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EP0653485B1 - Composition détergente - Google Patents

Composition détergente Download PDF

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Publication number
EP0653485B1
EP0653485B1 EP19940203197 EP94203197A EP0653485B1 EP 0653485 B1 EP0653485 B1 EP 0653485B1 EP 19940203197 EP19940203197 EP 19940203197 EP 94203197 A EP94203197 A EP 94203197A EP 0653485 B1 EP0653485 B1 EP 0653485B1
Authority
EP
European Patent Office
Prior art keywords
active
oil
capsule
enzyme
polymer
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.)
Expired - Lifetime
Application number
EP19940203197
Other languages
German (de)
English (en)
Other versions
EP0653485A1 (fr
Inventor
Liang Sheng Tsaur
Shiji Shen
Michael Paul Aronson
David Joseph Pocalyko
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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
Priority claimed from US08/150,701 external-priority patent/US5434069A/en
Priority claimed from US08/151,605 external-priority patent/US5441660A/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0653485A1 publication Critical patent/EP0653485A1/fr
Application granted granted Critical
Publication of EP0653485B1 publication Critical patent/EP0653485B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the present invention relates to a novel capsule capable of protecting sensitive active ingredients (e.g., enzymes, peracid bleaches or bleach catalysts) in liquid detergent compositions and to liquid detergent compositions comprising the capsules.
  • sensitive active ingredients e.g., enzymes, peracid bleaches or bleach catalysts
  • liquid detergents may provide a hostile environment to sensitive ingredients (e.g., enzymes, peracid bleach, bleach catalysts or perfumes) used in these detergents.
  • enzymes are subject to attack by, anionic actives, high pH conditions and/or by other enzymes.
  • Bleaches, in particular peracid bleaches are known to be particularly harsh on enzyme components. Encapsulation has been used to protect these sensitive ingredients in liquid detergent.
  • Another method which has been used to protect active components from the liquid medium is to place the active in a hydrophobic oil such that the active is protected by the oil from diffusing into the composition where it is subject to degradative attack.
  • hydrophobic oil alone, however, does not provide sufficient protection, particularly when the composition also contains powerful degradative components such as the peracid bleaches mentioned above. This may be because the hydrophobic oils were simply not selected carefully enough to deter migration of the degradative components toward the active or, conversely, migration of the active toward the degradative component.
  • U.S. Patent No. 4,906,396 to Falholt et al. discloses a detergent enzyme dispersed in a hydrophobic oil.
  • the hydrophobic oil is simply incapable of slowing degradation of the enzyme, for example, when placed in a bleach containing liquid composition. Again, whether this is because the hydrophobic oil was not properly selected to sufficiently slow migration of enzyme to bleach or visa versa is unknown.
  • the hydrophobic oil alone simply does not function effectively such as the capsules of the subject invention.
  • Allied Colloids Limited teaches a particulate composition comprising particles having a substantially anhydrous core comprising a matrix polymer containing active ingredient, a layer of hydrophobic oil around the core and a polymer shell around the oil. It is said that the matrix polymer (which contains the active) should be sufficiently hydrophobic that it will partition into the oil rather than the water.
  • the problem addressed by the patent is that, without the hydrophobic matrix polymer, the active migrates out of the oil too quickly and won't stay in the oil. In other words, the oil layer is incapable of holding a hydrophilic particle without the hydrophobic matrix polymer.
  • the retention of a hydrophilic active ingredient by the oil can be enhanced by entrapping the active ingredient with a hydrophobic matrix polymer, this requires modifying the active ingredient with hydrophobic matrix polymer before making the capsule. This in turn both is costly and causes the problem of not rapidly and efficiently releasing the active ingredient in use.
  • the subject invention differs from the reference in that the oil layer of the subject invention is selected such that it can retain a hydrophilic active in the absence of matrix polymer. Further, as noted above, since the active is not associated with a hydrophobic matrix polymer, it is more readily and efficiently released in use (e.g., when the polymer shell is dissolved).
  • the present invention is directed to a novel capsule system which protects actives in detergent compositions (i.e., particularly bleach containing compositions) and which effectively releases the actives in use
  • said capsule system comprises: (1) an oil dispersion containing the active and in which the oil is selected by meeting certain defined criteria; and (2) a certain outer polymer shell surrounding the oil dispersion.
  • the present invention provides a capsule composition, preferably for use in a liquid cleaning composition, comprising:
  • the polymer shell is a water soluble polymer or water dispersible polymers selected from at least one of the group consisting of polyvinyl alcohol, a polyacrylamide, polyvinyl pyrrolidone, carrageenan, guar gum, xanthan gum, cellulose and protein.
  • the present invention is further directed to detergent compositions comprising such capsules.
  • the present invention provides a detergent composition comprising:
  • the present invention relates to a novel capsule system which protects actives in detergent compositions and also rapidly and efficiently releases the encapsulated active in use. Further, the invention relates to compositions comprising these capsules.
  • the capsule system is in effect a combination of (1) an oil dispersion which holds the actives in place and both keeps the actives from diffusing into solution and also provides a barrier preventing bleach or other harsh factors/components (anionics or pH conditions) from coming into contact with the active; and (2) an outer polymer shell surrounding the oil dispersion to prevent the deformation of the oil dispersion during and after addition to the liquid detergent.
  • the oil in component (1) is selected by meeting a combination of defined criteria as defined in claim 1 and set forth in greater detail below.
  • the first component of the capsule system is the hydrophobic oil component.
  • the oil components of the invention are defined by meeting each of three defined criteria set forth below: (1) by their ability to retain active in the dispersion in an aqueous solution; (2) by their ability to withstand phase separation at ambient or elevated temperatures over time; and (3) by their ability to rapidly and effectively release the encapsulated active in use.
