EP0294904A2 - Verfahren zur Herstellung einer Perboratbleichmittel enthaltenden wässerigen flüssigen Waschmittelzusammensetzung - Google Patents

Verfahren zur Herstellung einer Perboratbleichmittel enthaltenden wässerigen flüssigen Waschmittelzusammensetzung Download PDF

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Publication number
EP0294904A2
EP0294904A2 EP88201175A EP88201175A EP0294904A2 EP 0294904 A2 EP0294904 A2 EP 0294904A2 EP 88201175 A EP88201175 A EP 88201175A EP 88201175 A EP88201175 A EP 88201175A EP 0294904 A2 EP0294904 A2 EP 0294904A2
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EP
European Patent Office
Prior art keywords
liquid detergent
composition according
detergent composition
water
perborate
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Granted
Application number
EP88201175A
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English (en)
French (fr)
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EP0294904A3 (en
EP0294904B1 (de
Inventor
Jozef Philomena Raymond Geudens
Tjay Yong Yap
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Procter and Gamble European Technical Center
Procter and Gamble Co
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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
    • C11D3/395—Bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to aqueous liquid detergent compositions which contain perborate bleach in the form of small particles, i.e., particles having a weight average particle diameter of from 0.5 to 20 micrometers.
  • the small particles are formed by in-situ crystallization, typically of perborate tetrahydrate.
  • the tetrahydrate may be formed, e.g., by recrystallizing perborate monohydrate, or by reacting a borate with hydrogen peroxide.
  • Insoluble peroxygen bleach compounds present the problem of poor physical stability of suspensions made therewith.
  • the aqueous liquid detergent compositions of the present invention have a pH of at least 8, comprise at least 5% of an organic non-soap anionic surfactant at least 5% of a builder, and from 1% to 40%, preferably from 10% to 20% of a perborate bleach in the form of particles having a weight average particle diameter of from 0.5 micrometer to 20 micrometers, said particles having been formed by in situ crystallization.
  • the perborate particles are formed by in situ crystallization of a perborate tetrahydrate , e.g. sodium perborate tetrahydrate.
  • Preferred liquid detergent compositions further com­prise from 5% to 70% of a water-miscible organic solvent.
  • the preferred water-miscible organic solvents are the low molecular weight monohydric alcohols; the most preferred of these solvents is ethanol.
  • Preferred herein are detergent compositions having a pH of at least 9, more preferably at least 9.5.
  • the present invention addresses the problem of formu­lating an aqueous liquid detergent composition having sus­pended therein small particles of a perborate bleach.
  • the per­borate particles have a weight average particle diameter of from 0.5 to 20 micrometers. It is not advisable to make such small particles by e.g., grinding, because this process is not very attractive economically. Moreover, such small particles in a dry state would pose serious industri­al hygien and safety problems. It has also been found that detergent compositions containing small perborate particles that are obtained by grinding have poorer phsical stability than compositions containing perborate particles of the same diameter that were obtained b in situ crystallization. Although this phenomenon is not fully understood, it is speculated that particle shape plays a role in it.
  • the required small per­borate particles can be formed by in situ crystallization in the presence of at least 5% of an organic, non-soap, anionic surfactant and at least 5% of a detergent builder.
  • Percentages as used herein are percentages by weight of the liquid detergent composition. Weight percentages of the perborate are calculated as perborate monohydrate, even through the particles may be different in composi­tion (e.g., the tetrahydrate).
  • in situ crystallization relates to process­es whereby perborate particles are formed from larger par­ticles or from solution, in the presence of the wa­ter/anionic surfactant/detergent builder matrix.
