WO1997024178A1 - Matieres particulaires polymeres et compositions les contenant - Google Patents

Matieres particulaires polymeres et compositions les contenant Download PDF

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Publication number
WO1997024178A1
WO1997024178A1 PCT/GB1996/003232 GB9603232W WO9724178A1 WO 1997024178 A1 WO1997024178 A1 WO 1997024178A1 GB 9603232 W GB9603232 W GB 9603232W WO 9724178 A1 WO9724178 A1 WO 9724178A1
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WIPO (PCT)
Prior art keywords
enzyme
particles
detergent
composition according
polymer
Prior art date
Application number
PCT/GB1996/003232
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English (en)
Inventor
John Graham Langley
Kishor Kumar Mistry
Kenneth Charles Symes
Original Assignee
Allied Colloids Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Allied Colloids Limited filed Critical Allied Colloids Limited
Priority to AU12037/97A priority Critical patent/AU1203797A/en
Publication of WO1997024178A1 publication Critical patent/WO1997024178A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • This invention relates to liquid detergents and to particulate materials which can contain detergent active ingredients and which can be utilised for introducing the active ingredients into a liquid detergent.
  • the invention relates to compositions wherein the active ingredient is a detergent enzyme.
  • the active ingredient is a detergent enzyme.
  • the polymer can be a synthetic polymer formed from an ethylenically unsaturated water soluble monomer or monomer blend which may be non-ionic or ionic, and it is mentioned that dimethyl amino ethyl (meth) acrylate can be used as a suitable cationic monomer.
  • the preferred polymer is based on 0%-50% acrylamide and 50%- 100% acrylic acid or soluble salt thereof. It is also stated that the polymer can be a polymer which is insoluble in water but is soluble or swellable in alkali, the monomers being a blend of anionic monomer and ethylenically unsaturated non-ionic monomer, for example, styrene.
  • the protection of enzyme can be improved if there is a layer of hydrophobic oil between the matrix polymer core and the outer shell of polymer and if the matrix is sufficiently hydrophobic that it will partition preferentially into the oil rather than the water.
  • the preferred polymers are co-polymers of ionic monomers with hydrophobic monomers, such as styrene, and can be made by solution polymerisation in organic solvent or by oil-in-water emulsion polymerisation. It is stated that the ionic monomer can be an amino-polymer which can be present initially as a water soluble salt but can be insolubilised by conversion to the free base.
  • a matrix which is formed of a water-insoluble hydrophobic polymer which contains recurring units of hydrophobic water-insoluble monomer and of cationic monomer having amino groups in free base form.
  • This free base polymer will remain in free base form both when it is exposed to the high electrolyte concentration (and often the alkaline environment) which prevails in detergent concentrates, and when it is exposed to the lower electrolyte concentration (and possible low alkalinity) which prevails in wash water into which the detergent concentrate has been distributed.
  • the release of the enzyme or other active ingredient from within the matrix cannot therefore be due to formation of a water soluble salt but instead is due to the matrix retaining the active ingredient prior to exposure to wash water but releasing the active ingredient when it is exposed to wash water.
  • a particulate composition comprises particles having a polymeric matrix including a detergency active ingredient, wherein the polymeric matrix is formed of a free base form of a cationic polymer which is a co-polymer of (a) an ethylenically unsaturated hydrophobic monomer with (b) a monomer of the formula
  • CH 2 CR 1 COXR 2 NR 3 R 4 where R 1 is hydrogen or methyl, X is O or NH, R is alkylene containing at least two carbon atoms, R is a hydrocarbon group containing at least 4 carbon atoms and R 4 is hydrogen or a hydrocarbon group.
  • the preferred monomers are those in which R is tertiary butyl since the presence of the tertiary butyl group imposes particularly useful swelling properties on the polymer formed from that monomer.