  • the oils must meet all three defined criteria to be selected as the oil component of the invention.
  • the oil component is defined by its ability to retain at least 80% active, preferably 90% after adding the active in oil dispersion to an aqueous solution containing 0.5 wt.% of surfactant for an hour without mixing. Testing was done using sodium lauryl sulfate although any suitable surfactant may be used.
  • a second criteria by which the oil component is defined is its ability to hold the active in place and to prevent the active from diffusing or precipitating out of the oil phase.
  • the stability of active in oil dispersion can be determined by adding the active in oil dispersion to a 10ml graduated cylinder and measuring the phase separation of the active from the hydrophobic oil. It should be less than 10%, preferably less than 5% of phase separation when measured at 37°C for 1 week.
  • the last criteria used to define the oil component is its ability to rapidly and effectively release the active in use.
  • the oil release property can be determined by a standard Terg-O-Meter washing method.
  • Terg-O-Meter are well known in the art such as, for example Terg-O-Tometer UR7227. In these devices, generally, 500 mls of wash liquid are agitated at above 70 rpm for about 20 minutes using desired wash liquid.
  • the capsules of the invention were tested using 1000 mls at 100 rpm for 15 minutes at 40°C.
  • the capsule should release more than 50%, preferably more than 70% of the active after the first five minutes of the wash cycle when measured at 40°C.
  • the hydrophobic oil component can be a liquid or a semisolid at room temperature.
  • Liquid oils alone with a viscosity of less than 10,000 centipoises (cps) such as mineral oils, silicone oils or vegetable oils are not suitable for this invention and require modification. These oils do not have the capability to hold and retain hydrophilic actives and do not provide a sufficient protection to the active in a liquid detergent.
  • the preferred liquid oil components are oils containing hydrophobic particles with particle size less than 3 ⁇ , preferably less than 1 ⁇ , more preferably less than 0.1 ⁇ .
  • hydrophobic particles examples include hydrophobic silica such as Cabot's Cab-O-Sil TS 720 and Cab-O-Sil TS 530 or Degussa's Aerosil 200; and hydrophobic clay such as Rheox's Bentone SD-1.
  • hydrophobic particles can be incorporated into the oil physically i.e., simply by mixing the oil with the hydrophobic particles or chemically, i.e., through the chemical interaction of oil with the surface of the particles.
  • the preferred hydrophobic particles are submicron sized hydrophobically modified fumed silica such as Cab-O-Sil TS 720.
  • hydrophobic particles can enhance the suspension of active in the oil and also increase the capability of oil to retain the active in an aqueous solution.
  • amount of hydrophobic particles in the oil is less than 15%, preferably less than 10%, more preferably less than 5% but more than 0.5% should be used.
  • the oil component is defined by the fact that it is a semisolid rather than a liquid at room temperature. Specifically, when the component has a melting temperature of from about 35°C to 70°C, preferably 40°C to 65°C, the semisolids are found to retain the active more readily. Moreover, such materials release active under wash condition rapidly enough to give wash performances comparable to compositions in which enzymes have been newly added. Since these semisolid oils will also slow migration of active out of the oil phase or slow migration of bleach and other harsh components toward the active, they are again preferred.
  • the semisolid oils are petrolatums such as Penreco's Penreco Snow, Mineral Jelly and Tro-Grees; Witco's Multiwax; and fats (e.g., glyceryl ester of C 12 -C 24 fatty acids) or fat derivatives such as mono-, di- or tri-glycerides and fatty alkyl phosphate ester.
  • Hydrophobic particles such as hydrophobic fumed silica are also desirably incorporated into these semisolid oils to further enhance their ability to retain actives, especially when the capsule of this invention is processed or stored at a temperature close to or above the melting point of the semisolid oils.
  • the oil around the active will generally comprise about 98% to 40%, preferably 90% to 70% of the active in oil dispersion.
  • the second component of the capsule system is the polymer coating surrounding the active in oil dispersion.
  • the polymer suitable for this invention must be insoluble in the composition of the liquid cleaning product and must disintegrate or dissolve during the use of the product simply by dilution with water, pH change or mechanical forces such as agitation or abrasion.
  • the polymers are water soluble or water dispersible polymers that are or can be made insoluble in the liquid detergent composition. Such polymers are described in EP 1,390,503; U.S. 4,777,089; U.S. 4,898,781; U.S. 4,908,233; U.S. 5,064,650 and WO-A-9322417.
  • water soluble polymers display an upper consulate temperature or cloud point.
  • solubility or cloud point of such polymers is sensitive to electrolyte and can be "salted out” by the appropriate type and level of electrolyte.
  • Such polymers can generally be efficiently salted out by realistic levels of electrolyte ( ⁇ 10%).
  • Suitable polymers in this class are synthetic nonionic water soluble polymers including: polyvinyl alcohol; polyvinyl pyrrolidone and its various copolymers with styrene and vinyl acetate; and polyacrylamide and its various modification such as those discussed by Molyneaux (see above) and McCormick (in Encyclopedia of Polymer Science Vol 17, John Wiley, New York).
  • Another class of useful polymers are modified polysaccharides such as carrageenan, guar gum, pectin, xanthan gum, partially hydrolyzed cellulose acetate, hydroxy ethyl, hydroxy propyl and hydroxybutyl cellulose, methyl cellulose and the like.
  • Proteins and modified proteins such as gelatin are still another class of polymers useful in the present invention especially when selected to have an isoelectric pH close to that of the liquid composition in which the polymers are to be employed.
  • hydrophilic polymers have potential utility as the polymer coating for the capsules of this invention.
  • the key is to select an appropriate hydrophilic polymer that would be essentially insoluble in the composition (preferably a concentrated liquid system) under the prevailing electrolyte concentration, yet would dissolve or disintegrate when this composition is under conditions of use.
