EP3472293B1 - Détergent à lessive liquide concentré à ph constant - Google Patents

Détergent à lessive liquide concentré à ph constant Download PDF

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Publication number
EP3472293B1
EP3472293B1 EP17730137.1A EP17730137A EP3472293B1 EP 3472293 B1 EP3472293 B1 EP 3472293B1 EP 17730137 A EP17730137 A EP 17730137A EP 3472293 B1 EP3472293 B1 EP 3472293B1
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Prior art keywords
agents
liquid washing
washing agent
agent
acid
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German (de)
English (en)
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EP3472293A1 (fr
Inventor
Ulrich Pegelow
Sabine SCHÜMANN
Simon PLUSZYNSKI
Thorsten Bastigkeit
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present application is aimed at highly concentrated liquid detergents with surfactant contents in the range from 32 to 38% by weight, which have optimized product stability by having optimally adjusted and stable pH values. Methods for washing textiles using the detergents described and their use are also recorded.
  • Liquid detergents are well known in the art and have become increasingly popular with consumers in recent years because they offer a number of advantages over solid detergents. These include, among other things, easier dosing, addition and dissolution in the washing liquor. In addition, they are perceived as safer and less aggressive towards the textiles and the environment. Especially for washing colored textiles, they have gained more and more popularity since their market launch.
  • US4075118 discloses concentrated liquid detergent compositions containing a mixture of nonionic and anionic surfactants, the total amount of surfactants being more than about 30%, and further a mixture of an inorganic base and an organic base.
  • EP100125 A2 discloses liquid detergent compositions containing a mixture of nonionic and anionic surfactants, the total amount of surfactants being more than about 20%, and further a mixture of an inorganic base and an organic base.
  • compositions are advantageous from the point of view of handling and consumer acceptance, the known compositions suffer from disadvantages with regard to their stability, especially with longer storage times. These disadvantages are further intensified by the trend towards more highly concentrated products.
  • highly concentrated liquid detergents the challenge is to accommodate more of the necessary performers (e.g. surfactants, polymers, enzymes, complexing agents, perfume, optical brighteners) in a smaller volume of liquid.
  • a particular challenge is to ensure a stable pH value in the formulation.
  • the pH value of such a liquid formulation must be optimally adjusted so that there are no negative effects on the product stability, such as phase separations or precipitation.
  • enzymes are only stable over a long storage period in a narrowly defined pH range.
  • an inorganic base such as sodium hydroxide (NaOH) or an organic base such as mono- or triethanolamine is used to adjust the pH.
  • inorganic bases have the disadvantage that they increase the electrolyte content in the formulations, which is particularly the case with highly concentrated ones Compositions leads to cloudy, unstable formulations.
  • organic bases allow clear compositions to be produced, they cause the pH to change over time, for example during storage of the product, which in turn causes stability problems.
  • the present invention therefore relates to a liquid detergent with a surfactant concentration of 32 to 38% by weight based on the total weight of the detergent, characterized in that the detergent contains at least one inorganic base and at least one organic base in a molar ratio of 1 :2 to 1:8, preferably 1:3 to 1:5, and at least two anionic surfactants and at least one nonionic surfactant, wherein the at least two anionic surfactants comprise at least one alkyl benzene sulfonate and at least one alkyl ether sulfate, and wherein the liquid detergent directly after manufacture has a pH in the range of 8.2 to 8.6.
  • the present invention relates to the use of a liquid detergent according to the invention for washing textiles.
  • the present invention relates to a method for cleaning textiles, characterized in that a liquid detergent according to the invention is used in at least one method step.
  • At least one refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compositions described herein, this statement does not refer to the absolute amount of molecules but to the type of component.
  • At least one inorganic base thus means, for example, one or more different inorganic bases, i.e. one or more different types of inorganic bases. Together with quantities, the quantities refer to the total quantity of the type of ingredient referred to.
  • the detergents described herein can be detergents for fabrics or natural fibers.
  • the detergents within the scope of the invention also include washing aids which are metered into the actual detergent in manual or machine laundry in order to achieve a further effect or to enhance an effect.