  • R may be other butyl or higher alkyl groups or it may be other hydro-carbon groups containing at least 4 carbon atoms (but usually not more than 8 carbon atoms) .
  • the t-butyl group is also advantageous because it seems to render the monomer units containing it more resistant to alkaline hydrolysis.
  • R is frequently hydrogen but it can be alkyl such as methyl, ethyl or higher alkyl or it can be other hydro carbon group.
  • the total number of carbon atoms in R and R 4 together is usually below 12, often below 8.
  • R is usually ethylene but it can be other linear or branched alkylene group containing two or more (for instance 2-4) carbon atoms.
  • R is usually methyl.
  • X can be NH, with the result that the cationic monomer is preferably a onoalkyl or dialkyl a inoalkyl (meth) acrylamide monomer, but preferably X is O, with the result that the cationic monomer is preferably a monoalkyl or dialkyl aminoalkyl (meth) acrylate.
  • the hydrophobic monomer can be any ethylenically unsaturated monomer which is insoluble in water, for instance generally having a partition coefficient K between hexane and deionised water at 20°C of at least 5 and preferably at least 10.
  • the hydrophobic monomer can be a water-insoluble alkyl ester of methacrylic acid or other aliphatic, water-insoluble monomer such as methyl, ethyl or butyl acrylate or methacrylate.
  • the preferred hydrophobic monomers are ethylenically unsaturated aromatic hydrocarbon monomers, such as styrenes, preferably styrene or a methyl styrene.
  • the amount of the cationic monomer which should be used will depend in part on the active ingredient which is entrapped within the monomer.
  • the proportion of cationic free based monomer should be such that there is little or no release of the active ingredient prior to exposure to the wash water but that there is significant swelling and release of the active ingredient upon exposure to the wash water.
  • the degrees of swelling which will result in retention or release of the active ingredient depend in part on the molecular size of the active ingredient, in that good retention of an active ingredient of small molecular size requires that the polymer should be less swollen (when exposed to the detergent concentrate) than when the active ingredient has a higher molecular size. Similarly, good release when exposed to wash water requires a higher degree of swelling for higher molecular size active ingredients than for lower molecular size active ingredients.
  • the amount of cationic monomer will be within the range 5-30 mole % or 10-50 weight %. Best results, especially when the active ingredient is an enzyme, are generally achieved with amounts of from around 12-25 mole % of the cationic free base monomer.
  • the free base monomer is t-butylamino-ethyl methacrylate and the hydrophobic monomer is a styrene or methyl styrene
  • the amount of cationic monomer is preferably from 20%-45% by weight, most preferably around 30%-40% by weight, especially when the active ingredient is a detergent enzyme.
  • the matrix can be formed of recurring units of monomers consisting solely of the hydrophobic monomer and the free base cationic monomer but if desired minor amounts of other monomers may be included.
  • the matrix is preferably formed by a method analogous to that which is described in EP 361677 or EP 356239 for the formation of a matrix of anionic polymer.
  • it may be made by dehydrating particles each of which is an oil- in-water emulsion of the free base polymer or it may be made by forming particles of a salt of the polymer with a volatile acid and evaporating the volatile acid during the drying so as to form the free base of the polymer.
  • the presence of cationic monomer as acid salt form can significantly increase the swellability, or even the solubility, of the polymer in the detergent concentrate or in the wash water and so preferably the polymer is as free as is reasonably possible of the cationic monomer in the form of water soluble acid salt.
  • the amount of cationic monomer groups in the form of salt, in the polymer should be as small as possible and should be below 20 mole %, preferably below 10 mole % and most preferably below 5 mole % based on the amount of free base cationic monomer groups in the polymer. Preferably it is substantially zero.
