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EP3107990A1 - Concentrés de lessive - Google Patents

Concentrés de lessive

Info

Publication number
EP3107990A1
EP3107990A1 EP15702793.9A EP15702793A EP3107990A1 EP 3107990 A1 EP3107990 A1 EP 3107990A1 EP 15702793 A EP15702793 A EP 15702793A EP 3107990 A1 EP3107990 A1 EP 3107990A1
Authority
EP
European Patent Office
Prior art keywords
washing
sub
liquor
winsor type
microemulsion system
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Withdrawn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
EP15702793.9A
Other languages
German (de)
English (en)
Inventor
Peter Schmiedel
Kaoru Tachikawa
Yvonne Willemsen
Arnd Kessler
Nicole BODE
Iwona Spill
Reinhard Strey
Anna KLEMMER
Christian Nitsch
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 EP3107990A1 publication Critical patent/EP3107990A1/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Withdrawn legal-status Critical Current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
    • 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
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F35/00—Washing machines, apparatus, or methods not otherwise provided for
    • D06F35/005—Methods for washing, rinsing or spin-drying
    • D06F35/006—Methods for washing, rinsing or spin-drying for washing or rinsing only
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/02—Devices for adding soap or other washing agents

Definitions

  • the present invention relates to concentrates which are suitable for use as laundry detergents in laundry machines, their use for the formation of microemulsions or a microemulsion system in a washing machine and a textile washing process, which is carried out to form a microemulsion or a microemulsion system.
  • WO 2005/003268 a washing process is known in which the detergent is dispersed in less water than in conventional processes and the laundry is thus contacted at a greater ratio of the amount of dry textile to the amount of water with a less dilute wash liquor.
  • the detergent formulation itself has no special requirements.
  • the ratio of the weight of the dry laundry amount to the weight of the water amount is 1: 2 to 4: 1.
  • WO 2013/134168 discloses a washing method in which, in at least two successive sub-washing cycles, the laundry in the first sub-washing cycle is treated with a more concentrated detergent composition than in a second sub-washing cycle.
  • a wash cycle is the period from the creation of a wash liquor to the removal of the wash liquor from the washing machine.
  • a wash cycle may be subdivided into sub-wash cycles whereby at the end of the first sub-wash cycle the wash liquor is not removed but at the beginning of the second cycle new, additional water is fed into the already existing wash liquor. It is preferred that the first sub-washing cycle lasts longer than the second.
  • the detergent formulation itself has no special requirements.
  • WO 2012/04891 1 discloses a washing method in a washing machine, wherein the cleaning agents and possibly various cleaning agents or components thereof are sprayed into the interior of the washing machine.
  • the process and control of the machine are designed to consume significantly less water for both cleaning and rinsing than traditional processes. Further requirements for the cleaning agents, with the exception of the property that they must be sprayable, are not provided.
  • microemulsions are thermodynamically stable emulsions and have extremely low interfacial tensions.
  • a person skilled in the art also knows that in order to remove dirt, the interfacial tension between water and the fat component of the soiling must be lowered.
  • WO 2013/1 10682 describes detergents, in particular for manual dishwashing, but also for the pretreatment of laundry, the compositions containing 1 to 50% by weight of anionic surfactants and 1 to 36% by weight of salts and which on contact with oils and / or fats spontaneously form a microemulsion.
  • microemulsions which contain 1 to 50% by weight of anionic surfactants, 1 to 36% by weight of salts, 10 to 80% by weight of water and 10 to 80% by weight of at least one triglyceride or a mixture of a triglyceride and a or more components from the group consisting of waxes, lipids, terpenes, triterpenes and fatty acids.
  • the formation of the microemulsion takes place in situ with the triglycerides or triglyceride-containing mixtures present on the surface to be cleaned.
  • US Pat. No. 6,112,120 discloses acidic hard surface cleaners which may be in the form of a microemulsion. An application of such emulsions in a washing machine is not recommended.
