EP4194535A1 - Zweiphasige reinigungszusammensetzung mit sichtbar unterschiedlichen waschmittelpartikeln - Google Patents

Zweiphasige reinigungszusammensetzung mit sichtbar unterschiedlichen waschmittelpartikeln Download PDF

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Publication number
EP4194535A1
EP4194535A1 EP22211491.0A EP22211491A EP4194535A1 EP 4194535 A1 EP4194535 A1 EP 4194535A1 EP 22211491 A EP22211491 A EP 22211491A EP 4194535 A1 EP4194535 A1 EP 4194535A1
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EP
European Patent Office
Prior art keywords
cleaning composition
liquid phase
composition according
forgoing
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.)
Pending
Application number
EP22211491.0A
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English (en)
French (fr)
Inventor
Peter Schmiedel
Marwa AMRAOUI
Ines Baranski
Sven Mueller
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP4194535A1 publication Critical patent/EP4194535A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention generally relates to two-phase cleaning compositions with visibly distinct detergent particles.
  • the present invention relates to a two-phase cleaning composition comprising a liquid phase and visibly distinct detergent particles dispersed in the liquid phase, the use of said cleaning composition in automatic dishwashing, an automatic dishwashing method using said cleaning composition and a container containing said cleaning composition.
  • Cleaning compositions are available in a variety of forms such as liquids, powders, sprays or solids and are generally used to remove dirt, including dust, stains and bad smells.
  • One class of cleaning compositions are automatic dishwashing (ADW) compositions which are expected to yield spot-less and film-free dishes and glasses.
  • ADW compositions are mixtures of ingredients whose purpose, in combination, is to break down and remove food solids, to inhibit foaming caused by certain food soils, and to remove stains which can be caused by beverages such as coffee or tea.
  • the cleaning properties are the chief criteria by which the performance of a cleaning composition is judged
  • consumers of liquid cleaning products, in particular ADW and laundry products have a preference for products having a certain optical appearance.
  • the addition of solid particles suspended in a liquid cleaning composition can improve the aesthetic acceptance of the product by simply improving the physical appearance of the product. Such solid particles can also serve to visualize the cleaning performance of the product and serve as general support for customer satisfaction.
  • Previously used particles in liquid ADW compositions have had the major disadvantage of contributing negatively to unwanted filming, particular on glass, stainless steel and plastic surfaces as the particles used were usually coated with water-insoluble coatings such as waxes which melt and are released into the wash solution due to the high temperatures encountered during ADW processes. Further, not all particles were compatible with the other ingredients of the composition and liquid compositions containing such particles usually showed poor storage stability due to sedimentation of the particles.
  • US 6,730,652 provides non-staining colored composite particles suitable for incorporation in a bleach-containing liquid detergent composition as well as a liquid automatic dishwashing detergent containing said particles.
  • the particles are formed by a process comprising the steps of a) forming a colored liquid dispersion of pigment particles in a first liquid medium, wherein the size of said pigment particles in said colored liquid dispersion is no greater than about 5 ⁇ m; b) mixing said colored liquid dispersion with a polymeric material and a second liquid medium to form a sprayable colored polymeric material, said polymeric material being selected from the group consisting of alkyl cellulose ethers and polyvinyl alcohol; and c) spraying said colored polymeric material on a composite particle and forming a colored polymeric coating on said composite particle.
  • US 7,357,755 discloses a liquid detergent composition
  • a liquid detergent composition comprising a liquid matrix having dispersed therein a plurality of visibly distinct beads, wherein the liquid matrix comprises a stripping agent, selected from the group consisting of enzymes, zwitterionic polymers, non-ionic detersive surfactants, transition metal catalysts, per-acid/organic catalysts, alternative singlet oxygen generators and mixtures thereof;
  • the visibly distinct beads have a diameter of 0.2 to 8 mm, are in the form of polyelectrolyte complex microcapsules comprising alginate and chitosan, and the complex microcapsules comprise a hueing agent; and the hueing agent is a dye conjugate selected from the group consisting of dye-polymer conjugates, dye-clay conjugates and combinations thereof.