  • detergents within the scope of the invention also include textile pre- and post-treatment agents, i.e. those agents with which the item of laundry is brought into contact before the actual wash, for example to loosen stubborn dirt, and also such agents in a step downstream of the actual textile wash give the laundry other desirable properties such as a pleasant feel, crease resistance or low static charge.
  • the latter means include fabric softeners. In preferred embodiments, however, it is a textile detergent.
  • the agents of the invention are distinguished in particular by the fact that after 12 weeks of storage at 23° C. they show a pH drift of less than 0.8, preferably less than 0.5, more preferably less than 0.3.
  • the pH in the agents according to the invention is adjusted using inorganic and organic bases which are used in specific molar ratios to one another.
  • Suitable inorganic bases include, but are not limited to, alkali metal hydroxides such as, in particular, NaOH and KOH.
  • the inorganic bases used are preferably strong bases with a pK a value >9, preferably >10, more preferably >12, most preferably ⁇ 14 (ie pK b values of ⁇ 5, ⁇ 4, ⁇ 2 or ⁇ 0) .
  • Suitable organic bases include, but are not limited to, organic amines, such as particularly ethanolamine, most preferably mono- or triethanolamine.
  • the ones used organic bases are preferably also strong bases with a pKa value >7, preferably >9.
  • the inorganic and organic bases are used in a molar ratio of 1:2 to 1:8, preferably 1:3 to 1:5, more preferably about 1:4.
  • the amount of base used depends on the other components. In general, the bases are used in amounts such that the desired pH of the agent can be set. In various embodiments of the invention, the pH of the agents according to the invention is adjusted to values >7.5, usually >8.0, for example in the range from 8.2 to 8.6, in particular 8.3 to 8.5.
  • base refers to bases as defined by Lewis (electron pair donor), preferably as more narrowly defined by Bronsted and Lowry (proton acceptors).
  • the agents according to the invention are highly concentrated, i.e. they contain 32 to 38% by weight of surfactants.
  • the composition contains at least two anionic surfactants and at least one nonionic surfactant, the at least two anionic surfactants comprising at least one alkyl benzene sulfonate and at least one alkyl ether sulfate.
  • anionic surfactants comprising at least one alkyl benzene sulfonate and at least one alkyl ether sulfate.
  • cationic, zwitterionic and/or amphoteric surfactants can also be present.
  • anionic surfactants are in particular those of the sulfonate type, preferably alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from monoolefins having 12 to 18 carbon atoms with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • Alkyl benzene sulfonates are preferably selected from linear or branched alkyl benzene sulfonates of the formula wherein R' and R" are independently hydrogen or alkyl and together contain 9 to 19, preferably 9 to 15 and more preferably 9 to 13 carbon atoms.
  • a most preferred representative is sodium dodecyl benzyl sulfonate.
  • the alk(en)yl sulfates used are the salts of the sulfuric acid monoesters of fatty alcohols with 12 to 18 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the oxo alcohols with 10 to 20 carbon atoms and those monoesters of secondary alcohols of these chain lengths are preferred.
  • Alkyl sulfates having 12 to 16 carbon atoms and alkyl sulfates having 12 to 15 carbon atoms and alkyl sulfates having 14 and 15 carbon atoms are preferred for reasons of washing technology.
  • 2,3-Alkyl sulfates are also suitable anionic surfactants.
  • the secondary alkanesulfonates are also particularly suitable.
  • "Secondary” as used herein refers to the well-known chemical meaning of this term, and indicates that the carbon atom to which the sulfonate group is covalently attached still has two covalent bonds to two organic (alkylic) radicals, ie carbon atoms, and a covalent bond to a hydrogen atom. Together with the carbon atom to which they are attached, the two organic (alkylic) groups form a linear or branched alkyl of 1 to 50 carbon atoms.
  • the alkanesulfonate according to the invention further comprises any cation, preferably selected from the group Na + , K + , NH4 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ and their Mixtures, particularly preferably Na + .
  • the secondary alkane sulfonate is one of the formula R 1 CH(SO 3 - X + )R 2 , wherein each R 1 and R 2 is independently linear or branched alkyl of 1 to 20 carbon atoms and, with the carbon atom to which they are attached, form linear or branched alkyl, preferably of 10 to 30 carbon atoms, preferably 10 to 20 carbon atoms and X + is selected from the group of Na + , K + , NH4 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ and mixtures thereof, preferably Na + .