  • German patent application DE 10129517 proposes the use of microemulsions of water, one or more hydrophobic components and sugar-based nonionic surfactants as stain pretreatment agents for textiles or for cleaning hard surfaces. The suitability of these microemulsions for use in washing machines is not described.
  • WO 201 1/073062 discloses bicontinuous microemulsion systems which are suitable as stain pretreatment agents and which are capable of dissolving solid and solidified fatty stains in the main wash at neutral pH.
  • the subject of the patent is therefore a mono- or multiphase non-solid concentrate for use as a laundry detergent, which is suitable for giving or maintaining a Winsor Type 2 microemulsion system when diluted in a washing machine with a short liquor washing technique.
  • Winsor microemulsion systems consisting of a water component, an oil component and amphiphile can be subdivided according to their phase equilibria into 4 types.
  • the surfactant is soluble primarily in water and in an O / W microemulsion form. It consists of a surfactant-rich aqueous phase (07W microemulsion) and an excess but low-surfactant oil phase.
  • the surfactant is especially soluble in an oil phase and in a W / O microemulsion form. It consists of a surfactant-rich oil phase (W / O microemulsion) and an excess but low-surfactant aqueous phase.
  • a Winsor Type 3 microemulsion system displays a bicontinuous microemulsion, also called a mid-phase microemulsion, of a surfactant-rich middle phase which coexists with a low surfactant aqueous phase as well as a low surfactant oil phase.
  • a Winsor Type 4 microemulsion system is a single phase homogeneous mixture and, unlike Winsor types 1 to 3, which consist of 2 or 3 phases of which only one phase is a microemulsion, is a microemulsion high surfactant concentrations to achieve this single phase, while in Winsor Type 1 and Type 2 microemulsion systems significantly lower surfactant concentrations are required to achieve a stable phase equilibrium. For this reason, while Winsor Type 4 microemulsions are often described in the patent literature, they are seldom or even not used in domestic machine washing processes. The large amount of surfactant required makes such a process uneconomical and is not least environmentally friendly.
  • the consumer product according to the invention is a single- or multiphase concentrate which is not solid, but may be liquid, gelatinous or pasty at room temperature, for example.
  • the teachings of the invention take advantage of the fact that the detergent composition used in the washing machine is intended to be a Winsor Type 2 microemulsion system, but the concentrate which constitutes the consumer product need not already be in the form of a Winsor Type 2 microemulsion system.
  • the concentrate it is sufficient if the concentrate can be converted to a Winsor Type 2 microemulsion system on dilution with water and especially in a shortwash washing machine.
  • the concentrate is present as a Winsor Type 4 microemulsion, if it can be converted into a Winsor Type 2 microemulsion system during the preparation of the wash liquor. Since a Winsor Type 2 microemulsion system is biphasic, it may be desirable in the interests of uniform distribution of the short liquor on the wash that the concentrate from a Winsor Type 2 microemulsion system be non-macroscopically separate during use, but application in a manner An emulsion of the two phases of the Winsor Type 2 system is applied. Such an emulsion can be made, for example, by appropriate mixing, in particular stirring of the microemulsion type before application to the laundry.
  • the type of emulsion depends both on the emulsifier and on the phase in which the emulsifier, for example a surfactant or various surfactants, dissolves. If water-soluble, ie hydrophilic, emulsifiers, for example anionic surfactants, are used, O / W emulsions are formed. However, anionic surfactants can be rendered more hydrophobic by addition of salts by electrostatic shielding the hydrophilic head group of the anionic surfactants so that W / O emulsions are achieved.
  • the behavior of the emulsifiers is influenced by the temperature. If hydrophobic emulsifiers, for example nonionic surfactants, are used, W / O emulsions are formed. An addition of salt is not required. Higher application temperatures make the nonionic surfactants more hydrophobic and can interact better with grease and oily dirt. If the temperature is reduced again during dilution of the liquor, the nonionic surfactants become hydrophilic again, the grease and oily soils can be better detached from the textile and dispersed in the aqueous liquor and ultimately transported away with the aqueous liquor.
