EP2534234A1 - Utilisation d'un copolymère comme épaississant dans les lessives liquides à tendance au grisage réduite - Google Patents

Utilisation d'un copolymère comme épaississant dans les lessives liquides à tendance au grisage réduite

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Publication number
EP2534234A1
EP2534234A1 EP11702844A EP11702844A EP2534234A1 EP 2534234 A1 EP2534234 A1 EP 2534234A1 EP 11702844 A EP11702844 A EP 11702844A EP 11702844 A EP11702844 A EP 11702844A EP 2534234 A1 EP2534234 A1 EP 2534234A1
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EP
European Patent Office
Prior art keywords
acid
units
weight
copolymer
ethylenically unsaturated
Prior art date
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EP11702844A
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German (de)
English (en)
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EP2534234B1 (fr
Inventor
Christofer Arisandy
Kati Schmidt
Reinhold Leyrer
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BASF SE
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BASF SE
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Priority to EP11702844.9A priority Critical patent/EP2534234B1/fr
Priority to PL11702844T priority patent/PL2534234T3/pl
Publication of EP2534234A1 publication Critical patent/EP2534234A1/fr
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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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the invention relates to the use of an alkali-soluble copolymer as thickener in liquid laundry detergents and a liquid washing or cleaning composition.
  • Transparent viscous liquid detergent compositions are becoming increasingly popular. There is therefore a need for thickeners which have high transparency in the dissolved, d. H. have neutralized state and show no turbidity when incorporated into surfactant-containing formulations.
  • thickeners are desirable which impart a very high viscosity to the thickened medium at rest, and a low viscosity when subjected to high shear forces.
  • alkali-soluble thickeners are associative thickeners.
  • Associative thickeners are water-soluble polymers and have surfactant-like hydrophobic constituents which are capable of associating with both themselves and other hydrophobic species in a hydrophilic, particularly aqueous medium, i. to interact.
  • the resulting associative network thickens or gels the medium.
  • EP-A-0 013 836 discloses emulsion copolymers containing (i) 20 to 69.5% by weight.
  • the copolymers serve as thickeners for paints, detergents and the like.
  • WO 99/65958 describes alkali-soluble thickeners comprising the reaction product of an unsaturated carboxylic acid, a monoethylenically unsaturated monomer and a hydrophobic alkoxylated macromonomer.
  • the monoethylenically unsaturated monomer includes a methyl group; it is preferably methyl acrylate.
  • These polymers should already be soluble at pH 4.5 to 6.0 and are therefore suitable for cosmetic products.
  • WO 2006/016035 relates to the use of a water-soluble acrylic polymer as thickener in pigmented aqueous preparations.
  • the acrylic polymer consists of an ethylenically unsaturated monomer having a carboxyl function, an ethylenically unsaturated nonionic monomer and an ethylenically unsaturated oxyalkylated monomer terminated with a hydrophobic non-aromatic branched chain of 10 to 24 carbon atoms.
  • One embodiment relates to a polymer in which the ethylenically unsaturated nonionic monomer is composed of ethyl acrylate and butyl acrylate (Example 7).
  • WO 2009/019225 discloses an associative thickener with copolymerized units of at least one ethylenically unsaturated carboxylic acid, at least one nonionic ethylenically unsaturated surfactant monomer, at least one C 1 -C 2 -alkyl methacrylate and at least one C 2 -C 4 -alkyl acrylate, the average being averaged over the number of alkyl groups of the alkyl acrylate Alkyl chain length is 2.1 to 4.0. Solutions of the associative thickener or its formulations with a high surfactant content are highly transparent and have a high thickening effect with simultaneous high shear thinning.
  • the term "graying” is understood to mean the gray coloration of textiles during washing, which is brought about, inter alia, by a resumption of already detached dirt on the fabric in a finer distribution. Rebuilding is likely triggered by electrostatic forces. The extent of rebuilding depends, among other things, on the type of fabric and soil, the degree of contamination of the fabric, the amount of water in the washing process and the degree of mechanical movement in the washing drum. Components of the detergent itself can cause graying by z. B. deposit on the fabric or promote the recovery of dirt. It is therefore desirable that the thickeners used in liquid detergents cause as little as possible graying of the laundry after the washing process.
  • the object is achieved by using a copolymer as a thickener in liquid laundry detergents, wherein the copolymer a) at least 15% by weight of units of an ethylenically unsaturated carboxylic acid, b) at least 15% by weight of units of a C 4 -C 8 -alkyl acrylate,
  • c) contains less than 5 wt .-% units of methyl methacrylate.