  • This term therefore encompasses processes involving chemical reactions, as when sodium perborate is formed by reacting stoichiometric amounts of hydrogen peroxide and sodium metaborate or borax. It also encompasses processes involv­ing dissolution and recrystallization, as in the dissolu­tion of perborate monohydrate and subsequent formation of perborate tetrahydrate. Recrystallization may also take place by allowing perborate monohydrate to take up crystal water, whereby the monohydrate directly recrystallizes into the tetrahydrate, without dissolution step.
  • a perborate com­pound e.g., sodium perborate tetrahydrate or sodium perbo­rate monohydrate
  • an aqueous liquid comprising the anionic surfactant and the detergent builder.
  • the re­sulting slurry is stirred.
  • the perbo­rate compound undergoes a process of dissolu­tion/recrystallization. Due to the presence of the anion­ic surfactant and the detergent builder this dissolu­tion/recrystallization process results in particles having the desired particle diameter.
  • Particle diameters herein are weight average particle diameters, unless otherwise specified.
  • the particle size distribution is relatively narrow; i.e., it is preferred that less than 10% of the perborate be present in the form of particles having a diameter greater than 25 micrometers,more preferably less than 10%(wt) has a particle diameter greater than 10 micrometers.
  • the perborate compound is formed in situ by chemical reaction.
  • sodium metaborate is added to an aqueous liquid com­prising the anionic surfactant and the detergent builder. Then a stoichiometric amount of hydrogen peroxide is added while stirring. Stirring is continued until the reaction is complete.
  • borate compounds included­ing e.g., borax and boric acid. If borax is used as the bo­ron compound, a stoichiometric amount of a base, e.g. sodi­um hydroxide, is added to ensure reaction of the borax to metaborate. The process then proceeds as described herein­above for metaborate conversion.
  • a base e.g. sodi­um hydroxide
  • hydrogen perox­ide other peroxides may be used (e.g., sodium peroxide), as known in the art.
  • Preferred liquid detergent compositions contain, in addition to water, a water-miscible organic solvent.
  • the solvent reduces the solubility of perborate in the liquid phase and thereby enhances the chemical stability of the composition.
  • organic solvent be fully miscible with water, provided that enough of the solvent mixes with the water of the composition to affect the solubility of the perborate compound in the liquid phase.
  • the water-miscible organic solvent must, or course, be compatible with the perborate compound at the pH that is used. Therefore, polyalcohols having vicinal hydroxy groups (e.g. 1,2-propanediol and glycerol) are less desirable.
  • suitable water-miscible organic solvents include the lower aliphatic monoalcohols, and ethers of diethylene glycol and lower monoaliphatic monoalcohols.
  • Preferred solvents are ethanol, iso-propanol, 1-methoxy 2-propanol and butyldiglycolether.
  • the amount of available oxygen in solution is largely determined by the ratio water : organic solvent. The smaller this ratio (i.e. the more organic solvent is used in the solvent system), the lower the amount of available oxygen in solution. Although this is good for stability of the bleach system, it is less desirable for a good solubility of other components (e.g. electrolyte, anionic surfactants).
  • the ratio water : organic solvent is, for most systems, in the range from 8:1 to 1:3, preferably from 5:1 to 1:2.
  • allowances should be made for water released in or taken up by chemical and physical processes that may take place during the preparation of the detergent composition. For example, water may be formed in the neutralization of an anionic surfactant, whereas water may be taken up in the conversion of metaborate to perborate tetrahydrate, as well as in the conversion of perborate monohydrate to perborate tet­rahydrate. Water is also present in most detergent raw materials, and should be taken into account.
  • compositions have an ionic strength of at least 0.8 moles/liter, preferably from 2 to 3.5 moles/liter. Ionic strengths are calculated on the assumption that all ionic materials other than perborate present in the composition are fully dissociated.