  • Short liquor washing technique means the provision of a first sub-wash cycle in which the first contact of the fabric or laundry with water and the example soaked or sprayed detergent, wherein the ratio of the weight of the dry textile or laundry lot to the aqueous liquor is at least 1: 8, but preferably a short liquor is used, in which the ratio of the weight of the dry textile or laundry lot to the aqueous liquor is at least 1: 4, in particular not less than 1: 2, for example 1: 2 to 4: 1, advantageously 1: 2 to 2: 1.
  • the aqueous liquor used in the first sub-wash cycle consists of a Winsor Type 2 microemulsion system.
  • the upper limit of the weight ratio of the dry fabric or laundry to the Winsor Type 2 aqueous liquor is limited to ensure that the entire batch of laundry may be thoroughly moistened during the first sub-wash cycle. Only then is it ensured that the microemulsion can interact with all contaminants.
  • the lower limit of the weight ratio of the dry textile or laundry lot to the aqueous liquor of Winsor type 2 is limited in preferred embodiments of the invention in that when used in the washing machine as little as possible "free liquor", ie as little as possible excess liquor, which For this reason, a weight ratio of the dry textile or laundry lot to the aqueous liquor of Winsor type 2 is from 1: 2 to 1 : 1, in particular not less than 1: 1, 5.
  • the concentrate preferably contains surfactants which serve as emulsifiers in the Winsor Type 2 microemulsion system.
  • the concentrates contain anionic and / or nonionic surfactants, with a combination of anionic and nonionic surfactants being particularly advantageous with regard to the removal of a wide variety of soils.
  • the content of the concentrates of surfactants and in particular of a combination of anionic and nonionic surfactants is preferably from 2 to 35% by weight, in particular from 5 to 30% by weight.
  • the Winsor Type 2 microemulsion systems used in the short liquor washing technique generally have at least 0.2% by weight of surfactants, in particular a combination of anionic and nonionic surfactants. Levels of at least 0.3% by weight, preferably from 0.5 to not more than 15% by weight and in particular from 1 to not more than 10% by weight, of surfactants, in particular of a combination of anionic and nonionic surfactants, are preferred here.
  • Suitable anionic surfactants include alkylbenzenesulfonic acid salts, olefin sulfonic acid salts, C 12-18 alkanesulfonic acid salts, fatty alcohol sulfate, fatty alcohol ether sulfates, but also fatty acid soaps or a mixture of two or more of these anionic surfactants.
  • alkylbenzenesulfonic acid salts, fatty alcohol (ether) sulfates and mixtures thereof are particularly preferred.
  • Preferred surfactants of the sulfonate type are C9-i3-alkylbenzenesulfonates, olefin-sulfonates, i. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from Ci2-i8 monoolefins with terminal or internal double bond by sulfonation ren with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration.
  • C 12 -is alkanesulfonates and the esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Alk (en) ylsulfates are the salts of the sulfuric acid half esters of C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths prefers.
  • the Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates and Ci4-Ci5-alkyl sulfates are preferred.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • fatty alcohol ether sulfates such as the sulfuric acid monoesters of the straight-chain or branched C7-2i alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-n alcohols having on average 3.5 mol of ethylene oxide (EO) or is fatty alcohols having 1 to 4 EO, in particular Ci2-i4 fatty alcohols with 2 EO are suitable.
  • Suitable anionic surfactants are fatty acid 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. Preferably, the content of the concentrates of fatty acid soaps 0 to 5 wt .-%.
  • the anionic surfactants including the fatty acid soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts and / or ammonium salts.
  • Amines which can be used for the neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being preferred.
  • Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof.
  • the alkoxylated fatty alcohols used are preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 2 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear.
  • EO ethylene oxide
  • alcohol ethoxylates having 12 to 18 C atoms for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14-alcohols with 2 EO, 3 EO, 4 EO or 7 EO, Cg-n-alcohol with 7 EO, C 12 -is alcohols with 3 EO, 5 EO or 7 EO , Ci6-is alcohols with 5 EO or 7 EO and mixtures of these.
