EP2828368A1 - Liquid detergent with increased cleaning performance - Google Patents

Liquid detergent with increased cleaning performance

Info

Publication number
EP2828368A1
EP2828368A1 EP13709919.8A EP13709919A EP2828368A1 EP 2828368 A1 EP2828368 A1 EP 2828368A1 EP 13709919 A EP13709919 A EP 13709919A EP 2828368 A1 EP2828368 A1 EP 2828368A1
Authority
EP
European Patent Office
Prior art keywords
cleaning agent
washing
alcohol
liquid
acid
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.)
Granted
Application number
EP13709919.8A
Other languages
German (de)
French (fr)
Other versions
EP2828368B1 (en
Inventor
Frank Meier
Sabine SCHÜMANN
Luca Bellomi
Matthias Sunder
Paula Barreleiro
Birgit GLÜSEN
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=47891728&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2828368(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL13709919T priority Critical patent/PL2828368T3/en
Publication of EP2828368A1 publication Critical patent/EP2828368A1/en
Application granted granted Critical
Publication of EP2828368B1 publication Critical patent/EP2828368B1/en
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • 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
    • C11D1/02—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
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the invention relates to a liquid washing or cleaning agent with a soil release polymer.
  • detergents or cleaning agents are used in addition to those for the
  • Washing aids include, for example, suds regulators, grayness inhibitors, bleaches, bleach activators, and dye transfer inhibitors which, if present during the washing process, support the soil release capacity of the remaining detergent ingredients
  • Soil release agents known in the art are polyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
  • polyesters of phthalic acid and / or terephthalic acid or of their derivatives in particular polyesters of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionically and / or nonionically modified derivatives of these are used in detergents or cleaners.
  • polyester fibers Because of their chemical similarity to polyester fibers, these polyesters show a particularly good soil release-enhancing effect in polyester-containing textile fabrics.
  • Liquid detergents or cleaners with the combination of oxo alcohols with 7 or 8 alkoxy units and soil release polymer show a high cleaning performance on greasy soils and an improved grayness inhibition.
  • the soil release polymer be a polyester of a
  • Dicarboxylic acid and a diol are particularly preferred.
  • soil release polymer is an end-capped polyester of terephthalic acid, polyethylene glycol and 1,2-propylene glycol, since these polyesters are particularly well and stable incorporated into liquid detergents or cleaners.
  • the washing or cleaning agent is packaged in a water-soluble wrapper.
  • Portion packs containing liquid detergents or cleaners on the one hand meet the consumer's desire for simplified dosage and on the other hand more and more consumers prefer liquid detergents or cleaners.
  • liquid washing or cleaning agent contains up to 10 wt .-%, based on the total detergent or cleaning agent, water.
  • Low-water liquid washing or cleaning agents are particularly advantageous for packaging in water-soluble coatings, since the risk of dissolution or dissolution of the water-soluble
  • Envelope is minimized before use of the liquid detergent or cleaning agent.
  • the detergent or cleaning agent contain an amine neutralized anionic surfactant.
  • the neutralization with amines does not lead to the formation of water and thus highly concentrated and / or water-poor detergents or cleaning agents can be prepared, for example, directly for the Use in water-soluble envelopes are suitable or can be offered in smaller packaging units.
  • Another object of the invention is the use of a combination of a
  • Yet another object of the invention is the use of a combination of a
  • the liquid washing or cleaning agent necessarily contains a soil release polymer and an alkoxylated oxo-alcohol with 7 or 8 alkoxy units.
  • polyesters obtainable from preferably terephthalic acid, isophthalic acid, sulfoisophthalic acid and / or their methyl esters, aliphatic
  • Dicarboxylic acids saturated and / or unsaturated
  • adipic acid for example adipic acid, and / or their
  • Anhydrides aliphatic substituted dicarboxylic acids, for example nonylsuccinic acid,
  • Alkylene glycols polyethylene glycols, alkyl polyethylene glycols, Polyethylenglykolbenzoeklareester, Polyethylenglykolsulfobenzoeklareester and optionally alkanolamines used.
  • Suitable soil release polymers include, for example, polyesters
  • Polyethylene terephthalate and polyethylene glycol polyesters of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid, methyl or ethyl end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units, polyesters which also substituted in addition to oxyethylene groups and terephthalic acid units contain ethylene units and glycerol units, or a polyester which, besides oxyethylene groups and terephthalic acid, 1, 2-propylene, 1, 2-butylene and / or 3-methoxy-1, 2-propylene groups and glycerol units contain and C to C 4 Alkyl groups are end-capped.
  • Preferred soil release polymers include polyesters that are formally permeable
  • Esterification of two monomer parts are accessible, wherein the first monomer is a dicarboxylic HOOC-Ph-COOH and the second monomer is a diol HO- (CHR-) a OH, also called polymeric diol H- (0- (CHR-) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R is hydrogen, a Alkyl radical having 1 to 22 carbon atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 5 to 300.
  • the polyesters obtainable from these monomers both Mondiol- O- (CHR) a O- and Polymer diol units - (0- (CHR) a ) b O- before.
  • the acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, metilitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the soil release polymer, they are preferably in salt form, in particular as alkali or ammonium salt.
  • the preferred diols HO- (CHR-) a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R is hydrogen or alkyl with 1 to 10, in particular 1 to 3 carbon atoms.
  • R is hydrogen and a is a number from 2 to 6
  • a has the value 2 and R is hydrogen or alkyl with 1 to 10, in particular 1 to 3 carbon atoms.
  • those of the formula HO-CH 2 -CHR-OH, in which R has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100.
  • the degree of polymerization b is preferably in the range of 5 to 300, especially 10 to 80.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution is more preferable soil release polyester is preferably in the range of 250 to 100,000.
  • these preferred soil release polymers can also be used.
  • end groups in particular alkyl groups having 1 to 5 carbon atoms in question.
  • the amount of soil release polymer is preferably between 0.5 and 10% by weight and more preferably between 1 and 5% by weight, based in each case on the total detergent or cleaning agent.
  • the liquid detergents or cleaners contain an alkoxylated oxo alcohol with 7 or 8 alkoxy units.
  • Oxo alcohols are primary, partially branched higher alcohols, which are obtained in the oxo synthesis. This oxo-aldehydes or their primary aldokondensations occur converted by catalytic hydrogenation in the corresponding oxo alcohols.
  • a C is preferably 3 _i 5 oxo-alcohol with 7 EO, a C 3 _i 5 oxo-alcohol with 8 EO or a mixture of these two oxo alcohols in the liquid washing or cleaning agents used.
  • the content of alkoxylated oxo-alcohol having 7 or 8 alkoxy units is preferably 5 to 35 wt .-%, and more preferably 10 to 25 wt .-%, each based on the total liquid washing or
  • the detergent or conditioner may contain other ingredients containing the
  • the washing or cleaning agent preferably additionally contains one or more substances from the group of the further nonionic surfactants, anionic surfactants, builders, bleaching agents, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers,
  • Fluorescers dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents,
  • Graying inhibitors anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, skin-care agents, swelling and anti-slip agents, softening components and UV absorbers.
  • Detergents contain, for example, other nonionic surfactants.
  • Suitable nonionic surfactants include alkoxylated fatty 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 on average 4 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.
  • preferred ethoxylated alcohols include with 4 EO or 7 EO, C 9 _n-alcohol with 7 EO, Ci 2 -i8-alcohols with 5 EO or 7 EO and mixtures of these.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • the amount of further nonionic surfactants is preferably less than 5 wt .-%, more preferably less than 2 wt .-% and particularly preferably less than 1 wt .-%, each based on the total amount of liquid detergent or cleaning agent.
  • liquid detergent or cleaning agent additionally contains an anionic surfactant.
  • Suitable anionic surfactant include alkylbenzenesulfonic acid salts, olefinsulfonic, C 12- 18 alkanesulfonic acids, salts of SchwefelTexTexremonoestern with a fatty alcohol, a fatty acid soaps, salts of Schwefelklamonoestern with an ethoxylated fatty alcohol or a mixture of two or more of these anionic surfactants can.
  • alkylbenzenesulfonic acid salts, fatty acid soaps and mixtures thereof are particularly preferred.
  • the content of anionic surfactant is preferably 5 to 50 wt .-% and more preferably 10 to 40 wt .-%, each based on the total liquid detergent or cleaning agent.
  • surfactants of the sulfonate type preferably come C 9 _i 3 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are for example from C
  • Alk (en) ylsulfates are the salts of the sulfuric acid semiesters of C 2 -C-
  • Ci 2 -Ci 6 alkyl sulfates and Ci 2 -Ci 5 alkyl sulfates and C 4 -C 5 alkyl sulfates preferred.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • fatty alcohol ether sulfates such as the sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with from 1 to 6 mol of ethylene oxide.
  • 2 alcohols such as 2-methyl-branched C 9 _n alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci 2 _i 8 -Fettalkohole with 1 to 4 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 from natural fatty acids, for example coconut,
  • Palm kernel olive oil or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the fatty acid soaps may be in the form of their sodium, potassium or magnesium or ammonium salts.
  • the anionic surfactants are in the form of their sodium salts 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.
  • the liquid washing or cleaning agent contains a monoethanolamine-neutralized alkylbenzenesulfonic acid, in particular C 9 _i 3 -alkylbenzenesulfonic acid, and / or a fatty acid neutralized with monoethanolamine.
  • the total amount of anion-neutralized with an amine anionic surfactant and an alkoxylated oxo alcohol having 7 or 8 alkoxy units in the liquid detergent or cleaning agent is preferably up to 85 wt .-%, preferably 40 to 75 wt .-% and particularly preferably 50 bis 70 wt .-%, based on the total liquid detergent or cleaning agent.
  • the washing or cleaning agent is liquid.
  • the washing or cleaning agents may contain water, wherein the content of water in a preferred embodiment is less than 10 wt .-%, and more preferably less than 8 wt .-%, each based on the total liquid detergent or cleaning agent.
  • the liquid washing or cleaning agent can be filled into a water-soluble casing and thus be part of a water-soluble packaging. If the liquid washing or cleaning agent is packaged in a water-soluble casing, it is preferred that the content of water is less than 10 wt .-%, based on the total liquid detergent or cleaning agent, and that the anionic surfactants in the form of their ammonium salts available.
  • low-water liquid detergents or cleaners can be prepared which are directly suitable for use in water-soluble coatings.
  • a water-soluble packaging contains, in addition to the liquid washing or cleaning agent, a water-soluble coating.
  • the water-soluble coating is preferably formed by a water-soluble film material.
  • Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.
  • the thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.
  • the water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Suitable water-soluble films for the preparation of the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight in the range of 10,000 to 1 .000,000 gmol "1 , preferably from 20,000 to 500,000 gmol " 1 , more preferably from 30,000 to 100,000 gmol "1 and especially from 40,000 to 80,000 gmol "1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a suitable for preparing the water-soluble coating sheet material may additionally polymers, selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Particularly preferably contain such
  • Methacrylic acid esters or mixtures thereof are Methacrylic acid esters or mixtures thereof.
  • Suitable water-soluble films for use in the casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films with the
  • the water-soluble package comprising the liquid detergent or water-soluble wrapper may have one or more chambers.
  • the water-soluble packaging with a chamber may have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.
  • the liquid detergent may be contained in one or more chambers, if any, of the water-soluble coating.
  • the water-soluble package has two chambers.
  • the first chamber contains the liquid washing or cleaning agent and the second chamber contains a solid or a liquid agent, preferably a solid or a liquid washing or cleaning agent.
  • the agents contained in the different chambers of a water-soluble package having two or more chambers may have the same composition.
  • the agents which are preferably all detergents or cleaners, in a water-soluble packaging with at least two chambers have compositions which differ at least in one ingredient or at least in the content of one ingredient.
  • Water soluble packages having at least two compartments have the advantage that incompatible ingredients may be present in separate compartments. Another advantage is found in suspension with solid and liquid ingredients, which are often considered by the user of the water-soluble packaging as little aesthetic and / or faulty. In such case, the solid or insoluble ingredients may be contained in a separate compartment of the water-soluble package. Examples
  • Liquid detergents or cleaners were prepared by conventional and known methods and procedures. Table 1 below shows the compositions of four detergents or cleaners E1 to E4 according to the invention and four detergents or cleaners V1 to V4 not according to the invention.
  • Cleansing performance in particular "soil release” performance, has on fat-containing stains, as a washing or cleaning agent without dirt-releasing polymer.
  • liquid detergents or cleaning agents E1, E4 and V1 to V4 are liquid detergents or cleaning agents E1, E4 and V1 to V4
  • test fabrics were five times in succession, each with 20 g of the liquid detergent or cleaning agent to be tested E1, E4, V1, V2, V3 or V4 in a household washing machine (Miele W 1514) with 5 SBL 2004 towels with standardized dirt load (32 g Dirt ballast) at 40 ° C.
  • the cotton fabrics are eight different commercially available cotton fabrics.
  • the fabrics of synthetic include ten different commercially available fabrics of, for example, polyamide, viscose, polyester, polyester-cotton blends, Lycra elastane blends, and polyacrylonitrile.
  • the day-old fabrics include four commercial everyday textiles such as kitchen toweling, toweling, barley grain towel and white T-shirts. Table 3: Whitenesses (average of the respective tissues)
  • the graying-inhibiting cleaning performance of a liquid detergent or cleaning agent can be increased not only on polyester fabrics, but especially on cotton fabrics.
  • the combination of a soil release polymer and an alkoxylated oxo-alcohol with 8 alkoxy units shows a particularly good graying-inhibiting cleaning performance on synthetic fabrics while the combination of a soil release polymer and a
  • alkoxylated oxo-alcohol with 7 alkoxy units a particularly good graying-inhibiting
  • a film of the type M 8630 (ex Monosol) was drawn with a thickness of 76 ⁇ for forming a bulge by means of vacuum in a trough. Subsequently, the bulge was filled with 30 ml of the liquid washing or cleaning agent E3. After covering the agent filled bulges with a second layer of M 8630 film, the first and second layers were sealed together. The sealing temperature was 150 ° C and the sealing time 1, 1 seconds.