  • the invention also relates to a liquid detergent composition containing the above-defined copolymer. It has surprisingly been found that thickeners which contain a high proportion of C 1 -C 2 -alkyl methacrylate units, in particular methyl methacrylate units, can impair the light remission of the washed laundry. A reduced light remission is perceived as graying. Surfactant monomers are often commercially available as a solution in methyl methacrylate. The copolymers obtained using these solutions inevitably contain copolymerized units of methyl methacrylate.
  • the copolymer used according to the invention contains less than 5% by weight, preferably less than 2% by weight, of units of methyl methacrylate and is particularly preferably substantially free of units of methyl methacrylate.
  • the copolymer contains less than 5% by weight, preferably less than 2% by weight, of units of C 1 -C 2 -alkyl methacrylates, and is more preferably substantially free of units of C 1 -C 2 -alkyl methacrylates.
  • the copolymer comprises a) from 15 to 50% by weight of units and more preferably from 28 to 35% by weight of units of an ethylenically unsaturated carboxylic acid,
  • the copolymer may contain copolymerized units of a Ci-C3-alkyl acrylate, for. In a range of 5 to 40% by weight, preferably in a range of 25 to 35% by weight.
  • the copolymer may also contain copolymerized units of a nonionic, ethylenically unsaturated surfactant monomer, e.g. In a range of 0.1 to 5 wt%, preferably in a range of 0.5 to 3 wt%.
  • the ethylenically unsaturated carboxylic acid is generally a monoethylenically unsaturated mono- or dicarboxylic acid having 3 to 8 carbon atoms.
  • Suitable ethylenically unsaturated carboxylic acids are, for. B. selected from acrylic acid, methacrylic acid, itaconic acid and maleic acid. Of these, methacrylic acid is particularly preferred.
  • Suitable C4-C8 alkyl acrylates are n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate and n-octyl acrylate, preferably n-butyl acrylate.
  • Suitable C 1 -C 3 -alkyl acrylates are methyl acrylate, ethyl acrylate, n-propyl acrylate and isopropyl acrylate, preferably ethyl acrylate.
  • Suitable nonionic, ethylenically unsaturated surfactant monomers are known per se. It is z. B. order
  • esters of ethylenically unsaturated carboxylic acids and nonionic surfactants (b) esters of ethylenically unsaturated carboxylic acids and nonionic surfactants,
  • Suitable nonionic surfactants are preferably alkoxylated C 6 -C 30 alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. At least 2 per mole of alcohol are used, eg. B. 2 to 100, preferably 3 to 20 moles of at least one C2-C4
  • Alkylene oxide Different alkylene oxide units can be arranged in blocks or randomly distributed.
  • the alkylene oxide used is preferably ethylene oxide and / or propylene oxide.
  • Another class of suitable nonionic surfactants are alkylphenol ethoxylates having C6-C14 alkyl chains and from 5 to 30 moles of ethylene oxide units.
  • the nonionic ethylenically unsaturated surfactant monomer has the general formula
  • R-O- (CH 2 -CHR'-O) n -CO-CR " CH 2 where R is C 6 -C 30 -alkyl, preferably C 2 -C 22 -alkyl,
  • R ' is hydrogen or methyl, preferably hydrogen, R "is hydrogen or methyl, preferably methyl, and n is an integer from 2 to 100, preferably 3 to 50, stands.
  • the repeating units in the bracket are derived from ethylene oxide or propylene oxide.
  • the meaning of R 'in each repeat unit is independent of other repeat units.
  • Different alkylene oxide units can be arranged in blocks or randomly distributed.
  • the aqueous dispersion generally contains an anionic and / or a nonionic emulsifier.
  • Typical emulsifiers are anionic emulsifiers such. Sodium lauryl sulfate, sodium tridecyl ether sulfates, dioctyl sulfosuccinate sodium salt and sodium salts of alkylaryl polyether sulfonates; and nonionic emulsifiers such.
  • Preferred emulsifiers have the general formula
  • R ' is hydrogen or methyl
  • X is hydrogen or S0 3 M
  • M is hydrogen or an alkali metal
  • n is an integer from 2 to 100
  • the copolymer can be prepared in various ways, preferably by emulsion polymerization.
  • a suitable polymerization initiator is used for polymerization.
  • Thermally activatable radical polymerization initiators are preferred.
