EP0368214B1 - Utilisation de copolymères estérifiés partiellement pour compositions détergentes liquides - Google Patents

Utilisation de copolymères estérifiés partiellement pour compositions détergentes liquides Download PDF

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EP0368214B1
EP0368214B1 EP89120522A EP89120522A EP0368214B1 EP 0368214 B1 EP0368214 B1 EP 0368214B1 EP 89120522 A EP89120522 A EP 89120522A EP 89120522 A EP89120522 A EP 89120522A EP 0368214 B1 EP0368214 B1 EP 0368214B1
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monoethylenically unsaturated
copolymers
units
acids
esters
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EP0368214A2 (fr
EP0368214A3 (en
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Johannes Dr. Perner
Paul Diessel
Heinrich Dr. Hartmann
Walter Denzinger
Alfred Dr. Oftring
Willibald Dr. Schoenleben
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BASF SE
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BASF SE
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    • 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
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • EP-PS 0 116 930 describes water-soluble copolymers of 40 to 90% by weight of at least one ethylenically unsaturated monocarboxylic acid with 3 to 5 C atoms and 60 to 10% by weight of at least one ethylenically unsaturated dicarboxylic acid with 4 to 8 C atoms and / or their corresponding dicarboxylic acid anhydrides are known, in which 2 to 60% by weight, based on the total weight of the carboxylic acids or carboxylic acid anhydrides, are esterified with alkoxylated C1 to C18 alcohols or C1 to C12 alkylphenols.
  • the partially esterified copolymers and their water-soluble salts are used, inter alia, in amounts of 0.5 to 10% by weight also used in liquid detergent formulations.
  • the compatibility of the partially esterified copolymers of at least one monoethylenically unsaturated monocarboxylic acid and at least one monoethylenically unsaturated dicarboxylic acid is significantly more favorable than that of the non-esterified products, so that there are fewer phase separations.
  • the partially esterified copolymers of the type described are not stable to hydrolysis, so that they hydrolyze in liquid detergent formulations. As a result, inhomogeneities occur, which can even go so far as to result in the phase separation of the liquid detergent.
  • liquid detergents which contain at least one nonionic surface-active agent in an amount of 5 to 25% by weight, 2 to 25% by weight of a builder, approximately 1 to 10% by weight of C4 to C30 Contain ⁇ -olefin-maleic anhydride copolymers and, to make up to 100% by weight, water. Although these liquid detergents initially represent clear solutions, they separate relatively quickly during storage.
  • liquid alkaline detergent formulations which, in addition to water and detergents as stabilizers, contain 0.1 to 5%, based on the entire formulation, of a hydrolyzed copolymer of an ⁇ , ⁇ -unsaturated carboxylic anhydride with a vinyl ester, vinyl ether or contain an ⁇ -olefin in partially esterified form.
  • Addition products of alkylene oxides, in particular ethylene oxide onto alkylphenols are also suitable as alcohol components for the esterification. Only 0.01 to 5% of the carboxyl groups of the copolymer are present as ester groups.
  • these liquid detergents contain components which are compatible with one another, the primary washing action of this liquid detergent formulation is still in need of improvement.
  • EP-A-0 215 251 describes the use of homopolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methacrylic acid and of copolymers of ethylenically unsaturated dicarboxylic acids with 4 to 6 carbon atoms and acrylic acid or methacrylic acid in each case partially neutralized and / or with long-chain amines and / or partially amidated form as a graying-inhibiting additive to detergents and cleaning agents which promotes the primary washing action in quantities of 0.05 to 10% by weight.
  • the partially amidated homopolymers and copolymers are prepared by reacting the polymers with long-chain amines.
  • the object of the present invention is to provide polymers for the production of stable liquid detergent formulations which have an improved primary and secondary washing action compared to the liquid detergent formulations of the prior art.
  • stable liquid detergent formulation should be understood to mean the fact that the individual components of the formulation are compatible with one another and do not separate even after prolonged storage.
  • liquid detergents which contain the copolymers to be used according to the invention, when mixed with aqueous neutral to alkaline solutions of anionic and / or nonionic surfactants, give clear aqueous solutions which are stable on storage, i.e. the individual components of the liquid detergent formulation are compatible with one another and do not separate after prolonged storage.
  • the copolymers to be used according to the invention contain, as essential constituents, units of monoethylenically unsaturated C3 to C8 monocarboxylic acids, monoethylenically unsaturated C4 to C8 dicarboxylic acids, half esters of monoethylenically unsaturated C4 to C8 dicarboxylic acids, esters of monoethylenically unsaturated C3 to C2 carboxylic acids, - Polymerized to C30-olefins, styrene, C1- to C3-alkylstyrenes, C1- to C28-alkyl vinyl ethers, vinyl esters of saturated C1- to C8-carboxylic acids or mixtures of units of these monomers.
