EP3107986A1 - Lessives ou détergents ayant un comportement de moussage amélioré en cas de fortes salissures - Google Patents

Lessives ou détergents ayant un comportement de moussage amélioré en cas de fortes salissures

Info

Publication number
EP3107986A1
EP3107986A1 EP14706532.0A EP14706532A EP3107986A1 EP 3107986 A1 EP3107986 A1 EP 3107986A1 EP 14706532 A EP14706532 A EP 14706532A EP 3107986 A1 EP3107986 A1 EP 3107986A1
Authority
EP
European Patent Office
Prior art keywords
washing
cleaning agent
cleaning
anionic surfactant
agents
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14706532.0A
Other languages
German (de)
English (en)
Inventor
Peter Schmiedel
Walter Heberlein
Danilo Panzica
Ketan Patil
Dieter Nickel
Ingrid Kraus
Robin KLEINSCHNITZ
Hans-Henning Wenk
Dirk Kuppert
Jürgen LATTICH
Ashraf MARZOUK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3107986A1 publication Critical patent/EP3107986A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D2111/12—

Definitions

  • the present invention relates to detergents or cleaners having improved
  • washing machines are of a simpler design than in Central Europe. Many such machines do not have a rotating drum in a tub, which is charged as a front or Toploader, but only via a stirring or circulating device in a fixed tub.
  • This stirring or circulating device can be located on the bottom of the tub or in simple embodiments on the side.
  • the agitator can perform a reversing rotational movement with standstill phases or else rotate continuously in the same direction.
  • Washing machines without rotating drum are also referred to as
  • foam boosters foam boosters
  • Alkyl ether carboxylates are known as foam-promoting compounds.
  • EP 071 1545 B1 discloses betaines, in particular alkylamidopropyl betaines, as surfactants for cosmetic purposes and as cleansing agents and is based on the low irritant effect of Cs / 10APB.
  • DE 2926479 B1 discloses the preparation C6-C18 Alkylamidopropylbetainen.
  • Vat washing machines cause overfoaming. An increase in foaming power in the absence of dirt would therefore not be advantageous here.
  • the washing or cleaning agent should also when dosing into a washing or cleaning liquor due to high
  • the invention therefore relates to a washing or cleaning agent, preferably detergent, particularly preferably solid detergent, comprising:
  • anionic surfactant wherein the total amount of anionic surfactant is from 3% to 25%, preferably from 5% to 20% by weight, based on the total weight of the detergent or cleaning agent, wherein at least a first anionic surfactant is included, preferably wherein the at least one first anionic surfactant is an alkyl benzene sulfonate; and
  • R is a, preferably linear, alkyl radical of 7 to 9 carbon atoms and R 2 and R 3 are the same or different Alkyl radicals having 1 to 3 carbon atoms are, preferably methyl; wherein the weight ratio of alkylamidopropylbetaine according to (ii) / total amount of anionic surfactant in the washing or cleaning agent is from 0.003 to 0.12, preferably from 0.01 to 0.06, particularly preferably from 0.02 to 0.04, wherein the
  • Weight ratio of the total amount of Alkylamidopropylbetain according to (ii) / total amount of Alkylamidopropylbetain in the washing or cleaning agent 0.25 to 1, 0, particularly preferably 0.5 to 1, 0.
  • the total amount of anionic surfactant is 3 wt% to 25 wt%, 5 wt% to 20 wt%, 7 wt% to 18 wt%, 9 wt% to 16% by weight, 11% by weight to 14% by weight, 3% by weight to 20% by weight, 3% by weight to 18% by weight or 5% by weight to 18 wt .-% based on the total weight of the washing or cleaning agent, wherein at least a first anionic surfactant is included.
  • the weight ratio of alkylamidopropyl betaine according to (ii) / total amount of anionic surfactant in the detergent or cleaning agent is from 0.005 to 0.10, preferably from 0.007 to 0.09, from 0.008 to 0.08, from 0.009 to 0.08 , from 0.01 to 0.07, from 0.01 to 0.06, from 0.012 to 0.05, from 0.015 to 0.04, or from 0.02 to 0.03, most preferably from 0.02 to 0.04.
  • the weight ratio of the total amount of alkylamidopropyl betaine according to (ii) / total amount of alkylamidopropylbetaine in the detergent or cleaning agent is 0.25 to 1.0, from 0.30 to 1.0 from 0.40 to 1.0 from 0.5 to 1.0, from 0.6 to 1.0, from 0.7 to 1.0, from 0.8 to 1.0 of 0.9 to 1.0, more preferably 1.0.
  • the detergents or cleaners of the invention do not comprise cocoamidopropylbetaine.
  • Cocoamidopropyl betaine is a mixture of Cs-ds
  • Alkylamidopropyl betaine as EP071 1545 B1 discloses. This means that in certain embodiments, the short chain alkylamidopropyl betaines are not
  • Cocoamidopropyl betaine come.
  • the number of carbon atoms not only refers to the carbon atoms of the alkyl chain but also includes the carbonyl carbon atom of the amide group.
  • the radical R relates exclusively to the carbon atoms of the alkyl chain.
  • the foaming power is increased, especially in the presence of dirt, while in a washing or cleaning fleet without contamination only little or no foam-improving effect is observed. This is advantageous for the consumer, as this can prevent overfoaming of the initially clean washing or cleaning liquor.
  • the washing or cleaning agent formulations according to the invention have improved foam quality in a polluted washing or cleaning liquor. Under otherwise identical conditions, the foam of the washing or cleaning agent according to the invention appears whiter and creamier.
  • the improved foaming power is understood by the consumer as an indicator for a higher cleaning power and a greater range of detergents or cleaning agents. This is advantageous in terms of environmental and sustainability properties.