  • the tailoring of such polar polymers is well within the scope of those skilled in the art once the general requirements are known and the principle set forth.
  • the capsule of this invention can be produced by a variety of known encapsulation processes.
  • the capsule can be prepared according to the coacervation process in which the active in oil dispersion is dispersed to an aqueous solution of a water soluble or water dispersible polymer.
  • a non-solvent for the polymer or an electrolyte is added or a pH change or a pressure change is effected to make the capsule. Examples of this coacervation process are described in U.S. 4,777,089, U.S. 3,943,063 and U.S. 4,978,483.
  • the capsule can be formed by adding the emulsion of active in oil in polymer solution to the nonsolvent.
  • the oil composition and the emulsification process are critical because the active must stay within the oil rather than diffuse out during the emulsification of the active in oil dispersion to a polymer solution.
  • Hydrophobic particles especially submicron fumed silica, are especially useful to help the retention of actives in the oil during emulsification.
  • the oil should contain a sufficient amount of the hydrophobic particles to prevent the diffusion of the hydrophilic active out of oil.
  • the amount of hydrophobic particles in the oil is greater than 0.5%, preferably greater than 3% and less than 10%.
  • the emulsification process should be carried out in a mild condition to prevent overmixing of the active in oil dispersion with the polymer solution and to ensure the resulting oil droplet size is larger than the particle size of the active.
  • the capsule of the invention also can be prepared by extrusion nozzles as taught in U.S. 3,310,612, U.S. 3,389,194 or U.S. 2,799,897 and GB 1,390,503.
  • the active in oil dispersion is extruded through the inert orifice of the nozzle.
  • the water soluble polymer solution is extruded through the outer orifice of the nozzle to form a uniform coating on the surface of active in oil dispersion.
  • the capsule is then formed by breaking the coextrudate at the end of the nozzle orifice by air, centrifuge force, blade or carry fluid to form droplets which are hardened in a nonsolvent of the water-soluble polymer to form the capsule.
  • the active materials which are desired to be encapsulated by the capsule of this invention are those materials which will lose their activity in a cleaning product, especially a bleach-containing liquid cleaning product, if no hydrophobic oil coating is added according to this invention.
  • the active materials protected by the oil layer may be a hydrophilic active (e.g., enzyme or bleach catalyst) or a hydrophobic active (e.g., perfume) and can be solid, liquid or in aqueous solution. If it is a solid material, the particle size of the active should be less than 200 ⁇ m preferably less than 50 ⁇ m.
  • Hydrophilic active materials include enzymes, bleach catalysts peracid bleaches, bleach activators and optical brighteners.
  • the enzymes may be amylases, proteases, lipases, oxidases, cellulases or mixtures thereof.
  • the amylolytic enzymes for use in the present invention can be those derived from bacteria or fungi.
  • Preferred amylolytic enzymes are those described in British Patent Specification No. 1,296,839, cultivated from the strains of Bacillus licheniformis NCIB 8061, NCIB 8059, ATCC 6334, ATCC 6598, ATCC 11,945, ATCC 8480 and ATCC 9945A.
  • a particularly preferred enzyme is an amylolytic enzyme produced and distributed under the trade name, Termamyl, by Novo Industri A/S, Copenhagen, Denmark.
  • amylolytic enzymes are generally sold as granules and may have activities from about 2 to 10 Maltose units/milligram.
  • the amylolytic enzyme is normally included in an amount of from 1% to 40% by weight of the capsule, in particular from 5 to 20% by weight.
  • the active may also be a proteolytic enzyme.
  • suitable proteolytic enzymes are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis, such as those commercially available under the trade names Maxatase, supplied by Gist-Brocades NV, Delft, Netherlands, and Alcalase, supplied by Novo Industri A/S, Copenhagen, Denmark.
  • Particularly preferred are the proteases obtained from a strain of Bacillus having a maximal activity throughout the pH range of 8-12, being commercially available under the trade names of Esperase and Savinase, sold by Novo Industri A/S.
  • proteolytic enzymes are generally sold as granules and may have enzyme activities of from about 500 to 50,000 glycine units/milligram.
  • the proteolytic enzyme is normally included in an amount of from 1% to 40% by weight of the capsule, in particular of from 5% to 20% by weight.
  • Lipolytic enzymes may also be included in order to improve removal of fatty soils.
  • the lipolytic enzymes are preferably included in an amount of from 1% to 40%, preferably from 5% to 20% by weight.
  • Cellulase enzymes may be used in an amount from about 1% to 40% by weight of the capsule.
  • the total content of the enzyme in the capsules of the present invention is from 1% to 40%, preferably from 5% to 20%.
  • the enzyme may also be a genetically engineered variation of any of the enzymes described have engineered to have a trait (e.g., stability) superior to its natural counterpart.
  • the protected active may also be peroxygen compound activators, peracid bleaches, bleach catalysts, optical brighteners or perfumes.
  • Peroxygen compound activators are organic compounds which react with the peroxygen salts (e.g. sodium perborate, percarbonate, persilicate) in solution to form an organic peroxygen acid as the effective bleaching agent.
  • Preferred activators include tetraacetylethylenediamine, tetraacetyglycoluril, glucosepentaacetate, xylose tetraacetate, sodium benzoyloxybenzene sulfonate and choline sulfophenyl carbonate. The activators may be released from the capsule to combine with peroxygen compound in the composition.
  • the ratio between the peroxygen in solution and the activator lies in the range of from 8:1 to 1:3, preferably 4:1 to 1:2, and most preferably is 2:1.
  • peroxyacids are generally contemplated for use in the composition rather than the capsule, peroxyacid compounds may be used as the active in the capsule as well, particularly in compositions where conditions are so harsh as to deactivate the peroxyacid.