  • the ethylenically unsaturated C3 to C8 monocarboxylic acids include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, allylacetic acid, propylidene acetic acid, ethylidene acetic acid, ⁇ -ethyl acrylic acid and ⁇ , ⁇ -dimethylacrylic acid. From this group of monomers, acrylic acid and methacrylic acid are preferably used.
  • Suitable monoethylenically unsaturated C4 to C8 dicarboxylic acids are, for example, maleic acid, itaconic acid, fumaric acid, mesaconic acid, methylene malonic acid and citraconic acid.
  • copolymers to be used according to the invention preferably contain units of maleic acid or itaconic acid copolymerized.
  • Half-esters of monoethylenically unsaturated Crelit to C8 dicarboxylic acids are also suitable, which are derived from mono- or polyhydric alcohols with 1 to 8 C atoms.
  • Such alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, 2-ethylhexyl alcohol, glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol and 1,6-hexanediol.
  • the alcohols mentioned can also be used for the preparation of esters of monoethylenically unsaturated C3- to C8-monocarboxylic acids, which are also suitable as component (a) for the preparation of the copolymers to be used according to the invention.
  • esters are, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and the corresponding esters of methacrylic acid.
  • Suitable olefins having 2 to 30 carbon atoms are, for example, ethylene, propylene, isobutylene, n-hexene, n-octene, diisobutene, n-decene, n-dodecene and n-octadecene.
  • the longer-chain olefins can have the double bonds in the ⁇ or also in the ⁇ position.
  • the use of ⁇ -olefins is particularly preferred.
  • Preferably used as olefins are branched C6 to C18 olefins or mixtures thereof.
  • mixtures of 2,4,4'-trimethylpentene-1 and 2,4,4'-trimethylpentene-2 is particularly preferred.
  • Commercially available mixtures of diisobutylene contain approximately 80% trimethylpentene-1 and approximately 20% trimethylpentene-2.
  • the copolymers may also contain units of styrene or C1- to C3-alkylstyrenes polymerized as an essential component of component (a).
  • Suitable alkylstyrenes are, for example, ⁇ -methylstyrene and ⁇ -ethylstyrene.
  • component (a) are also C1 to C28 alkyl vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, dodecyl vinyl ether and octadecyl vinyl ether.
  • vinyl esters of saturated C1 to C8 carboxylic acids for example vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate.
  • the copolymers contain mixtures of units of monoethylenically unsaturated C4 to C8 dicarboxylic acids with units of half esters of monoethylenically unsaturated C4 to C8 dicarboxylic acids, esters of monoethylenically unsaturated C3 to C8 monocarboxylic acids, C2- bis C30-olefins, styrene, C1- to C3-alkylstyrenes, C1- to C28-alkyl vinyl ethers, vinyl esters of saturated C1- to C8-monocarboxylic acids, monoethylenically unsaturated C3- to C8-monocarboxylic acids or optionally their salts in copolymerized form.
  • Preferred monoethylenically unsaturated C4 to C8 dicarboxylic acids are maleic acid and itaconic acid.
  • the units of these dicarboxylic acids are in the preferred embodiment of the invention except for the others Dicarboxylic acid units, with the units of at least one other monomer, which are mentioned under (a), contained in the copolymers.
  • the monomers of component (a) make up 50 to 99, preferably 60 to 90 mol% of the copolymers.
  • the amides of component (b) are preferably derived from the amides of acrylic acid and methacrylic acid and the mono- and diamides of maleic acid and itaconic acid of the amide structures given above.
  • the amides of the component (B) the copolymers are prepared, for example, by using a monoethylenically unsaturated C3 to C8 carboxylic acid or the acid chlorides of these carboxylic acids with amines of the formula in which the substituents R1 and R2 have the meaning given above for the amide structure, to the amides or half-amides or diamides in a known manner.
  • R-OH C1- to C28-alkyl
  • the following compounds are suitable as amides of ethylenically unsaturated compounds of component (b):
  • the monomers of component (b) make up 50 to 1, preferably 40 to 10 mol%, of the copolymers.
  • the copolymers can be obtained by copolymerizing the monomers specified under (a) and (b) by the customary methods of substance, solution, precipitation or suspension polymerization using initiators which decompose into free radicals under the polymerization conditions.