  • the liquid detergent compositions herein contain from 5% to 60% of the liquid detergent composition, preferably from 15% to 40%, of an organic surface-active agent selected from nonionic, anionic, and zwitterionic surface-active agents and mixtures thereof. At least 5% of the detergent composition must be anionic surfactant.
  • Synthetic anionic surfactants can be represented by the general formula R1SO3M wherein R1 represents a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from about 8 to about 24 carbon atoms and alkyl phenyl radicals containing from about 9 to about 15 carbon atoms in the alkyl group.
  • M is a salt forming cation which typically is selected from the group consisting of sodium, potassium, ammonium and mixtures thereof.
  • a preferred synthetic anionic surfactant is a water-soluble salt of an alkylbenzene sulfonic acid containing from 9 to 15 carbon atoms in the alkyl group.
  • Another preferred synthetic anionic surfactant is a water-soluble salt of an alkyl sulfate or an alkyl polyethoxylate ether sulfate wherein the alkyl group contains from about 8 to about 24, preferably from about 10 to about 18 carbon atoms and there are from about 1 to about 20, preferably from about 1 to about 12 ethoxy groups.
  • Other suitable anionic surfactants are disclosed in U.S. Patent 4,170,565, Flesher et al., issued October 9, 1979.
  • the nonionic surfactants are conventionally produced by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl, or amido group, in the presence of an acidic or basic catalyst, and include compounds having the general formula RA(CH2CH20)nH wherein R represents the hydrophobic moiety, A represents the group carrying the reactive hydrogen atom and n represents the average number of ethylene oxide moieties. R typically contains from about 8 to 22 carbon atoms. They can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n usually varies from about 2 to about 24.
  • the hydrophobic moiety of the nonionic compound is preferably a primary or secondary, straight or branched, aliphatic alcohol having from about 8 to about 24, preferably from about 12 to about 20 carbon atoms.
  • suitable nonionic surfactants can be found in U.S. Patent 4,111,855. Mixtures of nonionic surfactants can be desirable.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 24 carbon atoms and another substituent contains, at least, an anionic water-solubilizing group.
  • Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al., issued December 9, 1975 and 3,929,678, Laughlin et al., issued December 30, 1975.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl or hydroxy alkyl moiety of from about 8 to about 28 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups, containing from 1 to about 3 carbon atoms which can optionally be joined into ring structures.
  • Suitable anionic synthetic surface-active salts are selected from the group of sulfonates and sulfates.
  • anionic detergents are well-known in the detergent arts and have found reexported application in commercial detergents.
  • Preferred anionic synthetic water-soluble sul­fonate or sulfate salts have in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms.
  • anionic surfactant salts are the reaction products obtained by sulfating C8-C18 fatty alcohols derived from tallow and coconut oil; alkylbenzene sulfonates wherein the alkyl group contains from about 9 to about 15 carbon atoms; sodium alkylglyceryl ether sulfonates; ether sulfates of fatty alcohols derived from tallow and coconut oils; coconut fatty acid monoglyceride sulfates and sulfonates; and water-soluble salts of paraffin sulfonates having from about 8 to about 22 carbon atoms in the alkyl chain.
  • Sulfonated olefin surfactants as more fully described in e.g. U.S,. Patent Specification 3,332,880 can also be used.
  • the neutralizing cation for the anionic synthetic sulfonates and/or sulfates is represented by conventional cations which are widely used in detergent technology such as sodium and potassium.
  • a particularly preferred anionic synthetic surfac­tant component herein is represented by the water-soluble salts of an alkylbenzene sulfonic acid, preferably sodium alkylbenzene sulfonic acid, preferably sodium alkylbenzene sulfonates having from about 10 to 13 carbon atoms in the alkyl group.
