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EP0240057A1 - Compositions d'activateurs de blanchiment, granulaires, libres de phosphore et leur utilisation dans des compositions détergentes de blanchiment granulaires - Google Patents

Compositions d'activateurs de blanchiment, granulaires, libres de phosphore et leur utilisation dans des compositions détergentes de blanchiment granulaires Download PDF

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Publication number
EP0240057A1
EP0240057A1 EP87200466A EP87200466A EP0240057A1 EP 0240057 A1 EP0240057 A1 EP 0240057A1 EP 87200466 A EP87200466 A EP 87200466A EP 87200466 A EP87200466 A EP 87200466A EP 0240057 A1 EP0240057 A1 EP 0240057A1
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EP
European Patent Office
Prior art keywords
granular
bleach activator
phosphorus
weight
bleach
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87200466A
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German (de)
English (en)
Other versions
EP0240057B1 (fr
EP0240057B2 (fr
Inventor
James Gavin De Bernat
Ian Donald Robb
Raymond John Wilde
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.)
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Publication date
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0240057A1 publication Critical patent/EP0240057A1/fr
Publication of EP0240057B1 publication Critical patent/EP0240057B1/fr
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • This invention relates to granular non-phosphorus-­containing bleach activator compositions, their manufacture and use in granular detergent compositions. Particularly it pertains to granular compositions containing activators for peroxygen bleaching agents in the form of organic peroxyacid bleach precursors usable in low phosphorus or phosphorus-free granular detergent bleach compositions.
  • Granular detergent compositions which contain organic bleach activators in addition to the usual detergent substances having a cleaning action, builders and peroxygen bleaching agents are known in the art.
  • the peroxygen bleaching agents commonly used are those which release hydrogen peroxide in aqueous solution, such as alkalimetal perborates, persilicates, percarbonates, perphosphates and urea peroxide. These peroxygen bleaching agents will hereinafter also be referred to as "persalts".
  • the most commonly used persalt in detergent compositions is alkalimetal perborate, particularly sodium perborate, tetrahydrate or monohydrate.
  • the organic bleach activators referred to herein are generally organic N-acyl or O-acyl compounds, or carbonic or pyrocarbonic esters, which react with hydrogen peroxide (e.g. from the persalts) in solution forming a peroxy acid or percarbonic acid, a bleaching species which, unlike the persalts, is effective in bleaching at lower temperatures, e.g. from ambient to 60°C.
  • bleach activators are amply described in literature, for example in a series of articles by Allan H. Gilbert in Detergent Age, June 1967, pages 18-20, July 1967, pages 30-33, and August 1967, pages 26, 27 and 67, and further in British Patent Specifications 836,988; 855,735; 907,356; 907,358; 970,950; 1,003,310 and 1,246,339; US Patent Specifications 3,332,882, 3,277,750, 4,128,494 and 4,412,934.
  • bleach activator compounds are generally hydrolysable materials, they need to be protected from the surrounding media when incorporated in detergent compositions.
  • any proper method of protecting the bleach activator from the environment must allow a relatively quick release or dissolution of the activator in the wash liquor. Release of the activator must be achieved at a period well before the end of the wash cycle so as to give time for the activator to react with the persalt forming the peroxyacid. Preferably this should occur as early as possible in the wash cycle for maximum bleaching to occur.
  • bleach activator granules Various compositions and forms of bleach activator granules have been proposed in the art, most of them using a phosphate, particularly sodium triphosphate, as an essential component of the granulating agent because of its typical property of imparting good structure combined with quick dispersion to the granule.
  • a representative example of such bleach activator granule compositions having good storage stability and satisfactory release is that which comprises a mixture of sodium triphosphate and potassium triphosphate as the granulating agent, currently used in the majority of commercial detergent powder formulations.