  • Secondary alkanesulfonates of the formula are particularly preferred H 3 C-(CH 2 ) n -CH(SO 3 - X + )-(CH 2 ) m -CH 3 , where m and n are independently an integer between 0 and 15. Preferably, m and n are independently an integer between 7 and 15 and preferably between 11 and 14.
  • X + is also selected from the group Na + , K + , NH4 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ and mixtures thereof, preferably Na + .
  • anionic surfactants are those of the sulfate type and in particular the alkyl ether sulfates.
  • Preferred alkyl ether sulfates are those of the formula below R 4 -O-(AO) n -SO 3 - X + , wherein R 4 is linear or branched alkyl of 5 to 30 carbon atoms, preferably 7 to 25 carbon atoms, and preferably 10 to 19 carbon atoms.
  • R 4 is linear or branched alkyl of 5 to 30 carbon atoms, preferably 7 to 25 carbon atoms, and preferably 10 to 19 carbon atoms.
  • AO in the above formula stands for an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide (EO) moiety and n is an integer from 1 to 50, preferably from 1 to 20 and preferably from is 2 to 10.
  • X + is any cation and is preferably selected from the group of Na + , K + , NH4 + , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2 and mixtures thereof, particularly preferably Na + .
  • R 4 represents a linear or branched, substituted or unsubstituted alkyl group.
  • R 4 is a linear or branched, preferably unsubstituted, alkyl radical having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and in particular having 10 to 19 carbon atoms.
  • Preferred radicals R 4 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, representatives with an even number of carbon atoms being preferred.
  • Particularly preferred radicals R 4 are derived from fatty alcohols having 12 to 19 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols having 10 to 19 carbon atoms.
  • AO is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • the index m is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7.
  • the agent according to the invention can Contain mixtures of nonionic surfactants that have different degrees of ethoxylation.
  • the degree of ethoxylation given represents a statistical average, which can be a whole or a fractional number for a specific product. In general, the degrees of alkoxylation given represent statistical averages, which can be an integer or a fractional number for a specific product.
  • Preferred alkoxylates/ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • the agents according to the invention contain at least one nonionic surfactant.
  • the at least one nonionic surfactant can be any nonionic surfactant known and suitable for the purpose of the invention.
  • the agents described herein contain at least one fatty alcohol alkoxylate with the formula below as nonionic surfactant R 3 -O-(AO) m -H wherein R 3 is a linear or branched alkyl radical, AO is an ethylene oxide (EO) or propylene oxide (PO) moiety and m is an integer from 1 to 50.
  • R 3 represents a linear or branched, substituted or unsubstituted alkyl group.
  • R 3 is a linear or branched alkyl group having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and in particular having 10 to 19 carbon atoms.
  • Preferred radicals R 3 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, representatives with an even number of carbon atoms being preferred.
  • radicals R 3 are derived from fatty alcohols having 12 to 19 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols having 10 to 19 carbon atoms.
  • AO is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • the index m is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7.
  • the agent according to the invention can Contain mixtures of nonionic surfactants that have different degrees of ethoxylation.
  • Such fatty alcohol ethoxylates are available under the trade names Dehydol® LT7 (Cognis), Lutensol® AO7 (BASF), Lutensol® M7 (BASF) and Neodol® 45-7 (Shell Chemicals).
  • the detergent can also contain amine oxide as a nonionic surfactant.
  • amine oxides established in the prior art for this purpose can be used as amine oxides, i.e. compounds which have the formula R 1 R 2 R 3 NO, in which each R 1 , R 2 and R 3 independently of the others is an optionally substituted hydrocarbon chain with 1 to 30 carbon atoms can be used.
  • Particularly preferred amine oxides employed are those in which R 1 is alkyl of 12 to 18 carbon atoms and R 2 and R 3 are each independently alkyl of 1 to 4 carbon atoms, especially alkyl dimethyl amine oxides of 12 to 18 carbon atoms.
  • Suitable amine oxides are N-cocoalkyl-N,N-dimethylamine oxide, N-tallowalkyl-N,N-dihydroxyethylamine oxide, myristyl/cetyldimethylamine oxide or lauryldimethylamine oxide.