  • the polymerization temperatures are in the range from 30 to 200 ° C. A shorter polymerization time is required at a higher temperature, while a longer polymerization time has to be accepted at lower temperatures.
  • Suitable inert organic solvents are e.g. Toluene, o-xylene, p-xylene, m-xylene, isopropylbenzene, tetralin, tetrahydrofuran, dioxane and aliphatic hydrocarbons, such as hexane, cyclohexane, n-heptane, n-octane, isooctane and mixtures of the solvents mentioned.
  • the esterification is preferably carried out only to such an extent that about 5 to 50% of the carboxyl groups formed from the anhydride groups during the hydrolysis are esterified.
  • Copolymers of this type which are partially esterified, for example, with an adduct of 10 moles of ethylene oxide and 1 mole of a C13- / C15-oxo alcohol, have particular stability in alkaline aqueous liquid detergent formulations.
  • these are terpolymers e.g. Terpolymers of (a1) maleic acid, (a2) acrylic acid and an amide (b), these terpolymers as well as the other copolymers not mentioned by name, can contain the monomers (a1) and (a2) in copolymerized form in any ratio, the sum (a1) and (a2) is involved in the structure of the copolymers to 50 to 99 mol%.
  • the residues R1 and R2 of the amide structures of the compounds of formula (b) are derived - as already mentioned - from alkoxylated C1 to C28 alcohols.
  • the alkoxylation of these alcohols can be carried out with ethylene oxide alone, with mixtures of ethylene oxide and propylene oxide and, if appropriate, butylene oxides, or else as block copolymerization, by first adding propylene oxide and then ethylene oxide or in the reverse order, ie first ethylene oxide and then propylene oxide, to the alcohols.
  • the end group in the two block copolymers described can be a butylene oxide grouping.
  • the amides to be used according to (b) generally contain enough ethylene oxide units to ensure that these monomers are soluble in water.
  • copolymers which contain at least one monomer from groups (a) and (b) in copolymerized form as essential units, may optionally contain in copolymerized form further ethylenically unsaturated monomers which are different from (a) and (b) and dissolve in water.
  • Such monomers are, for example, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamidomethylpropanesulfonic acid, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, vinylphosphonic acid, N-vinylimidazole, N-vinylethanolimylamethylamylamylamylamylamylamylamethylamylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamylamethylamy
  • the basic monomers are preferably used as salts or in quaternized form.
  • the monomers containing acid groups can also be polymerized in partially or completely neutralized form. If these monomers are used in the preparation of the copolymers to be used according to the invention, they are present in the copolymerization in amounts of 1 to 20% by weight, based on the monomers (a) and (b).
  • the copolymerization can optionally be carried out in the presence of conventional regulators, e.g. Thio and mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, thiolactic acid, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan and dodecyl mercaptan.
  • suitable regulators are aldehydes such as acetaldehyde, butyraldehyde, acrolein and methacrolein and allyl compounds, e.g.
  • the regulators are used in amounts of 0.01 to 20, preferably 0.05 to 10,% by weight, based on the monomers used.
  • Chain extenders contain at least 2 ethylenically unsaturated double bonds that are not conjugated.
  • Suitable chain extenders of this type are, for example, diacrylates or dimethacrylates of at least dihydric saturated alcohols, for example ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol-1,4-diacrylate, butanediol-1,4-dimethacrylate, Hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol dimethacrylate.
  • Acrylic acid and methacrylic acid esters of alcohols with more than 2 hydroxyl groups can also be used as chain extenders, for example trimethylolpropane triacrylate or trimethylolpropane trimethacrylate.
  • Another class of chain extenders are diacrylates and dimethacrylates of polyethylene glycols or polypropylene glycols with molecular weights which are preferably in the range from 400 to 2,000 each.
  • block copolymers of ethylene and propylene oxide or statistical copolymers of ethylene and propylene oxide are also suitable, each of which is esterified in the ⁇ , ⁇ position with acrylic acid, methacrylic acid or maleic acid.
  • Chain extenders of this type are, for example, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate as well as the diacrylates or dimethacrylates of polyethylene glycols from C 3 or vinyl itaconate.
  • vinyl esters of saturated carboxylic acids containing at least 2 carboxyl groups and di- and polyvinyl ethers of at least dihydric alcohols for example divinyl adipate, butanediol divinyl ether and trimethylolpropane trivinyl ether.
  • Further chain extenders are allyl esters of ethylenically unsaturated carboxylic acids, for example allyl acrylate and allyl methacrylate, allyl ethers of polyhydric alcohols, for example pentaerythritol triallyl ether, triallylsucrose and pentaallylsucrose.