  • the peroxyacids are amido or imido peroxyacids and are present in the range from 0.5 to 50%, preferably from 15 to 30% by weight of the capsule.
  • the peroxyacid is an amide peracid. More preferably, the amide is selected from the group of amido peracids consisting of N,N'-Terephthaloyl-di(6-aminopercarboxycaproic acid) (TPCAP), N,N'-Di(4-percarboxybenzoyl)piperazine (PCBPIP), N,N'-Di(4-Percarboxybenzoyl)ethylenediamine (PCBED), N,N'-di(4-percarboxybenzoyl)-1,4-butanediamine (PCBBD), N,N'-Di(4-Percarboxyaniline)terephthalate (DPCAT), N,N'-Di(4-Percarboxybenzoyl)-1,4-dia
  • peroxyacids which may be used include the amidoperoxy acids disclosed in U.S. Patent Nos. 4,909,953 to Sadowski and U.S. Patent No. 5,055,210 to Getty.
  • the active inside the compounds may be a bleach catalyst (i.e. for activating peracids found in the composition outside the capsule).
  • Such catalysts include manganese catalysts of the type described in U.S. Patent No. 5,153,161 or U.S. patent No. 5,194,416, both of which are incorporated by reference into the subject application; sulfonomine catalysts and derivatives such as described in U.S. Patent Nos. 5,041,232 to Batal, U.S. Patent No. 5,045,223 to Batal and U.S. patent No. 5,047,163 to Batal.
  • manganese catalysts include, for example, manganese complexes of the formula: [LMn IV (OR) 3 ]Y wherein:
  • Sulfonomine derivatives include compounds having the structure: wherein:
  • Bleach activators are particularly good candidates for bleach encapsulation both because they are used in very small amounts and because they are readily deactivated in solution.
  • bleach activators are used in an amount from about 1% to 30% by weight of the capsule composition, preferably, 3% to 15% by weight.
  • the actives may also be optical brighteners or perfumes.
  • the invention is further directed to the use of the capsules in compositions, particularly in liquid detergent composition, more particular in aqueous liquid detergent compositions.
  • the compositions are bleach containing aqueous detergent compositions.
  • the benefits of the invention became readily apparent since it has previously been extremely difficult, if not impossible, to formulate capsules for use in bleach containing aqueous compositions wherein the actives are well protected in the capsule (e.g., greater than 80% active as defined above), yet readily release upon dilution.
  • aqueous detergent compositions of the invention are typically structured (duotropic) or unstructured (isotropic) detergent compositions such as described in U.S. Patent No. 5,089,163 to Aronson et al. or 4,908,150 to Hessel et al. (for isotropic liquids) or U.S. Patent No. 4,992,194 to Liberati et al. or. U.S. Patent No. 5,147,576 to Montague et al. (for structured liquids).
  • compositions will generally comprise water, surfactants, electrolyte (for structuring and/or building purposes) and other ingredients such as are described below.
  • the surfactants may be anionic, nonionic , cationic, zwitterionic, or soap or mixtures thereof such as those described, for example, in U.S. Patent No. 4,642,198 at columns 3 to 4.
  • the total surfactant amount in the liquid composition of the invention may vary from 2 to 60% by weight, preferably from 10 to 50% by weight, depending on the purpose of use.
  • suspending liquids comprising an anionic and a nonionic surfactant the ratio thereof may vary from about 10:1 to 1:10.
  • anionic surfactant used in this context includes the alkali metal soaps of synthetic or natural long-chain fatty acids having normally from 12 to 20 carbon atoms in the chain.
  • the total level of electrolyte(s) present in the composition to provide structuring may vary from about 1.5 to about 30%, preferably from 2.5 to 25% by weight.
  • the heavy duty liquid detergent compositions of the invention may also contain certain optional ingredients in minor amounts.
  • optional ingredients are suds-controlling agents, fluorescers, perfumes, coloring agents, abrasives, hydrotropes, sequestering agents, enzymes, and the like in varying amount.
  • Bleaches used in the invention may be any of those described in U.S. patent No. 4,992,194 to Liberati.
  • Peroxygen salts include salts such as sodium perborate, tetrahydrate or monohydrate, percarbonate, persilicate, persulfate, dipersulfate and the like.
  • Other peroxygen compounds include perphosphates, peroxide and perpolyphosphates.
  • the peroxygen salts may be activated by activators which may be encapsulated actives.
  • the decoupling polymer is also as disclosed in U.S. Patent No. 4,992,194 Liberati.
  • the bleaches may also be any of the peracid bleaches described in the "actives" section (i.e., the mono- or di- percarboxylic amido or imido acids) or the amido peroxy acids disclosed in U.S. Patent Nos. 4,409,953 and 5,055,210.
  • the composition is a peracid bleach containing composition and the capsule of the invention (first embodiment) protects the active (e.g., enzyme or bleach catalyst) from the action of the peracid bleach (and other harsh components) in the liquid compositions.
  • the peracid bleach may be any of the peracid bleaches described above and are preferably amides selected from amido peracids such as TPCAP, PCBPIP, PCBED and any of the other above recited amides peracids when used in the composition, the peracid will comprise 0.1% to 50% by weight, preferably 0.5% to 25% by weight, more preferably 1 to 10% by weight of the composition.
  • the capsule of this invention was prepared as described below using an enzyme slurry available from NOVO.
  • This capsule was incorporated into the liquid detergent formula having the composition shown in Table 1 below: BASE FORMULA OF LIQUID DETERGENT Water 24.8 Sorbitol (70%) 15.8 Glycerol 4.76 Sodium Borate 10H20 4.76 Sodium Citrate 2H20 9.52 Narlex DC-1 (ex. National Starch & Chem.) 3.0 50% NaOH 5.43 DB100 (Dow Chem.) (Antifoam) 0.1 Alkyl Benzene Sulfonic Acid 21.83 Neodol 25-9 (Nonionic) 10.0 Total 100.00
  • the composition additionally contained sufficient amount of the peracid SBPB to have 1000 ppm active oxygen and was stored at 37°C.