  • compositions herein may also contain several of the nonionic surfactants described above.
  • the surfactants described above are used in customary amounts, the total surfactant content of the compositions according to the invention, as described above, being in the range from 32 to 38% by weight.
  • the agents contain at least two anionic surfactants and at least one nonionic surfactant.
  • the anionic surfactants are alkylbenzene sulfonates, as described above, which are usually present in the compositions in amounts of 10 to 25% by weight, preferably 12 to 20% by weight, particularly preferably 14 to 18% by weight.
  • the agents also contain alkyl ether sulfates, usually in amounts of 2 to 10% by weight, in particular 3 to 8% by weight.
  • the total content of anionic surfactants is typically 15 to 25% by weight.
  • nonionic surfactants are also present, usually in amounts of 10 to 25% by weight, preferably 12 to 20% by weight.
  • the alkyl ethers as described above, are particularly preferred here.
  • the liquid detergents therefore contain 12-20% by weight, preferably 14-18% by weight, of alkyl benzene sulfonates, 2 to 10% by weight, preferably 3 to 8% by weight, of alkyl ether sulfates and 12-20% by weight of alkyl ethers, in particular fatty alcohol alkoxylates.
  • the detergent can contain at least one fatty acid soap. These are particularly beneficial for cold wash performance. Preferred detergents are therefore characterized in that they contain--based on their weight--from 0.1 to 15% by weight, preferably from 0.2 to 12.5% by weight, of soap(s). Especially preferred are soaps of fatty acids having 12 to 18 carbon atoms.
  • the fatty acid soaps can be in the form of their sodium, potassium or magnesium or ammonium salts. They are preferably in the form of their sodium salts and/or ammonium salts.
  • liquid detergents described herein also preferably contain at least one enzyme.
  • the at least one enzyme can be any enzyme known in the prior art that can display catalytic activity in a detergent or cleaning agent and includes, without being limited to, for example proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin -Cleaving enzymes, tannases, xylanases, xanthanases, ß-glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof.
  • the at least one enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof. In principle, these enzymes are of natural origin, but based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN' and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus , subtilisin DY and the subtilases, but no longer the subtilisins in the narrower sense, thermitase, proteinase K and the enzymes assigned proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A/S, Bagsvaerd, Denmark.
  • subtilisins 147 and 309 are marketed under the trade names Esperase® and Savinase® by the Novozymes company.
  • the protease variants listed under the name BLAP® are derived from the protease from Bacillus lentus DSM 5483.
  • proteases are, for example, those sold under the trade names Durazym®, Relase® , Everlase® , Nafizym® , Natalase® , Kannase® and Ovozyme® from Novozymes, which are available under the trade names Purafect® , Purafect® OxP , Purafect® Prime, Excellase ® and Properase ® from Genencor, sold under the trade name Protosol ® from Advanced Biochemicals Ltd., Thane, India, sold under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, sold under the trade names Proleather ® and Protease P ® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • the proteases from Bacillus gibsonii and Bacillus pumilus are also used with particular preference.
  • amylases are the ⁇ -amylases from Bacillus licheniformis , from B. amyloliquefaciens or from B. stearothermophilus and their improved developments for use in detergents or cleaning agents.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl® and from Genencor under the name Purastar® ST. Further development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl® and Termamyl® ultra, from Genencor under the name Purastar® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase® .
  • amyloliquefaciens is marketed by the company Novozymes under the name BAN® , and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG® and Novamyl® , also from the company Novozymes. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Fusion products of all the molecules mentioned can also be used.
  • Examples of usable lipases or cutinases which are included in particular because of their triglyceride-splitting activities, but also to generate peracids in situ from suitable precursors, are the lipases originally available from Humicola lanuginosa ( Thermomyces lanuginosus ), or further developed ones, in particular those with the amino acid exchange D96L. They are marketed, for example, by the Novozymes company under the trade names Lipolase® , Lipolase® Ultra, LipoPrime® , Lipozyme® and Lipex® . Furthermore, for example, the cutinases can be used which were originally isolated from Fusarium solani pisi and Humicola insolens .