  • the preferred way of making the particles of polymeric matrix is by forming a reverse phase dispersion in a water immiscible non-aqueous liquid of droplets containing the chosen active ingredient and either an oil-in-water emulsion of the polymer or an aqueous solution of a salt of the polymer with a volatile acid and then distilling the dispersion so as to eliminate the water and, if necessary, to drive off the volatile acid.
  • the formation of the reverse phase dispersion is preferably conducted in the presence of a polymeric (generally amphipathic) stabiliser and/or an emulsifier, for instance as described in EP 356239 and EP 361677 and WO 92/20771.
  • the matrix particles are made by providing a solution of a water soluble salt form of the polymer
  • this solution can be made by acidifying, using a volatile acid, an oil-in-water emulsion formed by oil-in- water emulsion polymerisation of the monomers.
  • the solution is made by polymerising the free base monomer and the hydrophobic monomer while dissolved in an organic solvent so as to form a solution of the free base polymer inorganic solvent.
  • an aqueous solution of a volatile acid wherein the solvent has higher volatility than the acid.
  • the solvent is then distilled off so as to leave a solution in water of the salt form of the polymer.
  • a suitable volatile acid is acetic acid, in which event a suitable solvent is n-butyl acetate.
  • the product In order to maximise the conversion of the salt form of the cationic polymer to the free base form, it is desirable to bake the product, after distilling off the water, at a temperature of at least 95°C and usually 100°C for at least 15 minutes and usually at least 20 or 30 minutes. Preferably this is conducted under sufficient vacuum (if necessary) to maximise the removal of volatile acid.
  • the active ingredient can be incorporated in the polymeric matrix as a substantially uniform solution or dispersion or it can be distributed non-uniformly.
  • It can be any active ingredient which can usefully be incorporated into a detergent concentrate and which should preferably be released from the matrix only after dilution of the concentrate into wash water. Accordingly it can be a material such as, for instance, a bleach activator, an optical brightener or a photobleach. Preferably, however, it is a detergent enzyme, that is to say an enzyme that is usefully incorporated into a detergent. It can be, for instance, a lipase, protease, cutinase, amylase, cellulase or oxidoreductase (eg a peroxidase, or an oxidase such as laccase) .
  • a detergent enzyme that is to say an enzyme that is usefully incorporated into a detergent. It can be, for instance, a lipase, protease, cutinase, amylase, cellulase or oxidoreductase (eg a peroxidase, or an oxidas
  • the invention is of particular value when the liquid detergent is to include a protease and at least one other type of enzyme since by encapsulating the protease, or by encapsulating the or each enzyme other than protease, interaction between the enzymes in the detergent concentrate can be minimised.
  • a polymeric shell may be formed around the particles of core, for instance by a coacervation technique as described in EP-A-356,239 or WO92/20771 or, preferably, by interfacial condensation as described in, for instance, Application ... filed even date herewith reference PRL03620WO claiming priority from GB 9526707.
  • the particles have a shell (around the core) of a polyamide or other condensation polymer, preferably formed by interfacial condensation.
  • the particles that are formed can, depending upon the dispersion conditions and components, be in the form of beads which can be recovered as dry powder, for instance wherein the beads have a dry size of at least 90% by weight above 50 ⁇ m and often above 100 ⁇ m, for instance up to 1000 ⁇ m. Preferably, however, the particles have a smaller size, generally 90% by weight below 30 ⁇ m and often below 10 ⁇ m or 20 ⁇ m down to, for instance, 0.5 ⁇ m or less. It is then generally preferred that the particles remain as a substantially stable dispersion in a non-aqueous liquid. Thus, either the particles do not settle out (which is preferred) or any settled particles can easily be redispersed by stirring or shaking.
  • the initial formation and the subsequent dehydration of the reverse phase dispersion are generally both conducted while the continuous phase of the dispersion is a hydrocarbon non-aqueous liquid, but various other non- aqueous liquids which are known to be suitable for reverse phase dispersions can be used.