  • Suitable thermally activatable radical initiators are especially those of the peroxy and azo type. These include, among others, hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-bis (hydroperoxy) hexane, perbenzoic acid, t-butyl Butyl peroxypivalate, t-butyl peracetate, dilauroyl peroxide, dicapryloyl peroxide, distearoyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, didecyl peroxydicarbonate, dieicosyl peroxydicarbonate, di-t-butyl perbenzoate, azobisisobutyronitrile, 2,2'-azobis-2,4-
  • the persulfates (peroxodisulfates), especially sodium persulfate, are the most preferred.
  • the initiator is used in an amount sufficient to initiate the polymerization reaction.
  • the initiator is usually used in an amount of about 0.01 to 3 wt .-%, based on the total weight of the monomers used.
  • the amount of initiator is preferably about 0.05 to 2 wt .-% and in particular 0.1 to 1 wt .-%, based on the total weight of the monomers used.
  • the emulsion polymerization is usually carried out at 35 to 130 ° C. It can be carried out both as a batch process and in the form of a feed process.
  • the feed-in procedure in which at least part of the polymerization initiator and optionally a part of the monomers are initially charged, is heated to the polymerization temperature and then the remainder of the polymerization batch, usually via several separate feeds, one or more of which is monoserated in pure or emulsified form Contain mold, continuously or stepwise while maintaining the polymerization supplies.
  • the monomer feed takes place in the form of a monomer emulsion. Additional polymerization initiator can be added in parallel to the monomer feed.
  • the total amount of initiator is given, i. H. no additional initiator feed takes place parallel to the monomer feed. It has surprisingly been found that this procedure leads to particularly high transparency of the associative thickener.
  • the thermally activatable radical polymerization initiator is completely introduced and the monomer mixture, preferably in the form of a monomer emulsion, is allowed to run in.
  • the template is brought to the activation temperature of the thermally activatable radical polymerization initiator or a higher temperature.
  • the activation temperature is considered to be the temperature at which at least half of the initiator has decomposed after one hour.
  • the copolymer is obtained by polymerizing a monomer mixture in the presence of a redox initiator.
  • a redox initiator system comprises at least one oxidizing agent component and at least one reducing agent component, wherein heavy metal ions are preferably present in addition as catalyst in the reaction medium, for example cerium, manganese or iron (II) salts.
  • Suitable oxidizing agent components are, for example, peroxides and / or hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, diisopropylphenyl hydroperoxide, dicyclohexyl percarbonate, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide. Hydrogen peroxide and tert-butyl hydroperoxide are preferred.
  • Suitable reducing agent components are alkali metal sulfites, alkali metal dithionites, alkali metal hyposulfites, sodium hydrogen sulfite, Rongalit C (sodium formaldehyde sulfoxylate), mono- and dihydroxyacetone, sugars (e.g., glucose or dextrose), ascorbic acid and its salts, acetone bisulfite adduct and / or an alkali metal salt of hydroxymethanesulfinic acid. Ascorbic acid is preferred.
  • iron (II) salts e.g. Iron (II) sulfate, stannous salts, e.g. Tin (II) chloride, titanium (III) salts such as titanium (III) sulfate.
  • the amounts of oxidizing agent are from 0.001 to 5.0 wt .-%, preferably from 0.005 to 1, 0 wt .-% and particularly preferably from 0.01 to 0.5 wt .-%, based on the total weight of the monomers used.
  • Reducing agents are used in amounts of from 0.001 to 2.0% by weight, preferably from 0.005 to 1.0% by weight and more preferably from 0.01 to 0.5% by weight, based on the total weight of the used monomers.
  • a particularly preferred redox initiator system is the system sodium peroxodisulfate / ascorbic acid, z. B. 0.001 to 5.0 wt .-% sodium peroxodisulfate and 0.001 to 2.0 wt .-% ascorbic acid, in particular 0.005 to 1, 0 wt .-% sodium peroxodisulfate and 0.005 to 1, 0 wt .-% ascorbic acid, particularly preferably 0 , 01 to 0.5 wt .-% sodium peroxodisulfate and 0.01 to 0.5 wt .-% ascorbic acid.
  • Another particularly redox initiator system is the system t-butyl hydroperoxide / hydrogen peroxide / ascorbic acid, z. B. 0.001 to 5.0 wt .-% t-butyl hydroperoxide, 0.001 to 5.0 wt .-% hydrogen peroxide and 0.001 to 2.0 wt .-% ascorbic acid, in particular 0.005 to 1, 0 wt .-% t-butyl hydroperoxide , 0.005 to 1, 0 wt .-% hydrogen peroxide and 0.005 to 1, 0 wt .-% ascorbic acid, particularly preferably 0.01 to 0.5 % By weight of t-butyl hydroperoxide, 0.01 to 0.5% by weight of hydrogen peroxide and 0.01 to 0.5% by weight of ascorbic acid.