  • liquid cleaning compositions in particular for automatic dishwashing, in which the cleaning performance can be visualized by visibly displaying the active component.
  • a first aspect of the present invention is a two-phase cleaning composition for automatic dishwashing comprising a liquid phase and visibly distinct detergent particles dispersed in the liquid phase, characterized in that the detergent particles comprise one or more surfactants having a Krafft temperature of 30 to 55 °C, determined according to DIN 53918.
  • the Krafft temperature within the meaning of the present invention defines the minimum temperature from which micelle formation takes place, i.e. the surfactant becomes soluble in the liquid phase.
  • the Krafft temperature in some cases also referred to as Krafft point, can be determined as set out in DIN 53918.
  • Dispersed within the meaning of the present invention is to be understood as at least 70%, preferably at least 80%, especially at least 90% and in particular at least 95% of the detergent particles, based on the total amount of detergent particles present, being homogenously suspended and floating in the liquid phase.
  • the inventive cleaning composition shows a high transparency of the liquid phase and a low level of sedimentation of the detergent particles. Therefore, preference is given to an embodiment of the present invention wherein the liquid phase of the cleaning composition is transparent or translucent.
  • the transmittance of the liquid phase is in a range between 100% and 20%, preferably between 100% and 30%, in particular between 100% and 40%. To measure the light transmission (transmittance), the transmittance in % at 600 nm was determined against water as reference at 20 °C.
  • the composition (without the particles) was poured into a 11 mm round cuvette and measured after 12 h storage time at room temperature in a LICO 300 colorimetric system according to Lange.
  • the inventive cleaning composition is free of any sediment, preferably the amount of sedimented detergent particles is less than 10%, preferably less than 5% and in particular less than 1%, based on the total amount of detergent particles.
  • the Krafft temperature of the one or more surfactant comprised in the detergent particles is 35 to 50 °C, preferably 40 to 45 °C, determined according to DIN 53918.
  • the one or more surfactant employed in the present invention is preferably an ionic surfactant, in particular one selected from the group of anionic surfactants and cationic surfactants.
  • the one or more surfactant is selected from the group consisting of alkyl sulfonates with ⁇ C14, alkyl sulfates with ⁇ C16 and alkyl benzenesulfonates with ⁇ C12, C depicting the number of carbon atoms.
  • the one or more surfactant is selected from the group consisting of alkyl sulfonates with ⁇ C14, C depicting the number of carbon atoms.
  • At least 50 wt.%, preferably at least 60 wt.-%, more preferably at least 70 wt.%, most preferred at least 80 wt% of the surfactant comprised in the particles, based on the weight of the surfactant contained in the particles, is selected from alkyl sulfonates with ⁇ C14, C depicting the number of carbon atoms. Especially preferred are C14 alkyl sulfonates, C16 alkyl sulfonates and/or C18 alkyl sulfonates.
  • Surfactants exhibiting a suitable Krafft temperature to be employed in the present invention can be easily identified by the person skilled in the art and are, for example, listed in Milton J. Rosen, Surfactants and Interfacial Phenomena, 3rd Edition, Wiley-Interscience, A John Wiley & Sons, Inc., Publication, USA, 2004 .
  • the cleaning composition according to the invention is distinguished by the visibly distinct detergent particles dispersed in the liquid phase which allow visualization of the active cleaning agent to improve customer satisfaction.
  • the particle size of the detergent particles should not be too small, also to avoid clouding of the liquid phase.
  • the particles should not be too large to ensure sufficient pourability of the cleaning composition. Therefore, in a preferred embodiment, detergent particles with an average particle size of 0.1 to 4 mm, preferably 0.25 to 3 mm, in particular 0.5 to 2 mm, determined by a sieving column, are chosen. Appropriate methods for determining the particle size can, for example, be found in ASTM C 136.