  • Lipases that can also be used are available from the Amano company under the names Lipase CE® , Lipase P® , Lipase B® , or Lipase CES® , Lipase AKG® , Bacillus sp. Lipase ® , Lipase AP ® , Lipase M-AP ® and Lipase AML ® available.
  • the lipases or cutinases from Genencor can be used, the starting enzymes of which were originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • Lipase® and Lipomax® originally marketed by Gist-Brocades and the enzymes marketed by Meito Sangyo KK, Japan, under the names Lipase MY- 30® , Lipase OF® and Lipase PL® Mention should also be made of the product Lumafast® from Genencor .
  • cellulases can be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various aspects of performance. These performance aspects include, in particular, the contributions of cellulase to the primary washing performance of the agent (cleaning performance), to the secondary washing performance of the agent (antiredeposition effect or graying inhibition), to finishing (fabric effect) or to exerting a "stone washed" effect.
  • cleaning performance the contributions of cellulase to the primary washing performance of the agent
  • antiredeposition effect or graying inhibition to finishing (fabric effect) or to exerting a "stone washed” effect.
  • a usable fungal, endoglucanase (EG)-rich cellulase preparation, or its further developments, is offered by the company Novozymes under the trade name Celluzyme® .
  • Endolase® and Carezyme® which are also available from Novozymes, are based on the 50 kD EG or the 43 kD EG from H. insolens DSM 1800.
  • Other commercial products from this company that can be used are Cellusoft® , Renozyme® and Celluclean® .
  • Also usable are, for example, the 20 kD EG from Melanocarpus, which are available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch® .
  • Other commercial products from AB Enzymes are Econase® and Ecopulp® .
  • Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, wherein the Bacillus sp.
  • CBS 670.93 is available from Genencor under the trade name Puradax®. Further Commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge® Neutra. Variants of these enzymes obtainable by point mutations can also be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from Melanocarpus , in particular Melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.
  • hemicellulases can be used in particular to remove certain problem soils.
  • these include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulases, pectin-splitting enzymes and ß-glucanases.
  • the ⁇ -glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes.
  • Hemicellulases that are particularly preferred according to the invention are mannanases, which are marketed, for example, under the trade names Mannaway® by the company Novozymes or Purabrite® by the company Genencor.
  • the pectin-splitting enzymes also include enzymes with the designations pectinase, pectate lyase, pectin esterase, pectin demethoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectinoesterase, pectin pectyl hydrolase, pectin depolymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin polygalacturonase EndoPolygalacturonase, Poly- ⁇ -1,4-Galacturonide Glycanohydrolase, Endogalacturonase, Endo-D-galacturonase, Galacturan 1,4- ⁇ -galacturonidase, Exopolygalacturonase, Poly(galacturonate) Hydrolase, Exo-
  • enzymes suitable in this regard are, for example, under the names Gamanase® , Pektinex AR® , X- Pect® or Pectaway® from the company Novozymes, under the name Rohapect UF®, Rohapect TPL® , Rohapect PTE100® , Rohapect MPE® , Rohapect MA plus HC, Rohapect DA12L® , Rohapect 10L® , Rohapect B1L® from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
  • oxidoreductases for example oxidases, oxygenases, catalases (which react as peroxidases at low H 2 O 2 concentrations), peroxidases such as halo-, chloro-, bromo-, lignin -, glucose or manganese peroxidases, dioxygenases or laccases (Phenol oxidases, polyphenol oxidases) may be included. Suitable commercial products are Denilite® 1 and 2 from Novozymes.
  • the detergents in particular liquid detergents, contain the at least one enzyme in total amounts established in the prior art.
  • the at least one enzyme can be present in a total amount of 1 ⁇ 10 -8 to 5% by weight based on active protein or in a total amount of 0.001 to 3% by weight, or 0.01 to 1.5% by weight. % or 0.05 to 1.25% by weight.
  • the amounts given are to be understood in such a way that each enzyme contained can be contained in the amounts mentioned.
  • the enzymes are preferably used as enzyme liquid formulation(s).
  • the at least one enzyme that is present in a washing or cleaning agent supports the cleaning performance of the agent on specific soiling or stains.
  • An agent according to the invention particularly preferably contains a number of enzymes, it being possible for the enzymes to belong to the same or different enzyme classes.