  • Applicants additionally compared the residual enzyme activity of the enzyme after 2 and 6 days both when the enzymes were unprotected (i.e., liquid composition alone) and when the enzyme is used in a PVA/PS (i.e, polyvinylalcohol polystyrene) capsule as described in US-A-5281356, published on 25.01.94.
  • PVA/PS polyvinylalcohol polystyrene
  • compositions comprising bleach peracids when the enzyme is protected by the capsules of the invention
  • stability of Savinase was tested in composition comprising one of two peracids, N,N'-Di(4-Percarboxybenzoyl)piperazine (PCBPIP), or N,N'-terephthaloyl-di (6-aminopercarboxycaproic acid) (TPCAP). While the presence of peracids would normally destroy all enzyme activity almost immediately, the following results were seen using the capsules of the invention.
  • PCBPIP N,N'-Di(4-Percarboxybenzoyl)piperazine
  • TPCAP N,N'-terephthaloyl-di (6-aminopercarboxycaproic acid)
  • Capsule composition is that of preparative example (Table 1 above). Stability studies conducted at 37°C in the same HDL as Table 1 except that it contained one of the two peracids dosed at 1000 ppm of active oxygen instead of SBPB
  • release from capsules is more than 70% at the first 5 minutes wash and is complete after 10 minutes.
  • the example again shows that the encapsulated oils release well.
  • compositions were made comprising concentrated savinase and an oil as follows: Composition Savinase Activity (GU/g) of Slurry Slurry Composition 1 70% Rodisil LV461 (Silicone antifoam 10,000 cps); and 30% Savinase concentrate 1.6 x 10 7 Slurry Composition 2 (comparative) 70% Silicone oil 30% Savinase concentrate 2.4 x 10 7 Slurry Composition 3 (comparative) 60% Mineral oil 40% Savinase concentrate 2.7 x 10 7 Slurry Composition 4 36% Mineral oil 24% Petrolatum 40% Savinase concentrate 2.7 x 10 7
  • compositions were then formed from the slurry compositions comprising 66.6% by weight of the slurry composition and 33.4% by weight ASE 95 solution (1.5%).
  • compositions were then made into capsules using the matrix encapsulation method.
  • Capsules formed from slurry compositions 1 and 4 were designated as Examples 4, 5 and capsules formed from slurry compositions 2 & 3 were designated as comparative examples A&B.
  • Examples 4 and 5 which represent oil or oils meeting all three criteria of the invention, retained a high % of original activity (28% and 3.7%) relative to the Comparative examples (1.2% at 0.4%) which oils did not meet all criteria. In addition, the residual activity after three days was also clearly superior.
  • the silicone oil (Comparative A) and mineral oil (Comparative B) showed poor trapping efficiency and also lost enzyme activity rapidly in the bleach containing liquid.
  • Addition of petrolatum to mineral oil (Example 5) can enhance the oil trapping efficiency during capsule preparation and can also dramatically enhance the performance of the capsule.
  • Rhodisil LV461 which is a silicone oil containing hydrophobically modified silica.
  • the examples shows the oil composition is not only important to the trapping efficiency of enzyme during preparation of the capsule, but is also critical in enhancing enzyme stability when enzyme is used in a peracid-containing heavy duty liquid detergent.
  • oils having the capability to stop the enzyme from dispersing or diffusing out of the oil and the capability to minimize the penetration of harsh detergent ingredients into the capsule during capsule preparation and storage are the ones which show greatest yield and residual activity over time.
  • Enzyme dispersions were first prepared by dispersing Savinase enzyme particles (protease) in various oils using Dispermate (UMA-GETZMANN) at 2000 rpm for 10 minutes: The following seven (7) oil dispersions were prepared: Oil (% by wt.) Savinase particle (% by wt.) Comparative C 92% SAG1000 Silicone Antifoam (Union Carbide) 8% 6 92% Rhodosil LV461 Silicone Antifoam (Rhone-Poulenc) 8% Comparative D 92% Silicone Oil 10,000 (Union Carbide) 8% Comparative E 95% Mineral Oil (Fisher) 8% 7 88.7% Mineral Oil (Fisher)/3.7% Carbosil TS720 8% 8 92% Tro-Gress (penreco) 8% 92% Snow White Petrolatum (Penreco) 8%
  • Core shell Savinase enzyme capsules (as distinct from the matrix capsule preparation) were then prepared by encapsulating the enzyme dispersions noted above with a polymer solution containing polyvinyl alcohol (Airvol 540) and Acrysol ASE-60 (which is an alkali-soluble emulsion thickener from Rohm & Haas) using a concentric triple nozzle.
  • a polymer solution containing polyvinyl alcohol Airvol 540
  • Acrysol ASE-60 which is an alkali-soluble emulsion thickener from Rohm & Haas
  • the enzyme-in-oil dispersion was fed through the inside orifice, the polymer aqueous solution was fed through the middle orifice and a compressed air was passed through the outside orifice to make enzyme capsules of 600 to 800 micrometers.
  • These capsules were hardened and stored in a salt solution containing 15 weight percent of sodium sulfate and 2 weight percent of sodium borax with a pH in a range of 6 to 7.
  • the following capsule examples 6-9 and Comparative Examples C-E were thus prepared from the seven dispersions.
  • Enzyme capsules 6-9 and capsules comparative C-E were then formulated into a liquid detergent containing 95.4 wt.% of a stable liquid detergent formula having the following composition.
  • Neodol 25-9 (Nonionic) 10.0 Total 100.00 and additionally contain 4.6 wt.% of stable peracid N,N'-Terephthaloyl di(6-aminopercarboxycaproic acid) (TPCAP) which was prepared as described in WO Patent 9,014,336.