  • 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. It is particularly preferred that a Ci2-is-alcohol, in particular a Ci2-Ci4-alcohol or a Ci3-alcohol with an average of 2 EO or 3 EO is used as a nonionic surfactant.
  • corresponding propylene oxide adducts in particular also EO / PO mixed adducts, are advantageous, with particular preference being given to C 16 -C 18 -alkyl polyglycol ethers having in each case 2 to 8 EO and PO units.
  • EO / BO mixed adducts and even EO / PO / BO mixed adducts are also preferred.
  • Particularly preferred EO / PO mixed adducts include C 16-18 fatty alcohols having fewer PO than EO units, in particular C 16-18 fatty alcohols having 4 PO and 6 EO or C 16-18 fatty alcohols having 2 PO and 4 EO.
  • inorganic salts are not absolutely necessary in order to be able to produce Winsor Type 2 microemulsions.
  • concentrates in particular anionic surfactant-containing concentrates, which contain one or more inorganic salts are preferred.
  • Preferred inorganic salts are alkali metal sulfates and alkali metal halides, especially chlorides, and also alkali metal carbonates.
  • Very particularly preferred inorganic salts are sodium sulfate, sodium hydrogen sulfate, sodium carbonate, Natnumhydogencarbonat and mixtures from these.
  • the content of the concentrates of one or more inorganic salts is preferably 20 to 70% by weight.
  • the content of one or more inorganic salts is preferably 2 to 20% by weight and more preferably 5 to 15% by weight, with concentrations of 8 to 12% by weight being particularly preferred have exposed.
  • the concentrates also contain one or more additional oils.
  • an additional oil which is used additionally and deliberately to the greasy and oily soils present on the textiles to be washed, is in principle any organic non-surfactant liquid which is not miscible with water or forms two phases in combination with water understood, which itself has a grease dissolving ability.
  • additional oils are preferred, which not only have a good fat dissolving power, but are also biodegradable and acceptable odor.
  • Particularly preferred concentrates have as additional oil dioctyl ether, oleic acid, limonene, low molecular weight paraffins and / or low molecular weight silicone oils, for example, the well-known from chemical cleaning solvent cyclosiloxane D5 on.
  • aromatic solvents such as toluene are of course effective additive oils for the purposes stated herein; but they are usually omitted for toxicological reasons.
  • the content of the concentrates in one or more additional oils is preferably from 2 to 60% by weight and in particular from 5 to 50% by weight.
  • additional oils function as solvents for the fats, which are solid at the application temperatures in the washing machine.
  • the oil and grease-like dirt on the laundry is usually not well defined. It is therefore not known in advance which surfactants must be present in the W / O emulsion in order to actually interact with the soil in such a way that it becomes relaxed and can be flushed out of the textile.
  • the grease and oily soils on the fabrics could unbalance the microemulsion system.
  • the content of one or more additional oils is preferably 0.2 to 20% by weight and in particular 0.5 to 15% by weight, with concentrations of 1 to 12% by weight. -% have been found to be particularly preferred.
  • Winsor Type 2 microemulsion systems can be prepared from the concentrates of this invention by dilution with water containing from 0.2% to 5% by weight of surfactants, preferably from 0.3% to 1% by weight of surfactants, with particular preference to less than zero , 1 wt .-% surfactants, and 0.5 to 5 wt .-%, advantageously 1 to 3 wt .-% additional oils.
  • the aforementioned Winsor 2 microemulsion systems comprise from 80 to 94.6% by weight of water and from 0.2 to 15% by weight of inorganic salts, preferably from 1 to 12% by weight of inorganic salts, in particular from 5 to 10% by weight .-% inorganic salts.
  • the concentrates have inorganic salts and / or additive oils. It has proven to be particularly advantageous, especially when anionic and nonionic surfactants are contained in the concentrates, that the concentrates have both one or more inorganic salts and one or more additional oils.