  • a particularly preferred anionic synthetic surfac­tant component herein is represented by the water-soluble salts of an alkylbenzene sulfonic acid, preferably sodium alkylbenzene sulfonates having from about 10 to 13 carbon atoms in the alkyl group.
  • a preferred class of nonionic ethoxylates is repre­sented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from about 4 to 10 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable species of this class of ethoxylates include : the condensation product of C12-C15 oxo-alcohols and 7 or 9 moles of ethylene oxide per mole of alcohol; the condensation product of narrow cut C14-C15 oxo-alcohols and 7 or 9 moles of ethylene oxide per mole of fatty (oxo)alcohol; the condensation product of a narrow cut C12-C13 fatty(oxo)alcohol and 6,5 moles of ethylene oxide per mole of fatty alcohol; and the condensation products of a C10-C14 coconut fatty alcohol with a degree of ethoxylation (moles EO/mole fatty alcohol) in the range from 5 to 8.
  • a degree of branching in the range from 15% to 50% (weight%) is frequently found in commercial oxo alcohols.
  • Preferred nonionic ethoxylated components can also be represented by a mixture of 2 separately ethoxylated nonionic surfactants having a different degree of ethoxyla­tion.
  • the nonionic ethoxylate surfactant con­taining from 3 to 7 moles of ethylene oxide per mole of hydrophobic moiety and a second ethoxylated species having from 8 to 14 moles of ethylene oxide per mole of hydropho­bic moiety.
  • a preferred nonionic ethoxylated mixture con­tains a lower ethoxylate which is the condensation product of a C12-C15 oxo-alcohol, with up to 50% (wt) branch­ing, and from about 3 to 7 moles of ethylene oxide per mole of fatty oxo-alcohol, and a higher ethoxylate which is the condensation product of a C16-C19 oxo-alcohol with more than 50% (wt) branching and from about 8 to 14 moles of ethylene oxide per mole of branched oxo-alcohol.
  • the liquid detergent compositions herein optionally contain a fatty acid component.
  • Preferred saturated fatty acids have from 10 to 16, more preferably 12 to 14 carbon atoms.
  • Preferred unsaturated fatty acids are oleic acid and palmitoleic acid.
  • Detergent enzymes can be used in the liquid deter­gent compositions of this invention.
  • Suit­able enzymes include the detergent proteases, amylases, lipases and cellulases.
  • Enzymatic stabilizing agents for use in aqueous liquid detergents are well known. Pre­ferred herein is a salt of formic acid, e.g., sodium for­mate. The amount of this stabilizing agent typically rang­es from 0.5% to 2%.
  • compositions contain an inorganic or organ­ic builder.
  • inorganic builders include the phosphorous-based builders, e.g., sodium tripolyphosphate, sodium pyrophosphate, and aluminosilicates (zeolites).
  • organic builders are represented by polyacids such as citric acid, nitrilotriacetic acid, and mixtures of tartrate monosuccinate with tartrate discuccinate.
  • Preferred builders for use herein are citric acid and alk(en)yl-substituted succinic acid compounds, wherein alk(en)yl contains from 10 to 16 carbon atoms.
  • alk(en)yl contains from 10 to 16 carbon atoms.
  • An example of this group of compounds is dodecenyl succinic acid.
  • Polymeric carboxylate builders inclusive of polyacrylates, polyhydroxy acrylates and polyacrylates/polymaleates copolymers can also be used.
  • compositions herein can contain a series of further optional ingredients which are mostly used in additive levels, usually below about 5%.
  • additives include : polyacids, enzymes and enzymatic stabilizing agents, suds regulants, opacifiers, agents to improve the machine compatibility in relation to enamel-coated surfaces, bactericides, dyes, perfumes, brighteners and the like.
  • liquid compositions herein can contain further additives of a level from 0.05 to 2%.
  • additives include polyaminocarboxylates such as ethylenediaminotetracetic acid, diethylenetriaminopentacetic acid, ethylenediamino disuccinic acid or the water-soluble alkali metals thereof.
  • Other additives include organo-phosphonic acids; particularly preferred are ethylenediamino tetramethylenephosphonic acid, hexamethylenediamino tetramethylenephosphonic acid, diethylenetriamino pentamethylenephosphonic acid and aminotrimethylenephosphonic acid.