  • Methylene bisacrylamide, methylene bis methacrylamide, N-divinylethylene urea, divinylbenzene, divinyldioxane, tetrallylsilane and tetravinylsilane are also suitable as chain extenders. If the copolymerization of the monomers (a) and (b) is carried out in the presence of chain extenders, they are used in amounts of 0.01 to 20, preferably 0.05 to 10,% by weight.
  • Regulators and chain extenders can also be used together in the copolymerization to produce polymers with special properties.
  • copolymers which have K values of 8 to 200, preferably 10 to 80 (determined according to H. Fikentscher in one percent aqueous solution at 25 ° C. and pH 7.5 in the form of the sodium salt).
  • the K values correspond to molecular weights (weight average) of about 500 to 500,000, preferably 1,000 to 150,000.
  • the composition of the copolymer should always be chosen so that the copolymers in the form of the free acid or at least as salts have solubility or dispersibility in water.
  • copolymers to be used according to the invention can be present in the form of the free acids, in partially or completely neutralized form and in each case added to liquid detergents in one of these forms.
  • the copolymers which contain units of the monomers (a) and (b) in copolymerized form are water-soluble or water-dispersible at least in the form of the salts.
  • the liquid detergent formulations which contain the above-described partially esterified copolymers in an amount of 0.1 to 20, preferably 1 to 10% by weight, are usually made alkaline and have at least one anionic surfactant, a nonionic surfactant or as a further essential constituent their mixtures and water. These are clear aqueous solutions.
  • Suitable anionic surfactants are, for example, sodium alkylbenzenesulfonates, fatty alcohol sulfates and fatty alcohol polyglycol ether sulfates.
  • Individual compounds of this type are, for example, C8 to C12 alkyl benzene sulfonates, C12 to C16 alkane sulfonates, C12 to C16 alkyl sulfates, C12 to C16 alkyl sulfosuccinates and sulfated ethoxylated C12 to C16 alkanols.
  • anionic surfactants are sulfated fatty acid alkanolamines, fatty acid monoglycerides or reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.
  • anionic surfactants are fatty acid esters or fatty acid amides of hydroxy or amino carboxylic acids or sulfonic acids, such as, for example, the fatty acid sarcosides, glycolates, lactates, taurides or isothionates.
  • the anionic surfactants can be in the form of the sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine or other substituted amines.
  • the anionic surfactants also include the usual soaps, ie the alkali salts of the natural fatty acids.
  • Nonionic surfactants e.g. Addition products of 3 to 40, preferably 4 to 20, moles of ethylene oxide and 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used.
  • the addition products of 5 to 16 moles of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in are particularly important the alkyl residues.
  • non-fully or not fully water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol ether, alkylene diaminopolypropylene glycol and alkyl polypropylene glycols with 1 to 10 C atoms in the alkyl chain, in which the polypropylene glycol ether chain acts as a hydrophobic residue.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants. A reduction can also be achieved by adding non-surfactant-like organic substances.
  • the liquid, aqueous detergents contain 10 to 50% by weight of surfactants. You can contain an anionic or nonionic surfactant in the amount specified. However, it is also possible to use mixtures of anionic and nonionic surfactants. In such a case, the content of anionic surfactants in the liquid detergent is chosen from 10 to 30% by weight and the content of nonionic surfactants in the liquid detergent from 5 to 20% by weight, based on the total detergent formulation.
  • the liquid detergents contain the copolymers to be used according to the invention in amounts of 0.1 to 20, preferably 1 to 10% by weight and water in amounts of 10 to 60, preferably 20 to 50% by weight.
  • the liquid detergents may also contain other substances for modification. These include, for example, alcohols, such as ethanol, n-propanol and isopropanol. If used, these substances are used in amounts of 3 to 8% by weight, based on the total detergent formulation.
  • the liquid detergents may also contain hydrotropes. This includes compounds such as 1,2-propanediol, cumene sulfonate and toluene sulfonate. If such compounds are used to modify the liquid detergent, their amount, based on the total weight of the liquid detergent, is 2 to 5% by weight. In many cases, addition of complexing agents has also proven to be advantageous for modification.
  • Complexing agents are, for example, ethylenediaminetetraacetic acid, nitrilotriacetate and isoserinediacetic acid and phosphonates, such as aminotrismethylenephosphonic acid, hydroxyethanephosphonic acid, ethylenediaminetetraethylenephosphonic acid and their salts.
  • the complexing agents are used in amounts of 0 to 10% by weight, based on the liquid detergent.