  • the enzymes particularly preferably show synergistic effects with regard to their action on specific soiling or stains, i.e. the enzymes contained in the composition support each other in their cleaning performance.
  • the stabilization of the pH of the agent through the use of inorganic and organic bases according to the invention stabilizes the enzymes that are sensitive to pH fluctuations and thus ensures their activity even after prolonged storage.
  • the detergent can contain other ingredients that further improve the performance and/or aesthetic properties of the detergent.
  • the detergent preferably additionally contains one or more substances from the group of builders/complexing agents, bleaches, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bitterns, ironing aids, repellents and impregnating agents, swelling and non-slip agents, softening components, pH adjusters and UV absorbers.
  • polymers based on terephthalate-PEG such as those commercially available under the trade name Texcare®
  • Texcare® can be used as anti-redeposition agents.
  • (co)polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol can also be used.
  • Any substance that destroys or absorbs dyes through oxidation, reduction or adsorption and thereby decolorizes materials can be used as a bleaching agent.
  • hypohalite-containing bleaches hydrogen peroxide, perborate, percarbonate, peroxoacetic acid, diperoxoazelaic acid, diperoxododecanedioic acid and oxidative enzyme systems.
  • liquid detergents are typically free of non-enzymatic bleaches.
  • silicates aluminum silicates (in particular zeolites), carbonates, phosphonates, organic di- and polycarboxylic acids or their salts and mixtures of these substances should be mentioned as builders which can be present in the detergent.
  • Organic builders which can be present in the detergent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • aminocarboxylic acids such as in particular glutamine diacetic acid (GLDA) and methylglycine diacetic acid (MGDA).
  • Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g/mol.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 15,000 g/mol. Due to their superior solubility, the short-chain polyacrylates which have molar masses from 1000 to 10,000 g/mol, and particularly preferably from 1000 to 5000 g/mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • the polymers can also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid, as a monomer.
  • liquid detergents preference is given to using soluble builders, such as citric acid, or acrylic polymers with a molar mass of 1000 to 5000 g/mol.
  • the detergents can also contain phosphonates, such as HEDP (1-hydroxyethane-1,1-diphosphonic acid) or DTPMP (diethylene triamine penta(methylene phosphonate), as builders and complexing agents.
  • phosphonates such as HEDP (1-hydroxyethane-1,1-diphosphonic acid) or DTPMP (diethylene triamine penta(methylene phosphonate), as builders and complexing agents.
  • Preferred liquid detergents preferably contain water as the main solvent. It is preferred that the detergent contains more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 25% by weight, in each case based on the total amount of detergent, water. Particularly preferred liquid detergents contain--based on their weight--5 to 65% by weight, preferably 10 to 60% by weight, particularly preferably 25 to 55% by weight and in particular 30 to 50% by weight of water. Alternatively, the liquid detergents can be low-water to anhydrous detergents, with the water content in a preferred embodiment being less than 10% by weight and more preferably less than 8% by weight, based in each case on the total liquid detergent .
  • non-aqueous solvents can be added to the detergent.
  • Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range.
  • the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, 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 ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol,
  • the detergent contains such an alcohol, in particular 1,2-propanediol and/or glycerol, in amounts of between 0.5 and 15% by weight, based on the detergent as a whole.
  • the detergents described herein in particular the low-water to water-free liquid detergents described, can be filled into a water-soluble envelope and thus be part of a water-soluble packaging. If the detergent is packaged in a water-soluble envelope, it is preferred that the water content is less than 10% by weight, based on the detergent as a whole.
  • a water-soluble packaging contains a water-soluble cover in addition to the detergent.
  • the water-soluble cover is preferably formed by a water-soluble film material.
  • Such water soluble packages can be made by either vertical form fill seal (VFFS) processes or thermoforming processes.
  • the thermoforming process generally includes forming a first sheet of water-soluble film material to form recesses for receiving a composition therein, filling the composition into the recesses, covering the composition-filled recesses with a second sheet of water-soluble film material, and sealing the first and second layers together at least around the bulges.
  • the water-soluble cover is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the cover can be formed from one or from two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if any, can be the same or different.