  • compositions may further contain bleach stabilizers of the kinds known in the art. If a process involving the use of hydrogen peroxide is used for the preparation of the liquid detergent, typical bleach stabilizers may be present as introduced with the commercially available hdrogen peroxide. Examples of suitable bleach stabilizers include ascorbic acid, dipicolinic acid, sodium stannates and 8-hydroxyquinoline can also be included in these compositions, at levels between 0.01 and 1%.
  • the beneficial utilization of the claimed compositions under various usage conditions can require the utilization of a suds regulant. While generally all detergent suds regulants can be utilized preferred for use herein are alkylated polysiloxanes such as dimethylpolysiloxane also frequently termed silicones. The silicones are frequently used in a level not exceeding 1.5%, most preferably between 0.1% and 1.0%.
  • opacifiers can also be desirable to utilize opacifiers inasmuch as they contribute to create a uniform appearance of the concentrated liquid detergent compositions.
  • suitable opacifiers include : polystyrene commercially known as LYTRON 621 manufactured by MONSANTO CHEMICAL CORPORATION. The opacifiers are frequently used in an amount from 0.3% to 1.5%.
  • liquid detergent compositions of this invention further can comprise an agent to improve the washing machine compatibility, particularly in relation to enamel-coated surfaces.
  • additives include : sodium carboxymethylcellulose; hydroxy-C 1-6-alkylcellulose; polycarboxylic homo- or copolymeric ingredients, such as : polymaleic acid, a copolymer of maleic anhydride and methylvinylether in a molar ratio of 2:1 to 1:2; and a copolymer of an ethylenically unsaturated monocarboxylic acid monomer, having not more than 5, preferably 3 or 4 carbon atoms, for example (methyl)-acrylic acid, and an ethylenically unsaturated dicarboxylic acid monomer having not more than 6, preferably 4 carbon atoms, whereby the molar ratio of the monomers is in the range from 1:4 to 4:1, said copolymer being described in more detail in EUROPEAN Patent Application 0 066 915, filed May 17, 1982.
  • Liquid detergent compositions are prepared by mixing the listed ingredients in the stated proportions : Ingredients Composition (weight %) I II III IV V Water 33 32 26 23 34 Ethanol 14 15 18 22 11 Linear dodecylbenzene sulfonic acid 12 10 8 8 12 12 Condensation product of 1 mole of C13-C15 oxo alcohol and 7 moles of ethylene oxide 7 9 10 8 7 Sodium cocoyl sulfate 2 3 4 2 2 2 Dodecenyl succinic acid 13 10 12 15 13 Citric acid 0.8 1 1 0.8 0.8 Oleic acid 3.3 4 3 2 3.3 Protease 0.3 0.5 - 0.5 - Diethylenetriamine pentamethylene phosphonic acid 0.05 0.85 0.05 0.05 0.05 0.05 Sodium formate 0.9 1 - 1 - Sodium perborate monohydrate 10 10 12 10 10 10*) Sodium hydroxide (to adjust to) pH 9 10 9 11 8.2 Perfume, minors balance *) sodium perborate te
  • the sodium perborate compound is added after all the other ingredients have been mixed.
  • the composition is stirred overnight.
  • the resulting recrystallized perborate particles have a weight average particle diameter of about 7 micrometers.
  • compositions are prepared in the same manner.
  • a liquid detergent matrix is prepared by mixing water, the organic solvent(s), the surfactant(s), and the builder material(s). The matrix is trimmed with sodium hydroxide to a pH of 8.5-9. Metaborate powder is added under stirring. A milky suspension is obtained. Then hydrogen peroxide is added as an aqueous solution. Small crystals of perborate tetrahydrate are formed. Typically, the perborate tetrahydrate crystals have a weight average particle size of about 4 micrometers.
  • the detergent composition is cooled to out 25 deg. C prior to addition of heat sensitive ingredients, like enzymes and perfume.
  • borax may be added in lieu of metaborate.
  • the necessary amount of sodium hydroxide is added for the conversion of borax to metaborate.
  • the metaborate is then converted to perborate through addition of hydrogen peroxide. After cooling to about 25 deg. C the heat sensitive components of the composition are added.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP88201175A 1987-06-12 1988-06-08 Verfahren zur Herstellung einer Perboratbleichmittel enthaltenden wässerigen flüssigen Waschmittelzusammensetzung Revoked EP0294904B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB878713756A GB8713756D0 (en) 1987-06-12 1987-06-12 Liquid detergent
GB8713756 1987-06-12