  • the liquid detergents can also contain citrates, di- or triethanolamine, opacifiers, optical brighteners, enzymes, perfume oils and dyes. If these substances are used to modify the liquid detergents, they are present together in amounts of up to 5% by weight.
  • the liquid detergents according to the invention are preferably phosphate-free.
  • phosphates e.g. Pentasodium triphosphate and / or tetrapotassium pyrophosphate. If phosphates are used, the proportion of phosphates in the total formulation of the liquid detergent is 10 to 25% by weight.
  • liquid detergents described above have the advantage over the powder detergents that they are easy to dose and have a very good fat and oil dissolving power at greasy soiled laundry at lower washing temperatures.
  • Liquid detergents contain high levels of detergent substances that remove dirt from the textile fabric effect at wash temperatures of 40 to 60 ° C.
  • the dispersing properties of polymers have hitherto not been able to be used in aqueous liquid detergents because, as a result of high electrolyte concentrations in the detergents, it was not possible to obtain stable solutions with the polymers. With the copolymers to be used according to the invention, it is now possible to prepare stable aqueous solutions of liquid detergents and to significantly improve the washing properties of liquid detergents.
  • the effectiveness of the copolymers to be used according to the invention in liquid detergents is demonstrated in the examples with the aid of the stability of the liquid detergents and the primary and secondary washing action of these detergents.
  • the primary washing effect is the actual removal of dirt from the textile material.
  • the difference in the degree of whiteness between the unwashed and the washed textile material after washing is determined as the degree for dirt removal.
  • Cotton, cotton / polyester and polyester fabrics with standard soiling are used as the textile test material. After each wash, the degree of whiteness of the fabric in% remission is determined in an Elrephophotometer from Zeiss.
  • Secondary washing is understood to mean the effects which arise from the re-accumulation of the dirt detached from the fabric on the fabric in the wash liquor.
  • the secondary washing effect can only take place after several washes, e.g. 3, 5, 10 or even 20 washes become visible, which becomes increasingly gray (noticeable), i.e. Accumulation of dirt from the wash liquor on the fabric.
  • standard soiling fabric is washed several times together with white test fabric and the soiled fabric is renewed after each wash.
  • the dirt detached from the dirt fabric, which is drawn onto the white test fabric during washing causes a drop in the degree of whiteness that is measured.
  • the copolymers to be used in liquid detergents according to the invention or their water-soluble salts can also be used for the formulation of powder detergents.
  • the percentages in the examples are percentages by weight.
  • the K values were determined according to H. Fikentscher, Cellulose Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932).
  • the K values of the copolymers were measured in aqueous solution at 25.degree. C., a pH of 7.5 and a polymer concentration of 1% by weight of the Na salts of the copolymers.
  • a polymerization reactor which is provided with a stirrer, thermometer, cooler, nitrogen inlet and outlet devices and metering devices, 75 g of xylene, 13.5 g of maleic anhydride and 0.09 g of K 50 value (measured as one percent in cyclohexanone are added) 25 ° C) as a protective colloid and heated to 80 ° C in a weak stream of nitrogen.
  • the reaction mixture is polymerized for a further hour at 135 ° C., then cooled to room temperature and the copolymer is isolated from the low-viscosity suspension by filtering and drying. It is dried at 65 ° C under reduced pressure.
  • the K value of the copolymer neutralized to pH 7.5 with the sodium hydroxide solution is 54.
  • the reaction mixture is then kept at 135 ° C. for a further hour, then cooled, and the copolymer is isolated from the suspension by filtering off and then drying at 65 ° C. in vacuo.
  • the copolymer is soluble in water and can be neutralized by adding sodium hydroxide solution.
  • the K value of the sodium salt is 29.
  • the procedure is as described for the preparation of the copolymer 5, but the compound of the formula is used as component (b) of the copolymer
  • the copolymer thus obtainable has a K value in the form of the sodium salt of 37.
  • the amines listed in Table 1 are prepared by alkoxylating a C13 / C15 alcohol and then aminating the reaction product.
  • Table 1 shows the amounts of amine and the K values of the sodium salt of the copolymers.
  • the aqueous copolymer solutions were each treated with an acidic ion exchanger to remove free, unreacted amine.
  • the pH was then adjusted to about 7 by adding 50% aqueous sodium hydroxide solution.
  • Copolymers 1 to 13 described above were tested in the following two liquid detergent formulations A and B.