Abstract

The invention relates to a liquid detergent or cleaning agent that comprises a) an alkoxylated oxo-alcohol with 7 or 8 alkoxy units, and b) a polymer that allows the removal of dirt. The liquid detergent or cleaning agent demonstrates an increased cleaning performance, particularly where the soiling contains fat, and an improved anti-redeposition effect.

Description

„Flüssiges Waschmittel mit erhöhter Reinigungsleistung"  "Liquid detergent with increased cleaning performance"
Die Erfindung betrifft ein flüssiges Wasch- oder Reinigungsmittel mit einem schmutzablösevermögenden Polymer. The invention relates to a liquid washing or cleaning agent with a soil release polymer.
Zur Erhöhung der Reinigungsleistung werden Wasch- oder Reinigungsmitteln neben den für den To increase the cleaning performance, detergents or cleaning agents are used in addition to those for the
Waschprozeß unverzichtbaren Tensiden und Buildermaterialien in der Regel weitere Bestandteile zugesetzt, die unter dem Begriff„Waschhilfsstoffe" zusammengefasst werden können. Zu den Waschhilfsstoffen gehören beispielsweise Schaumregulatoren, Vergrauungsinhibitoren, Bleichmittel, Bleichaktivatoren und Farbübertragungsinhibitoren. Weitere Waschhilfsstoffe sind Substanzen, welche der Wäschefaser schmutzabstoßende Eigenschaften verleihen und die, falls während des Waschvorgangs anwesend, das Schmutzablösevermögen der übrigen Waschmittelbestandteile unterstützen. Derartige Washing aids include, for example, suds regulators, grayness inhibitors, bleaches, bleach activators, and dye transfer inhibitors which, if present during the washing process, support the soil release capacity of the remaining detergent ingredients
schmutzablösevermögende Substanzen werden oft als "Soil-Release"-Wirkstoffe oder wegen ihres Dirt-depleting substances are often referred to as "soil-release" agents or because of their
Vermögens, die behandelte Oberfläche, zum Beispiel Gewebe, schmutzabstoßend auszurüsten, als "Soil- Repellents" bezeichnet. Ability to render the treated surface, such as fabric, dirt repellent, referred to as "soil repellents".
Im Stand der Technik bekannte Soil-Release-Wirkstoffe sind Polyester, die Dicarbonsäureeinheiten, Alkylenglykoleinheiten und Polyalkylenglykoleinheiten enthalten. Insbesondere Polyester der Phthalsäure und/oder Terephthalsäure bzw. von deren Derivaten, insbesondere Polyester aus Ethylenterephthalaten und/oder Polyethylen- und/oder Polypropylenglykolterephthalaten oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen werden in Wasch- oder Reinigungsmitteln eingesetzt. Soil release agents known in the art are polyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. In particular, polyesters of phthalic acid and / or terephthalic acid or of their derivatives, in particular polyesters of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionically and / or nonionically modified derivatives of these are used in detergents or cleaners.
Wegen ihrer chemischen Ähnlichkeit zu Polyesterfasern zeigen diese Polyester eine besonders gute schmutzablösevermögende Wirkung bei Polyester-haltigen textilen Flächengebilden. Because of their chemical similarity to polyester fibers, these polyesters show a particularly good soil release-enhancing effect in polyester-containing textile fabrics.
Aus der WO 96/16150 ist bekannt, dass die Reinigungsleistung von Wasch- oder Reinigungsmitteln durch ein Zusammenwirken von schmutzablösevermögenden Polymeren mit einer Tensidkombination aus Ethersulfat und Alkyloligoethoxylaten gesteigert werden kann. From WO 96/16150 it is known that the cleaning performance of detergents or cleaners can be increased by an interaction of soil release polymers with a surfactant combination of ether sulfate and Alkyloligoethoxylaten.
Es besteht aber weiterhin Bedarf, die Reinigungsleistung von Wasch- oder Reinigungsmitteln mit einem schmutzablösevermögenden Polymer zu verbessern. However, there is still a need to improve the cleaning performance of detergents or cleaners with a soil release polymer.
Entsprechend war es eine Aufgabe der vorliegenden Erfindung, ein flüssiges Wasch- oder Reinigungsmittel mit schmutzablösevermögendem Polymer bereit zu stellen, welches eine erhöhte Reinigungsleistung aufweist. Diese Aufgabe wird gelöst durch ein flüssiges Wasch- oder Reinigungsmittel, umfassend Accordingly, it has been an object of the present invention to provide a liquid detergent or soil release polymer detergent having enhanced cleaning performance. This object is achieved by a liquid washing or cleaning agent comprising
a) einen alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten und a) an alkoxylated oxo-alcohol having 7 or 8 alkoxy units and
b) ein schmutzablösevermögendes Polymer. b) a soil release polymer.
Es hat sich überraschenderweise gezeigt, dass die Kombination von Oxo-Alkoholen mit 7 oder 8 It has surprisingly been found that the combination of oxo alcohols with 7 or 8
Alkoxyeinheiten mit einem schmutzablösevermögenden Polymer zu flüssigen Wasch- oder Reinigungsmitteln mit erhöhter Reinigungsleistung führt. Flüssige Wasch- oder Reinigungsmittel mit der Kombination aus Oxo- Alkoholen mit 7 oder 8 Alkoxyeinheiten und schmutzablösevermögendem Polymer zeigen eine hohe Reinigungsleistung an Fett-haltigen Anschmutzungen und eine verbesserte Vergrauungsinhibierung. Alkoxy units with a soil release polymer wealthy leads to liquid detergents or cleaning agents with increased cleaning performance. Liquid detergents or cleaners with the combination of oxo alcohols with 7 or 8 alkoxy units and soil release polymer show a high cleaning performance on greasy soils and an improved grayness inhibition.
Eine besonders hohe Reinigungsleistung an Fett-haltigen Anschmutzungen und eine besonders gute Vergrauungsinhibierung werden bei Einsatz von Ci3_i5-Oxo-Alkoholen mit 7 EO, Ci3_i5-Oxo-Alkoholen mit 8 EO oder einer Mischung dieser beiden Oxo-Alkohole in den flüssigen Wasch- oder Reinigungsmitteln erhalten. A particularly high cleaning performance of soils containing grease and a particularly good grayness inhibition when using Ci 3 _i 5 -oxo-alcohols with 7 EO, Ci 3 _i 5 -oxo-alcohols with 8 EO or a mixture of these two oxo-alcohols in obtained the liquid detergents or cleaning agents.
Es ist weiterhin bevorzugt, dass das schmutzablösevermögende Polymer ein Polyester von einer It is further preferred that the soil release polymer be a polyester of a
Dicarbonsäure und einem Diol ist. Dabei ist es insbesondere bevorzugt, dass das Dicarboxylic acid and a diol. It is particularly preferred that the
schmutzablösevermögende Polymer ein endgruppenverschlossener Polyester aus Terephthalsäure, Polyethylenglykol und 1 ,2-Propylenglykol ist, da diese Polyester besonders gut und stabil in flüssige Waschoder Reinigungsmittel eingearbeitet werden können. soil release polymer is an end-capped polyester of terephthalic acid, polyethylene glycol and 1,2-propylene glycol, since these polyesters are particularly well and stable incorporated into liquid detergents or cleaners.
In einer bevorzugten Ausführungsform ist das Wasch- oder Reinigungsmittel in einer wasserlöslichen Umhüllung verpackt. In a preferred embodiment, the washing or cleaning agent is packaged in a water-soluble wrapper.
Portionspackungen mit flüssigen Wasch- oder Reinigungsmitteln erfüllen einerseits den Wunsch des Verbrauchers nach vereinfachter Dosierung und andererseits bevorzugen immer mehr Verbraucher flüssige Wasch- oder Reinigungsmittel. Portion packs containing liquid detergents or cleaners on the one hand meet the consumer's desire for simplified dosage and on the other hand more and more consumers prefer liquid detergents or cleaners.
Es kann bevorzugt sein, dass das flüssige Wasch- oder Reinigungsmittel bis zu 10 Gew.-%, bezogen auf das gesamte Wasch- oder Reinigungsmittel, Wasser enthält. It may be preferred that the liquid washing or cleaning agent contains up to 10 wt .-%, based on the total detergent or cleaning agent, water.
Wasserarme flüssige Wasch- oder Reinigungsmitteln sind besonders vorteilhaft zur Verpackung in wasserlöslichen Umhüllungen geeignet, da das Risiko des An- oder Auflösens der wasserlöslichen Low-water liquid washing or cleaning agents are particularly advantageous for packaging in water-soluble coatings, since the risk of dissolution or dissolution of the water-soluble
Umhüllung vor dem Einsatz des flüssigen Wasch- oder Reinigungsmittels minimiert wird. Envelope is minimized before use of the liquid detergent or cleaning agent.
Es ist auch bevorzugt, dass das Wasch- oder Reinigungsmittel ein Amin neutralisiertes anionisches Tensid enthält. Die Neutralisation mit Aminen führt nicht zu Bildung von Wasser und somit können hochkonzentrierte und/oder wasserarme Wasch- oder Reinigungsmittel hergestellt werden, die beispielsweise direkt für die Verwendung in wasserlöslichen Umhüllungen geeignet sind oder in kleineren Verpackungseinheiten angeboten werden können. It is also preferred that the detergent or cleaning agent contain an amine neutralized anionic surfactant. The neutralization with amines does not lead to the formation of water and thus highly concentrated and / or water-poor detergents or cleaning agents can be prepared, for example, directly for the Use in water-soluble envelopes are suitable or can be offered in smaller packaging units.
Ein weiterer Gegenstand der Erfindung ist die Verwendung einer Kombination aus einem Another object of the invention is the use of a combination of a
schmutzablösevermögenden Polymer und einem alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten in einem flüssigen Wasch- oder Reinigungsmittel zur Erhöhung der Reinigungsleistung an Fett-haltigen Anschmutzungen. soil release polymer and an alkoxylated oxo-alcohol with 7 or 8 alkoxy units in a liquid detergent or cleaner to increase the cleaning performance of greasy soils.
Ein noch weiterer Gegenstand der Erfindung ist Verwendung einer Kombination aus einem Yet another object of the invention is the use of a combination of a
schmutzablösevermögenden Polymer und einem alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten in einem flüssigen Wasch- oder Reinigungsmittel zur Erhöhung der Vergrauungsinhibierung. soil release polymer and an alkoxylated oxo-alcohol with 7 or 8 alkoxy units in a liquid detergent or cleaner to increase the grayness inhibition.