  • the final product can be added direct to a detergent concentrate, it is preferred to provide the particles as a dispersion in a water miscible liquid, generally a non-ionic surfactant as described in WO 94/25560 to which reference should be made for description of suitable materials, amounts and methods.
  • the amount of particles in such a dispersion is usually above 10% by weight of the dispersion.
  • the particles may be dispersed in a liquid detergent, for instance by blending a dispersion of particles (usually after dehydration) in a surfactant or in another water- immiscible liquid or in an water-immiscible liquid into the liquid detergent.
  • the liquid detergent containing the particles may be aqueous, typically containing up to 70% water and 0-30% organic solvent, or non-aqueous.
  • the detergent composition comprises one or more surfactants, each of which may be anionic, non-ionic, cationic, or zwitterionic.
  • the detergent will usually contain 0-50% of anionic surfactant such as linear alkylbenzenesulfonate (LAS) , alpha-olefinsulfonate (AOS) , alkyl sulfate (fatty alcohol sulfate) (AS), alcohol ethoxysulfate (AEOS or AES) , secondary alkanesulfonates (SAS) , alpha-sulfo fatty acid methyl esters, alkyl- or alkenylsuccinic acid, or soap.
  • anionic surfactant such as linear alkylbenzenesulfonate (LAS) , alpha-olefinsulfonate (AOS) , alkyl sulfate (fatty alcohol sulfate) (AS), alcohol ethoxysulfate (AEOS or AES) , secondary
  • non-ionic surfactant such as alcohol ethoxylate (AEO or AE) , carboxylated alcohol ethoxylates, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, or polyhydroxy alkyl fatty acid amide (e.g. as described in WO 92/06154) .
  • AEO or AE alcohol ethoxylate
  • carboxylated alcohol ethoxylates carboxylated alcohol ethoxylates
  • nonylphenol ethoxylate nonylphenol ethoxylate
  • alkylpolyglycoside alkyldimethylamine oxide
  • ethoxylated fatty acid monoethanolamide e.g. as described in WO 92/06154
  • polyhydroxy alkyl fatty acid amide e.g. as described in WO 92/06154
  • the detergent if built, may contain 1-65% of a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, citrate, nitrilotriacetic acid (NTA) , ethylenediaminetetraacetic acid (EDTA) , diethylenetriaminepentaacetic acid (DTMPA) , alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from Hoechst) .
  • a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, citrate, nitrilotriacetic acid (NTA) , ethylenediaminetetraacetic acid (EDTA) , diethylenetriaminepentaacetic acid (DTMPA) , alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from
  • the detergent may comprise one or more polymers .
  • examples are carboxy ethylcellulose (CMC) , poly vinyl ⁇ pyrrolidone) (PVP) , polyethyleneglycol (PEG) , poly (vinyl alcohol) (PVA) , polycarboxylates such as polyacrylates , maleic/ acryl ic acid copolymers and lauryl methacrylate/acrylic acid copolymers .
  • the detergent may contain a bleaching system which may comprise a H 2 0 2 source such as perborate or percarbonate which may be combined with a peracid-forming bleach activator such as tetraacetylethylenediamine (TAED) or nonanoyloxybenzenesulfonate (NOBS) .
  • TAED tetraacetylethylenediamine
  • NOBS nonanoyloxybenzenesulfonate
  • the bleaching system may comprise peroxyacids of, e.g., the amide, imide, or sulfone type.
  • the enzymes of the detergent composition of the invention may be stabilized using conventional stabilizing agents, e.g. a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative such as, e.g., an aromatic borate ester, and the composition may be formulated as described in, e.g., WO 92/19709 and WO 92/19708.
  • the stabiliser may be incorporated in the capsules (generally in the core) or may be in the liquid phase, especially when there is enzyme in the liquid phase.
  • the detergent may also contain other conventional detergent ingredients such as, e.g., fabric conditioners including clays, foam boosters, suds suppressors, anti- corrosion agents, soil-suspending agents, anti-soil- redeposition agents, dyes, bactericides, optical brighteners, or perfume.
  • fabric conditioners including clays, foam boosters, suds suppressors, anti- corrosion agents, soil-suspending agents, anti-soil- redeposition agents, dyes, bactericides, optical brighteners, or perfume.