  • the secondary washing effect which is a measure of the graying of the fabric, was determined as follows:

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Claims (6)

  1. Utilisation de copolymères qui contiennent, à titre de constituants essentiels et incorporées par polymérisation,
    (a) 50 à 99% molaires d'unités d'acides monocarboxyliques en C₃ à C₈, monoéthyléniquement insaturés, d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, d'esters d'acides monocarboxyliques en C₃ à C₈, monoéthyléniquement insaturés, d'oléfines en C₂ à C₃₀, de styrène, d'alkyl(C₁-C₃)styrènes, d'éthers alkyl(C₁-C₂₈)vinyliques, d'esters vinyliques d'acides carboxyliques en C₁ à C₈, saturés, ou de mélanges d'unités de ces monomères et
    (b) 50 à 1% molaires d'unités d'amides d'acides carboxyliques en C₃ à C₈, monoéthyléniquement insaturés, possédant des groupes amide de la structure
    Figure imgb0041
     dans laquelle
    R¹   représente un radical
    Figure imgb0042
    R³, R⁴   représentent chacun un atome d'hydrogène, un radical CH₃ ou C₂H₅,
    R   représente un radical alkyle en C₁ à C₂₈,
    R²   représente H ou R¹ et
    n   a une valeur qui varie de 2 à 100,
    qui possèdent des valeurs K de 8 à 200 (déterminées selon H. Fikentscher à 25°C, en solution aqueuse, à un pH de 7,5 et à une concentration en polymère de 1% en poids), ou de sels de ces copolymères, à titre de détergents liquides, en une proportion de 0,1 à 20% en poids.
  2. Procédé suivant la revendication 1, caractérisé en ce que les polymères contiennent, à titre de constituants essentiels du composant
    (a) des mélanges d'unités d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, et d'hémiesters d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, d'esters d'acides monocarboxyliques en C₃ à C₈, monoéthyléniquement insaturés, d'oléfines en C₂ à C₃₀, de styrène, d'alkyl(C₁-C₃)styrènes, d'éthers alkyl(C₁-C₂₈)vinyliques, d'esters vinyliques d'acides monocarboxyliques en C₁ à C₈, saturés, d'acides monocarboxyliques en C₃ à C₈, monoéthyléniquement insaturés, ou de leurs sels,
    incorporés par polymérisation.
  3. Utilisation suivant la revendication 1 ou 2, caractérisé en ce que les copolymères contiennent, à titre de constituants essentiels des composants
    (a) des mélanges d'unités d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, et d'hémiesters d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, d'esters d'acides monocarboxyliques en C₃ à C₈, monoéthyléniquement insaturés, d'oléfines en C₂ à C₃₀, de styrène, d'alkyl(C₁-C₃)styrènes, d'éthers alkyl (C₁-C₂₈)vinyliques, d'esters vinyliques d'acides monocarboxyliques en C₁ à C₈, saturés, d'acides monocarboxyliques en C₃ à C₈, monoéthyléniquement insaturés, ou de leurs sels et
    (b) 50 à 1% molaires d'unités d'amides d'acides carboxyliques en C₃ à C₈, monoéthyléniquement insaturés, possédant des groupes amide de la structure
    Figure imgb0043
     dans laquelle
    R¹   représente un radical
    Figure imgb0044
    R³, R⁴   représentent chacun un atome d'hydrogène, un radical CH₃ ou C₂H₅,
    R   représente un radical alkyle en C₁ à C₂₈,
    R²   représente H ou R¹ et
    n   a une valeur qui varie de 2 à 100,
    incorporés par polymérisation.
  4. Utilisation suivant l'une quelconque des revendications 1 à 3, caractérisée en ce que l'on peut obtenir les copolymères par la copolymérisation
    (a) de mélanges d'anhydrides d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés et d'hémiesters d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, d'esters d'acides carboxyliques en C₃ à C₈, monoéthyléniquement insaturés, d'oléfines en C₂ à C₃₀, de styrène, d'alkyl(C₁-C₃)styrènes, d'éthers alkyl(C₁-C₂₈)vinyliques, d'esters vinyliques d'acides monocarboxyliques en C₁ à C₈, insaturés, ou de leurs sels, avec les composés du composant (b), dans des solvants organiques, en présence d'amorceurs de polymérisation et l'hydrolyse des radicaux anhydride des copolymères.
  5. Utilisation suivant la revendication 1, caractérisée en ce que l'on peut obtenir les copolymères par la copolymérisation
    (a) d'acides monocarboxyliques en C₃ à C₈, monoéthyléniquement insaturés, d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, ou d'esters vinyliques d'acides carboxyliques en C₁ à C₈, saturés,
    avec des composés du composant (b), en solution aqueuse et en présence d'amorceurs de polymérisation.