  • the weight ratio of inorganic salt to additional oil can vary within a wide range, depending on the surfactants used. Weight ratios of inorganic salt / inorganic salts to additional oil (s) of from 15: 1 to 0.3: 1, preferably from 10: 1 to 0.5: 1 and in particular from 5: 1 to 1: 1, are advantageous.
  • Particularly preferred additional oils, which are present in combination with inorganic salts are di-ethers. Di-n-octyl ether is used with particular advantage.
  • the concentrate contains sodium sulfate and di-n-octyl ether in a weight ratio of 10: 1 to 0.5: 1, preferably from 10: 1 to 1: 1 and in particular from 5: 1 to 1: 1.
  • the concentrate may further comprise at least one, preferably two or more, selected from the group consisting of builders, bleaches, electrolytes, nonaqueous but water miscible solvents, enzymes, pH modifiers, perfumes, perfume carriers, fluorescers, dyes, hydrotropes , Foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, shrinkage inhibitors, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, softening components as well as UV absorbers.
  • Suitable builders which may be present in the concentrate are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Organic builders which may be present in the concentrate 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, 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 thereof.
  • 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 600 to 750,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methylallyl sulfonic acid, as monomer.
  • liquid detergents but preferably soluble builders, such as citric acid, or acrylic polymers having a molecular weight of 1,000 to 5,000 g / mol are used.
  • nonaqueous solvents which are miscible with water can be added to the concentrate.
  • Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methyl propanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n- butyl ether, diethyl englykolmethylether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol
  • non-aqueous, but water-miscible solvents must be selected so that when creating the short liquor a microemulsion system of Winsor type 2 can arise.
  • Preferred concentrates therefore contain only such organic solvents as the stated ethers and di-ethers, in particular di-n-octyl ethers, which may already be used as additional oils.
  • Organic solvents used in conventional liquid detergents are used and which are miscible with water without forming 2 phases, for example, ethanol, propylene glycol or glycerol, are used, if at all, only in minor amounts, wherein omitted in particularly preferred embodiments, such with water without formation of 2 phases miscible organic solvent becomes.
  • anhydrous or at least nearly anhydrous concentrates are used.
  • anhydrous is understood to mean that the content of water in the concentrates is not more than 2% by weight, preferably not more than 1% by weight.
  • the concentrates are in the form of an anhydrous paste which contains surfactants, in particular a mixture of anionic and nonionic surfactants.
  • the surfactant content, in particular the mixture of anionic and nonionic surfactants, in the anhydrous pastes in the same areas as in the aqueous concentrates. The same applies to the other constituents of the concentrates.
  • the pastes in preferred embodiments may contain additional finely divided solids, for example aluminosilicates, such as zeolites or smectites or bentonites, or else silicic acids, for example of the Aerosile® type.
  • aluminosilicates such as zeolites or smectites or bentonites
  • silicic acids for example of the Aerosile® type.
  • the concentrates of the invention may be prepared by any method known in the art.
  • the concentrates according to the invention in the form of disposable portions.
  • disposable portions include in particular containers of water-soluble materials which are filled with the concentrates according to the invention.
  • Particular preference is given to single-chamber or multi-chamber containers, in particular of polyvinyl alcohol or polyvinyl alcohol derivatives or copolymers with vinyl alcohol or vinyl alcohol derivatives as monomer.
  • These disposable portions ensure that the correct amount of the concentrate according to the invention is used in the first sub-washing cycle for the preparation of the Winsor Type 2 microemulsion system and for the corresponding power associated therewith.
  • multiple disposable portions may also be used.
  • a further embodiment of the invention provides that the concentrates are in granulated form on a carrier.
  • suitable carrier materials are the carrier materials known from the prior art for detergents.
  • ingredients of detergents such as builders and alkali metal, for example alkali metal carbonates or zeolites, or bleaching agents such as percarbonates or enzyme granules, but also sodium sulfates or silicates and in particular those substances which have a high absorption capacity for liquids, for example silicic acids.
  • Such granulated products may also be powdered with fancy materials known in the art for this purpose.
  • Particular preference is given to silicic acids, zeolites or other aluminosilicates, but also mixtures of silicic acids and zeolites.