  • At least 80 % of the particles should have a particle size that is from 0.5 to 2 mm.
  • the cleaning composition according to the invention combines appealing aesthetic as well as excellent cleaning properties.
  • the detergent particles comprised in the inventive cleaning composition are designed to dissolve under washing conditions thus releasing the one or more surfactant.
  • each detergent particle comprises at least 50 wt.%, preferably at least 60 wt.%, in particular at least 70 wt.% of the one or more surfactant, based on the total weight of the particle, respectively.
  • the detergent particles do not comprise further additives such as dyes and hueing agents or bleach catalysts. Rather, embodiments are preferred wherein the presence of such additives is limited to the liquid phase.
  • the cleaning composition according to the invention is provided in form of a liquid.
  • liquid as used herein includes liquids and gels, both being in particular characterized by their yield point.
  • gel is used for a composition which acts as a solid body below its yield strength while “liquid” refers to compositions which exhibit a fluid behavior below their yield strength.
  • the provision of the cleaning composition according to the invention in the form of a liquid entails that the composition also needs to exhibit a good pourability, despite the presence of the solid detergent particles. It was surprisingly found that excellent pourability could be achieved, while at the same time maintaining suitable stability to suspend the solid detergent particles, by carefully adapting the rheological yield strength of the liquid phase of the cleaning composition according to the invention.
  • the liquid phase thus has a rheological yield strength of at least 0.1 Pa.
  • the liquid phase exhibits a rheological yield strength of 0.1 to 10 Pa, preferably 0.5 to 7.5 Pa, in particular 1 to 5 Pa. It was surprisingly found that the inventive cleaning composition also showed an excellent long-term stability if the yield strength was controlled to be within the claimed ranges. The sedimentiation of particles from the liquid phase is reduced.
  • the determination of the yield strength for the purpose of the present invention can be carried out by means of a shear stress controlled Rheometer, e.g. AR G2 from TA Instruments or Malvern Kinexus, at a temperature of 25 °C with a cone-plate measuring system 40 mm in diameter and 2° cone angle.
  • the samples were measured in the rheometer with a shear stress s increasing with time t within 60 minutes from the lowest possible value to a value above the expected yield strength.
  • the deformation ⁇ of the sample was measured and plotted as a function of the shearstress s(t) in a double logarithmic plot. If the sample has a yield point, two different regions can be distinguished in this graph.
  • the liquid phase has a viscosity at a shear rate of 10 s -1 of less than 2000 mPas, preferably less than 1000 mPas.
  • the viscosity at a shear rate of 10 s -1 of the liquid phase is at least 100 mPas.
  • the viscosity can be determined under the following conditions: Malvern Kinexus, KP 40 mm, 1°, 25°C.
  • the liquid phase preferably comprises at least one rheological modifier.
  • the rheological modifier is selected from the group consisting of polysaccharide gums such as xanthan gum, guar, carageenan, pectin, alginate, and succinoglycan gum; synthetic rheology modifiers based on acrylates (such as Carbopol ® Aqua 30, Acusol ® 810, Acusol ® 830, Acusol ® 835 or Acusol ® 842) or urethanes (such as Acusol ® 880 and Acusol ® 882); "low-molecular-weight gelators" "LMWG", such as dibenzylidene sorbitol (DBS), hydrogenated castor oil (HCO), urea derivatives (such as Rheobyk ® 7420) or cyclic dipeptides.
  • polysaccharide gums such as xanthan gum, guar, carageenan, pectin, alg
  • cleaning composition wherein the liquid phase contains from 0.15 to 5.0 wt.%, preferably from 0.20 to 2.5 wt.%, more preferably to 0.25 to 1.5 wt.% of rheological modifier, most preferred from 0.3 to 1.0 wt.%, based on the weight of the liquid phase.
  • Preferred rheological modifiers are selected from the group of xanthan gum, crosslinked polyacrylate and urea derivatives.