  • phosphates such as sodium triphosphate
  • non-phosphorus-containing detergency builders are the alkalimetal carbonates, such as sodium carbonate; the alkalimetal silicates, such as sodium silicate; the alumino silicates, such as the various zeolite types of alumino silicates; the nitrilotriacetic acid compounds, such as sodium nitrilotriacetate (NTA); the carboxymethyloxy succinates; sodium citrate; the various polymeric carboxylate builders, such as the oxydisuccinates, hydrofuran tetracarboxylates, O-, S-­or N-linked sulphosuccinates, oxydiacetic acid, oxidised polysaccharides, polyacrylic acids, alkyl and alkenyl succinates; soaps and sulpho fatty acid soaps; and mixtures thereof.
  • alkalimetal carbonates such as sodium carbonate
  • the alkalimetal silicates such as sodium silicate
  • Non-phosphorus-containing bleach activator granule compositions are known in the art and various methods of preparing such granules and their use in detergent compositions have been proposed.
  • an organic compound or a mixture of organic compounds were proposed as the binding or coating agent, such as for example nonionic compounds, fatty acids, fatty alcohols, waxes and polymeric materials with or without the optional use of inorganic salts.
  • German DE-OS 2,657,042 discloses a detergent composition comprising tetraacetyl ethylene diamine (TAED) in the form of granules, which consist of said TAED activator and a nonionic surfactant having a melting point of at least 35°C as the binding agent.
  • TAED tetraacetyl ethylene diamine
  • European EP-B-0051987 discloses bleach activator granule compositions comprising a bleach activator and a nonionic surfactant having a melting point of not more than 40°C as binding agent.
  • nonionics tend to bleed and cause stickiness, giving rise to caking problems, especially under hot summer temperature conditions. Migration of nonionics in the formulation would also tend to aid decomposition of bleach-sensitive ingredients owing to interaction with the oxidising bleach system. Higher melting nonionics will have poor dispersing ability, resulting in a poor release of the bleach activator, with the deleterious consequence of the granules sedimenting and being lost in the dead spaces of the washing machines, known as mechanical loss. The same applies to fatty acids, fatty alcohols and waxes.
  • EP-0070474 and EP­0037026 disclose methods of using water-­soluble cellulose ether, starch or starch ether as granulation binder for preparing bleach activator granules having a bleach activator content of from 90-­99% by weight. The methods as described here are only viable if coarse particle size bleach activators are used.
  • European Patent Application EP-0075818 discloses water-free activator granules comprising a) 70-99.5% bleach activator and b) 0.5-30% of a swelling agent, prepared by compacting the compounds a) and b) without the addition of water, optionally followed by breaking into smaller particles.
  • swelling agents are mentioned high molecular weight carbohydrates, such as starch, powdered cellulose, wood pulp; cross-linked polyvinyl pyrrolidone (PVP) and also starch ether and carboxymethyl cellulose.
  • PVP polyvinyl pyrrolidone
  • a finely divided particulate bleach activator is granulated with a mixture comprising an inert non-alkaline, non-phosphate inorganic or organic salt, a water-soluble, film-forming polymeric material of average molecular weight of from about 500­1,000,000, and a smectite or alumino silicate clay material, to form granules of a size of from about 0.2 to 2.0 mm.
  • the invention provides a granular bleach activator composition which is substantially free of phosphorus materials, the composition comprising:
  • Preferred bleach activators are the N-diacylated and N,N′-tetraacylated amines mentioned under a) above, particularly N,N,N′,N′-tetraacetyl ethylene diamine, the esters of carbonic or pyrocarbonic acids mentioned under m) and the reactive phenol esters as described in US Patent Specification 4,412,934.
  • One single activator or mixtures of two or more activators may be used as desired.
  • non-alkaline, non-phosphate inorganic salts which can be used in the invention are, for example, sodium sulphate, sodium nitrate, sodium citrate, sodium chloride, calcium sulphate and calcium chloride.
  • a preferred salt is sodium sulphate.
  • Film-forming polymeric materials which can be used in the invention are, for example, carbohydrates and derivatives, such as carbohydrate ethers; polymers or copolymers from vinyl monomers, such as vinylacetate (and its hydrolysate vinyl alcohol), vinyl pyrrolidone, methyl acrylate, acrylic acid, methacrylic acid, maleic acid (anhydride), styrene, styrene sulphonate or mixtures thereof.