  • a monomer mixture is allowed to run into an aqueous receiver, preferably in the form of a monomer emulsion.
  • an oxidizing agent component and a reducing agent component of the redox initiator system are allowed to run.
  • a portion of the oxidizer component of the redox initiator system is provided.
  • the copolymer dispersion may be subjected to chemical deodorization.
  • further initiator e.g. added a redox initiator.
  • Redox initiators suitable for chemical deodorization comprise as oxidizing component, for example, at least one organic peroxide and / or hydroperoxide, such as hydrogen peroxide, tert-butyl peroxide, cumene hydroperoxide, pinane hydroperoxide, diisopropylphenyl hydroperoxide, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide, and, for example, iron (II) as reducing component. salts, alkali metal sulfites, ascorbic acid, acetone bisulfite adduct and / or an alkali metal salt of hydroxymethanesulfinic acid.
  • the copolymer dispersion generally has a solids content of from 25 to 60% by weight, in particular from about 30 to 50% by weight.
  • the copolymer dispersion In unneutralized form, the copolymer dispersion has a relatively low viscosity. It is therefore easy to handle and can be easily dosed or pumped.
  • z. B. to a pH of more than 5.5, preferably more than 6, in particular 8 to 9, the copolymer is soluble and the viscosity of the aqueous medium medium increases sharply.
  • Suitable neutralizing agents are, for. For example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, amines such as triethylamine, triethanolamine, monoethanolamine, and other alkaline materials.
  • the liquid detergents or cleaners contain surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.
  • surfactant s
  • anionic, nonionic, cationic and / or amphoteric surfactants preference is given to mixtures of anionic and nonionic surfactants.
  • Washing or cleaning agent is preferably 5 to 60 wt .-% and particularly preferably 15 to 40 wt .-%, based on the total liquid detergent or cleaning agent.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue is linear or preferably methyl-branched in the 2-position may be or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO, 4 EO or 7 EO, Ce-Cn-alcohol with 7 EO, C 13 -C 15-
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly.
  • Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • 1 0 (G) x (1) can be used as further nonionic surfactants, alkyl glycosides of the general formula (1) R are used, wherein R 1 is a primary linear or methyl-branched, more particularly 2-methyl-branched, aliphatic radical containing 8 to 22, preferably 12 to 18 carbon atoms and G is a glycoside unit having 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially Fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula (2),
  • R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula
  • R 4 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 5 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms
  • R 6 is a linear, branched or is cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1 -C 4 -alkyl or phenyl radicals
  • [Z] 1 being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups , or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] 1 is preferably obtained by reductive amination of a sugar, for example glucose, fructose, malactose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, malactose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted, for example, according to WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.
  • the content of nonionic surfactants in the liquid detergents or cleaners is preferably 1 to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by weight, in each case based on the total agent.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • surfactants of the sulfonate type preferably C9-C13 alkylbenzenesulfonates, Olefinsulfonate, i. Mixtures of alkene and Hydroxyalkansul- fonates and disulfonates, as obtained for example from Ci2-Ci8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • alkanesulfonates which are obtained from C 12 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • Fatty acid glycerol esters are the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol - 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.
  • Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters secondary Alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of the aforementioned chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous degradation behavior to the adequate compounds based on oleochemical raw materials.
  • sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C7-C2i alcohols such as 2-methyl-branched Cg-Cn alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci2-Ci8 fatty alcohols with 1 up to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • alkylsulfosuccinic acid which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Ce-Cie fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di-triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of preferred liquid washing or cleaning agents in anionic surfactants is 2 to 30 wt .-%, preferably 2 to 40 wt .-% and in particular 5 to 22 wt .-%, each based on the total agent. It is particularly preferred that the amount of fatty acid soap is at least 2% by weight and more preferably at least 4% by weight and especially preferably at least 6% by weight.
  • the viscosity of the liquid detergents or cleaners can be measured by conventional standard methods (for example Brookfield Viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 100 to 5000 mPas.
  • Preferred agents have viscosities from 300 to 4000 mPas, with values between 1000 and 3000 mPas being particularly preferred.
  • the liquid detergents or cleaners may contain other ingredients which further enhance the performance and / or aesthetics of the liquid detergent or conditioner.