  • the pH (measured in aqueous solution at use con- centration) will usually be neutral or alkaline, e.g. in the range of 7-11.
  • compositions in which the novel particles can be dispersed include:
  • An aqueous liquid detergent composition comprising
  • An aqueous structured liquid detergent composition comprising
  • An aqueous liquid detergent composition comprising
  • An aqueous liquid detergent composition comprising
  • Alcohol ethoxylate e.g. C 12 . 15 alco ⁇ hol, 6 - 12% 7 EO, or C Fundamental. 1 ⁇ alcohol, 5 EO
  • Polymer e.g. maleic/acrylic acid copolymer, anchoring polymer such as, e.g. , lauryl 0 - 3% methacrylate/acrylic acid copolymer
  • Enzymes (calculated as pure enzyme 0.0001 - 0.1% protein)
  • Liquid nonionic surfactant e.g. alcohol ethoxylates 2.0 - 10.0%
  • Liquid carrier selected from higher glycols, polyglycols, polyoxides. 25.0 - 45.0% glycolethers
  • Stabilizer e.g. a partial ester of phosphoric acid and a C l6 -C 1 ⁇ 0.5 - 7.0% alkanol
  • Foam suppressor e.g. silicone 0 - 1.5%
  • Oleic acid 0 - 10%
  • Detergent composition formulated as a non-aqueous detergent liquid comprising a liquid nonionic surfactant such as, e.g. , linear alkoxylated primary alcohol, a builder system (e.g. phosphate) , enzyme and alkali.
  • a liquid nonionic surfactant such as, e.g. , linear alkoxylated primary alcohol, a builder system (e.g. phosphate) , enzyme and alkali.
  • the detergent may also comprise anionic surfactant and/or a bleach system.
  • the manganese catalyst may, e.g. , be one of the compounds described in "Efficient manganese catalysts for low- temperature bleaching", Nature 369. 1994, pp. 637-639.
  • the amount of the or each enzyme in the liquid detergent typically corresponds to an amount of 0.0001 to lmg pure enzyme protein per litre of wash liquor.
  • a co-polymer of about 65% by weight styrene and 45% by weight t-butyl amino ethyl methacrylate is synthesized by isothermal solution polymerisation in n-butyl acetate using t-butyl perbenzoate as initiator.
  • Aqueous acidic acid solution is then added to the organic solution and the butyl acetate was distilled off, leaving a 20%-30% weight solution of the co-polymer, as the acetate salt, in water at pH 4-5.5.
  • Example 2 The solution of Example l is mixed with a liquid
  • the dispersion is then held at 100°C for 30 minutes under vacuum to drive off acetic acid.
  • the particles produced in this Example are added to a typical European liquid detergent formulations at 0.10
  • the detergent sample is subjected to a storage test at the end of which 86% of the original enzyme activity is released into wash water and only 15% of the original enzyme activity had escaped into the liquid phase prior to the dilution with wash water.
  • Lipolase enzyme at l.OKLU/g lipolytic enzyme activity is dosed with either Savinase particles of Example 2 or with liquid Savinase enzyme at 0.10 KNPU/g protease enzyme activity. Each detergent sample is subjected to an accelerated storage test for 3 and 7 days.
  • Example 2 The process of Example 2 is repeated except that Lipolase is included in the particles instead of Savinase.
  • the particles of this Example are added to a typical European liquid detergent compositions at 1.0 KLU/g lipolytic enzyme activity.
  • the resulting detergent sample is subjected to a storage test at the end of which 6% of the original enzyme activity is in the liquid phase and 69% of the original enzyme activity is released upon dilution into wash liquor.
  • Example 5
  • a concentrated liquid detergent containing liquid Savinase enzyme at 0.10 KNPU/g enzyme activity is dosed with either Lipolase particles of Example 5 or with liquid Lipolase enzyme at l.OKLU/g enzyme activity.
  • the respective detergent samples are placed under accelerated storage test at 30°C for 7 days.
  • the samples are subjected to lipolytic enzyme activity determination.
  • the amount of lipase activity remaining after the test is given in Table 2.
  • Examples 1-5 The process of Examples 1-5 is repeated using different co-polymers.
  • the amount of the free base cationic monomer is increased above 40% by weight there is increased leakage of the Savinase, leading to reduced Lipolase activity in the test system of Example 3.
  • the amount of cationic monomer is reduced significantly below 30%, there is reduced proteolytic activity upon addition to wash water, indicating inferior release of the enzyme.