Im Folgenden soll die Erfindung, unter anderem anhand von Beispielen, eingehender erläutert werden. In the following, the invention will be explained in more detail, inter alia, by way of examples.
Das flüssige Wasch- oder Reinigungsmittel enthält zwingend ein schmutzablösevermögendes Polymer und einen alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten. The liquid washing or cleaning agent necessarily contains a soil release polymer and an alkoxylated oxo-alcohol with 7 or 8 alkoxy units.
Als schmutzablösevermögende Polymere kommen insbesondere Polyester erhältlich aus vorzugsweise Terephthalsäure, Isophthalsäure, Sulfoisophthalsäure und/oder deren Methylestern, aliphatischen Particularly suitable as soil release polymers are polyesters obtainable from preferably terephthalic acid, isophthalic acid, sulfoisophthalic acid and / or their methyl esters, aliphatic
Dicarbonsäuren (gesättigten und/oder ungesättigten), beispielsweise Adipinsäure, und/oder deren Dicarboxylic acids (saturated and / or unsaturated), for example adipic acid, and / or their
Anhydriden, aliphatischen substituierten Dicarbonsäuren, beispielsweise Nonylbernsteinsäure, Anhydrides, aliphatic substituted dicarboxylic acids, for example nonylsuccinic acid,
Alkylenglykolen, Polyethylenglykolen, Alkylpolyethylenglykolen, Polyethylenglykolbenzoesäureester, Polyethylenglykolsulfobenzoesäureester sowie gegebenenfalls Alkanolaminen zum Einsatz. Alkylene glycols, polyethylene glycols, alkyl polyethylene glycols, Polyethylenglykolbenzoesäureester, Polyethylenglykolsulfobenzoesäureester and optionally alkanolamines used.
Geeignete schmutzablösevermögenden Polymere umfassen beispielsweise Polyester aus Suitable soil release polymers include, for example, polyesters
Polyethylenterephthalat und Polyethylenglykol, Polyester von Ethylenglykol, Polyethylenglykol, aromatischer Dicarbonsäure und sulfonierter aromatischer Dicarbonsäure, Methyl- oder Ethylgruppen-endverschlossene Polyester mit Ethylen- und/oder Propylenterephthalat- und Polyethylenoxid-terephthalat-Einheiten, Polyester, die neben Oxethylen-Gruppen und Terephthalsäureeinheiten auch substituierte Ethyleneinheiten sowie Glycerineinheiten enthalten, oder Polyester, die neben Oxyethylen-Gruppen und Terephthalsäureeinheiten, 1 ,2-Propylen-, 1 ,2-Butylen- und/oder 3-Methoxy-1 ,2-propylengruppen sowie Glycerineinheiten enthalten und mit C bis C4-Alkylgruppen endgruppenverschlossen sind. Polyethylene terephthalate and polyethylene glycol, polyesters of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid, methyl or ethyl end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units, polyesters which also substituted in addition to oxyethylene groups and terephthalic acid units contain ethylene units and glycerol units, or a polyester which, besides oxyethylene groups and terephthalic acid, 1, 2-propylene, 1, 2-butylene and / or 3-methoxy-1, 2-propylene groups and glycerol units contain and C to C 4 Alkyl groups are end-capped.
Zu den bevorzugten schmutzablösevermögenden Polymeren gehören Polyester, die formal durch Preferred soil release polymers include polyesters that are formally permeable
Veresterung zweier Monomerteile zugänglich sind, wobei das erste Monomer eine Dicarbonsäure HOOC-Ph- COOH und das zweite Monomer ein Diol HO-(CHR-)aOH, das auch als polymeres Diol H-(0-(CHR-)a)bOH vorliegen kann, ist. Darin bedeutet Ph einen o-, m- oder p-Phenylenrest, der 1 bis 4 Alkylreste mit 1 bis 22 C- Atomen, Sulfonsäuregruppen, Carboxylgruppen und deren Mischungen, tragen kann, R Wasserstoff, einen Alkylrest mit 1 bis 22 C-Atomen und deren Mischungen, a eine Zahl von 2 bis 6 und b eine Zahl von 5 bis 300. Vorzugsweise liegen in den aus diesen herstellbaren Polyestern sowohl Monomerdioleinheiten -O- (CHR-)aO- als auch Polymerdioleinheiten -(0-(CHR)a)bO- vor. Esterification of two monomer parts are accessible, wherein the first monomer is a dicarboxylic HOOC-Ph-COOH and the second monomer is a diol HO- (CHR-) a OH, also called polymeric diol H- (0- (CHR-) a ) b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R is hydrogen, a Alkyl radical having 1 to 22 carbon atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 5 to 300. Preferably in the polyesters obtainable from these monomers both Mondiol- O- (CHR) a O- and Polymer diol units - (0- (CHR) a ) b O- before.
Die dem Rest Ph zugrundeliegende Säure wird vorzugsweise aus Terephthalsäure, Isophthalsäure, Phthalsäure, Trimellithsäure, Meilithsäure, den Isomeren der Sulfophthalsäure, Sulfoisophthalsäure und Sulfoterephthalsäure sowie deren Gemischen ausgewählt. Sofern deren Säuregruppen nicht Teil der Esterbindungen im schmutzablösevermögenden Polymer sind, liegen sie vorzugsweise in Salzform, insbesondere als Alkali- oder Ammoniumsalz vor. The acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, metilitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the soil release polymer, they are preferably in salt form, in particular as alkali or ammonium salt.
Zu den bevorzugten Diolen HO-(CHR-)aOH gehören solche, in denen R Wasserstoff und a eine Zahl von 2 bis 6 ist, und solche, in denen a den Wert 2 aufweist und R Wasserstoff oder Alkyl mit 1 bis 10, insbesondere 1 bis 3 C-Atomen ist. Unter den letztgenannten Diolen sind solche der Formel HO-CH2-CHR-OH, in der R die oben genannte Bedeutung besitzt, besonders bevorzugt. Beispiele für Diolkomponenten sind Ethylenglykol, 1 ,2-Propylenglykol, 1 ,3-Propylenglykol, 1 ,4-Butandiol, 1 ,5-Pentandiol, 1 ,6-Hexandiol, 1 ,8-Octandiol, 1 ,2- Decandiol, 1 ,2-Dodecandiol und Neopentylglykol. The preferred diols HO- (CHR-) a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R is hydrogen or alkyl with 1 to 10, in particular 1 to 3 carbon atoms. Among the latter diols, those of the formula HO-CH 2 -CHR-OH, in which R has the abovementioned meaning, are particularly preferred. Examples of diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
Das molare Verhältnis von Monomerdioleinheiten zu Polymerdioleinheiten beträgt vorzugsweise 100 : 1 bis 1 : 100. In den Polymerdioleinheiten liegt der Polymerisationsgrad b vorzugsweise im Bereich von 5 bis 300, insbesondere von 10 bis 80. Das Molekulargewicht beziehungsweise das mittlere Molekulargewicht oder das Maximum der Molekulargewichtsverteilung bevorzugter schmutzablösevermögender Polyester liegt vorzugsweise im Bereich von 250 bis 100.000. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100. In the polymer diol units, the degree of polymerization b is preferably in the range of 5 to 300, especially 10 to 80. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution is more preferable soil release polyester is preferably in the range of 250 to 100,000.
Gewünschtenfalls können diese bevorzugten schmutzablösevermögenden Polymere auch If desired, these preferred soil release polymers can also
endgruppenverschlossen sein, wobei als Endgruppen insbesondere Alkylgruppen mit 1 bis 5 C-Atomen in Frage kommen. be end-group capped, wherein as end groups in particular alkyl groups having 1 to 5 carbon atoms in question.
Ganz besonders bevorzugt werden als schmutzablösevermögendes Polymer endgruppenverschlossene Polyester aus Polyethylenglykolen, Terephthalsäure sowie Ethylenglykol und/oder 1 ,2-Propylenglykol eingesetzt. Very particular preference is given to using end-capped polyesters of polyethylene glycols, terephthalic acid and also ethylene glycol and / or 1,2-propylene glycol as a soil release-capable polymer.
Die Menge an schmutzablösevermögendem Polymer beträgt vorzugsweise zwischen 0,5 und 10 Gew.-% und mehr bevorzugt zwischen 1 und 5 Gew.-%, jeweils bezogen auf das gesamte Wasch- oder Reinigungsmittel. The amount of soil release polymer is preferably between 0.5 and 10% by weight and more preferably between 1 and 5% by weight, based in each case on the total detergent or cleaning agent.
Neben dem schmutzablösevermögenden Polymer enthalten die flüssigen Wasch- oder Reinigungsmittel einen alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten. Oxo-Alkohole sind primäre, teilweise verzweigte höhere Alkohole, die bei der Oxo-Synthese gewonnen werden. Dabei werden Oxo-Aldehyde oder deren primäre Aldokondensationsprodukte durch katalytische Hydrierung in die entsprechenden Oxo- Alkohole überführt. In addition to the soil release polymer, the liquid detergents or cleaners contain an alkoxylated oxo alcohol with 7 or 8 alkoxy units. Oxo alcohols are primary, partially branched higher alcohols, which are obtained in the oxo synthesis. This oxo-aldehydes or their primary aldokondensationsprodukte converted by catalytic hydrogenation in the corresponding oxo alcohols.
Bevorzugt wird ein Ci3_i5-Oxo-Alkohol mit 7 EO, ein Ci3_i5-Oxo-Alkohol mit 8 EO oder eine Mischung aus diesen beiden Oxo-Alkoholen in den flüssigen Wasch- oder Reinigungsmitteln eingesetzt. A C is preferably 3 _i 5 oxo-alcohol with 7 EO, a C 3 _i 5 oxo-alcohol with 8 EO or a mixture of these two oxo alcohols in the liquid washing or cleaning agents used.
Der Gehalt an alkoxyliertem Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten beträgt vorzugsweise 5 bis 35 Gew.-% und mehr bevorzugt 10 bis 25 Gew.-%, jeweils bezogen auf das gesamte flüssige Wasch- oder The content of alkoxylated oxo-alcohol having 7 or 8 alkoxy units is preferably 5 to 35 wt .-%, and more preferably 10 to 25 wt .-%, each based on the total liquid washing or
Reinigungsmittel. Cleaning supplies.
Zusätzlich zu dem schmutzablösevermögendem Polymer und einem alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten kann das Wasch- oder Reinigungsmittel weitere Inhaltsstoffe enthalten, die die In addition to the soil release polymer and an alkoxylated oxo alcohol having 7 or 8 alkoxy units, the detergent or conditioner may contain other ingredients containing the