  • Another object of the invention is the use of a concentrate as described above for forming a short liquor of a Winsor Type 2 microemulsion system. All facts and embodiments described for the concentrates are also valid for use.
  • Another object of the invention is a textile washing method in a washing machine, in particular in a household washing machine, with a washing cycle with at least two successive Unterwaschzyklen, wherein
  • the laundry item to be cleaned is placed in the laundry room of the washing machine,
  • a concentrate as described above or a granulated concentrate as described above are placed in a detergent storage room of the washing machine and
  • the method provides that a wash cycle is performed with at least 2 consecutive sub-wash cycles.
  • a washing cycle is the period of time from the creation of a first wash liquor containing detergent to the removal of the wash liquor from the washing machine.
  • the washing cycle is subdivided into at least two sub-washing cycles, whereby the washing liquor is not removed at the end of the first to penultimate sub-washing cycle.
  • the short liquor is in the form of a microemulsion. Winsor Type 2 system or maintained in the case that the concentrate used was already as Winsor Type 2 microemulsion system, while at the beginning of the second sub-washing cycle, new, additional water is fed into the existing wash liquor to form a long liquor.
  • Such a method is preferably carried out in a washing machine, in particular in a household washing machine which allows a short liquor washing technique.
  • a washing machine in particular in a household washing machine which allows a short liquor washing technique.
  • the statements already made above regarding the short liquor washing technology and the short liquor apply accordingly.
  • the machines in question allow the use of concentrates or granulated concentrates to create a short liquor in the machine.
  • Winsor Type 2 microemulsion system is biphasic, it is preferred that, in the interests of uniform distribution of the short liquor on the laundry, that the Winsor Type 2 microemulsion system not be macroscopically separate during application, but as an emulsion of the two phases placed in the laundry treatment room and applied to the laundry items.
  • This temporary emulsion can be formed, for example, by vigorous mixing, in particular by stirring.
  • the machine measures the weight of the dry fabric or laundry and supplies the amount of water required to form the short liquor. This is mixed with the concentrates according to the invention in the above-mentioned mixing device to form a Winsor Type 2 microemulsion system.
  • the machine provide a space in which a temporary emulsion of the concentrate and the water supplied thereto can be formed. This can be supported by the provision of a mixing device, preferably a stirring device in this mixing chamber.
  • the mixing space for producing a temporary emulsion may be the dispensing rinsing chamber of a washing machine, in particular a domestic washing machine, but also an additional space in the machine, in particular the household washing machine.
  • the machine after reading the weight of the laundry item displays its weight readable for the consumer, so that the consumer can dose the appropriate amount of the concentrate.
  • the corresponding metered quantities of the concentrates can be read by the consumer on the overwrap of the concentrates and / or indicated by the machine itself in a suitably programmable machine. Since a free wash liquor, so fleet, which can not be absorbed by the laundry items and remains in Laugensumpf the machine, which would result in an unnecessary dilution of the system and possibly even a deterioration of the washing result, the inventive method provides that as little as possible free fleet arises.
  • a ratio of the weight of the dry textile or linen lot to the short liquor is at least 1: 8, preferably at least 1: 4, in particular not less than 1: 2, for example 1: 2 to 4: 1 is formed.
  • a ratio of the weight of the dry textile or the laundry lot to the short liquor is not less than 1: 1.5. In particular, this ratio may be 1: 1, 2 to 1, 2: 1, ideally 1: 1.
  • the uniform distribution of the short liquor on the laundry items takes place in the washing machine, in particular a household washing machine, preferably by an injection, spraying or pumping system, for example a circulating pump.
  • a method which provides a ratio of the weight of the dry textile or laundry lot to short liquor of 1: 2 to 1: 1, 5, whereby the distribution of the short liquor takes place by means of a circulating pump.
  • the wash liquor is not removed.
  • additional feed of water occurs, ultimately leading to the formation of a liquor known from conventional washing processes.
  • this most dilute liquor is called a long liquor for better distinction from the short liquor.