  • the short chain alkylamidopropyl betaines are particularly effective at particularly low levels in the proportions to the anionic surfactants described herein. Therefore, the claimed detergent or cleaning composition are particularly inexpensive.
  • the proportion of short chain alkylamidopropyl betaine in the composition is from 0.009 to 4.2 wt%, preferably from 0.03 to 4.0 wt%, more preferably from 0.1 to 3.5 wt% more preferably 0.2 to 3.0% by weight, particularly preferably 0.5 to 2.0% by weight.
  • Detergents or cleaning agents which have at least one alkylbenzenesulfonate as anionic surfactant are particularly suitable.
  • the at least one alkyl benzene sulfonate is a linear or branched Ce-19 alkyl benzene sulfonate, preferably a C9-13 linear alkyl benzene sulfonate (LAS).
  • the at least one anionic surfactant is the wash or
  • Detergent at least one alkylbenzenesulfonate, wherein the amount of alkylbenzenesulfonate 3 wt .-% to 25 wt .-%, 5 wt .-% to 20 wt .-%, 7 wt .-% to 18 wt .-%, 9 wt. % to 16% by weight, 1% to 14% by weight, 3% to 20% by weight, 3% to 18% by weight or 5% by weight to 18 wt .-% based on the total weight of the washing or cleaning agent.
  • the at least one alkylbenzenesulfonate is a LAS.
  • the washing or cleaning agent exclusively
  • Alkylbenzenesulfonate preferably LAS, as an anionic surfactant.
  • laundry detergents or cleaners according to the invention have a higher foam generation rate under high soil load than comparison detergent or comparison detergent. Since the foam degradation rate by Coalescence is proportional to the amount of foam present, is due to the increased
  • the invention relates to a washing or cleaning process comprising the process steps:
  • washing or cleaning solution preferably comprises dirt
  • Yet another aspect is directed to the use of at least one alkylamidopropyl betaine to improve the lathering performance of a washing or cleaning agent, especially in the presence of soil, wherein
  • the washing or cleaning agent comprises anionic surfactant, wherein the
  • Total amount of anionic surfactant 3 wt .-% to 25 wt .-%, preferably 5 wt .-% to 20 wt .-%, based on the total weight of the detergent or cleaning agent, wherein at least a first anionic surfactant is included, wherein preferably, the at least one first anionic surfactant is an alkylbenzenesulfonate;
  • the at least one alkylamidopropyl betaine is a compound of the formula
  • R is a, preferably linear, alkyl radical of 7 to 9 carbon atoms and R 2 and R 3 are the same or various alkyl radicals having 1 to 3 carbon atoms are, preferably methyl;
  • anionic surfactant in the washing or cleaning agent is from 0.003 to 0.12, preferably from 0.01 to 0.06, particularly preferably from 0.02 to 0.04;
  • (ii) / total amount of alkylamidopropyl betaine in the washing or cleaning agent is 0.25 to 1.0, more preferably 0.5 to 1.0.
  • the present invention relates to the use of the detergents or cleaners defined herein as detergents or cleansers.
  • the present invention relates to the use of the detergents or cleaners defined herein as laundry detergents, hand wash detergents, travel detergents, dishwashing detergents, especially dishwashing detergents, more preferably hand dishwashing detergents or toilet cleaners.
  • the composition of the invention in a sink produces excellent foam in the cleaning liquor when the liquor carries dirt.
  • At least one refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more In the context of components of those described herein
  • At least one anionic surfactant means one or more different anionic surfactants, ie, one or more different types of anionic surfactants the quantities given to the total amount of the corresponding designated type of ingredient, as already defined above.
  • alkylamidopropylbetaines described herein are preferably C8 or C10 linear alkylamidopropyl betaines, i. Caprylamidopropyl betaine (N- (3-octanoyl) aminopropyl) -N-carboxymethyl-N, N-dimethyl-1-propanaminium) or capramidopropyl betaine (N- (3-decanoyl) aminopropyl) -N-carboxymethyl-N, N-dimethyl-1 propanaminium), or, most preferably, mixtures of C8 and C10 linear alkyl amidopropyl betaines.
  • Such a betaine blend is commercially available, for example, as Tegotens® B 810 from Evonik Industries.
  • washing or cleaning agents according to the invention
  • Alkylamidopropylbetaines which are substantially short chain.
  • Short-chain alkylamidopropyl betaines are compounds of the formula
  • R is a, preferably linear, alkyl radical of 7 to 9 carbon atoms and R 2 and R 3 are the same or different alkyl radicals having 1 to 3 carbon atoms are, preferably methyl.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Preferred surfactants of the sulfonate type are C9-i3-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C12 -18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfo fatty acids are esters of ⁇ -sulfo fatty acids.
  • Suitable alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula
  • a particularly preferred representative is sodium dodecylbenzylsulfonate.
  • Alk (en) ylsulfates are the alkali metal and in particular the sodium salts of
  • Sulfuric acid half esters of C 12 -18 fatty alcohols for example from coconut fatty alcohol,
  • alk (en) ylsulfates of said chain length which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates and C14-C15-alkyl sulfates are preferred.
  • sulfuric acid monoesters of straight-chain or branched C7-2i alcohols ethoxylated with from 1 to 6 moles of ethylene oxide such as 2-methyl-branched C9-n alcohols having on average 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 up to 4 EO, are suitable.