Publications (3)

Publication Number Publication Date
EP0294904A2 true EP0294904A2 (de) 1988-12-14
EP0294904A3 EP0294904A3 (en) 1989-06-14
EP0294904B1 EP0294904B1 (de) 1994-08-17

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EP88201175A Revoked EP0294904B1 (de) 1987-06-12 1988-06-08 Verfahren zur Herstellung einer Perboratbleichmittel enthaltenden wässerigen flüssigen Waschmittelzusammensetzung

Country Status (16)

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EP (1) EP0294904B1 (de)
JP (1) JP2505537B2 (de)
KR (1) KR950013921B1 (de)
CN (1) CN1026013C (de)
AU (1) AU624328B2 (de)
CA (1) CA1307714C (de)
DE (1) DE3851096T2 (de)
DK (1) DK318088A (de)
EG (1) EG18526A (de)
FI (1) FI90786C (de)
GB (1) GB8713756D0 (de)
MX (1) MX169404B (de)
MY (1) MY103581A (de)
NZ (1) NZ224980A (de)
PH (1) PH25774A (de)
PT (1) PT87722B (de)

Cited By (22)

* Cited by examiner, † Cited by third party
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EP0368575A2 (de) * 1988-11-11 1990-05-16 Imperial Chemical Industries Plc Bleichformulierung und wässerige Waschmittelzusammensetzung
EP0378261A2 (de) * 1989-01-10 1990-07-18 The Procter & Gamble Company Enzym und Enzymstabilisationssystem enthaltendes flüssiges Waschmittel
EP0384515A1 (de) * 1989-02-22 1990-08-29 The Procter & Gamble Company Stabilisierte, Bleichmittel enthaltende, flüssige Waschmittelzusammensetzungen
US4992194A (en) * 1989-06-12 1991-02-12 Lever Brothers Company, Division Of Conopco Inc. Stably suspended organic peroxy bleach in a structured aqueous liquid
EP0429124A1 (de) * 1989-11-21 1991-05-29 The Procter & Gamble Company Chlorfreie flüssige Zusammensetzungen für die automatische Geschirreinigung
EP0430330A2 (de) * 1989-11-24 1991-06-05 The Procter & Gamble Company Suspendierfähige, flüssige Reinigungsmittel
WO1991009103A1 (en) * 1989-12-19 1991-06-27 The Procter & Gamble Company Concentrated aqueous liquid bleach compositions
WO1991012308A1 (en) * 1990-02-08 1991-08-22 Unilever N.V. Liquid bleach composition
EP0460555A1 (de) * 1990-06-06 1991-12-11 Solvay Interox GmbH Verfahren zur Herstellung von mikrokristallinen Perborat-Produkten
WO1992005238A1 (en) * 1990-09-17 1992-04-02 The Procter & Gamble Company Liquid detergent compositions
US5160655A (en) * 1989-02-27 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds
US5445756A (en) * 1990-10-22 1995-08-29 The Procter & Gamble Company Stable liquid detergent compositions containing peroxygen bleach suspended by a hydropholic silica
US5464552A (en) * 1989-11-30 1995-11-07 The Clorox Company Stable liquid aqueous oxidant detergent
WO1996001311A1 (en) * 1994-07-01 1996-01-18 Warwick International Group Limited Bleaching compositions
WO1996033258A1 (en) * 1995-04-20 1996-10-24 Albright & Wilson Uk Limited Stabilised aqueous suspensions of bleach containing perborate particles
US5597790A (en) * 1990-10-22 1997-01-28 The Procter & Gamble Company Liquid detergent compositions containing a suspended peroxygen bleach
US5681805A (en) * 1995-05-25 1997-10-28 The Clorox Company Liquid peracid precursor colloidal dispersions: microemulsions
US5776877A (en) * 1995-05-25 1998-07-07 The Clorox Company Liquid peracid precursor colloidal dispersions: macroemulsions
US5792385A (en) * 1995-05-25 1998-08-11 The Clorox Company Liquid peracid precursor colloidal dispersions: liquid crystals
US5877137A (en) * 1995-05-25 1999-03-02 The Clorox Company Liquid peracid precursor colloidal dispersions oil-core vesicles
US6080710A (en) * 1993-11-16 2000-06-27 Warwick International Group Limited Bleach activator compositions
US20120172281A1 (en) * 2010-07-15 2012-07-05 Jeffrey John Scheibel Detergent compositions comprising microbially produced fatty alcohols and derivatives thereof