  • the liquor which includes the dilution stages of the short liquor up to the long liquor, is called diluent liquor in the context of the present invention.
  • the concentration of the detergent in the liquor is reduced.
  • the dilution of the concentration of the salt preferably contained increases the hydrophilicity and water solubility of a preferably contained nonionic surfactant.
  • a phase inversion is caused, wherein first a microemulsion system of the Winsor type 3 and finally with further dilution a microemulsion system of the Winsor type 1 is formed.
  • the Applicant believes that the formation of the Winsor Type 3 microemulsion system is responsible for the improved release of the soil relaxed by the Winsor Type 2 microemulsion system.
  • the skilled person knows that the interfacial tension in the three-phase region of the Winsor Type 3 microemulsion system is very low. It is also known that low interfacial tensions promote the detachment of fat.
  • Another advantage of the low interfacial tensions of the Winsor Type 3 microemulsion systems is that The better fat dissolving power of less surfactant can be used than with conventional Winsor Type 4 microemulsions, making the process more economical and environmentally friendly.
  • the second sub-washing cycle is started by the supply of water, whereby the short liquor is diluted. If the remaining addition of the water until final dilution and thus formation of the long liquor without further time interruption, the phase inversion takes place via the Winsor Type 3 microemulsion system to the Winsor Type 1 microemulsion system in the second subwash cycle.
  • a textile washing process is carried out as described above, in which the phase inversion takes place during the second sub-washing cycle or during the further sub-washing cycles, wherein first a microemulsion system of Winsor type 3 and last of Winsor type 1 is formed.
  • the second sub-wash cycle may comprise multiple stages representing different levels of dilution, but at all stages there is a Winsor Type 3 microemulsion system.
  • the third sub-wash cycle begins. Further addition of water in this third sub-wash cycle is of course possible, but not required for performance reasons, nor desirable for environmental or economic reasons and therefore not preferred.
  • the heating of the machine in the first sub-washing cycle and only in the first sub-washing cycle, is switched on while the heating in the second sub-washing cycle and, if present, further sub-washing cycles and in optionally subsequent rinsing cycles is switched off.
  • This is particularly advantageous when the Winsor Type 2 microemulsion system in the short liquor contains nonionic surfactants. Niotenoids become more hydrophobic with increasing temperature, and more hydrophilic with decreasing temperature.
  • the heated nonionic surfactants cause higher hydrophobicity of the short liquor, thereby improving the interaction with fat and oily soils and their relaxation on the fabrics, while the nonionic surfactants in the cooling dilution liquor and the colder long liquor become more hydrophilic and coexist with the water Rinse the dirt better and have it removed.
  • the first sub-washing cycle is carried out at temperatures of 10 to 60 ° C, preferably of at least 20 to 40 ° C.
  • the method has the advantage that, in contrast to conventional methods, heating energy is consumed only in the first sub-wash cycle. Since the first sub-washing cycle involves only a short liquor, this saves energy, in contrast to conventional processes in which a long liquor, that is to say a larger quantity of aqueous liquor, has to be heated up.
  • a non-aqueous liquor can be provided, wherein less than 10 wt .-%, based on the liquor, of water is supplied to the preparation of the non-aqueous liquor in the present invention.
  • further cleaning steps or care steps for example impregnation of textiles with respect to water and / or dirt, can be carried out.
  • This further washing, cleaning or care step or the further steps may take place before and / or after the rinsing cycles, depending on their intention.
  • WFK 10A cotton lumps were stained with 0.3 ml of olive oil or lard for the preparation of the native stain stains olive oil and lard.
  • commercially available soiled polyester / cotton test fabrics were selected 50:50.
  • the washing experiments were carried out in a Launder-Ometer ® (ATLAS Textile Test Products) with a 60-minute wash cycle at 40 ° C.
  • 2 cotton lobes oval oil and lard
  • 2 soiled test cloths made of polyester / cotton 50/50 were placed together with 10 filling laps WFK 10A (2.2 g each) and 10 steel balls each.