  • Xanthan gum, urea derivatives, such as Rheobyk ® 7420, and/or crosslinked polyacrylate, such as Acusol ® 810 are able to stabilize the dispersion of the detergent particles in the liquid phase and minimize disintegration of this mixture. Especially, they reduce sedimentation of the detergent particles and also aggregation of the particles. A floating up of a larger portion of the particles contained in the liquid phase to the upper surface of the liquid phase is reduced or even inhibited.
  • the liquid phase of the cleaning composition according to the present invention comprises a significant amount of water.
  • Organic solvents might be present as well but are preferably limited to an amount of up to 15 wt.%, based on the weight of the liquid phase. More preferably the organic solvent content is limited up to 10 wt.%, based on the weight of the liquid phase.
  • Especially preferred organic solvents are propane diol, glycerol and/or sorbitol. These amount of organic solvents add to the pourability as well as to the stabilization of active ingredients and also to the stabilization of the gel, especially via reduction of particle sedimentation.
  • the amount of water is at least 20 wt.%, based on the weight of the liquid phase.
  • cleaning composition wherein the liquid phase contains from 40 to 80 wt.%, preferably from 45 to 75 wt.%, more preferably from 50 to 70 wt.% of water, based on the weight of the liquid phase.
  • the liquid phase of the cleaning composition contains 45 to 75 wt.% water and 0.2 to 2.5 wt.% of rheological modifiers, each based on the weight of the liquid phase. More preferably the liquid phase contains 50 to 70 wt.% water and 0.25 to 1.5 wt.% of rheological modifier, selected from xanthan gum or crosslinked polyacrylates or urea derivates, each based on the weight of the liquid phase.
  • the cleaning composition according to the present invention may further comprise a variety of detergent ingredients such as builders.
  • Builder materials are used to provide alkalinity and buffering capacity, maintain ionic strength, extract metals from soils and/or remove alkaline earth metals from washing solutions.
  • the builder is selected from the group consisting of aminocarboxylic acids and their salts, carbonates, organic cobuilders and silicates.
  • Amino carboxylic acids and/or the salts thereof represent another important class of builders. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) or the salts thereof, and glutamic diacetic acid (GLDA) or the salts thereof or ethylenediaminediacetic acid or the salts thereof (EDDS). Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are also suitable.
  • the content of these amino carboxylic acids or the salts thereof can, for example, be between 0.1 and 25 wt.%, preferably between 0.5 and 20.0 wt.%, and in particular between 0.5 and 17 wt.%, based in the total weight of the liquid phase.
  • Amino carboxylic acids and the salts thereof can be used together with the aforementioned builders, in particular also with phosphate-free builders.
  • cleaning composition wherein the liquid phase contains between 0.1 to 20 wt.%, preferably between 0.5 to 17.0 wt.%, more preferably between 1.0 to 15 wt.% of methylglycine diacetic acid (MGDA) or the salts thereof, based on the weight of the liquid phase.
  • MGDA methylglycine diacetic acid
  • Polycarboxylates/polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins are particularly noteworthy as organic cobuilders.
  • Suitable organic builders are polycarboxylic acids that can be used in the form of the free acids and/or the sodium salts thereof, with polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. These include, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that the use of NTA is not objectionable for ecological reasons, and mixtures thereof.
  • NTA nitrilotriacetic acid
  • Alkali carbonates, in particular sodium carbonate can also be used as pH adjusters, and in various embodiments of the invention are preferably contained in an amount of 5 to 40 wt.%, more preferably 10 to 30 wt.%, based on the total weight of the liquid phase.
  • Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a weight-average molecular weight of 500 to 70,000 g/mol.
  • Suitable polymers are in particular polyacrylates which preferably have a weight-average molecular weight of 2,000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates which have a weight-average molecular weight of 2,000 to 10,000 g/mol, and particularly preferably 3,000 to 5,000 g/mol, can be preferred from this group.
  • a copolymeric polyacrylate preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the polycarboxylate.