  • EO ethylene oxide
  • C12-C18 fatty alcohols with 1 up to 4 EO are suitable.
  • Alkyl ether sulfates are, for example, compounds of the formula
  • R is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
  • Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms are preferred.
  • radicals R are derived from C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols.
  • AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • EO ethylene oxide
  • PO propylene oxide
  • the index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + including Na, with Na + being extremely preferred.
  • Other cations X + can be selected from NhV,
  • the alkyl ether sulfate may be selected from
  • Degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product.
  • the indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • anionic surfactants does not mean soaps
  • the detergents according to the invention may comprise soaps, but they are not included in the scope of the present invention as anionic surfactants.
  • soaps come as additional ingredients of detergents or cleaning agents into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants as well as soaps may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants and soaps are in the form of their sodium, potassium or magnesium salts, especially in the form of the sodium salts.
  • anionic surfactants are the freedom from formulation no conditions to be observed in the way. It is only to be considered that soaps are not counted among the anionic surfactants.
  • Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, in particular the alkylbenzenesulfonates.
  • Anionic surfactants i. in particular alkylbenzenesulfonates and alkyl ether sulfates, are preferably present in the washing or cleaning agent to a certain proportion by weight, namely with 3 to 25 wt .-% based on the total weight of the washing or
  • Detergent formulation Preference is given to amounts of from 5 to 20% by weight of anionic surfactants, based on the total weight of the detergent formulation. Regardless of whether the detergent contains one or more of the anionic surfactants, the amounts given refer to the total amount of all anionic surfactants contained in the detergent.
  • the detergents or cleaning agents further comprise soaps, preferably 0, 1 to 5 wt .-% soaps. Preferably, the washing or cleaning agents have no soaps.
  • the detergents or cleaning agents may of course contain conventional ingredients of such agents.
  • the washing or cleaning agent may contain other ingredients that the
  • the washing or cleaning agent preferably additionally contains one or more substances from the group of enzymes, bleaching agents, bleach activators, complexing agents, builders, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, optical brighteners, dyes , Speckies, Hydrotropes, Silicone Oils, Anti Redeposition Agents, Grayness Inhibitors, Pre-Runner Inhibitors, Crease Inhibitors, Color Transfer Inhibitors, Antimicrobial Agents, Germicides, Fungicides, Antioxidants, Preservatives, Corrosion Inhibitors, Antistatic Agents, Bitter Agents,
  • compositions may nevertheless comprise speckles having soap components. In this case, the composition has soaps only in the speckles.
  • 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 radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, cis-is alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and Ci2-is-alcohol with 5 EO.
  • 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 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.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the glycosidation degree z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylaminoxid, and the fatty acid alkanolamides may 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.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid,
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus serve, for example, in US Pat
  • Granules according to the invention also for adjusting a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates are suitable, these are for example the
  • Alkali metal salts of polyacrylic acid or polymethacrylic acid for example, those having a molecular weight of 500 to 70,000 g / mol. This class of substances has already been described in detail above.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids, such as, for example, in EP-B-0 727 448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • allylsulfonic acids such as, for example, in EP-B-0 727 448 allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers of more than two different monomer units for example those which, according to DE-A-43 00 772, as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 contain as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids, their salts or their precursors are particularly preferred.
  • polyaspartic acids or their salts and derivatives which is disclosed in the German patent application DE-A-195 40 086, that they also have a bleach-stabilizing effect in addition to cobuilder properties.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European Patent Application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • they are hydrolysis products with middle
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also so-called yellow dextrins and white dextrins with relatively high molecular weights in the range from 2000 to 30 000 g / mol are useful.
