acid (NAPAA) and decyldiperoxysuccinic acid (DDPSA).
• DPDA peroxydodecanedioic acid
• NAPSA nonylamide of Peroxysuccinic acid
• NAPAA nonyl amide of peroxyadipic acid
• DDPSA decyldiperoxysuccinic acid
• the peroxy acid is preferably in contain a soluble granulate, according to the method from US-4,374,035.
• Suitable amounts of the peroxyacid-containing bleaching agent based on a Unit dose of the detergent composition according to the invention as it is is used for a typical wash liquor containing about 65 liters of water from 15 to 60 ° C, produce between about 1 ppm to about 150 ppm available Oxygen, preferably between about 2 ppm to about 20 ppm Oxygen.
• the wash liquor should have a pH between 7 and 11, preferably between 7.5 and 10.5 in order to obtain a sufficient bleaching result achieve. Reference is made to column 6, lines 1 through 10 of US 4,374,035.
• the bleach composition can be an appropriate one organic peroxyacid precursor containing one of the above Peroxyacids generated when in an aqueous alkaline solution Hydrogen peroxide reacts.
• the source of the hydrogen peroxide can be any be inorganic peroxide, which releases hydrogen peroxide in aqueous solution, such as such as sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.
• the detergent compositions according to the invention can be one or contain several conventional enzymes. Such enzymes are e.g. Lipases, Amylases, proteases and cellulases.
• a preferred enzyme is cellulase.
• the cellulase used here can be obtained from bacteria or fungi and should have an optimal pH range between 5 and 9.5.
• Suitable Cellulases are disclosed in US 4,435,307. It is cellulase that is produced by a strain of Humicola insolens, especially the strain Humicola DSM 1800 or another cellulase-212-producing mushroom that belongs to the genus Aeromonas, and cellulase from the hepatopancreas certain marine molluscs were extracted. Suitable cellulases are also in GB-A-2,075,028, GB-A-2,085,275 and DE-OS-2,247,832.
• the comb polymers according to the invention can be used to achieve soil release Finish also in commercially available fabric softeners for household use be used. These essentially contain softening components, Co-plasticizers, emulsifiers, perfumes, dyes and electrolytes, and are on set an acidic pH of below 7, preferably between 3 and 5.
• Examples include distearyldimethylammonium chloride, Ditalgalkyldimethylammonium chloride, ditalgalkylmethylhydroxypropylammonium chloride, cetyltrimethylammonium chloride or the corresponding benzyl derivatives such as dodecyldimethylbenzylammonium chloride. Cyclic quaternary ammonium salts such as alkyl morpholine derivatives can also be used.
• a particularly preferred class of compounds are the so-called ester quats. It are reaction products of alkanolamines and fatty acids, which then with conventional alkylation or hydroxyalkylation agents be quaternized.
• Triethanolamine and methyldiethanolamine are particularly preferred.
• Alkylation or hydroxyalkylation agents are preferred, preferably alkyl halides Methyl chloride, dimethyl sulfate, ethylene oxide and propylene oxide.
• ester quats are compounds of the formulas: where RCO is derived from C 8 -C 24 fatty acids, which can be saturated or unsaturated. Examples include caproic acid, caprylic acid, hydrogenated or not or only partially hydrogenated tallow fatty acids, stearic acid, oleic acid, linolenic acid, behenic acid, palmitic stearic acid, myristic acid and elaidic acid. n is in the range from 0 to 10, preferably 0 to 3, particularly preferably 0 to 1.
• a radical R 3 which can be C 1 -C 4 -alkyl, preferably methyl
• a counterion X which can be chloride, bromide, iodide or methyl sulfate
• Amidoaminooxethylates and their quaternized secondary products are offered under the trade names ®Varisoft 510, ®Varisoft 512, ®Rewopal V 3340 and ®Rewoquat W 222 LM.
• the preferred application concentrations of the invention Comb polymers in the fabric softener formulations correspond to those for Detergent formulations are called.
• Laundry aftertreatment agents can comb polymers according to the invention in all household cleaning agents and all technical cleaning agents have a good soil release effect compared to hydrophobic To achieve contamination.
• Household cleaning supplies and technical Detergents can use the above representative examples of surfactants, Contain builders, optical brighteners, bleaches and enzymes.
• household cleaning agents are all-purpose cleaners, dishwashing detergents, Carpet cleaning and waterproofing agents, cleaning and care products for floors and other hard surfaces, e.g. made of plastic, ceramic, glass.
• Examples of technical cleaning agents are plastic cleaning and Care products, such as for housings and car fittings, as well as cleaning and Care products for painted surfaces such as car bodies.
• Liquid-formulated cleaning agents containing the comb polymers according to the invention contain, generally have a pH below 8.
• the mixture was then inertized with nitrogen and opened within half an hour 165 - 167 ° C heated. The temperature rose within a further 2.5 hours 210 - 220 ° C increased. At an internal temperature of approx. 165 ° C the transesterification or Esterification and thus the distillation of methanol and water. After about 5 hours, more than 95% of the expected amount had distilled off. In the course of about 1 hour, the pressure was reduced to 1-5 mbar and at 220 - 225 ° C condensed for a further 2 - 5 hours, a mixture of Ethylene glycol and 1,2-propylene glycol distilled off and the batch increasingly viscous will, but still stirrable. After the condensation was finished with Nitrogen vented and cooled. The product solidifies on cooling Room temperature to a solid brittle mass. Yield 440 g.
• the comb polymers according to the invention were designed for their soil release effect compared with prior art soil release polymers.
• the substances were added in a concentration of 1% to a washing powder containing phosphate and one containing no phosphate.
• Polyester WFK 30 A test fabric (laundry research institute Krefeld) was prewashed with these washing powders. The fabric pretreated in this way was dried and soiled with used motor oil. After an exposure time of 1 hour, the test fabric was washed with the same washing powders. For comparison, test fabric was washed both without the addition of soil release polymers and with the addition of 1% of commercial soil release polymers. The reflectance of the test tissue was measured to assess the dirt detachment. The following compounds were used as the prior art soil release polymer:

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• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
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• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 1999
  • 1999-02-16 DE DE19906367A patent/DE19906367A1/de not_active Withdrawn
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