  • the copolymers can have two, three, four, or more different monomer units.
  • Preferred copolymeric polysulfonates contain, besides sulfonic acid group-containing monomer(s), at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylene malonic acid, sorbic acid, cinnamic acid, or mixtures thereof.
  • Unsaturated dicarboxylic acids can of course also be used.
  • the liquid phase contains a polymer comprising at least one sulfonic acid group-containing monomer.
  • the liquid phase comprises a polymer comprising, as a sulfonic acid group-containing monomer, acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid.
  • Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, allyloxybenzene sulfonic acid, methallyloxybenzene sulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinylsulfonic acid, 3-sulfopropylacrylate, 3-sulfopropylmethacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, as well as
  • the sulfonic acid groups can be present in the polymers in a fully or partially neutralized form, i.e., the acidic hydrogen atom of the sulfonic acid group can be replaced in some or all of the sulfonic acid groups with metal ions, preferably alkali metal ions, and in particular with sodium ions.
  • metal ions preferably alkali metal ions, and in particular with sodium ions.
  • partially or fully neutralized sulfonic acid group-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers that are preferably used according to the invention is preferably 5 to 95 wt.% in each case; particularly preferably, the proportion of the sulfonic acid group-containing monomer is 50 to 90 wt.%, and the proportion of the carboxylic acid group-containing monomer is 10 to 50 wt.%, with the monomers preferably being selected from those mentioned above.
  • the molar mass of the sulfo-copolymers that are preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred cleaning compositions are characterized in that the copolymers have molar masses of from 2,000 to 200,000 gmol -1 , preferably 4,000 to 25,000 gmol -1 , and in particular 5,000 to 15,000 gmol -1 .
  • the copolymers comprise not only a carboxyl group-containing monomer and sulfonic acid group-containing monomer but also at least one non-ionic, preferably hydrophobic monomer.
  • the rinsing performance of dishwasher detergents according to the invention was able to be improved through the use of these hydrophobically modified polymers.
  • the liquid phase of the cleaning composition according to the invention further comprises an anionic copolymer, the copolymer comprising
  • non-ionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methlypentene-1, 3-methlypentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4- trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexene, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • the proportion of the anionic polymer is preferably 1 wt.% to 35 wt.%, in particular 3 wt.% to 30 wt.%, in particular 4 wt.% to 25 wt.%, preferably 5 wt.% to 20 wt.%, for example 10 wt.%, based on the total weight of the liquid phase.
  • the proportion of sulfopolymers in particular the preferred copolymeric polysulfonates which contain not only sulfonic acid group-containing monomer(s) but also at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in particular the proportion of said sulfopolymers having AMPS as a sulfonic acid group-containing monomer, for example Acusol 590, Acusol 588 or Sokalan CP50, is preferably 1 wt.% to 25 wt.%, in particular 3 wt.% to 18 wt.%, particularly 4 wt.% to 15 wt.%, preferably 5 wt.% to 12 wt.%, based on the weight of the liquid phase.
  • any molecular weight given herein refers to the number average molecular weight M, unless explicitly stated otherwise.
  • the number average molecular weight can, for example, be determined by means of gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 with THF as eluent.
  • the liquid phase of the inventive cleaning composition can also contain, as a builder, crystalline layered silicates of general formula NaMSi x O 2x+1 *y H 2 O, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with 2, 3 or 4 being particularly preferred values for x, and y represents a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with an Na 2 O : SiO 2 modulus of 1:2 to 1:3.3, preferably 1:2 to 1:2.8, and in particular 1:2 to 1:2.6, can also be used which preferably exhibit retarded dissolution and secondary washing properties.
  • the silicate and/or silica content is limited to amounts below 10 wt.%, preferably below 5 wt.%, and in particular below 2 wt.%, based on the total weight of the liquid phase.
  • the liquid phase is silicate-free and/or silica free.