  • a preferred dextrin is described in British Patent Application 94 19 091.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are described, for example, in European Patent Applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and International Patent Applications WO 92 WO-A-93/16110, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95 / 20608 known.
  • an oxidized oligosaccharide according to the German patent application DE-A-196 00 018.
  • a product oxidized on Ce of the saccharide ring may be particularly advantageous
  • Ethylenediamine disuccinate are other suitable cobuilders.
  • Ethylenediamine-N, N '- disuccinate (EDDS) whose synthesis is described for example in US 3,158,615, preferably used in the form of its sodium or magnesium salts.
  • EDDS Ethylenediamine-N, N '- disuccinate
  • glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which have at least 4 carbon atoms and at least one hydroxyl group and a maximum of two
  • Such co-builders are used, for example, in the international
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • Hydroxyalkane phosphonates are the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as co-builders. It is preferably used as the sodium salt, the
  • Aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • a preferred inorganic builder is fine crystalline, synthetic and bound water-containing zeolite.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite X and mixtures of A, X and / or P, for example a cocrystal of zeolites A and X are also suitable.
  • the zeolite can be used as a spray-dried powder or as undried, still moist from their production, stabilized suspension used.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C12- Ci8 fatty alcohols having 2 to 5 ethylene oxide groups, Ci2-Ci4 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
  • zeolites are contained in the premix in amounts of from 10 to 94.5% by weight, it being particularly preferred that zeolites are present in amounts of from 20 to 70, in particular from 30 to 60% by weight.
  • Suitable partial substitutes for zeolites are phyllosilicates of natural and synthetic origin.
  • Such layered silicates are known, for example, from the patent applications DE-A-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not on a special one
  • NaMSixOx + iyH20 where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4, are suitable for the substitution of zeolites or phosphates ,
  • Such crystalline layered silicates are described, for example, in European Patent Application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O yH 2 O are preferred.
  • the preferred builders also include amorphous sodium silicates having a modulus of Na2 ⁇ : S1O2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, and more preferably from 1: 2 to 1: 2.6 , which are delay-delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous". This means that the silicates are present
  • diffraction maxima This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a dissolution delay compared to the conventional water glasses are
  • compacted / compacted amorphous silicates Especially preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates, wherein in particular the overdried silicates preferably also occur as a carrier in the granules according to the invention or are used as carriers in the process according to the invention.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished agent.
  • tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished composition, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.
  • the washing or cleaning agent may further contain at least one enzyme.
  • all the enzymes established in the prior art for this purpose can be used in this regard.
  • it is one or more enzymes that are in a washing or
  • Detergents can develop a catalytic activity, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-cleaving enzyme, tannase, xylanase, xanthanase, ß-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreductase and mixtures thereof.
  • a catalytic activity in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-cleaving enzyme, tannase, xylanase, xanthanase, ß-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreductase and mixtures thereof.
  • Preferred hydrolytic enzymes include in particular proteases, amylases, in particular ⁇ -amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, ⁇ -glucanases, and mixtures thereof.
  • proteases are particularly preferred, and proteases are particularly preferred.
  • These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • the enzymes to be used can also be used together with accompanying substances, such as from
  • Fermentation or be prepared with stabilizers.
  • a bleaching agent can serve all substances by oxidation, reduction or adsorption
  • Dyes destroy or absorb and thereby discolor materials. These include, among others, hypohalite-containing bleach, hydrogen peroxide, perborate, percarbonate,
  • the detergents or cleaners according to the invention may additionally comprise one or more of the substances additionally mentioned above, in particular those from the groups of bleach activators, pH adjusters, perfumes,
  • Perfume carriers fluorescers, dyes, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors and color transfer inhibitors. Suitable agents are known in the art.
  • organic solvents may also be present in the compositions.
  • it is monohydric or polyhydric alcohols having 1 to 4 carbon atoms.
  • Preferred alcohols in such agents are ethanol, 1, 2-propanediol, glycerol and mixtures of these alcohols.
  • such agents contain from 2 to 12% by weight of such alcohols.
  • the agents can have different states of aggregation.