  6. Compositions aqueuses liquides de détergents, qui contiennent, à titre de constituants essentiels,
    (1) au moins un agent tensioactif ou surfactif anionique, un agent tensioactif ou surfactif non ionique, ou leurs mélanges,
    (2) un copolymère et
    (3) de l'eau,
    caractérisées en ce qu'elles contiennent, à titre de constituant (2) des copolymères en une proportion de 0,1 à 20% en poids et en ce que les copolymères (2) contiennent, à titre de constituants essentiels et incorporées par polymérisation,
    (a) 50 à 99% molaires d'unités d'acides monocarboxyliques en C₃ à C₈, monoéthyléniquement insaturés, d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, d'acides dicarboxyliques en C₄ à C₈, monoéthyléniquement insaturés, d'esters d'acides monocarboxyliques en C₃ à C₈, monoéthyléniquement insaturés, d'oléfines en C₂ à C₃₀, de styrène, d'alkyl(C₁-C₃)styrènes, d'éthers alkyl(C₁-C₂₈)-vinyliques, d'esters vinyliques d'acides carboxyliques en C₁ à C₈, saturés, ou de mélanges d'unités de ces monomères et
    (b) 50 à 1% molaires d'unités d'amides d'acides carboxyliques en C₃ à C₈, monoéthyléniquement insaturés, possédant des groupes amide de la structure
    Figure imgb0045
     dans laquelle
    R¹   représente un radical
    Figure imgb0046
    R³, R⁴   représentent chacun un atome d'hydrogène, un radical CH₃ ou C₂H₅,
    R   représente un radical alkyle en C₁ à C₂₈,
    R²   représente H ou R¹ et
    n   a une valeur qui varie de 2 à 100,
    qui possèdent des valeurs K de 8 à 200 (déterminées selon H. Fikentscher à 25°C, en solution aqueuse, à un pH de 7,5 et à une concentration en polymère de 1% en poids), ou de sels de ces copolymères.
EP89120522A 1988-11-10 1989-11-06 Utilisation de copolymères estérifiés partiellement pour compositions détergentes liquides Expired - Lifetime EP0368214B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3838093 1988-11-10
DE3838093A DE3838093A1 (de) 1988-11-10 1988-11-10 Verwendung von copolymerisaten als zusatz zu fluessigwaschmitteln

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Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE902759A1 (en) * 1990-02-16 1991-08-28 Rohm & Haas Liquid cleaning compositions containing water-soluble¹polymer
DE4016002A1 (de) * 1990-05-18 1991-11-21 Basf Ag Verwendung von wasserloeslichen oder wasserdispergierbaren gepfropften proteinen als zusatz zu wasch- und reinigungsmitteln
DE4023820A1 (de) * 1990-07-27 1992-01-30 Basf Ag Verwendung von n-(alkyloxy-polyalkoxymethyl)carbonamid-gruppen aufweisenden polymerisaten als zusatz zu wasch- und reinigungsmitteln
DE4034334A1 (de) * 1990-10-29 1992-04-30 Basf Ag Verwendung von weinsaeure einkondensiert enthaltenden polyestern als waschmittelzusatz, verfahren zur herstellung der polyester und polyester aus weinsaeure und tetracarbonsaeuren
US5409629A (en) * 1991-07-19 1995-04-25 Rohm And Haas Company Use of acrylic acid/ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents
DE4142130A1 (de) * 1991-12-20 1993-06-24 Basf Ag Verwendung von polyacetalen auf basis von vinylethern und dihydroxyverbindungen in wasch- und reinigungsmitteln und polyacetale
ES2056042T3 (es) * 1992-12-28 1997-04-01 Sika Ag Copolimeros solubles en agua de acetato de vinilo y acidos maleamicos. uso como fluidizadores o reductores de agua de amplio intervalo para suspensiones acuosas.