  • the cleaning composition according to the invention further contains at least one additive selected from the group consisting of alkali and alkaline-earth metal salts, such as sodium sulfate, fillers, corrosion inhibitors, foam inhibitors, surfactants, bitterns, sequestering agents, electrolytes, fragrances, antimicrobial active ingredients and dyes.
  • alkali and alkaline-earth metal salts such as sodium sulfate, fillers, corrosion inhibitors, foam inhibitors, surfactants, bitterns, sequestering agents, electrolytes, fragrances, antimicrobial active ingredients and dyes.
  • cleaning compositions according to the invention preferably contain enzyme(s) in the liquid phase.
  • Suitable enzymes include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, as well as preferably mixtures thereof. Said enzymes are in principle of natural origin; proceeding from the natural molecules, improved variants for use in cleaning agents are available which are preferably used accordingly.
  • Cleaning agents according to the invention preferably contain enzymes in total quantities of from 1 x 10 -6 wt.% to 5 wt.% based on active protein. The protein concentration can be determined with the aid of known methods, for example the BCA method or the Biuret method.
  • subtilisin-type proteases are preferred. Examples of these are the subtilisins BPN' and Carlsberg, as well as the further-developed forms thereof, protease PB92, subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K and proteases TW3 and TW7
  • amylases examples include ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger, and A. oryzae, as well as the further developments of the above-mentioned amylases that have been improved for use in cleaning agents.
  • Others that are particularly noteworthy for this purpose are the ⁇ -amylases from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • amylases commercially available from Novoyzmes (i.e. Stainzyme ® , Stainzyme ® Plus, Achieve ® ) and IFF (i.e. Excellenz ® S1000 and S3300). All amylases are preferably added in liquid enzyme preparations.
  • lipases or cutinases can be used according to the invention, in particular due to their triglyceride-cleaving activities, but also in order to produce peracids in situ from suitable precursors.
  • lipases that could originally be obtained from Humicola lanuginosa (Thermomyces lanuginosus) and those that have been further developed, particularly those with the amino acid exchange in positions D96LT213R and/or N233R, particularly preferably all of the exchanges D96L, T213R, and N233R.
  • oxidoreductases such as oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin, glucose, or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases)
  • organic, particularly preferably aromatic compounds that interact with the enzymes are additionally added in order to potentiate the activity of the relevant oxidoreductases (enhancers) or, in the event of greatly differing redox potentials, to ensure the flow of electrons between the oxidizing enzymes and the contaminants (mediators).
  • a protein and/or enzyme can be protected, especially during storage, against damage such as inactivation, denaturing, or decomposition caused for example by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturing, or decomposition caused for example by physical influences, oxidation or proteolytic cleavage.
  • the proteins and/or enzymes are obtained microbially, it is particularly preferable for proteolysis to be inhibited, particularly if the agents also contain proteases.
  • Cleaning agents may contain stabilizers for this purpose; the provision of such agents constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not made available in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • These ready-made preparations include, for example, the solid preparations obtained through granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel agents, solutions of the enzymes, advantageously maximally concentrated, low-water, and/or supplemented with stabilizers or other auxiliaries.
  • the enzymes can also be encapsulated, for example by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed in a set gel, or in those of the core-shell type in which an enzyme-containing core is coated with a water-, air-, and/or chemical-impermeable protective layer.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are enclosed in a set gel, or in those of the core-shell type in which an enzyme-containing core is coated with a water-, air-, and/or chemical-impermeable protective layer.
  • other active substances such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be additionally applied.
  • Such capsules are applied using inherently known methods, for example by shaking or roll granulation or in fluidized bed processes. Such granular materials are advantageously low in dust, for example due to the application of polymeric film
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations used according to the invention contain between 1 and 40 wt.%, preferably between 2 and 30 wt.%, particularly preferably between 3 and 25 wt.% of the enzyme protein.
  • those cleaning agents are preferred which contain, based on their total weight, 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and in particular 0.5 to 8 wt.% of the respective enzyme preparations, based on the weight of the liquid phase.