  • preferred agents in addition to the associative thickener and surfactant (s) contain one or more of builders, bleaches, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, hydrotopes , Foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and impregnating agents, swelling and sliding agents and UV absorbers ,
  • Suitable builders or builders which may be present in the liquid detergents or cleaners are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Suitable low molecular weight polycarboxylates as organic builders are, for example: C4-C20-D1-, -tri- and -tetracarboxylic acids such as succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl- and alkylene-succinic acids with C2-C16-alkyl or -alkylene radicals; C 4 -C 20 -hydroxycarboxylic acids, such as, for example, malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
  • Aminopolycarboxylates such as e.g. Nitrilotriacetic acid, methylglycinediacetic acid, alanine diacetic acid, ethylenediaminetetraacetic acid and serinediacetic acid;
  • Salts of phosphonic acids e.g. Hydroxyethanediphosphonic acid, ethylenediaminetetra (methylenephosphonate) and diethylenetriaminepenta (methylenephosphate).
  • Suitable oligomeric or polymeric polycarboxylates as organic builders are, for example:
  • Suitable unsaturated C 4 -C 8 -dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid (methylmaleic acid). Preference is given to maleic acid.
  • Group (i) comprises monoethylenically unsaturated Cs-Cs monocarboxylic acids, e.g. Acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Preferably, from group (i), acrylic acid and methacrylic acid are used.
  • Group (ii) comprises monoethylenically unsaturated C 2 -C 22 -olefins, vinyl-alkyl ethers having C 1 -C 8 -alkyl groups, styrene, vinyl esters of C 1 -C 6 -carboxylic acid, (meth) acrylamide and vinyl pyrrolidone. From the group (ii), preference is given to using C 2 -C 6 -olefins, vinylalkylene ethers having C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate.
  • Group (iii) comprises (meth) acrylic esters of C 1 -C 8 -alcohols, (meth) acrylonitrile, (meth) acrylamides, (meth) acrylamides of C 1 -C 8 -amines, N-vinylformamide and vinylimidazole.
  • polymers of group (ii) contain copolymerized vinyl esters, this may also be partially or completely hydrolyzed to vinyl alcohol structural units.
  • Suitable copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 and SE-A 43 13 909.
  • Suitable copolymers of dicarboxylic acids are preferably organic copolymers: copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molecular weights of 10,000 to 150,000;
  • Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates are also suitable as organic builders.
  • Suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and Vinyl acetic acid and mixtures of acrylic acid and maleic acid grafted in amounts of 40 to 95 wt .-%, based on the component to be grafted.
  • Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).
  • Copolymers alkoxylated mono- or polybasic Ci-C22 alcohols, see. US 4,746,456.
  • Grafted degraded or degraded reduced starches and grafted polyethylene oxides are preferably used from this group, with from 20 to 80% by weight of monomers, based on the grafting component, being used in the graft polymerization.
  • a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used.
  • Polyglyoxylic acids as organic builders are described, for example, in EP-B 0 001 004, US Pat. No. 5,399,286, DE-A 41 06 355 and EP-A 0 656 914.
  • the end groups of the polyglyoxylic acids may have different structures.
  • Polyamidocarboxylic acids and modified polyamidocarboxylic acids as organic builders are known, for example, from EP-A 0 454 126, EP-B 0 51 1037, WO-A
  • Polyaspartic acid or cocondensates of aspartic acid with further amino acids, C4-C25-mono- or -dicarboxylic acids and / or C4-C25-mono- or diamines are preferably also used as organic builders. Particular preference is given to using polyaspartic acids prepared in phosphorus-containing acids and modified with C 6 -C 22 -mono- or -dicarboxylic acids or with C 6 -C 22 -mono- or -diamines.
  • Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds as organic builders are known, for example, from WO-A 93/22362 and WO-A 92/16493. Such condensates containing carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.
  • bleaches are of particular importance.
  • Further bleaches that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the detergents or cleaners.
  • Suitable bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) 1 N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diamine cetoxy-2,5-dihydrofuran.
  • TAED tetraacetyl
  • bleach catalysts can also be incorporated into the liquid detergents or cleaners.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can also be used as bleach catalysts.
  • Suitable enzymes are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, celluloses or other glycosyl hydrolases and mixtures of the enzymes mentioned. 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.
  • Bacillus subtilis Bacillus licheniformis
  • Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or 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 a-amylases, iso-amylases, pullulanases and pectinases.
  • Cellulases used are preferably cellobiohydrolases, endoglucanases and .beta.-glucosidases, which are also cellobiases, or mixtures thereof. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by means of targeted mixtures of the cellulases.
  • the enzymes may be adsorbed to carriers to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2.5 wt .-%.