  • TPCAP stable peracid N,N'-Terephthaloyl di(6-aminopercarboxycaproic acid)
  • the enzyme capsules were incorporated into the above-identified formulation to give 16,000 GU enzyme activity per gram of the formulated liquid detergent. These formulated samples were stored at 37°C and the residual Savinase activity of these stored samples was determined and given in the left column of the Table shown below: Residual Enzyme Activity of Examples % Residual Enzyme Activity (when encapsulated) % Residual Enzyme Activity (when not encapsulated) Comparative C 45% after 6 days 28% after 20 days 0% after 3 days Example 6 22.4% after 14 days 0% after 3 days Comparative D 35% after 6 days 18% days after 20 days 0% after 3 days Comparative E 38.3% after 14 days 0% after 3 days Example 7 61.7% after 14 days 0% after 3 days Example 8 76.8% after 14 days 0% after 3 days Example 9 76.6% after 14 days 7% after 6 days
  • the slurry-only examples were prepared by stirring the prepared enzyme-in-oil dispersion into the same liquid detergent as used in the capsule examples which contained 4.6% TPCAP peracid and was stored at 37°C. As noted, the residual Savinase enzyme activity of these slurry-only examples was shown in the right column of the Table.
  • the enzyme stability data summarized in the Table clearly shows that the protected enzyme system as claimed by U.S. 4,906,396 did not provide a protection to the enzyme in the bleach-containing liquid detergent. Almost 0% of enzyme activity remained for all of the slurry-only examples after being stored at 37°C for less than 1 week. Depending on the oil used in the capsule composition of this invention, 22 to 78% of enzyme activity still remained after being stored in this bleach-containing liquid for 2 weeks.
  • a Lipolase enzyme particle was prepared by spray drying a mixture of 30 wt.% Lipolase 100L (Novo) and 70 wt.% of Airvol 1603/polystyrene latex to give an enzyme particle with 210 x 10 3 LU/g Lipolase activity.
  • a Lipolase-in-oil dispersion was prepared by dispersing 25 wt.% of this Lipolase particle to 75 wt.% of Rhodosil LV461 Silicone antifoam (ex. Rhone-Poulenc).
  • a matrix enzyme capsule was prepared by adding the Lipolase-in-oil-in-water emulsion dropwise to an acid bath containing 98% water and 2% concentrate H 2 SO 4 .
  • the capsule has a particle size about 1,000 micrometers and 19 x 10 3 LU/g Lipolase activity.
  • a liquid detergent containing 88 wt.% of the base liquid detergent of Examples 6-9, 10 wt.% benzoyl peroxide and 2% of Lipolase capsule was formulated and stored at 37°C.
  • a comparative example containing the nonencapsulated Lipolase 100L was also formulated with the same liquid detergent containing 10 wt.% benzoyl peroxide and stored at 37°C for 1 week is: 0% for the comparative example and 58% for the Lipolase capsule of this invention.
  • PAP phthalamidoperoxycaproic acid
  • Each of these oils has the characteristics defining the oils of the invention (i.e., retains greater than 80% crystals, preferably greater than 90% crystal after capsule preparation, suspends active with less than 10% phase separation under defined conditions and releases per defined conditions).
  • Core-shell PAP capsules were then prepared by encapsulating the PAP dispersions noted above with a polymer solution containing 3.3 wt.% of polyvinyl alcohol (Airvol 540, Air Products) and 1.7 wt.% of alkaline soluble polymer (ASE-60, Rhom & Haas) using a concentric triple nozzle.
  • PAP-in-oil dispersion Specifically, the PAP-in-oil dispersion, polymer solution, and compressed air were simultaneously fed to the nozzle tip through the central, middle, and outer orifices, respectively.
  • Three PAP capsules of 600-800 ⁇ m were prepared from the three dispersions, as shown in the Table below: PAP Core-Shell Capsules Example Capsule Composition Capsule 12 1 part of PAP dispersion 1 (Silicone Antifoam) and 5 parts of polymer solution Capsule 13 1 part of PAP dispersion 2 parts of polymer (Tro-Grees) and 5 solution Capsule 14 1 part of PAP dispersion 3 parts of polymer (Petrolatum) and 5 solution
  • PAP capsules 1-3 were then formulated into a liquid detergent having the following composition: Basic Formula of Liquid Detergent Ingredients Wt.% Sorbitol (70%) 15.8 Glycerol 4.8 Sodium Borate 10 H 2 O 4.8 Sodium Citrate 2 H 2 O 9.5 Narlex DC-1 (33%) 2.9 Sodium Hydroxide (50%) 5.5 DB 100 (Silicone antifoam) 0.1 BDA (Alkyl benzene sulphonic acid) 21.8 Neodol 25-9 (Nonionic surfactant having average alkoxylation of about 9) 10.0 Water 24.9
  • Basic Formula of Liquid Detergent Ingredients Wt.% Sorbitol (70%) 15.8 Glycerol 4.8 Sodium Borate 10 H 2 O 4.8 Sodium Citrate 2 H 2 O 9.5 Narlex DC-1 (33%) 2.9 Sodium Hydroxide (50%) 5.5 DB 100 (Silicone antifoam) 0.1 BDA (Alkyl benzene
  • PAP capsule was incorporated into the formulation to give 4000 ppm of active oxygen per gram of the formulated liquid detergent. These formulated samples were stored at 37°C and the residual PAP activity of these stored samples was determined and given in the Table below. Residual PAP Activity of Examples 12-14 Example No. Storage Time (days) Residual Activity (%) PAP Crystal 2 50 3 25 Capsule 12 4 50 6 25 Capsule 13 8 50 15 30 Capsule 14 15 75 30 52
  • Catalyst dispersions were prepared by mixing the manganese bleach catalyst in various oils using Dispermat (Fl, VMA-Getzmann) at 2000 rpm for 10 minutes.