anwendungstechnischen und/oder ästhetischen Eigenschaften des Wasch- oder Reinigungsmittels weiter verbessern. Im Rahmen der vorliegenden Erfindung enthält das Wasch- oder Reinigungsmittel vorzugsweise zusätzlich einen oder mehrere Stoffe aus der Gruppe der weiteren nichtionische Tenside, anionischen Tenside, Gerüststoffe, Bleichmittel, Enzyme, Elektrolyte, pH-Stellmittel, Parfüme, Parfümträger, further improve the performance and / or aesthetic properties of the washing or cleaning agent. In the context of the present invention, the washing or cleaning agent preferably additionally contains one or more substances from the group of the further nonionic surfactants, anionic surfactants, builders, bleaching agents, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers,
Fluoreszenzmittel, Farbstoffe, Hydrotope, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, Fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents,
Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, nicht-wässrigen Lösungsmittel, Germizide, Fungizide, Antioxidantien, Konservierungsmittel, Korrosionsinhibitoren, Antistatika, Bittermittel, Bügelhilfsmittel, Phobier- und Imprägniermittel, Haut-pflegende Wirkstoffe, Quell- und Schiebefestmittel, weichmachenden Komponenten sowie UV-Absorber. Graying inhibitors, anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, skin-care agents, swelling and anti-slip agents, softening components and UV absorbers.
Neben dem alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten kann das flüssige Wasch- oder In addition to the alkoxylated oxo alcohol with 7 or 8 alkoxy units, the liquid washing or
Reinigungsmittel beispielsweise weitere nichtionische Tenside enthalten. Geeignete nichtionische Tenside umfassen alkoxylierte Fettalkohole, alkoxylierte Fettsäurealkylester, Fettsäureamide, alkoxylierte Detergents contain, for example, other nonionic surfactants. Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated
Fettsäureamide, Polyhydroxyfettsäureamide, Alkylphenolpolyglycolether, Aminoxide, Alkylpolyglucoside und Mischungen daraus. Fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.
Als alkoxylierte Fettalkohole werden vorzugsweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 4 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear ist. Insbesondere sind Alkoholethoxylate mit 12 bis 18 C-Atomen, zum Beispiel aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 5 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise mit 4 EO oder 7 EO, C9_n-Alkohol mit 7 EO, Ci2-i8-Alkohole mit 5 EO oder 7 EO und Mischungen aus diesen. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Auch nichtionische Tenside, die EO- und PO-Gruppen zusammen im Molekül enthalten, sind erfindungsgemäß einsetzbar. Geeignet sind ferner auch eine Mischung aus einem (stärker) verzweigten ethoxylierten Fettalkohol und einem unverzweigten ethoxylierten Fettalkohol, wie beispielsweise eine Mischung aus einem Ci6_i8-Fettalkohol mit 7 EO und 2-Propylheptanol mit 7 EO. Die Menge an weiteren nichtionischen Tensiden beträgt vorzugsweise weniger als 5 Gew.-%, mehr bevorzugt weniger als 2 Gew.-% und insbesondere bevorzugt weniger als 1 Gew.-%, jeweils bezogen auf die gesamte Menge an flüssigem Wasch- oder Reinigungsmittel. The alkoxylated fatty alcohols used are preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear. In particular, 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. For example, preferred ethoxylated alcohols include with 4 EO or 7 EO, C 9 _n-alcohol with 7 EO, Ci 2 -i8-alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a Ci 6 _i 8 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. The amount of further nonionic surfactants is preferably less than 5 wt .-%, more preferably less than 2 wt .-% and particularly preferably less than 1 wt .-%, each based on the total amount of liquid detergent or cleaning agent.
Es ist bevorzugt, dass das flüssige Wasch- oder Reinigungsmittel zusätzlich ein anionisches Tensid enthält. It is preferred that the liquid detergent or cleaning agent additionally contains an anionic surfactant.
Geeignete anionische Tensid umfassen Alkylbenzolsulfonsäuresalze, Olefinsulfonsäuresalze, C12-18- Alkansulfonsäuresalze, Salze von Schwefelsäuremonoestern mit einem Fettalkohol, eine Fettsäureseifen, Salze von Schwefelsäuremonoestern mit einem ethoxylierten Fettalkohol oder eine Mischung aus zwei oder mehr dieser anionischen Tenside ist. Von diesen anionischen Tensiden sind Alkylbenzolsulfonsäuresalze, Fettsäureseifen und Mischungen daraus besonders bevorzugt. Suitable anionic surfactant include alkylbenzenesulfonic acid salts, olefinsulfonic, C 12- 18 alkanesulfonic acids, salts of Schwefelsäuremonoestern with a fatty alcohol, a fatty acid soaps, salts of Schwefelsäuremonoestern with an ethoxylated fatty alcohol or a mixture of two or more of these anionic surfactants can. Of these anionic surfactants, alkylbenzenesulfonic acid salts, fatty acid soaps and mixtures thereof are particularly preferred.
Der Gehalt an anionischem Tensid beträgt vorzugsweise 5 bis 50 Gew.-% und mehr bevorzugt 10 bis 40 Gew.-%, jeweils bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel. The content of anionic surfactant is preferably 5 to 50 wt .-% and more preferably 10 to 40 wt .-%, each based on the total liquid detergent or cleaning agent.
Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9_i3-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C-|2_ i8-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem As surfactants of the sulfonate type preferably come C 9 _i 3 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are for example from C | 2 _ i 8 -monoolefins with terminal or internal double bond by sulfonation with gaseous
Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Ci2_i8-Alkansulfonate und die Ester von α-Sulfofettsäuren (Estersulfonate), zum Beispiel die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren. Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are 2 Ci _i 8 alkanesulfonates and the esters of α-sulfofatty acids (ester sulfonates), for example, the α-sulfonated Methylester of hydrogenated coconut, palm kernel or tallow fatty acids.
Als Alk(en)ylsulfate werden die Salze der Schwefelsäurehalbester der Ci2-C-|8-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der Ci0-C20-Oxo- Alkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Aus Alk (en) ylsulfates are the salts of the sulfuric acid semiesters of C 2 -C- | 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Ci 0 -C 20 -Oxo- alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Out
waschtechnischem Interesse sind die Ci2-Ci6-Alkylsulfate und Ci2-Ci5-Alkylsulfate sowie Ci4-Ci5-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate sind geeignete anionische Tenside. washing technical interest are the Ci 2 -Ci 6 alkyl sulfates and Ci 2 -Ci 5 alkyl sulfates and C 4 -C 5 alkyl sulfates preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.
Auch Fettalkoholethersulfate, wie die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7.2 Alkohole, wie 2-Methyl-verzweigte C9_n-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder Ci2_i8-Fettalkohole mit 1 bis 4 EO, sind geeignet. Also, fatty alcohol ether sulfates, such as the sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with from 1 to 6 mol of ethylene oxide. 2 alcohols, such as 2-methyl-branched C 9 _n alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci 2 _i 8 -Fettalkohole with 1 to 4 EO, are suitable.
Weitere geeignete anionische Tenside sind Fettsäureseifen. Geeignet sind gesättigte und ungesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, (hydrierten) Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Further 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 from natural fatty acids, for example coconut,
Palmkern-, Olivenöl- oder Talgfettsäuren, abgeleitete Seifengemische. Palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
Die anionischen Tenside einschließlich der Fettsäureseifen können in Form ihrer Natrium-, Kalium- oder Magnesium- oder Ammoniumsalze vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natriumsalze oder Ammoniumsalze vor. Zur Neutralisation einsetzbare Amine sind vorzugsweise Cholin, Triethylamin, Monoethanolamin, Diethanolamin, Triethanolamin, Methylethylamin oder eine Mischung daraus, wobei Monoethanolamin bevorzugt ist. 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 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.
In einer ganz besonders bevorzugten Ausführungsform enthält das flüssige Wasch- oder Reinigungsmittel eine mit Monoethanolamin neutralisierte Alkylbenzolsulfonsäure, insbesondere C9_i3-Alkylbenzolsulfonsäure, und/oder eine mit Monoethanolamin neutralisierte Fettsäure. In a very particularly preferred embodiment, the liquid washing or cleaning agent contains a monoethanolamine-neutralized alkylbenzenesulfonic acid, in particular C 9 _i 3 -alkylbenzenesulfonic acid, and / or a fatty acid neutralized with monoethanolamine.
Die Gesamtmenge an mit einem Amin neutralisierten anionischen Tensid und einem alkoxylierten Oxo- Alkohol mit 7 oder 8 Alkoxyeinheiten in dem flüssigen Wasch- oder Reinigungsmittel beträgt vorzugsweise bis zu 85 Gew.-%, vorzugsweise 40 bis 75 Gew.-% und besonders bevorzugt 50 bis 70 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel. The total amount of anion-neutralized with an amine anionic surfactant and an alkoxylated oxo alcohol having 7 or 8 alkoxy units in the liquid detergent or cleaning agent is preferably up to 85 wt .-%, preferably 40 to 75 wt .-% and particularly preferably 50 bis 70 wt .-%, based on the total liquid detergent or cleaning agent.
Das Wasch- oder Reinigungsmittel ist flüssig. Die Wasch- oder Reinigungsmittel können Wasser enthalten, wobei der Gehalt an Wasser in einer bevorzugten Ausführungsform weniger als 10 Gew.-% und mehr bevorzugt weniger als 8 Gew.-%, jeweils bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel, beträgt. The washing or cleaning agent is liquid. The washing or cleaning agents may contain water, wherein the content of water in a preferred embodiment is less than 10 wt .-%, and more preferably less than 8 wt .-%, each based on the total liquid detergent or cleaning agent.