  • the amount of dry textile was thus 26.6 g.
  • Concentrates K1 to K5 were prepared and converted to Winsor Type 2 (M1 to M5) microemulsions by mixing with water.
  • the cotton lobules / test cloths as well as the stuffing lobules were sprayed by a trigger pump to 100% moisture penetration of the fabrics (the weight ratio of the dry test fabrics to the microemulsion system of the Winsor Type 2 was 1: 1).
  • the washing program was started with the formation of a long fleet. After the wash, 3 rinses followed for 10 minutes at 20 ° C. After the wash and after each rinse, the liquors were poured off and the lobes briefly expressed. For each rinse, 200 ml of water was added. After hanging drying and lack of Stoffläppchen / test fabric whose whiteness was determined spectrophotometrically.
  • the experiment according to the invention was repeated with a commercial premium solid detergent (liquid detergent).
  • a concentrate of 30, 15 g of premium solid detergent was dissolved / emulsified in one liter of water (V1).
  • V1 was sprayed onto the test fabrics for 100% moisture so that the weight ratio of the dry test fabrics to V1 was 1: 1 as in the experiment according to the invention.
  • 0.8 g of the premium washing detergent were used in this experiment.
  • a liquor of 4.07 g / l of the same premium full detergent was prepared as in the first comparative experiment and a liquor of 200 ml was provided in the wash cycle.
  • the amount of premium solid detergent used was 0.8 g, as in the first comparative test.
  • the concentrates according to the invention and the Winsor Type 2 microemulsion systems prepared therefrom show significantly better performance both compared to a conventional washing process with a commercially available premium liquid detergent and also with respect to the new process with the commercially available premium liquid laundry detergent. It can also be seen that conventional liquid premium heavy-duty detergents in the new process (V1) sometimes perform significantly worse than in standard washing processes (V2).
  • Table 3 shows anhydrous concentrates (pastes) and Winsor Type 2 microemulsion systems obtainable therefrom. Table 3: (amounts in% by weight)
  • Aerosil As a substitute for Aerosil also finely divided aluminosilicates, especially zeolites can be used. Both do not affect the phase boundaries.
  • Table 4 shows another example of the composition of a short liquor in the form of a Winsor Type 2 microemulsion system (M1 1) having a surfactant content of less than 1% by weight.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des concentrés non solides monophasiques ou polyphasiques appropriés à produire ou à conserver un système de microémulsion de Winsor de type 2 au cours d'une dilution dans une machine à laver avec la technique de lavage en bain court. Lesdits concentrés présentent des performances améliorées sur les salissures graisseuses ou huileuses dans de nouveaux procédés, au cours desquels on passe par plusieurs types de Winsor en partant du type 2.
EP15702793.9A 2014-02-19 2015-02-06 Concentrés de lessive Withdrawn EP3107990A1 (fr)

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DE102014202990.2A DE102014202990A1 (de) 2014-02-19 2014-02-19 Konzentrate
PCT/EP2015/052464 WO2015124439A1 (fr) 2014-02-19 2015-02-06 Concentrés de lessive

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DE102014213314A1 (de) 2014-07-09 2016-01-14 Henkel Ag & Co. Kgaa Neuartiges Waschverfahren
EP3216907A1 (fr) * 2016-03-09 2017-09-13 Herbert Kannegiesser GmbH Procédé de traitement par voie humide de linge
DE102016204268A1 (de) 2016-03-15 2017-09-21 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung
DE102016204390A1 (de) 2016-03-16 2017-09-21 Henkel Ag & Co. Kgaa Verfahren zum Reinigen von Wäsche in einer Waschmaschine sowie eine Waschmaschine
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WO2018145898A1 (fr) 2017-02-13 2018-08-16 Unilever Plc Additif pour composition de lessive
DE102017215038A1 (de) 2017-08-29 2019-02-28 Henkel Ag & Co. Kgaa Verfahren zum Waschen von Wäsche einer Waschladung, Vorrichtung, Computerprogramm und System

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US20160348042A1 (en) 2016-12-01

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