  • the dispersion contained 81% of Tro-Grees, 9% of Petrolatum, and 10% of manganese bleach catalyst.
  • the core-shell bleach catalyst capsule was then prepared by encapsulating the bleach catalyst dispersions same as Examples 12-14 with a polymer solution containing 3.3 wt.% of polyvinyl alcohol (Airvol 540, Air Products) and 1.7 wt.% of alkaline soluble polymer (ASE-60, Rhom & Haas) using a concentric triple nozzle.
  • a polymer solution containing 3.3 wt.% of polyvinyl alcohol (Airvol 540, Air Products) and 1.7 wt.% of alkaline soluble polymer (ASE-60, Rhom & Haas) using a concentric triple nozzle a polymer solution containing 3.3 wt.% of polyvinyl alcohol (Airvol 540, Air Products) and 1.7 wt.% of alkaline soluble polymer (ASE-60, Rhom & Haas) using a concentric triple nozzle.
  • compositions of Bleach Catalyst Capsules Example No.
  • the capsules were then formulated into a liquid detergent having the following composition: Basic Formula of Liquid Detergent Ingredients Wt.% Sodium Metaborate 1.50 Sodium Perborate 10.00 Sodium Citrate 10.00 Narlex DC-1 (33%) 4.50 BDA (97%) 20.10 Neodol 25-9 8.60 Antifoam 0.25 Water 35.0 Sodium Hydroxide (50%) adjust pH to 10
  • the capsule was incorporated into the formulation to give 0.2% of active bleach catalyst in the formulated liquid detergent.
  • the formulated samples were stored at 37°C and 22°C the residual catalyst activity of these stored samples was determined and given in the Table below.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Claims (8)

  1. Composition de capsule contenant :
    (a) un ingrédient actif qui n'est pas associé à un polymère de matrice hydrophobe ;
    (b) une dispersion d'huile contenant lesdits ingrédients actifs, dans laquelle ladite huile est définie : (1) par sa capacité à retenir au moins 80 % des ingrédients actifs après une heure lorsque la dispersion d'ingrédients actifs dans l'huile est ajoutée à une solution aqueuse contenant 0,5 % en masse de lauryl sulfate de sodium ; (2) sa capacité à mettre en suspension ledit ingrédient actif avec une séparation de phase inférieure à 10 % lors d'un stockage à 37°C pendant 1 semaine ; et (3) sa capacité à libérer plus de 50 % d'ingrédients actifs après 5 minutes d'un cycle de lavage, tel que mesuré à 40°C ; et
    (c) une coque de polymère entourant la dispersion d'huile de (b) ;
    dans laquelle ladite huile est sélectionnée parmi au moins l'un des groupes composé du Pétrolatum, de l'huile d'hydrocarbure modifiée avec une silice hydrophobe, de l'huile de silicone modifiée avec une silice hydrophobe, des graisses, des dérivés de graisse et des alkyl phosphate esters gras ; et dans laquelle ledit polymère de (c) est un polymère soluble dans l'eau ou pouvant être dispersé dans l'eau sélectionné à partir du groupe composé des polymères synthétiques non ioniques solubles dans l'eau, des polysaccharides modifiés, des protéines et des protéines synthétiques modifiées.
  2. Capsule selon la revendication 1, dans laquelle ledit ingrédient actif est un ingrédient actif hydrophile.
  3. Capsule selon les revendications 1 à 2, dans laquelle ledit ingrédient actif est sélectionné à partir du groupe composé des enzymes, des blanchissants peracides, des catalyseurs de blanchiment, des activateurs de blanchiment et des éclaircissants optiques.
  4. Capsule selon les revendications 1 à 3, dans laquelle ledit ingrédient actif est une enzyme ou des enzymes sélectionnée(s) à partir du groupe composé des protéases, des lipases, des amylases, des cellulases et des oxydases.
  5. Capsule selon les revendications 1 à 3, dans laquelle ledit activateur de blanchiment est sélectionné à partir du groupe composé du tétraacétyléthylènediamine, du tétraacétylglycoluril, du pentaacétate de glucose, du tétraacétate de xylose, du benzoyloxybenzène sulfonate de sodium et du sulfophényl carbonate de choline.
  6. Capsule selon les revendications 1 à 3, dans laquelle le catalyseur de blanchiment est un catalyseur manganèse ou un catalyseur sulfonomine ou de dérivé de sulfonomine.
  7. Capsule selon l'une des revendications 1 à 6, dans laquelle ledit polymère (c) est un polymère soluble dans l'eau ou pouvant être dispersé dans l'eau sélectionné à partir d'au moins l'un des groupes composés de l'alcool de polyvinyle, d'un polyacrylamide, du polyvinyl pirrolidone, du carraghenane, de la gomme de guar, de la gomme de xanthane, de la cellulose et de la protéine.
  8. Composition détergente comprenant :
    (a) de 2 à 60 % en masse d'un agent tensioactif sélectionné à partir du groupe composé des agents tensioactifs anioniques, non ioniques, cationiques, zwitterioniques, du savon et des mélanges de ceux-ci ; et
    (b) une composition de capsule selon l'une des revendications précédentes.