DE4319935A1 (de) * 1993-06-16 1994-12-22 Basf Ag Verwendung von Glycin-N,N-diessigsäure-Derivaten als Komplexbildner für Erdalkali- und Schwermetallionen
EP0630965A1 (fr) * 1993-06-23 1994-12-28 The Procter & Gamble Company Compositions détergentes liquides concentrées pour surfaces dures contenant des copolymères d'acide maleique-oléfine
US5294692A (en) * 1993-06-30 1994-03-15 National Starch And Chemical Investment Holding Corporation Associative monomers and polymers
GB9315854D0 (en) * 1993-07-30 1993-09-15 Nat Starch Chem Corp Improvements in or relating to hydrotropes
DE4330971A1 (de) * 1993-09-13 1995-03-16 Basf Ag Copolymerisate sowie deren Reaktionsprodukte mit Aminen als Kraftstoff- und Schmierstoffadditiv
US5486307A (en) * 1993-11-22 1996-01-23 Colgate-Palmolive Co. Liquid cleaning compositions with grease release agent
US5573702A (en) * 1993-11-22 1996-11-12 Colgate-Palmolive Co. Liquid cleaning compositions with grease release agent
US5599784A (en) * 1994-03-04 1997-02-04 National Starch And Chemical Investment Holding Corporation Aqueous lamellar detergent compositions with hydrophobically capped hydrophilic polymers
US5489397A (en) * 1994-03-04 1996-02-06 National Starch And Chemical Investment Holding Corporation Aqueous lamellar detergent compositions with hydrophobically terminated hydrophilic polymer
US5534183A (en) * 1994-07-14 1996-07-09 Basf Corporation Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers
US5723427A (en) * 1994-12-05 1998-03-03 Colgate-Palmolive Company Granular detergent compositions containing deflocculating polymers and processes for their preparation
DE19755295A1 (de) * 1997-12-12 1999-06-17 Agfa Gevaert Ag Entwickler für bestrahlte, strahlungsempfindliche Aufzeichnungsmaterialien
US6100016A (en) * 1999-09-14 2000-08-08 Agfa-Gevaert Ag Developer for irradiated, radiation-sensitive recording materials
US6488808B2 (en) * 2001-01-19 2002-12-03 Huntsman Petrochemical Corporation Styrene copolymers in de-inking
CA2506422A1 (fr) * 2002-11-22 2004-06-10 Basf Aktiengesellschaft Synthese enzymatique d'acrylates de polyol
US20050176617A1 (en) * 2004-02-10 2005-08-11 Daniel Wood High efficiency laundry detergent
US9279097B1 (en) 2014-08-14 2016-03-08 Ecolab USA, Inc. Polymers for industrial laundry detergents
JP6953416B2 (ja) 2016-02-18 2021-10-27 ヴァーディザン ライフ サイエンシズ ユー．エス．，リミテッド ライアビリティー カンパニー リン酸固定を最小限にするポリマー組成物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE637821A (fr) * 1963-10-21
DE2056813A1 (de) * 1970-11-19 1972-05-25 Chemische Werke Hüls AG, 4370 Mari Waschmittel mit einem Gehalt an einer Gerustsubstanz
US4423199A (en) * 1982-09-30 1983-12-27 Rohm And Haas Company Acrylamide containing emulsion copolymers for thickening purposes
DE3305637A1 (de) * 1983-02-18 1984-08-23 Basf Ag, 6700 Ludwigshafen Copolymerisate, ihre herstellung und ihre verwendung als hilfsmittel in wasch- und reinigungsmitteln
LU84752A1 (fr) * 1983-04-15 1984-11-28 Oreal Composition lavante et moussante a base d'agents tensio-actifs et de polymeres anioniques
GB8311002D0 (en) * 1983-04-22 1983-05-25 Unilever Plc Detergent compositions
GB8333815D0 (en) * 1983-12-20 1984-02-01 Procter & Gamble Fabric softeners
DE3528460A1 (de) * 1985-08-08 1987-02-19 Basf Ag Verwendung von neutralisierten und amidierten, carboxylgruppen enthaltenden polymerisaten als zusatz zu waschmitteln und reinigungsmitteln
PH25826A (en) * 1986-03-14 1991-11-05 Johnson & Son Inc S C Prespotter laundry detergent
DE3716544A1 (de) * 1987-05-16 1988-11-24 Basf Ag Verwendung von wasserloeslichen copolymerisaten, die monomere mit mindestens zwei ethylenisch ungesaettigten doppelbindungen einpolymerisiert enthalten, in wasch- und reinigungsmitteln
DE3716543A1 (de) * 1987-05-16 1988-11-24 Basf Ag Verwendung von wasserloeslichen copolymerisaten, die monomere mit mindestens zwei ethylenisch ungesaettigten doppelbindungen einpolymerisiert enthalten, in wasch- und reinigungsmitteln

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DE58908529D1 (de) 1994-11-24
US5009805A (en) 1991-04-23
AU620465B2 (en) 1992-02-20
EP0368214A2 (fr) 1990-05-16
AU4450589A (en) 1990-05-17
CA2001660A1 (fr) 1990-05-10
ES2061885T3 (es) 1994-12-16
JPH02173095A (ja) 1990-07-04
EP0368214A3 (en) 1990-11-07
ATE113068T1 (de) 1994-11-15
DE3838093A1 (de) 1990-05-17

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