Das flüssige Wasch- oder Reinigungsmittel kann in eine wasserlösliche Umhüllung gefüllt werden und somit Bestandteil einer wasserlöslichen Verpackung sein. Ist das flüssige Wasch- oder Reinigungsmittel in einer wasserlöslichen Umhüllung verpackt, ist es bevorzugt, dass der Gehalt an Wasser weniger als 10 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel, beträgt und dass die anionischen Tenside in Form ihrer Ammoniumsalze vorliegen. The liquid washing or cleaning agent can be filled into a water-soluble casing and thus be part of a water-soluble packaging. If the liquid washing or cleaning agent is packaged in a water-soluble casing, it is preferred that the content of water is less than 10 wt .-%, based on the total liquid detergent or cleaning agent, and that the anionic surfactants in the form of their ammonium salts available.
Die Neutralisation mit Aminen führt, anders als bei Basen wie NaOH oder KOH, nicht zu Bildung von Wasser. Somit können wasserarme flüssige Wasch- oder Reinigungsmittel hergestellt werden, die direkt für die Verwendung in wasserlöslichen Umhüllungen geeignet sind. The neutralization with amines, unlike bases such as NaOH or KOH, does not lead to the formation of water. Thus, low-water liquid detergents or cleaners can be prepared which are directly suitable for use in water-soluble coatings.
Eine wasserlösliche Verpackung enthält neben dem flüssigen Wasch- oder Reinigungsmittel eine wasserlösliche Umhüllung. Die wasserlösliche Umhüllung wird vorzugsweise durch ein wasserlösliches Folienmaterial gebildet. Solche wasserlöslichen Verpackungen können entweder durch Verfahren des vertikalen Formfüllversiegelns (VFFS) oder Warmformverfahren hergestellt werden. A water-soluble packaging contains, in addition to the liquid washing or cleaning agent, a water-soluble coating. The water-soluble coating is preferably formed by a water-soluble film material. Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.
Das Warmformverfahren schließt im Allgemeinen das Formen einer ersten Lage aus einem wasserlöslichen Folienmaterial zum Bilden von Ausbuchtungen zum Aufnehmen einer Zusammensetzung darin, Einfüllen der Zusammensetzung in die Ausbuchtungen, Bedecken der mit der Zusammensetzung gefüllten Ausbuchtungen mit einer zweiten Lage aus einem wasserlöslichen Folienmaterial und Versiegeln der ersten und zweiten Lagen miteinander zumindest um die Ausbuchtungen herum ein. The thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.
Die wasserlösliche Umhüllung wird vorzugsweise aus einem wasserlöslichen Folienmaterial ausgewählt aus der Gruppe, bestehend aus Polymeren oder Polymergemischen gebildet. Die Umhüllung kann aus einer oder aus zwei oder mehr Lagen aus dem wasserlöslichen Folienmaterial gebildet werden. Das wasserlösliche Folienmaterial der ersten Lage und der weiteren Lagen, falls vorhanden, kann gleich oder unterschiedlich sein. The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.
Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält. It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 10.000 bis 1 .000.000 gmol"1, vorzugsweise von 20.000 bis 500.000 gmol"1 , besonders bevorzugt von 30.000 bis 100.000 gmol"1 und insbesondere von 40.000 bis 80.000 gmol"1 liegt. Suitable water-soluble films for the preparation of the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight in the range of 10,000 to 1 .000,000 gmol "1 , preferably from 20,000 to 500,000 gmol " 1 , more preferably from 30,000 to 100,000 gmol "1 and especially from 40,000 to 80,000 gmol "1 .
Die Herstellung von Polyvinylalkohol geschieht üblicherweise durch Hydrolyse von Polyvinylacetat, da der direkte Syntheseweg nicht möglich ist. Ähnliches gilt für Polyvinylalkoholcopolymere, die aus entsprechend aus Polyvinylacetatcopolymeren hergestellt werden. Bevorzugt ist, wenn wenigstens eine Lage der wasserlöslichen Umhüllung einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht. The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
Ein zur Herstellung der wasserlöslichen Umhüllung geeignetes Folienmaterial kann zusätzlich Polymere, ausgewählt aus der Gruppe umfassend Acrylsäure-haltige Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether Polymilchsäure, und/oder Mischungen der vorstehenden Polymere, zugesetzt sein. A suitable for preparing the water-soluble coating sheet material may additionally polymers, selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.
Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol Dicarbonsäuren als weitere Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further
Monomere. Geeignete Dicarbonsäure sind Itaconsäure, Malonsäure, Bernsteinsäure und Mischungen daraus, wobei Itaconsäure bevorzugt ist. Ebenso bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesättige Carbonsäure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred. Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Particularly preferably contain such
Polyvinylalkoholcopolymere neben Vinylalkohol Acrylsäure, Methacrylsäure, Acrylsäureester, Polyvinyl alcohol copolymers in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters,
Methacrylsäureester oder Mischungen daraus. Methacrylic acid esters or mixtures thereof.
Geeignete wasserlösliche Folien zum Einsatz in den Umhüllungen der wasserlöslichen Verpackungen gemäß der Erfindung sind Folien, die von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8630, C8400 oder M8900 vertrieben werden. Andere geeignete Folien umfassen Folien mit der Suitable water-soluble films for use in the casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films with the
Bezeichnung Solublon® PT, Solublon® GA, Solublon® KC oder Solublon® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray. Designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
Die wasserlösliche Verpackung, umfassend das flüssige Wasch- oder Reinigungsmittel und die wasserlösliche Umhüllung, kann eine oder mehr Kammern aufweisen. Die wasserlöslichen Verpackungen mit einer Kammer können eine im Wesentlichen formstabile kugelförmige und kissenförmige Ausgestaltung mit einer kreisförmigen, elliptischen, quadratischen oder rechteckigen Grundform aufweisen. Das flüssige Wasch- oder Reinigungsmittel kann in einer oder mehreren Kammern, falls vorhanden, der wasserlöslichen Umhüllung enthalten sein. The water-soluble package comprising the liquid detergent or water-soluble wrapper may have one or more chambers. The water-soluble packaging with a chamber may have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape. The liquid detergent may be contained in one or more chambers, if any, of the water-soluble coating.
In einer bevorzugten Ausführungsform weist die wasserlösliche Verpackung zwei Kammern auf. In dieser Ausführungsform enthält die erste Kammer das flüssige Wasch- oder Reinigungsmittel und die zweite Kammer ein festes oder ein flüssiges Mittel, vorzugsweise ein festes oder ein flüssiges Wasch- oder Reinigungsmittel. In a preferred embodiment, the water-soluble package has two chambers. In this embodiment, the first chamber contains the liquid washing or cleaning agent and the second chamber contains a solid or a liquid agent, preferably a solid or a liquid washing or cleaning agent.
Die Mittel, die in den unterschiedlichen Kammern einer wasserlöslichen Verpackung mit zwei oder mehr Kammern enthalten sind, können dieselbe Zusammensetzung aufweisen. The agents contained in the different chambers of a water-soluble package having two or more chambers may have the same composition.
Vorzugsweise weisen die Mittel, welche bevorzugt alle Wasch- oder Reinigungsmittel sind, in einer wasserlöslichen Verpackung mit mindestens zwei Kammern Zusammensetzungen auf, die sich mindestens in einem Inhaltsstoff oder sich mindestens im Gehalt eines Inhaltsstoffes unterscheiden. Preferably, the agents, which are preferably all detergents or cleaners, in a water-soluble packaging with at least two chambers have compositions which differ at least in one ingredient or at least in the content of one ingredient.
Wasserlösliche Verpackungen mit mindestens zwei Kammern weisen den Vorteil auf, dass nicht kompatible Inhaltsstoffe in getrennten Kammern vorhanden sein können. Ein weiterer Vorteil ergibt sich bei Suspension mit festen und flüssigen Inhaltsstoffen, welche oftmals vom Anwender der wasserlöslichen Verpackung als wenig ästhetisch und/oder fehlerhaft angesehen werden. In einem solchen Fall können die festen bzw. unlöslichen Inhaltsstoffe in einer separaten Kammer der wasserlöslichen Verpackung enthalten sein. Beispiele Water soluble packages having at least two compartments have the advantage that incompatible ingredients may be present in separate compartments. Another advantage is found in suspension with solid and liquid ingredients, which are often considered by the user of the water-soluble packaging as little aesthetic and / or faulty. In such case, the solid or insoluble ingredients may be contained in a separate compartment of the water-soluble package. Examples
Es wurden flüssige Wasch- oder Reinigungsmittel mittels üblicher und bekannter Methoden und Verfahren hergestellt. In der folgenden Tabelle 1 sind die Zusammensetzungen von vier erfindungsgemäßen Waschoder Reinigungsmitteln E1 bis E4 sowie vier nicht erfindungsgemäßen Wasch- oder Reinigungsmitteln V1 bis V4 gezeigt. Liquid detergents or cleaners were prepared by conventional and known methods and procedures. Table 1 below shows the compositions of four detergents or cleaners E1 to E4 according to the invention and four detergents or cleaners V1 to V4 not according to the invention.
Tabelle 1 : Flüssige Wasch- oder Reinigungsmittel E1 bis E4 sowie V1 bis V4 [alle Mengen sind in Gew.-% Aktivstoff, bezogen auf die Zusammensetzung, angegeben] Table 1: Liquid washing or cleaning agents E1 to E4 and also V1 to V4 [all amounts are given in% by weight of active ingredient, based on the composition]
Inhaltsstoffe E1 E2 E3 E4 V1 V2 V3 V4Ingredients E1 E2 E3 E4 V1 V2 V3 V4
Cio-Ci3-Alkylbenzolsulfonsäure 20 2 17 20 20 20 20 20Cio-Ci 3 alkyl benzene 17 20 20 2 20 20 20 20
C13-C15-Oxo-Alkohol mit 8 EO 18 19 18 C 13 -C 15 oxo-alcohol with 8 EO 18 19 18
C13-C15-Oxo-Alkohol mit 7 EO 7 18 18 C 13 -C 15 oxo-alcohol with 7 EO 7 18 18
Ci2-i8-Fettalkohol mit 7 EO 18 18 Ci2-i8 fatty alcohol with 7 EO 18 18
Ci2_i8-Fettsäure 12 4,5 15 12 12 12 12 12Ci2_i8 fatty acid 12 4,5 15 12 12 12 12 12
Na-Laurylethersulfat (2 EO) 5 1 1 5 5 5 5 5Na lauryl ether sulfate (2 EO) 5 1 1 5 5 5 5 5
Ci2-Ci4-Alkylpolyglykosid 2 Ci2-Ci 4 -Alkylpolyglykosid 2