  • electrolytes from the group of inorganic salts a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgC in the compositions is preferred.
  • the proportion of electrolytes in the agents is usually 0.5 to 5 wt .-%.
  • Non-aqueous solvents which can be used in the liquid detergents or cleaners, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible in the specified concentration range with water.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl -, -ethyl or -propyl ether, dipropylene glycol monomethyl or - ethyl ether, di-isopropylene glycol monomethyl or -ethyl ether, methoxy, ethoxy or Butoxytriglykol, i-butoxy-ethoxy-2-propanol, 3-methyl-3-methoxybutanol , Propylene glycol t
  • pH adjusters may be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. Usually, the amount of these adjusting agents does not exceed 7% by weight of the total formulation.
  • dyes In order to improve the aesthetic impression of the liquid washing or cleaning agents, they can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • Suitable foam inhibitors which can be used in the liquid detergents or cleaners are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable anti-redeposition agents which are also referred to as "soil repellents" are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case on the nonionic cellulose ether.
  • Suitable soil-release polymers are, for example, polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids; Polyesters of unilaterally end-capped polyethylene oxides with dihydric and / or polyhydric alcohols and dicarboxylic acid, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modifiable ornamented derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • polyesters are known, for example from US 3,557,039, GB-A 1 1 54 730, EP-A 0 185 427, EP-A 0 241 984, EP-A 0 241 985, EP-A 0 272 033 and US-A 5,142,020 .
  • Further suitable soil-release polymers are amphiphilic graft copolymers or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (compare US Pat. Nos. 4,746,456, 4,846,995, DE-A 37 1 1 299, 4,904,408, 4,846,994 and 4,849,126) or modified Celluloses such as methylcellulose, hydroxypropylcellulose or carboxymethylcellulose.
  • Optical brighteners can be added to the liquid detergents or cleaners to eliminate graying and yellowing of the treated fabrics. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure with the yellowness of the grayed or yellowed wash White results.
  • Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavone acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, Benzoxazole, benzisoxazole and benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • the optical brighteners are usually used in amounts of between 0.03 and 0.3 wt .-%, based on the finished composition.
  • 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 glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions.
  • fabrics, particularly rayon, rayon, cotton and blends thereof can tend to wrinkle because the individual fibers are susceptible to flexing, buckling, squeezing and squeezing across the grain, the compositions may contain synthetic crease inhibitors.
  • liquid washing or cleaning agents may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate.
  • compositions may contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • External antistatics are for example in the patent applications
  • the lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed herein are useful as antistatics for textile fabrics or as an additive to laundry detergents, with a softening effect being additionally achieved.
  • 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-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
  • the liquid detergents or cleaning agents may also contain UV absorbers, which wick on the treated fabrics and improve the light fastness of the fibers.
  • UV absorbers which wick on the treated fabrics and improve the light fastness of the fibers.
  • Compounds having 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-specific urocanic acid.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • MGDA methylglycinediacetic acid
  • alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates which are present in preferred liquid detergents or cleaners in amounts of from 0.01 to 2.5% by weight, preferably 0.02 to 2% by weight and in particular 0.03 to 1, 5 wt .-% are included.
  • These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylene phosphonic acid) (ATMP), diethylene triamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1 , 2,4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts.
  • organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylene phosphonic acid) (ATMP), diethylene triamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1 , 2,4
  • the resulting aqueous liquid detergents or cleaning agents have no sediment; in a preferred embodiment they are transparent or at least least translucent.
  • the aqueous liquid detergents or cleaners have a transmission of visible light of at least 30%, preferably 50%, more preferably 75%, most preferably 90%.
  • the thickeners according to the invention can be incorporated into opaque detergents or cleaners.
  • an aqueous washing or cleaning agent may contain dispersed particles whose diameter along their greatest spatial extent is 0.01 to 10,000 ⁇ .
  • Particles may be microcapsules as well as granules, compounds and fragrance beads, with microcapsules being preferred.
  • microcapsule is understood to mean aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s). These are usually finely dispersed liquid or solid phases coated with film-forming polymers, during the production of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization.
  • the microscopic capsules can be dried like powder.
  • multinuclear aggregates also called microspheres, are known, which contain two or more cores distributed in the continuous shell material.
  • Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath.
  • the shell may be made of natural, semi-synthetic or synthetic materials. Natural shell materials are, for example, gum arabic, agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, sucrose and wax.
  • Natural shell materials are, for example, gum arabic, agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, sucrose and wax.
  • Semisynthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and also starch derivatives, in particular starch ethers and esters.
  • microcapsules for example, optical brighteners, surfactants, complexing agents, bleaching agents, bleach activators, dyeing, fragrances, antioxidants, Builders, enzymes, enzyme stabilizers, antimicrobials, graying inhibitors, anti-redeposition agents, pH adjusters, electrolyte, foam inhibitors and UV absorbers.
  • the microcapsules may further contain cationic surfactants, vitamins, proteins, preservatives, detergency boosters or pearlescing agents.
  • the fillings of the microcapsules may be solids or liquids in the form of solutions or emulsions or suspensions.
  • the microcapsules may have any shape in the production-related framework, but they are preferably approximately spherical.
  • microcapsules Their diameter along their largest spatial extent, depending on the components contained in their interior and the application between 0.01 ⁇ (not visually recognizable as a capsule) and 10 000 ⁇ . Preference is given to visible microcapsules having a diameter in the range from 100 ⁇ m to 7000 ⁇ m, in particular from 400 ⁇ m to 5 000 ⁇ m.
  • the microcapsules are accessible by known methods, coacervation and interfacial polymerization being the most important.
  • Suitable microcapsules are all surfactant-stable microcapsules available on the market, for example the commercial products (the shell material is indicated in parentheses) Hallcrest microcapsules (gelatin, gum arabic), coletica thalaspheres (marine collagen), lipotec millicapsules (alginic acid, agar). Agar), Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified Agar Agar) and Kuhs Probiol Nanospheres (phospholipids).
  • particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckies”.
  • a preferred matrix-forming material is alginate.
  • an aqueous alginate solution which also contains the active ingredient to be enclosed or the active ingredients to be enclosed, is dripped off and then cured in a precipitation bath containing Ca 2+ ions or Al 3+ ions.
  • matrix-forming materials can be used instead of alginate.
  • matrix-forming materials include polyethylene glycol, polyvinyl pyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, Dextran, Ficoll®, starch, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hyaluronic acid, carboxymethylcellulose, carboxymethylcellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials.
  • the matrix formation takes place with these materials, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions.
  • the production of particles with these matrix-forming materials is known per se.
  • the particles can be stably dispersed in the aqueous liquid detergent or cleaner.
  • Stable means that the compositions are stable at room temperature and at 40 ° C for a period of at least 4 weeks, and preferably at least 6 weeks, without the medium creaming or sedimenting. Due to the increase in viscosity, the thickeners according to the invention bring about a kinetic slowing down of the sedimentation of the particles and thus their stabilization in the suspended state.
  • the release of the active ingredients from the microcapsules or speckles is usually carried out during the application of the agents containing them by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action.
  • the washing or cleaning agents according to the invention can be used for cleaning textile surface fabrics and / or hard surfaces.
  • Detergents of the invention may be in the form of a hand or machine dishwashing detergent, general-purpose cleaners for non-textile surfaces, e.g. made of metal, lacquered wood or plastic, or cleaning agents for ceramic products, such as porcelain, tiles, tiles.
  • the detergents or cleaners can be formulated as liquid or pasty.
  • the surfactants, the thickener and the optional components can be combined in any order.
  • the acidic components such as the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc. may be initially charged and the nonionic surfactants added.
  • a base such as NaOH, KOH, triethanolamine or monoethanolamine followed by the fatty acid, if present, is added.
  • the remaining ingredients and the solvents of the aqueous liquid detergent or cleaning agent are added to the mixture.
  • the associative thickener according to the invention is added and, if appropriate, the pH corrected, for. B.
  • a particular advantage of the thickeners used according to the invention is that they are suitable for subsequent incorporation into a washing or cleaning agent preformulation (post-addition). Subsequent incorporation of the thickener dispersion simplifies the production process and is advantageous since the detergents or cleaning agents only attain a high viscosity at a late stage of their production. It allows a precise viscosity adjustment. Since the handling, for. As the pumping, mixing or homogenizing, low-viscosity liquids faster and easier, the low-viscosity preformulation can be prepared with a shorter time and less energy consumption.
  • particles to be dispersed may be finally added and dispersed homogeneously in the aqueous liquid detergent or cleaner by mixing.
  • stirrer consisting of a 4 liter HWS vessel with anchor stirrer (150 rpm), reflux condenser, internal thermocouple and dosing, were as a template 631, 99 g of deionized water (deionized water) and 10.71 g of emulsifier Texapon NSO-28ig in water mixed.