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CA1327503C (en) * 1988-06-14 1994-03-08 Charles Randolph Minns Carpet cleaning composition and method of use
DE69033783T2 (de) * 1989-02-27 2002-04-18 Unilever N.V., Rotterdam Flüssiges Reinigungsmittel
CA2073432A1 (en) * 1990-02-08 1991-08-09 Johannes C. Van De Pas Liquid bleach composition
US5595801A (en) * 1991-07-30 1997-01-21 International Paper Company Laminated shielding material and method for shielding an enclosure therewith
KR100469075B1 (ko) * 2002-04-03 2005-02-02 위아 주식회사 조향장치용 토션바의 토크 감지장치

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DE1567583A1 (de) * 1966-06-08 1970-09-10 Henkel & Cie Gmbh Lagerbestaendige,als Oxydations-und Bleichmittel brauchbare,Natriumperborat enthaltende waessrige Suspensionen
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FR2140822A5 (en) * 1971-06-09 1973-01-19 Air Liquide Bleaching liquids - contg hydrogen peroxide or persalts in alkaline medium with stabilisers
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EP0293040A1 (de) * 1987-05-27 1988-11-30 The Procter & Gamble Company Flüssiges Reinigungsmittel, welches festes Peroxy-Bleichmittel enthält

Cited By (37)