Soil-Release-Polymer* 2 1 ,3 1 ,5 2 2 Soil release polymer * 2 1, 3 1, 5 2 2
Glycerin 4 5 22 4 4 4 4 4Glycerol 4 5 22 4 4 4 4 4
1 ,2-Propandiol 5,2 9 5,2 5,2 5,2 5,2 5,21, 2-Propanediol 5.2 9 5.2 5.2 5.2 5.2 5.2
Ethanol 2 3,3 2 2 2 2 2Ethanol 2 3,3 2 2 2 2 2
Phosphonat 0,7 0,5 0,9 0,7 0,7 0,7 0,7 0,7Phosphonate 0.7 0.5 0.9 0.7 0.7 0.7 0.7 0.7
Monoethanolamin 10 7 10 10 10 10 10Monoethanolamine 10 7 10 10 10 10 10
NaOH (50%ig) 1 ,9 NaOH (50%) 1, 9
Citronensäure 2,3 2 2,3 2,3 2,3 2,3 2,3 Citric acid 2.3 2 2.3 2.3 2.3 2.3 2.3
Borsäure 1 1 1 1 1 1 1Boric acid 1 1 1 1 1 1 1
Farbstoffe, Enzyme (Cellulase, Dyes, enzymes (cellulase,
4,5 4,5 1 ,8 4,5 4,5 4,5 4,5 4,5 Amylase & Protease), optischer  4.5 4.5 1, 8 4.5 4.5 4.5 4.5 4.5 amylase & protease), optical
Aufheller, Parfüm  Brightener, perfume
Wasser auf 100 auf 100 auf 100 auf 100 auf 100 auf 100 auf 100 auf 10  Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 10
* Soil-Release-Polymer = Texcare® SRN 170 (ex Clariant) * Soil Release Polymer = Texcare® SRN 170 (ex Clariant)
Zur Bestimmung der "Soil-Release"-Leistung der flüssigen Wasch- oder Reinigungsmittel wurden verschiedene verschiedene Stofflappen aus Polyester zunächst drei Mal mit je 35 g des zu prüfenden flüssigen Wasch- oder Reinigungsmittels E1 oder V1 in einer Haushaltswaschmaschine (Miele W 1514) mit 3,5 kg Begleitwäsche bei 40 °C gewaschen und danach mit Fett-haltigen Anschmutzungen mit einem Durchmesser von jeweils ca. 2 cm versehen. Anschließend wurde eine Haushaltswaschmaschine (Miele W 1 14) mit 3,5 kg Begleitwäsche sowie den verschmutzten Stofflappen aus Polyester beladen. Zusätzlich wurden 35 g des zu prüfenden Waschmittels zudosiert E1 oder V1 und sechs Mal bei 40 °C gewaschen. Nach hängender Trocknung und Mangeln der Stofflappen wurde deren Remission spektralphotometrisch (Minolta CR200-1 ) als Y-Wert bestimmt (siehe Tabelle 2). Die Bewertung der Fleckentfernung erfolgte über den Y-Wert. To determine the "soil release" performance of the liquid detergents or cleaners, various different polyester cloths were first of all mixed with 35 g of the liquid detergent or cleaning agent E1 or V1 to be tested in a household washing machine (Miele W 1514) with 3 , 5 kg accompanying laundry at 40 ° C washed and then provided with greasy soiling with a diameter of about 2 cm. Subsequently, a household washing machine (Miele W 1 14) was loaded with 3.5 kg accompanying laundry as well as the soiled polyester cloth rags. In addition, 35 g of the detergent to be tested were added to E1 or V1 and washed six times at 40 ° C. After hanging drying and shortage of the cloth rags, their remission was determined spectrophotometrically (Minolta CR200-1) as the Y value (see Table 2). The stain removal was evaluated by the Y value.
Tabelle 2: Weißgrade (Mittel aus 6 Bestimmungen) Table 2: Whitenesses (average of 6 determinations)
E1 vs. V1 E1 vs. V1
Hautfett (blau eingefärbt) + 19,7  Skin fat (dyed blue) + 19.7
Staub/Hautfett mit Mineralöl +10,4  Dust / skin fat with mineral oil +10,4
Gebrauchtes Maschinenöl +8,7  Used machine oil +8.7
Make Up (Sans Soucis) +7,8  Make Up (Sans Soucis) +7.8
Make Up (Manhattan) +3,1  Make Up (Manhattan) +3,1
Schwarze Schuhcreme (Kiwi) +13,1  Black Shoe Polish (Kiwi) +13,1
Die Ergebnisse zeigen deutlich, dass das flüssige Wasch- oder Reinigungsmittel E1 eine höhere The results clearly show that the liquid washing or cleaning agent E1 has a higher
Reinigungsleistung, insbesondere„Soil-Release"-Leistung, an Fett-haltigen Anschmutzungen aufweist, als ein Wasch- oder Reinigungsmittel ohne schmutzablösevermögendes Polymer. Cleansing performance, in particular "soil release" performance, has on fat-containing stains, as a washing or cleaning agent without dirt-releasing polymer.
Außerdem wurden mit den flüssigen Wasch- oder Reinigungsmitteln E1 , E4 sowie V1 bis V4 In addition, with the liquid detergents or cleaning agents E1, E4 and V1 to V4
Untersuchungen zur Vergrauungsinhibierung durchgeführt. Investigations on the grayness inhibition carried out.
Dazu wurden verschiedene Testgewebe fünf Mal hintereinander mit je 20 g des zu prüfenden flüssigen Wasch- oder Reinigungsmittels E1 , E4, V1 , V2, V3 oder V4 in einer Haushaltswaschmaschine (Miele W 1514) mit je 5 SBL 2004 Tüchern mit standardisierter Schmutzbeladung (32 g Schmutzballast) bei 40 °C gewaschen. For this purpose, various test fabrics were five times in succession, each with 20 g of the liquid detergent or cleaning agent to be tested E1, E4, V1, V2, V3 or V4 in a household washing machine (Miele W 1514) with 5 SBL 2004 towels with standardized dirt load (32 g Dirt ballast) at 40 ° C.
Nach hängender Trocknung und Mangeln der Wäsche wurde deren Weißgrad spektralphotometrisch bestimmt. In Tabelle 3 sind diese Messwerte im Vergleich zum jeweiligen Ausgangswert der Testgewebe angegeben. After hanging drying and mangling of the laundry their whiteness was determined spectrophotometrically. In Table 3 these measurements are given in comparison to the respective initial value of the test fabrics.
Bei den Geweben aus Baumwolle handelt es sich um acht verschiedene kommerziell erhältliche Baumwollgewebe. Die Gewebe aus Synthetik umfassen zehn verschiedene kommerziell erhältliche Gewebe aus beispielsweise Polyamid, Viskose, Polyester, Polyester-Baumwolle-Mischungen, Lycra-Elasthan- Mischungen und Polyacrylnitril. Die Alttagsgewebe umfassen vier handelsübliche Alltagstextilien wie zum Beispiel Küchen-, Frottier-, Gerstenkornhandtuch und weiße T-Shirts. Tabelle 3: Weißgrade (Mittelwert der jeweiligen Gewebe) The cotton fabrics are eight different commercially available cotton fabrics. The fabrics of synthetic include ten different commercially available fabrics of, for example, polyamide, viscose, polyester, polyester-cotton blends, Lycra elastane blends, and polyacrylonitrile. The day-old fabrics include four commercial everyday textiles such as kitchen toweling, toweling, barley grain towel and white T-shirts. Table 3: Whitenesses (average of the respective tissues)
Wasch- oder Baumwolle Synthetik Alltag Gesamt Reinigungsmittel Wash or cotton synthetics everyday overall cleanser
E1 -9,8 -7,2 -13,4 -10,1 E1 -9.8 -7.2 -13.4 -10.1
E4 -10,3 -8,4 -9,8 -9,5E4 -10.3 -8.4 -9.8 -9.5
V1 -10,9 -1 1 ,2 -13,4 -11 ,8V1 -10.9 -1 1, 2 -13.4 -11, 8
V2 -12,7 -9,0 -13,6 -11 ,8V2 -12.7 -9.0 -13.6 -11, 8
V3 -13,5 -9,3 -14,8 -12,5V3 -13.5 -9.3 -14.8 -12.5
V4 -12,1 -8,3 -14,4 -11 ,6 V4 -12.1 -8.3 -14.4 -11, 6
Die Ergebnisse zeigen deutlich, dass durch Verwendung einer Kombination aus einem The results clearly show that by using a combination of a
schmutzablösevermögenden Polymer und einem alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten die vergrauungsinhibierende Reinigungsleistung eines flüssigen Wasch- oder Reinigungsmittels nicht nur an Polyester-Geweben, sondern insbesondere auch an Geweben aus Baumwolle erhöht werden kann. Dabei zeigt die Kombination aus einem schmutzablösevermögenden Polymer und einem alkoxylierten Oxo-Alkohol mit 8 Alkoxyeinheiten eine besonders gute vergrauungsinhibierende Reinigungsleistung an synthetischen Geweben während die Kombination aus einem schmutzablösevermögenden Polymer und einem soil release-rich polymer and an alkoxylated oxo alcohol with 7 or 8 alkoxy units, the graying-inhibiting cleaning performance of a liquid detergent or cleaning agent can be increased not only on polyester fabrics, but especially on cotton fabrics. The combination of a soil release polymer and an alkoxylated oxo-alcohol with 8 alkoxy units shows a particularly good graying-inhibiting cleaning performance on synthetic fabrics while the combination of a soil release polymer and a
alkoxylierten Oxo-Alkohol mit 7 Alkoxyeinheiten eine besonders gute vergrauungsinhibierende alkoxylated oxo-alcohol with 7 alkoxy units a particularly good graying-inhibiting
Reinigungsleistung an Alltagsgeweben aufweist. Has cleaning performance of everyday tissues.
Zur Herstellung einer wasserlöslichen Verpackungen mit dem Wasch- oder Reinigungsmittel E3 wurde eine Folie vom Typ M 8630 (ex Monosol) mit einer Dicke von 76 μητι zum Ausbilden einer Ausbuchtung mittels Vakuum in eine Mulde gezogen. Anschließend wurde die Ausbuchtung mit 30 ml des flüssigen Wasch- oder Reinigungsmittel E3 befüllt. Nach Bedecken der mit dem Mittel befüllten Ausbuchtungen mit einer zweiten Lage einer Folie vom Typ M 8630 wurden die erste und zweite Lage miteinander versiegelt. Die Siegelungstemperatur betrug 150 °C und die Siegelungsdauer 1 ,1 Sekunden. To produce a water-soluble packaging with the detergent E3, a film of the type M 8630 (ex Monosol) was drawn with a thickness of 76 μητι for forming a bulge by means of vacuum in a trough. Subsequently, the bulge was filled with 30 ml of the liquid washing or cleaning agent E3. After covering the agent filled bulges with a second layer of M 8630 film, the first and second layers were sealed together. The sealing temperature was 150 ° C and the sealing time 1, 1 seconds.
Nach 4, 8 und 12 Wochen Lagerzeit der wasserlöslichen Verpackungen mit dem Wasch- oder After 4, 8 and 12 weeks storage time of the water-soluble packaging with the washing or
Reinigungsmitteln E3 unter verschiedenen klimatischen Bedingungen konnte keinerlei An- oder Auflösung der wasserlöslichen Umhüllung beobachtet werden. Zudem konnten keine Poren oder Löcher, die ebenfalls zum Produktaustritt oder Leckagen führen würden, festgestellt werden. Detergents E3 under various climatic conditions, no arrival or dissolution of the water-soluble coating could be observed. In addition, no pores or holes, which would also lead to product leakage or leaks, were found.
Wasserlösliche Verpackungen mit dem Wasch- oder Reinigungsmitteln E3 lösten sich in Waschgängen bei Temperaturen, die im Bereich von 20 bis 95 °C lagen, rückstandslos auf und zeigten eine sehr gute Soil- Release-Reinigungsleistung, insbesondere an Fett-haltigen Anschmutzungen, sowie eine sehr gute vergrauungsinhibierende Reinigungsleistung. Water-soluble packaging with detergent or cleaning agent E3 dissolved in washes at temperatures ranging from 20 to 95 ° C, without residue on and showed a very good soil release cleaning performance, especially on greasy soiling, as well as a very good graying-inhibiting cleaning performance.