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

Abstract

Particule possédant une matrice polymère qui renferme une enzyme ou autres ingrédients actifs détergents et qui est formée d'un copolymère (a) d'un monomère hydrophobe éthyléniquement insaturé avec (b) un monomère à base libre de la formule CH?2 = CR1COXR2NR3R4¿ dans laquelle R représente hydrogène ou méthyle, R2 représente alkylène contenant au moins deux atomes de carbone, X représente O ou NH, R3 représente un groupe hydrocarbure contenant au moins quatre atomes de carbone et R4 représente hydrogène ou un groupe hydrocarbure.
PCT/GB1996/003232 1995-12-29 1996-12-23 Matieres particulaires polymeres et compositions les contenant WO1997024178A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU12037/97A AU1203797A (en) 1995-12-29 1996-12-23 Polymeric particulate materials and compositions containing them

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9526668.0 1995-12-29
GBGB9526668.0A GB9526668D0 (en) 1995-12-29 1995-12-29 Polymeric particulate materials and compositions containing them

Publications (1)

Publication Number Publication Date
WO1997024178A1 true WO1997024178A1 (fr) 1997-07-10

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AU (1) AU1203797A (fr)
GB (1) GB9526668D0 (fr)
WO (1) WO1997024178A1 (fr)
ZA (1) ZA9610929B (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001004257A1 (fr) * 1999-07-09 2001-01-18 Basf Aktiengesellschaft Preparations de microcapsules et detergents et nettoyants contenant des microcapsules
WO2002028991A1 (fr) * 2000-10-02 2002-04-11 Novozymes A/S Particules renfermant une substance active dispersees dans des liquides viscoelastiques
WO2002090445A1 (fr) * 2001-05-04 2002-11-14 Ciba Specialty Chemicals Water Treatments Limited Colorants encapsules dans une matrice polymere
WO2002102951A1 (fr) * 2001-06-19 2002-12-27 Ciba Specialty Chemicals Water Treatments Limited Particules contenant un agent de conditionnement de tissus
US6617026B2 (en) 2000-10-02 2003-09-09 Novozymes A/S Particles containing active in visco-elastic liquids
WO2006034758A1 (fr) 2004-09-29 2006-04-06 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage et de nettoyage comprenant des substances actives immobilisees
US7271142B2 (en) * 2001-06-27 2007-09-18 Ciba Specialty Chemicals Water Treatments Ltd Process for making polymeric particles
EP2246408A2 (fr) 1999-11-12 2010-11-03 M-I L.L.C. Procédé et composition pour la libération déclenchée d'agents de dégradation de polymères pour une utilisation dans les champs pétrolifères
WO2010139564A2 (fr) 2009-06-01 2010-12-09 Basf Se Banches murales et systèmes
WO2011000686A2 (fr) 2009-07-03 2011-01-06 Basf Se Composition de mousse

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Publication number Priority date Publication date Assignee Title
JPS6128441A (ja) * 1984-07-20 1986-02-08 Lion Corp ｐＨ感応性マイクロカプセルの製造方法
EP0356239A2 (fr) * 1988-08-24 1990-02-28 Ciba Specialty Chemicals Water Treatments Limited Compositions détergentes
WO1992020771A1 (fr) * 1989-08-24 1992-11-26 Allied Colloids Limited Compositions polymeres

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Publication number Priority date Publication date Assignee Title
JPS6128441A (ja) * 1984-07-20 1986-02-08 Lion Corp ｐＨ感応性マイクロカプセルの製造方法
EP0356239A2 (fr) * 1988-08-24 1990-02-28 Ciba Specialty Chemicals Water Treatments Limited Compositions détergentes
WO1992020771A1 (fr) * 1989-08-24 1992-11-26 Allied Colloids Limited Compositions polymeres

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Title
DATABASE WPI Section Ch Week 8612, Derwent World Patents Index; Class A14, AN 86-079085, XP002029165 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001004257A1 (fr) * 1999-07-09 2001-01-18 Basf Aktiengesellschaft Preparations de microcapsules et detergents et nettoyants contenant des microcapsules
US6849591B1 (en) 1999-07-09 2005-02-01 Basf Aktiengesellschaft Microcapsule preparations and detergents and cleaning agents containing microcapsules
EP2246408A2 (fr) 1999-11-12 2010-11-03 M-I L.L.C. Procédé et composition pour la libération déclenchée d'agents de dégradation de polymères pour une utilisation dans les champs pétrolifères
WO2002028991A1 (fr) * 2000-10-02 2002-04-11 Novozymes A/S Particules renfermant une substance active dispersees dans des liquides viscoelastiques
US6617026B2 (en) 2000-10-02 2003-09-09 Novozymes A/S Particles containing active in visco-elastic liquids
WO2002090445A1 (fr) * 2001-05-04 2002-11-14 Ciba Specialty Chemicals Water Treatments Limited Colorants encapsules dans une matrice polymere
US7648715B2 (en) 2001-05-04 2010-01-19 Ciba Specialty Chemicals Water Treatments Ltd. Colourants encapsulated in polymer matrix
AU2002316861B2 (en) * 2001-05-04 2006-11-30 Ciba Specialty Chemicals Holding Inc. Colourants encapsulated in a polymer matrix
AU2002320825B2 (en) * 2001-06-19 2007-10-11 Ciba Specialty Chemicals Holding Inc. Particles containing fabric conditioner
WO2002102951A1 (fr) * 2001-06-19 2002-12-27 Ciba Specialty Chemicals Water Treatments Limited Particules contenant un agent de conditionnement de tissus
US7271142B2 (en) * 2001-06-27 2007-09-18 Ciba Specialty Chemicals Water Treatments Ltd Process for making polymeric particles
WO2006034758A1 (fr) 2004-09-29 2006-04-06 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage et de nettoyage comprenant des substances actives immobilisees
WO2010139564A2 (fr) 2009-06-01 2010-12-09 Basf Se Banches murales et systèmes
WO2011000686A2 (fr) 2009-07-03 2011-01-06 Basf Se Composition de mousse
US9249269B2 (en) 2009-07-03 2016-02-02 Basf Se Foam composition

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GB9526668D0 (en) 1996-02-28
ZA9610929B (en) 1997-12-30

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