  • the washing or cleaning agents are powdered or granular agents.
  • the compositions according to the invention can have any bulk densities.
  • the range of possible bulk densities ranges from low bulk densities below 600 g / l, for example 300 g / l, over the range of average apparent weights of 600 to 750 g / l up to the range of high bulk densities of at least 750 g / l.
  • the washing or cleaning agent is in the form of moldings, which are preferably tablets, which may consist of a single or of several, in particular 2 or 3 different phases.
  • any of the detergents or cleaners described herein may be any method known in the art.
  • Washing or cleaning process i.
  • processes for cleaning textiles are generally distinguished by the fact that cleaning-active substances are applied to the items to be cleaned and washed off after the action time in one or more process steps, or that the items to be cleaned in any other way with a detergent or a solution of this agent is treated.
  • temperatures of up to 95 ° C or less, 90 ° C or less, 60 ° C or less, 50 ° C or less, 40 ° C or less , 30 ° C or less than or equal to 20 ° C or less. These temperatures are based on the temperatures used in the washing or cleaning steps.
  • washing or cleaning processes are preferred in which air is continuously introduced into the wash liquor.
  • the methods according to the invention are preferably washing methods.
  • the washing methods are preferably carried out in tub washing machines, in particular in those with a fixed tub and a stirring or circulating device.
  • Circulating device can be arranged on the floor or on the side of the tub. It is hereby preferred that the stirring or circulating device is arranged such that during the stirring or circulating process, air is continuously introduced into the wash liquor.
  • Such tub washing machines are used as HS machines of the type "Ideal”, for example in Egypt, or as machines of the type "Sibir”, “Feya” and “Mini Vjatka” in Russia.
  • the wash solution may be used for multiple wash loads, i. several successive washes can be carried out with the same wash liquor.
  • the invention also relates to the use of at least one Alkylamidopropylbetains as defined above to improve the foaming behavior of a detergent or cleaning agent, especially in the presence of dirt, especially under high soil contamination, wherein the detergent or cleaning agent is one as defined herein is.
  • high soil load &quot generally refers to high levels of debris relative to the amount of wash liquor articles such as textiles that have soil provide, when incorporated into the laundry or cleaning liquor, for
  • a high pollution load is when the dirt in the washing or cleaning liquor achieves a defoaming effect, as is achieved when more than 3g dirt / L washing or cleaning liquor, preferably more than 4 g Dirt / L Washing or cleaning liquor, which is adjusted in a wash liquor when using WFK SBL wipes according to the test procedure set out in the examples
  • a high dirt load is used when under control conditions, ie in the absence of short chain
  • Alkylamidopropylbetain leading to a decrease in the foam height of at least 5, at least 10, at least 20, at least 30, at least 40 or at least 50%.
  • the high soil load leads to a decrease in foam height of at least 20%.
  • the foam height is determined according to the test method for the determination explained in the examples the foam height (see “Performing the foam tests") determined under appropriate conditions after 15 minutes.
  • Alkylamidopropyl betaines and anionic surfactants are also preferred for the use described.
  • the washing or cleaning agent is preferably a solid, in particular powdery or granular washing or cleaning agent and / or contains the individual
  • the washing or cleaning agent is preferably a liquid, pasty or gel-like washing or cleaning agent.
  • the liquid, paste or gel detergents or cleaners may contain the individual surfactant ingredients in the amounts and ratios disclosed above in connection with the disclosed laundry detergent or cleaning composition.
  • a first less soiled wash liquor was prepared (theoretical amount of dirt 2.3 g / L) and the respective additive to be tested added (according to the invention: Tegotens® B 810 (Cs / ioAPB)) from Evonik Industries; Comparative Example: LAS) and filled into a test cylinder (inner diameter 8 cm, height inside 46.5 cm) of a Contifoam® foam tester.
  • the wash liquor is sucked by the pump in this test and through a nozzle (0.5 cm diameter) from a height of 45 cm in the
  • the specified LAS quantity refers to the added amount of LAS, ie the amount of LAS in addition to the LAS already contained in the detergent. At the ratio of betaine (Cs / 10APB) to LAS, the amount of LAS is the amount of LAS contained in the detergent.
  • Alkylamidopropylbetainen can achieve a larger foam volume.
  • the "Ideal" type washing machine with lateral agitator was used, the water volume was 33 liters, the water hardness was 16 ° dH and the water temperature was 20 ° C.
  • 5 terry towels were always washed with the same wash 6 washes of 8 minutes each in a row
  • a total of 100 g of detergent was added, as usual in the relevant areas, namely 50 g in the first wash and another 50 g in the second wash
  • SBL-2004 was used in each wash Wipes were added, and in each case 3 wipes in the 1st, 4th, 5th and 6th wash and 6 wipes in the 2nd and 3rd
  • Wash cycle read on a scale.
  • Example 3 Exemplary compositions 1-80 according to the invention
  • Total APB is the total content of alkylamidopropylbetaine in the detergent and includes Cs / ioAPB.