Claims

Patentansprüche claims
1. Flüssiges Wasch- oder Reinigungsmittel, umfassend 1. A liquid washing or cleaning agent, comprising
a) einen alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten und  a) an alkoxylated oxo-alcohol having 7 or 8 alkoxy units and
b) ein schmutzablösevermögendes Polymer.  b) a soil release polymer.
2. Flüssiges Wasch- oder Reinigungsmittel gemäß Anspruch 1 , dadurch gekennzeichnet, dass der alkoxylierte Oxo-Alkohol ausgewählt ist aus der Gruppe bestehend aus Ci3_i5-Oxo-Alkoholen mit 7 EO, Ci3_i5-Oxo-Alkoholen mit 8 EO und Mischungen daraus. 2. Liquid washing or cleaning agent according to claim 1, characterized in that the alkoxylated oxo-alcohol is selected from the group consisting of Ci 3 _i 5 -oxo-alcohols with 7 EO, Ci3_i 5 -oxo-alcohols with 8 EO and mixtures it.
3. Flüssiges Wasch- oder Reinigungsmittel gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass das schmutzablösevermögende Polymer ein Polyester von einer Dicarbonsäure und einem Diol ist. 3. A liquid washing or cleaning agent according to claim 1 or 2, characterized in that the soil release polymer is a polyester of a dicarboxylic acid and a diol.
4. Flüssiges Wasch- oder Reinigungsmittel gemäß Anspruch 3, dadurch gekennzeichnet, dass das schmutzablösevermögende Polymer ein endgruppenverschlossener Polyester aus Terephthalsäure, Polyethylenglykol und 1 ,2-Propylenglykol ist. 4. Liquid detergent or cleaning agent according to claim 3, characterized in that the soil release polymer is an end-capped polyester of terephthalic acid, polyethylene glycol and 1, 2-propylene glycol.
5. Flüssiges Wasch- oder Reinigungsmittel gemäß einem Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Wasch- oder Reinigungsmittel bis zu 10 Gew.-%, bezogen auf das gesamte Wasch- oder Reinigungsmittel, Wasser enthält. 5. Liquid washing or cleaning agent according to one of claims 1 to 4, characterized in that the washing or cleaning agent up to 10 wt .-%, based on the total washing or cleaning agent, water.
6. Flüssiges Wasch- oder Reinigungsmittel gemäß einem Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Wasch- oder Reinigungsmittel ferner ein Amin neutralisiertes anionisches Tensid enthält. 6. A liquid washing or cleaning agent according to any one of claims 1 to 5, characterized in that the washing or cleaning agent further contains an amine neutralized anionic surfactant.
7. Flüssiges Wasch- oder Reinigungsmittel gemäß einem Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Wasch- oder Reinigungsmittel in einer wasserlöslichen Umhüllung verpackt ist. 7. Liquid washing or cleaning agent according to one of claims 1 to 6, characterized in that the washing or cleaning agent is packaged in a water-soluble wrapper.
8. Verwendung einer Kombination aus einem schmutzablösevermögenden Polymer und einem 8. Use of a combination of a soil release polymer and a
alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten in einem flüssigen Wasch- oder  alkoxylated oxo-alcohol with 7 or 8 alkoxy units in a liquid wash or
Reinigungsmittel zur Erhöhung der Reinigungsleistung an Fett-haltigen Anschmutzungen.  Detergent to increase the cleaning performance of soils containing grease.
9. Verwendung einer Kombination aus einem schmutzablösevermögenden Polymer und einem 9. Use of a combination of a soil release polymer and a
alkoxylierten Oxo-Alkohol mit 7 oder 8 Alkoxyeinheiten in einem flüssigen Wasch- oder  alkoxylated oxo-alcohol with 7 or 8 alkoxy units in a liquid wash or
Reinigungsmittel zur Erhöhung der Vergrauungsinhibierung.  Cleaning agent to increase the grayness inhibition.
EP13709919.8A 2012-03-19 2013-03-18 Liquid detergent composition with increased cleaning performance Revoked EP2828368B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13709919T PL2828368T3 (en) 2012-03-19 2013-03-18 Liquid detergent composition with increased cleaning performance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012204270A DE102012204270A1 (en) 2012-03-19 2012-03-19 Liquid detergent with increased cleaning performance
PCT/EP2013/055524 WO2013139726A1 (en) 2012-03-19 2013-03-18 Liquid detergent with increased cleaning performance