  • reaction mixture was then stirred for a further hour at 75 ° C. and then cooled to room temperature. introduced. At room temperature, 0.3 g of a 4% Dissolvine E-FE-6 solution (ferrous salt solution) and 12 g of a 5% hydrogen peroxide solution were added and 90 g of a 1% ascorbic acid solution for 30 min. evenly metered. An aqueous polymer dispersion having a solids content of 31% was obtained.
  • Lutencryl 250 is a mixture of (Ci6-Ci8) alkyl (EO) 25-methacrylate with 50 wt .-% methacrylic acid. The amounts given for the starting materials are given in parts per 100 parts by hundred monomer (pphm).
  • Solid content The dispersion was dried at 140 ° C. for 30 minutes and the solids content in percent was determined from the ratio of dry residue to weighed-in weight.
  • Particle size The dispersion was diluted to 0.01% and the particle size was measured by light scattering in the High Performance Particle Sizer 5001 (HPPS) from Malvern Instruments.
  • LD value The dispersion was diluted to 0.01%, and the light transmittance (LD) of the dispersion was visually measured in the Hach DR / 2010 as compared with pure water as a measure of the particle size.
  • the above ingredients were mixed and made up to 90% by weight with water, i. There remained a formulation gap of 10 wt .-%.
  • the stock formulations were adjusted to pH 8.6 with KOH.
  • the master formulations were made up to 100% by weight with water.
  • the master formulations were made up with thickener dispersion and water so that, taking into account the solids content of the dispersion, a thickener concentration of 1.5% by weight, based on the finished formulation, was established. Before the viscosity measurement, the formulations were allowed to rest for at least 5 hours.
  • the low-shear viscosity was measured with the Brookfield Viscometer Model RV-03 at a speed of 20 revolutions per minute with spindle no. 63 at 20 ° C, taking into account the requirements of DIN 51550, DIN 53018, DIN 53019.
  • the washing tests were carried out with the detergent formulations (types A and B) already described.
  • the washing conditions are:
  • Test fabric 5.0 g Cotton fabric 221 (basis weight 132 g / m 2 ), 5.0 g
  • Blended fabric 768 (65:35 PES: BW, basis weight 155 g / m 2 )
  • the thickener dispersions containing higher proportions of methyl methacrylate have reduced remission values.
  • the examples show a relationship between the amount of methylmethacrylic in the thickener dispersion and the remission values, the higher the methyl methacrylate content the lower the remission.

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Abstract

Dans le cadre de l'invention, des copolymères qui contiennent a) au moins 15 % en poids d'unités d'un acide carboxylique éthyléniquement insaturé, b) au moins 15 % en poids d'unités d'un acrylate d'alkyle en C4 à C8, c) moins de 5 % en poids d'unités de méthacrylate de méthyle, sont utilisés comme épaississants dans des lessives liquides pour textiles. Ces copolymères peuvent en outre contenir des unités, polymérisées par ajout, d'un monomère tensioactif non ionique éthyléniquement insaturé. Les épaississants présentent, pour une forte action épaississante et une forte rhéofluidification simultanée, un grisage plus faible du linge après le lavage.
EP11702844.9A 2010-02-12 2011-02-11 Utilisation d'un copolymère comme épaississant dans les lessives liquides à tendance au grisage réduite Active EP2534234B1 (fr)

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EP2776478A1 (fr) * 2011-11-11 2014-09-17 Basf Se Épaississant contenant au moins un polymère à base de monomères associatifs
WO2014154244A1 (fr) * 2013-03-25 2014-10-02 Ecolab Usa Inc. Composition de détergent liquide
FR3024874B1 (fr) * 2014-08-14 2016-09-02 Roquette Freres Copolymere de dextrine avec du styrene et un ester acrylique, son procede de fabrication et son utilisation pour le couchage papetier
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WO2018210700A1 (fr) * 2017-05-15 2018-11-22 Unilever Plc Composition
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MX341054B (es) 2016-08-05
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WO2011098571A1 (fr) 2011-08-18
PL2534234T3 (pl) 2015-06-30
EP2534234B1 (fr) 2015-01-14
CN102753671A (zh) 2012-10-24
ES2534766T3 (es) 2015-04-28
US20130040870A1 (en) 2013-02-14
CN102753671B (zh) 2015-10-07
MX2012008970A (es) 2012-08-23
JP5788414B2 (ja) 2015-09-30
CA2788046A1 (fr) 2011-08-18
KR101794368B1 (ko) 2017-11-06
BR112012020157A2 (pt) 2017-12-05
KR20130010115A (ko) 2013-01-25

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