  • the water-soluble packaging comprising the detergent and the water-soluble envelope can have one or more compartments.
  • the liquid detergent may be contained in one or more compartments, if any, of the water-soluble envelope.
  • the amount of liquid detergent preferably corresponds to the full or half dose required for one wash cycle.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Suitable water-soluble films for producing the water-soluble casing are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 g/mol, preferably from 20,000 to 500,000 g/mol, particularly preferably from 30,000 to 100,000 g/mol and in particular from 40,000 to 80,000 g/mol.
  • polymers selected from the group consisting of polymers containing acrylic acid, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid and/or mixtures of the above polymers can be added to a film material suitable for producing the water-soluble covering.
  • preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
  • Suitable water-soluble films for use in the overwraps of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL films from Aicello Chemical Europe GmbH or Kuraray VF-HP films.
  • the water-soluble packaging can have an essentially dimensionally stable spherical and cushion-shaped configuration with a circular, elliptical, square or rectangular basic shape.
  • the water-soluble packaging can have one or more chambers for storing one or more agents. If the water-soluble packaging has two or more compartments, at least one compartment contains a liquid detergent. The other chambers can each contain a solid or a liquid detergent.
  • Another subject of the invention is a method for cleaning textiles, which is characterized in that a detergent according to the invention is used in at least one method step and the use of a liquid detergent according to the invention for washing textiles.
  • Processes for cleaning textiles are generally characterized in that various cleaning-active substances are applied to the items to be cleaned in several process steps and washed off after the exposure time, or that the items to be cleaned are treated in some other way with a detergent or a solution or dilution of this agent. All conceivable washing methods can be enriched in at least one of the method steps by the use of a detergent according to the invention and then represent embodiments of the present invention. All facts, objects and embodiments that are described for agents according to the invention are also applicable to this subject of the invention. Therefore, at this point, reference is expressly made to the disclosure at the appropriate point, with the indication that this disclosure also applies to the above methods and uses according to the invention.
  • Table 1 Detergent formulation, components in % by weight substance Linear alkyl benzene sulfonate 16.0 fatty alcohol ether sulfate 5.0 NOK surfactant 16.0 soap 0.5 DTPMP (phosphonate) 1.0 boric acid 1.0 citric acid 3.0 Optical brightener 0.1 monoethanolamine 5.5 NaOH 1.5 1,2-propylene glycol 10.0 enzymes 1.5 water ad 100

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Claims (8)

  1. Agent de lavage liquide comportant une concentration en tensioactif de 32 à 38 % en poids par rapport au poids total de l'agent, caractérisé en ce que l'agent contient au moins une base inorganique et au moins une base organique dans un rapport molaire de 1:2 à 1:8, de préférence de 1:3 à 1:5, et au moins deux tensioactifs anioniques et au moins un tensioactif non ionique, les au moins deux tensioactifs anioniques comprenant au moins un alkylbenzènesulfonate et au moins un alkyléthersulfate et
    l'agent de lavage liquide présentant un pH dans la plage de 8,2 à 8,6 directement après la fabrication.
  2. Agent de lavage liquide selon la revendication 1, caractérisé en ce que l'au moins une base inorganique est une base forte comportant une valeur de pKs > 9, de préférence > 10, plus préférablement > 12, le plus préférablement ≥ 14, de préférence choisie parmi les hydroxydes de métaux alcalins, en particulier NaOH et KOH.
  3. Agent de lavage liquide selon la revendication 1 ou 2, caractérisé en ce que l'au moins une base organique est une base forte comportant une valeur de pKs > 7, de préférence > 9, de manière particulièrement préférée choisie parmi les amines organiques, plus préférablement les éthanolamines, de manière tout particulièrement préférée le monoéthanolamine et la triéthanolamine.
  4. Agent de lavage liquide selon l'une des revendications 1 à 3, caractérisé en ce qu'il contient l'au moins un alkylbenzènesulfonate en une quantité de 10 à 25 % en poids, de préférence de 12 à 20 % en poids, de manière particulièrement préférée de 14 à 18 % en poids, par rapport au poids total de l'agent, et l'au moins un alkyléthersulfate en une quantité de 2 à 10 % en poids, en particulier de 3 à 8 % en poids, par rapport au poids total de l'agent.