Abstract

L'invention concerne des lessives ou des détergents ayant un comportement de moussage amélioré en cas de fortes salissures, qui contiennent au moins un tensioactif anionique en une quantité allant de 3 % en poids à 25 % en poids par rapport au poids total de la lessive, et au moins une alkylamidopropylbétaïne de formule (R1)C(=O)NH(CH2)3N+(R2)(R3)CH2COO-, dans laquelle R1 est un radical alkyle ayant de 7 à 9 atomes de carbone, et R2 et R3 sont des radicaux alkyle identiques ou différents, ayant de 1 à 3 atomes de carbone. Le rapport en poids de l'alkylamidopropylbétaïne définie ici/quantité totale de tensioactif anionique dans la lessive ou le détergent est de 0,003 à 0,12. Le rapport en poids de la quantité totale d'alkylamidopropylbétaïne telle que définie ici/quantité totale d'alkylamidopropylbétaïne dans la lessive ou le détergent est de 0,25 à 1,0. L'invention concerne également des procédés de lavage ou de nettoyage utilisant des lessives ou des détergents de ce type et elle concerne l'utilisation des alkylamidopropylbétaïnes, telles que définies ici, pour améliorer le comportement de moussage des lessives ou détergents en cas de fortes salissures.
EP14706532.0A 2014-02-20 2014-02-20 Lessives ou détergents ayant un comportement de moussage amélioré en cas de fortes salissures Withdrawn EP3107986A1 (fr)

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PCT/EP2014/053333 WO2015124189A1 (fr) 2014-02-20 2014-02-20 Lessives ou détergents ayant un comportement de moussage amélioré en cas de fortes salissures

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EP3107986A1 true EP3107986A1 (fr) 2016-12-28

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US (1) US10066191B2 (fr)
EP (1) EP3107986A1 (fr)
AU (1) AU2014383650B2 (fr)
MX (1) MX2016010817A (fr)
RU (1) RU2650684C2 (fr)
WO (1) WO2015124189A1 (fr)

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DE102017206013A1 (de) 2017-04-07 2018-10-11 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit verbessertem Schaumverhalten
CN108755007A (zh) * 2018-06-01 2018-11-06 青岛海尔洗衣机有限公司 一种洗衣机称重方法及洗衣机

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US10066191B2 (en) 2018-09-04
AU2014383650A1 (en) 2016-10-06
RU2650684C2 (ru) 2018-04-17
RU2016137262A3 (fr) 2018-03-23
MX2016010817A (es) 2016-10-26
AU2014383650B2 (en) 2018-01-18
RU2016137262A (ru) 2018-03-23
WO2015124189A1 (fr) 2015-08-27
US20160348033A1 (en) 2016-12-01

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