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EP0368575A3 (de) * 1988-11-11 1990-07-18 Imperial Chemical Industries Plc Bleichformulierung und wässerige Waschmittelzusammensetzung
EP0368575A2 (de) * 1988-11-11 1990-05-16 Imperial Chemical Industries Plc Bleichformulierung und wässerige Waschmittelzusammensetzung
EP0378261A2 (de) * 1989-01-10 1990-07-18 The Procter & Gamble Company Enzym und Enzymstabilisationssystem enthaltendes flüssiges Waschmittel
EP0378261A3 (de) * 1989-01-10 1991-09-11 The Procter & Gamble Company Enzym und Enzymstabilisationssystem enthaltendes flüssiges Waschmittel
WO1992007055A1 (en) * 1989-01-10 1992-04-30 The Procter & Gamble Company Liquid detergent compositions containing a suspended peroxygen bleach
EP0468103A1 (de) * 1989-02-22 1992-01-29 The Procter & Gamble Company Stabilisierte, Bleichmittel enthaltende, flüssige Reinigungsmittel
EP0384515A1 (de) * 1989-02-22 1990-08-29 The Procter & Gamble Company Stabilisierte, Bleichmittel enthaltende, flüssige Waschmittelzusammensetzungen
US5264143A (en) * 1989-02-22 1993-11-23 The Procter & Gamble Company Stabilized, bleach containing, liquid detergent compositions
TR25960A (tr) * 1989-02-22 1993-11-01 Procter & Gamble Kararli hale getirilmis agartici ihtiva eden, sivi deterjan terkipleri.
WO1992001774A1 (en) * 1989-02-22 1992-02-06 The Procter & Gamble Company Stabilized bleach containing liquid detergent compositions
US5160655A (en) * 1989-02-27 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds
US4992194A (en) * 1989-06-12 1991-02-12 Lever Brothers Company, Division Of Conopco Inc. Stably suspended organic peroxy bleach in a structured aqueous liquid
EP0429124A1 (de) * 1989-11-21 1991-05-29 The Procter & Gamble Company Chlorfreie flüssige Zusammensetzungen für die automatische Geschirreinigung
EP0430330A3 (en) * 1989-11-24 1991-12-18 The Procter & Gamble Company Suspending liquid detergent compositions
TR25074A (tr) * 1989-11-24 1992-11-01 Procter & Gamble SüSPANSIYE EDICI SIVI DETERJAN TERKIPLERI.
EP0430330A2 (de) * 1989-11-24 1991-06-05 The Procter & Gamble Company Suspendierfähige, flüssige Reinigungsmittel
US5464552A (en) * 1989-11-30 1995-11-07 The Clorox Company Stable liquid aqueous oxidant detergent
WO1991009103A1 (en) * 1989-12-19 1991-06-27 The Procter & Gamble Company Concentrated aqueous liquid bleach compositions
WO1991012308A1 (en) * 1990-02-08 1991-08-22 Unilever N.V. Liquid bleach composition
EP0460555A1 (de) * 1990-06-06 1991-12-11 Solvay Interox GmbH Verfahren zur Herstellung von mikrokristallinen Perborat-Produkten
US5290476A (en) * 1990-06-06 1994-03-01 Peroxid-Chemie Gmbh Process for preparing microcrystalline perborate products
US5229028A (en) * 1990-09-17 1993-07-20 The Procter & Gamble Company Liquid detergent compositions
WO1992005238A1 (en) * 1990-09-17 1992-04-02 The Procter & Gamble Company Liquid detergent compositions
US5597790A (en) * 1990-10-22 1997-01-28 The Procter & Gamble Company Liquid detergent compositions containing a suspended peroxygen bleach
US5445756A (en) * 1990-10-22 1995-08-29 The Procter & Gamble Company Stable liquid detergent compositions containing peroxygen bleach suspended by a hydropholic silica
US6080710A (en) * 1993-11-16 2000-06-27 Warwick International Group Limited Bleach activator compositions
US5801138A (en) * 1994-07-01 1998-09-01 Warwick International Group Limited Bleaching compositions
WO1996001311A1 (en) * 1994-07-01 1996-01-18 Warwick International Group Limited Bleaching compositions
WO1996033258A1 (en) * 1995-04-20 1996-10-24 Albright & Wilson Uk Limited Stabilised aqueous suspensions of bleach containing perborate particles
US5776877A (en) * 1995-05-25 1998-07-07 The Clorox Company Liquid peracid precursor colloidal dispersions: macroemulsions
US5792385A (en) * 1995-05-25 1998-08-11 The Clorox Company Liquid peracid precursor colloidal dispersions: liquid crystals
US5877136A (en) * 1995-05-25 1999-03-02 The Clorox Company Liquid peracid precursor colloidal dispersions: Liquid crystals
US5877137A (en) * 1995-05-25 1999-03-02 The Clorox Company Liquid peracid precursor colloidal dispersions oil-core vesicles
US5954998A (en) * 1995-05-25 1999-09-21 The Clorox Company Liquid peracid precursor colloidal dispersions: oil-core vesicles
US5977044A (en) * 1995-05-25 1999-11-02 Peterson; David Liquid peracid precursor colloidal dispersions: macroemulsions
US5681805A (en) * 1995-05-25 1997-10-28 The Clorox Company Liquid peracid precursor colloidal dispersions: microemulsions
US20120172281A1 (en) * 2010-07-15 2012-07-05 Jeffrey John Scheibel Detergent compositions comprising microbially produced fatty alcohols and derivatives thereof

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DE3851096T2 (de) 1995-04-06
CA1307714C (en) 1992-09-22
EP0294904A3 (en) 1989-06-14
KR950013921B1 (ko) 1995-11-18
NZ224980A (en) 1991-01-29
AU1756088A (en) 1988-12-15
FI882782A0 (fi) 1988-06-10
FI90786C (fi) 1994-03-25
AU624328B2 (en) 1992-06-11
KR890000653A (ko) 1989-03-16
PT87722B (pt) 1992-10-30
CN1026013C (zh) 1994-09-28
EP0294904B1 (de) 1994-08-17
PH25774A (en) 1991-10-18
FI882782A (fi) 1988-12-13
DK318088A (da) 1988-12-13
DE3851096D1 (de) 1994-09-22
PT87722A (pt) 1988-07-01
GB8713756D0 (en) 1987-07-15
JPS6465200A (en) 1989-03-10
DK318088D0 (da) 1988-06-10
CN1030605A (zh) 1989-01-25
EG18526A (en) 1993-04-30
FI90786B (fi) 1993-12-15
MX169404B (es) 1993-07-01
MY103581A (en) 1993-08-28
JP2505537B2 (ja) 1996-06-12

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