  • perfume oils or fragrances can be used as perfume oils or fragrances within the scope of the present invention.
  • mixtures of different odorants are preferably used which together produce an appealing fragrance note.
  • Perfume oils of this kind can also contain natural odorant mixtures, as are obtainable from plant sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the fragrances/perfume oils can be encapsulated, for example in microcapsules, or used in free form or both.
  • the cleaning composition according to the invention is phosphate-free.
  • “Phosphate-free” or “phosphonate-free” as used herein is to be understood as the cleaning composition being substantially free of phosphate or phosphonates, in particular as comprising phosphates or phosphonates in an amount of less than 0.1 wt.%, preferably less than 0.01 wt.%, based on the total weight of the composition.
  • the inventive cleaning composition may also be provided as such a dual-chamber system with the detergent particles being present in either chamber.
  • the cleaning composition according to the present invention can thus be provided as a single-chamber system or a dual chamber system. In the single chamber system, the cleaning composition is provided in a all-in-one manner with all components combined in one chamber.
  • the cleaning composition is provided as dual-chamber system containing at least two mutually spatially separated liquid compositions A and B which differ with respect to their pH value.
  • the pH of one of the compositions is less than 8.5, preferably less than 8, in particular from 7 to 8 and especially 7.5, whereas the pH of the other composition is preferably greater than 9, preferably greater 10, in particular from greater than 10 to less than 11.5.
  • the pH value as used herein refers to the value measured with a standard electrode in the undiluted composition at 25 °C.
  • the cleaning composition may be provided in a multi-chamber package, such as a bottle or pouch, wherein the respective compositions A and B are present in separate chambers.
  • one of the compositions A and B comprises at least one enzyme, at least one stabilizer for said enzyme and at least one builder while the other composition is preferably enzyme-free and comprises at least one phosphonate and at least one builder.
  • the enzyme is preferably selected from protease and amylase.
  • the phosphonate is preferably 1-hydroxyethane-(1,1-diphosphonic acid).
  • Suitable compositions for dual-chamber cleaning compositions are, for example, described in WO 2007/025665 , WO 2015/086761 , WO 2007/025666 and WO 2010/092066 .
  • the cleaning composition according to the invention is in particular designed for automatic dishwashing.
  • a further aspect of the present invention is therefore the use of the inventive cleaning composition in automatic dishwashing.
  • a further aspect of the present invention is an automatic dishwashing method employing the cleaning composition according to the invention.
  • the cleaning composition can be introduced directly into the washing compartment or the dishwasher.
  • a container comprising a cleaning composition according to the invention, preferably a bottle or a pouch.
  • the container may be a single chamber container or a multi-chamber container, in particular a dual-chamber container.
  • the container is made from recycled material, in particular recycled plastics and/or polymers.
  • Exemplary liquid phases I and II were prepared using the components summarized in Table 1 with the amounts given in wt.% referring to the total weight of the liquid phase unless otherwise specified.
  • Table 1 Component I II III IV Xanthan Gum 0.4 0.4 0.4 1-hydroxy-1-phosphonoethyl) phosphonic acid (HEDP) 4.0 0.0 0.0 0.0 Acusol ® 588 G (DOW Inc.) 1.0 0.0 0.0 0.0 Polyacrylate, Homopolymer 0.0 1.0 1.0 0.0 MGDA, tri sodium salt 11.00 15.00 5.0 6.0 Soda 6.00 6.00 0.0 0.0 cationic acrylic acid copolymer 0.5 0.5 0.1 0.1 Sodium Citrate 10.00 8.00 2.0 0.0 Low foaming nonionic surfactant (hydroxy mixed ether) 1.00 1.50 2.0 1.0 Stainzyme ® 12 L (Amylase available from Novozymes) 1.5 1.5 1.5 1.0 Protease (amount in active enzyme protein in mg/100g composition) 0.25 0.25
  • the pH of the undiluted liquid phase was adjusted to 7.8 at 20 °C.