  5. Agent de lavage liquide selon l'une des revendications 1 à 4, caractérisé en ce que l'au moins un tensioactif non ionique est choisi dans le groupe des alcoxylates d'alcool gras et en particulier dans des quantités de 10 à 25 % en poids, de préférence de 12 à 20 % en poids, par rapport au poids total de l'agent dans lequel il est contenu.
  6. Agent de lavage liquide selon l'une des revendications 1 à 5, caractérisé en ce que l'agent
    (1) contient au moins une enzyme ; et/ou
    (2) contient en outre au moins un autre constituant choisi dans le groupe constitué par les adjuvants, les agents de blanchiment, les électrolytes, les parfums, les supports de parfum, les agents fluorescents, les colorants, les hydrotropes, les inhibiteurs de mousse, les huiles de silicone, les agents anti-redéposition, les inhibiteurs de grisaillement, les agents anti-rétrécissement, les agents anti-froissage, les inhibiteurs de transfert de couleur, les substances actives antimicrobiennes, les germicides, les fongicides, les antioxydants, les conservateurs, les inhibiteurs de corrosion, les antistatiques, les agents amers, les auxiliaires de repassage, les agents de répulsion et d'imprégnation, les agents gonflants et antidérapants, les composants adoucissants, les agents de fixation du pH ainsi que les absorbeurs d'UV.
  7. Utilisation d'un agent de lavage liquide selon l'une des revendications 1 à 6 pour le lavage de textiles.
  8. Procédé permettant le nettoyage de textiles, caractérisé en ce qu'un agent de lavage liquide selon l'une des revendications 1 à 6 est utilisé dans au moins une étape de procédé.
EP17730137.1A 2016-06-16 2017-06-14 Détergent à lessive liquide concentré à ph constant Active EP3472293B1 (fr)

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DE102016210744.5A DE102016210744A1 (de) 2016-06-16 2016-06-16 Konzentrierte Flüssigwaschmittel mit konstantem pH-Wert
PCT/EP2017/064516 WO2017216214A1 (fr) 2016-06-16 2017-06-14 Détergent à lessive liquide concentré à ph constant

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011005943A1 (fr) 2009-07-10 2011-01-13 The Procter & Gamble Company Compositions contenant des particules délivrant un agent bénéfique
WO2013016368A1 (fr) 2011-07-25 2013-01-31 The Procter & Gamble Company Compositions de détergents
EP2791308B1 (fr) 2011-12-12 2015-12-16 Unilever Plc. Compositions pour lessiver

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US4079078A (en) * 1974-06-21 1978-03-14 The Procter & Gamble Company Liquid detergent compositions
US4105592A (en) * 1974-06-21 1978-08-08 The Procter & Gamble Company Liquid detergent compositions
US4075118A (en) * 1975-10-14 1978-02-21 The Procter & Gamble Company Liquid detergent compositions containing a self-emulsified silicone suds controlling agent
DE2847438A1 (de) * 1978-11-02 1980-05-22 Henkel Kgaa Fluessiges, kaeltestabiles waschmittelkonzentrat
DE3378637D1 (en) * 1982-07-27 1989-01-12 Procter & Gamble Liquid detergent compositions comprising coacervate mixture of alkylcellulose and carboxymethylcellulose and method for preparing them
WO1995029224A1 (fr) * 1994-04-22 1995-11-02 The Procter & Gamble Company Compositions de detergent contenant une amylase
EP0907702A1 (fr) * 1996-06-28 1999-04-14 The Procter & Gamble Company Compositions de nettoyage liquides et shampooings contenant des tensioactifs dianioniques et/ou alcoxyles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011005943A1 (fr) 2009-07-10 2011-01-13 The Procter & Gamble Company Compositions contenant des particules délivrant un agent bénéfique
WO2013016368A1 (fr) 2011-07-25 2013-01-31 The Procter & Gamble Company Compositions de détergents
EP2791308B1 (fr) 2011-12-12 2015-12-16 Unilever Plc. Compositions pour lessiver

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PL3472293T3 (pl) 2022-06-20
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ES2911472T3 (es) 2022-05-19
DE102016210744A1 (de) 2017-12-21

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