Publications (2)

Publication Number Publication Date
EP2828368A1 true EP2828368A1 (en) 2015-01-28
EP2828368B1 EP2828368B1 (en) 2018-06-06

Family

ID=47891728

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13709919.8A Revoked EP2828368B1 (en) 2012-03-19 2013-03-18 Liquid detergent composition with increased cleaning performance

Country Status (6)

Country Link
US (1) US9422509B2 (en)
EP (1) EP2828368B1 (en)
DE (1) DE102012204270A1 (en)
ES (1) ES2677906T3 (en)
PL (1) PL2828368T3 (en)
WO (1) WO2013139726A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012211028A1 (en) * 2012-06-27 2014-01-02 Henkel Ag & Co. Kgaa Highly concentrated liquid washing or cleaning agent
DE102012212726A1 (en) * 2012-07-19 2014-01-23 Henkel Ag & Co. Kgaa Stable, liquid detergent with graying-inhibiting performance
DE102014218952A1 (en) 2014-09-19 2016-03-24 Henkel Ag & Co. Kgaa Textile treatment agent containing at least one anionic aromatic polyester and at least one nonionic aromatic polyester
ES2694703T3 (en) 2015-07-30 2018-12-26 The Procter & Gamble Company Water soluble unit dose item
US10808206B2 (en) 2017-11-14 2020-10-20 Henkel IP & Holding GmbH Detergent boosters, detergent systems that include a detergent booster, and methods of laundering fabric
EP3517596B1 (en) * 2018-01-25 2024-03-20 The Procter & Gamble Company Method of making an opaque liquid detergent composition
EP3517597B1 (en) 2018-01-25 2024-03-20 The Procter & Gamble Company Polymer composition

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1049367A (en) * 1974-06-25 1979-02-27 The Procter And Gamble Company Liquid detergent compositions having soil release properties
GB1560073A (en) 1975-10-17 1980-01-30 Unilever Ltd Detergent compositions and the production thereof
DE2817834C2 (en) 1978-04-24 1983-05-19 Henkel KGaA, 4000 Düsseldorf Liquid detergent
DE2916656A1 (en) 1979-04-25 1980-11-06 Henkel Kgaa Optical brightener-free textile detergent compsn. - contg. aliphatic polyglycol ether(s), alkyl-pyridinium salt and standard additives
DE3277730D1 (en) * 1981-09-25 1988-01-07 Procter & Gamble LIQUID DETERGENT COMPOSITIONS CONTAINING AMINO-SILANES
US4886615A (en) 1985-08-05 1989-12-12 Colgate-Palmolive Company Hydroxy polycarboxylic acid built non-aqueous liquid cleaning composition and method for use, and package therefor
US5290475A (en) * 1990-05-08 1994-03-01 Colgate Palmolive Liquid softening and anti-static nonionic detergent composition with soil release promoting PET-POET copolymer
DE4125025A1 (en) 1991-07-29 1993-02-04 Henkel Kgaa LIQUID DETERGENT
DE69224376T2 (en) * 1992-06-29 1998-09-03 Procter & Gamble Polyvinylpyrrolidone and soil-repellent polymer based on concentrated aqueous-liquid detergent compositions containing polyterephthalates
ATE178090T1 (en) * 1992-07-31 1999-04-15 Procter & Gamble USE OF MODIFIED POLYESTERS TO REMOVE GREASE FROM TEXTILES
PT629690E (en) * 1993-06-09 2000-04-28 Procter & Gamble AQUEOUS EMULSES STABLE OF NON-IONIC TENSIOACTIVE AGENTS
DE4436151A1 (en) 1994-08-16 1996-05-02 Henkel Kgaa Process for the production of a liquid detergent with bleach
DE4440956A1 (en) 1994-11-17 1996-05-23 Henkel Kgaa Dirt-repellent detergent with a specific combination of surfactants
GB9520519D0 (en) 1995-10-04 1995-12-13 Unilever Plc Detergent composition
DE19541012A1 (en) * 1995-11-03 1997-05-07 Basf Ag Use of oxime esters as activators for inorganic per compounds
DE19725508A1 (en) * 1997-06-17 1998-12-24 Clariant Gmbh Detergents and cleaning agents
DE19826356A1 (en) * 1998-06-12 1999-12-16 Clariant Gmbh Soil-removing oligoester
DE10040724A1 (en) 2000-08-17 2002-03-07 Henkel Kgaa Mechanically stable, liquid formulated detergent, detergent or cleaning agent portions
GB0021113D0 (en) 2000-08-25 2000-10-11 Reckitt & Colmann Prod Ltd Improvements in or relating to containers
EP1354939A1 (en) * 2002-04-19 2003-10-22 The Procter & Gamble Company Pouched cleaning compositions
DE602005015532D1 (en) 2004-11-22 2009-09-03 Procter & Gamble Water-soluble bag filled with a liquid
DE102005061058A1 (en) * 2005-12-21 2007-07-05 Clariant Produkte (Deutschland) Gmbh New polyester compounds useful in detergents and cleaning agents e.g. color detergents, bar soaps and dishwash detergents, as soil releasing agents, fabric care agents and means for the equipments of textiles
GB0613069D0 (en) 2006-06-30 2006-08-09 Unilever Plc Laundry articles
PL2133410T3 (en) 2008-06-13 2012-05-31 Procter & Gamble Multi-compartment pouch
GB0810881D0 (en) 2008-06-16 2008-07-23 Unilever Plc Improvements relating to fabric cleaning
BR112012000492A2 (en) 2009-07-09 2019-09-24 Procter & Gamble moderately alkaline, low adjuvant detergent composition comprising peroxycaproic phitalimide acid for solid tissue treatment
WO2012104158A1 (en) * 2011-01-31 2012-08-09 Unilever Plc Soil release polymers
JP2014522896A (en) 2011-07-12 2014-09-08 クラリアント・インターナシヨナル・リミテツド Use of a combination of secondary paraffin sulfonate and amylase to enhance the cleaning capacity of a liquid laundry detergent

Also Published As

Publication number Publication date
WO2013139726A1 (en) 2013-09-26
EP2828368B1 (en) 2018-06-06
PL2828368T3 (en) 2018-11-30
ES2677906T3 (en) 2018-08-07
DE102012204270A1 (en) 2013-09-19
US20150005220A1 (en) 2015-01-01
US9422509B2 (en) 2016-08-23

Similar Documents

Publication Publication Date Title
EP2828368B1 (en) Liquid detergent composition with increased cleaning performance
EP2867352B1 (en) Highly concentrated liquid washing or cleaning composition
WO2015011062A1 (en) Detergent containing amine oxide
DE102014206064A1 (en) Liquid laundry detergent containing polymers to enhance the perfume performance
WO2013171095A1 (en) Low-water-content, liquid detergent comprising surfactants obtained from renewable raw materials
EP2804937A1 (en) Washing, cleaning or pre-treatment agent with increased cleaning power
EP2553077B1 (en) Washing composition for sensitive textiles
WO2013186170A1 (en) Detergent, cleaning agent, or pretreatment agent having greater cleaning power ii
WO2014146985A1 (en) Color-protecting detergent or cleaning agent having an optical brightener
EP3083914A2 (en) Detergent containing methyl ester sulfonates (mes) and methyl ester ethoxylates (mee)
EP2809759B1 (en) Low-water, liquid detergent having increased fat-dissolving power
EP2875107B1 (en) Stable, liquid detergent with anti-redeposition action
WO2010112312A1 (en) Fluid bleaching agent composition
DE102014205928A1 (en) Detergents or cleaning agents with anionic surfactant, fatty alcohol alkoxylate, fatty acid esters and alkylene glycol monoether
WO2015091108A1 (en) Washing composition comprising alkyl carboxylates
EP3450532B1 (en) Use of an amodimethicone/organosilicon-containing copolymer, detergent, use of the detergent and washing method
WO2014012868A1 (en) Stable, liquid detergent with anti-redeposition action
DE102013210271A1 (en) Washing, cleaning or pretreatment agent with increased cleaning power III
DE102012003342A1 (en) Washing with fibers
WO2014195216A1 (en) Washing, cleaning or pretreatment agent having increased cleaning power iv
WO2014206810A1 (en) Detergent or cleaning agent containing sucrose alkyl ester

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140306

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170228

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 1/83 20060101ALI20171215BHEP

Ipc: C11D 3/37 20060101ALI20171215BHEP

Ipc: C11D 17/04 20060101ALI20171215BHEP

Ipc: C11D 1/72 20060101AFI20171215BHEP

Ipc: C11D 3/00 20060101ALI20171215BHEP

INTG Intention to grant announced

Effective date: 20180119

INTG Intention to grant announced

Effective date: 20180119

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1006086

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013010323

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2677906

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20180807

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180606

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180906

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180906

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180907

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181006

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502013010323

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: DALLI-WERKE GMBH & CO. KG

Effective date: 20190228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190318

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190318

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181008

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1006086

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190318

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20210329

Year of fee payment: 9

Ref country code: FR

Payment date: 20210323

Year of fee payment: 9

R26 Opposition filed (corrected)

Opponent name: DALLI-WERKE GMBH & CO. KG

Effective date: 20190228

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20210319

Year of fee payment: 9

Ref country code: GB

Payment date: 20210324

Year of fee payment: 9

Ref country code: PL

Payment date: 20210305

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 502013010323

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 502013010323

Country of ref document: DE

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130318

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FI

Ref legal event code: MGE

27W Patent revoked

Effective date: 20210701

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20210701

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20210525

Year of fee payment: 9

REG Reference to a national code

Ref country code: AT

Ref legal event code: MA03

Ref document number: 1006086

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606