  • Solid detergent particles were made out of a mixture comprising 20 to 30 wt.% C12-14 fatty alcohol sulfonates and 70 to 80 wt.% C16-18 fatty alcohol sulfonates.
  • the solid detergent particles in an amount of 0.1 to 2 wt.% were added to the liquid composition to obtain a stable dispersion which showed no deviation in their optical appearance such as sedimentation of the detergent particles even after prolonged storage time.

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EP22211491.0A 2021-12-09 2022-12-05 Zweiphasige reinigungszusammensetzung mit sichtbar unterschiedlichen waschmittelpartikeln Pending EP4194535A1 (de)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880778A (en) * 1973-05-25 1975-04-29 Chevron Res Automatic dishwashing compositions
US6730652B1 (en) 1999-04-19 2004-05-04 The Procter & Gamble Company Process for making non-staining colored particles for improving aesthetics of a liquid automatic dishwashing detergent product, the particles, and a composition
US20070010415A1 (en) * 2005-04-21 2007-01-11 Kevin Kinscherf Composition for Visibility and Impact of Suspended Materials
WO2007025666A2 (de) 2005-09-02 2007-03-08 Henkel Kommanditgesellschaft Auf Aktien Reinigungsmittel
WO2007025665A2 (de) 2005-09-02 2007-03-08 Henkel Kommanditgesellschaft Auf Aktien Reinigungsmittel
US7357755B2 (en) 2004-09-29 2008-04-15 Honda Motor Co., Ltd. Engine speed control system for walk-behind truck
WO2010092066A1 (de) 2009-02-16 2010-08-19 Henkel Ag & Co. Kgaa Reinigungsmittel
WO2014198547A2 (en) * 2013-06-12 2014-12-18 Unilever N.V. Pourable detergent composition comprising suspended particles
WO2015086761A1 (de) 2013-12-13 2015-06-18 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges geschirrspülmittel
JP2016145307A (ja) * 2015-02-09 2016-08-12 花王株式会社 液体自動食器洗浄機用洗浄剤組成物
DE102018206663A1 (de) * 2018-04-30 2019-10-31 Henkel Ag & Co. Kgaa Filterreiniger mit reduzierender Belagsbildung

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880778A (en) * 1973-05-25 1975-04-29 Chevron Res Automatic dishwashing compositions
US6730652B1 (en) 1999-04-19 2004-05-04 The Procter & Gamble Company Process for making non-staining colored particles for improving aesthetics of a liquid automatic dishwashing detergent product, the particles, and a composition
US7357755B2 (en) 2004-09-29 2008-04-15 Honda Motor Co., Ltd. Engine speed control system for walk-behind truck
US20070010415A1 (en) * 2005-04-21 2007-01-11 Kevin Kinscherf Composition for Visibility and Impact of Suspended Materials
WO2007025666A2 (de) 2005-09-02 2007-03-08 Henkel Kommanditgesellschaft Auf Aktien Reinigungsmittel
WO2007025665A2 (de) 2005-09-02 2007-03-08 Henkel Kommanditgesellschaft Auf Aktien Reinigungsmittel
WO2010092066A1 (de) 2009-02-16 2010-08-19 Henkel Ag & Co. Kgaa Reinigungsmittel
WO2014198547A2 (en) * 2013-06-12 2014-12-18 Unilever N.V. Pourable detergent composition comprising suspended particles
WO2015086761A1 (de) 2013-12-13 2015-06-18 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges geschirrspülmittel
JP2016145307A (ja) * 2015-02-09 2016-08-12 花王株式会社 液体自動食器洗浄機用洗浄剤組成物
DE102018206663A1 (de) * 2018-04-30 2019-10-31 Henkel Ag & Co. Kgaa Filterreiniger mit reduzierender Belagsbildung

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Title
MILTON J. ROSEN: "Surfactants and Interfacial Phenomena", 2004, WILEY-INTERSCIENCE, A JOHN WILEY & SONS, INC.

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