EP19940203197 1993-11-12 1994-11-03 Composition détergente Expired - Lifetime EP0653485B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US150701 1993-11-12
US08/150,701 US5434069A (en) 1993-11-12 1993-11-12 Capsule comprising oil surrounding hydrophobic or hydrophilic active and polymeric shell surrounding oil
US08/151,605 US5441660A (en) 1993-11-12 1993-11-12 Compositions comprising capsule comprising oil surrounding hydrophobic or hydrophilic active and polymeric shell surrounding oil
US151605 1993-11-12

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US6844305B1 (en) 1999-08-27 2005-01-18 The Proctor & Gamble Company Aqueous liquid detergent compositions comprising a polymeric stabilization system
DE102007004054A1 (de) 2007-01-22 2008-07-24 Henkel Ag & Co. Kgaa Verfahren zur Herstellung teilchenförmiger Bleichmittelzusammensetzungen
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same

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EP0691398A1 (fr) 1994-07-08 1996-01-10 Unilever N.V. Procédé de fabrication de capsules de polymère
CZ288066B6 (cs) * 1995-10-16 2001-04-11 Unilever N. V. Zapouzdřená částice bělicího prostředku
DE19645024A1 (de) * 1996-10-31 1998-05-07 Basf Ag Bleichhilfsmittel enthaltende Mikrokapseln
GB9713810D0 (en) * 1997-06-30 1997-09-03 Allied Colloids Ltd Particulate polymeric materials and their use
GB9713804D0 (en) * 1997-06-30 1997-09-03 Novo Nordisk As Particulate polymeric materials and their use
DE19855346A1 (de) * 1998-12-01 2000-06-08 Henkel Kgaa Peroxidhaltige Zubereitungen mit stabilisierten optischen Aufhellern
DE69911254T2 (de) * 1998-12-16 2004-04-01 Unilever N.V. Waschmittelzusammensetzung
US6767880B1 (en) 1999-04-19 2004-07-27 The Procter & Gamble Company Liquid dishwashing detergent composition having polymeric particles
DE60020828T2 (de) * 1999-04-19 2006-05-18 The Procter & Gamble Company, Cincinnati Flüssiges geschirrspülmittel mit polymerteilchen
DE19918267A1 (de) * 1999-04-22 2000-10-26 Henkel Kgaa Handgeschirrspülmittel mit Mikrokapseln
EP1196533B2 (fr) † 1999-07-20 2010-11-24 The Procter & Gamble Company Particules d'huile encapsulees ameliorees
WO2002044313A1 (fr) * 2000-12-01 2002-06-06 Novozymes A/S Encapsulation de composes dans des vesicules
DE10100689A1 (de) * 2001-01-09 2002-07-18 Henkel Kgaa Wasch- und reinigungsaktive Substanzen enthaltende Mikrokapseln
US6730651B2 (en) * 2001-08-28 2004-05-04 Unilever Home & Personal Care Usa Division Of Conopco. Inc. Concentrated stock of capsules for detergent or personal care compositions
GB2406338A (en) * 2003-09-22 2005-03-30 Reckitt Benckiser Nv Package comprising a detergent composition
US20060049077A1 (en) * 2003-03-11 2006-03-09 Reckitt Benckiser N.V. Package comprising a detergent composition
DE10361081A1 (de) * 2003-06-13 2005-01-05 Henkel Kgaa Verfahren zur Stabilisierung von Peroxycarbonsäuren in tensidhaltigen Dispersionen
DE10361084A1 (de) 2003-06-13 2005-01-05 Henkel Kgaa Lagerstabile Bleichmittelzusammensetzungen auf Basis von Peroxycarbonsäuren
EP1502943A1 (fr) * 2003-08-01 2005-02-02 The Procter & Gamble Company Composition aqueuse liquide détergente comprenant des particules visibles
DE102004018790B4 (de) 2004-04-15 2010-05-06 Henkel Ag & Co. Kgaa Wasserlöslich umhüllte Bleichmittelteilchen
DE102004019139A1 (de) 2004-04-16 2005-11-10 Henkel Kgaa Flüssigkristallines Wasch- oder Reinigungsmittel mit teilchenförmigem Bleichmittel
SG170829A1 (en) * 2006-04-04 2011-05-30 Basf Se Bleach systems enveloped with polymeric layers
WO2012041774A1 (fr) * 2010-09-28 2012-04-05 Unilever Nv Composition de détergent
WO2018183662A1 (fr) * 2017-03-31 2018-10-04 Danisco Us Inc Formulations d'enzyme à libération retardée pour détergents contenant un agent de blanchiment
KR102699216B1 (ko) * 2019-05-08 2024-08-26 이 잉크 코포레이션 캡슐화된 효소를 포함하는 액체 세제 조성물
CN115873667B (zh) * 2022-11-28 2024-07-19 上饶市春宇科技有限公司 一种胶囊型浓缩洗洁精及其制备方法

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US6844305B1 (en) 1999-08-27 2005-01-18 The Proctor & Gamble Company Aqueous liquid detergent compositions comprising a polymeric stabilization system
US9321873B2 (en) 2005-07-21 2016-04-26 Akzo Nobel N.V. Hybrid copolymer compositions for personal care applications
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
DE102007004054A1 (de) 2007-01-22 2008-07-24 Henkel Ag & Co. Kgaa Verfahren zur Herstellung teilchenförmiger Bleichmittelzusammensetzungen
WO2008090025A1 (fr) 2007-01-22 2008-07-31 Henkel Ag & Co. Kgaa Procédé de préparation de compositions particulaires d'agent de blanchiment
US8093198B2 (en) 2007-01-22 2012-01-10 Henkel Ag & Co. Kgaa Method for the production of particulate bleaching agent compositions
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US9309489B2 (en) 2011-08-05 2016-04-12 Ecolab Usa Inc Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US10053652B2 (en) 2014-05-15 2018-08-21 Ecolab Usa Inc. Bio-based pot and pan pre-soak

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BR9404433A (pt) 1995-06-20
EP0653485A1 (fr) 1995-05-17
DE69424506T2 (de) 2000-09-14
ES2147217T3 (es) 2000-09-01
DE69424506D1 (de) 2000-06-21

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