  • carbohydrates and derivatives such as carbohydrate ethers
  • polymers or copolymers from vinyl monomers such as vinylacetate (and its hydrolysate vinyl alcohol), vinyl pyrrolidone, methyl acrylate, acrylic acid, methacrylic acid, maleic acid (anhydride), styrene, styrene sulphonate or mixtures thereof.
  • suitable polymeric materials are polyvinyl acetate, polyvinyl pyrrolidone, copolymers of polyvinyl alcohol/polyvinyl acetate; carboxy methyl cellulose; dextrine modified vinylacetate polymers; and homo- or copolymeric polycarboxylic acids or salts thereof, such as the polyacrylic acids or polyacrylates, copolymers of maleic acid (anhydride) and acrylic or methacrylic acid, and copolymers of maleic acid (anhydride) and vinyl-methyl ether.
  • the smectite clay materials usable in the present invention are preferably selected from the group consisting of alkali and alkaline earth metal montmorillonites, saponites and hectorites, and particularly those having an ion-exchange capacity of at least about 50 meq/100 g.
  • illite, attapulgite and kaolinite clays can also be used in the instant invention.$
  • the clay minerals used in the instant compositions can be described as expandable, three-layer clays, in which a sheet of aluminium/oxygen atoms or magnesium/oxygen atoms lies between two layers of silicon/oxygen atoms, i.e. alumino-slicates and magnesium silicates.
  • the term "expandable” as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water.
  • the three-layer expandable clays used therein are examples of the clay minerals classified geologically as smectites.
  • the dioctahedral minerals are primarily trivalent metal ion-based clays and are comprised of the prototype pyrophyllite and the members montmorillonite (OH)4Si 8-y Al y (Al 4-x Mg x )O20, nontronite (OH)4Si 8-y Al 4-x Fe x )O20 and volchonkoite (OH)4Si 8-y Al y (Al 4-x Cr x )O20, where x has a value of from 0 to about 2.0.
  • the trioctahedral minerals are primarily divalent metal ion based and comprise the prototype talc and the members hectorite (OH)4Si 8-y Al y (Mg 6-x Li x )O20, saponite (OH)4(Si 8-y Al y )(Mg 6-x Al x )O20, sauconite (OH)4-Si 8-y Al y (Zn 6-x Al x )O20, vermiculite (OH)4Si 8-y Al y (Mg 6-x Fe x )O20, wherein y has a value of 0 to about 2.0 and x has a value of 0 to about 6.0.
  • smectite clay minerals are:
  • smectite clays useful in the compositions herein are commercially available under various trade-­names, for example, Thixo-Jel 1 and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volclay 325, from American Colloid Co., Skokie, Illinois; and Veegum F, from R.T.Vanderbilt. It is to be recognized that such smectite minerals obtained under the foregoing tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures of the smectite minerals are suitable for use herein.
  • montmorillonite Within the classes of montmorillonite, hectorite, and saponite clay minerals, certain clays are preferred. For example, Gelwhite GP, Volclay BC and certain smectite clays marketed under the name "bentonite”.
  • Bentonite in fact, is a rock type originating from volcanic ash and contains montmorillonite (one of the smectite clays) as its principal clay component.
  • montmorillonite one of the smectite clays
  • the Table shows that materials commercially available under the name bentonite can have a wide range of cation exchange capacities. Each of these bentonites can in principle be used in the present invention without problems arising.
  • alumino silicate clay materials usable in the present invention are normally commercially available and can be naturally occurring or synthetically derived.
  • Preferred synthetic crystalline alumino silicate ion-­exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
  • the level of such clay materials for use as binder component in the granular bleach activator composition may be as low as about 0.5% and can be increased up to about 15% by weight.
  • the granular bleach activator compositions will comprise:
  • Water may be present in an amount of up to about 4.5%, preferably up to 3%.
  • the invention has particular applicability to non-phosphorus detergent compositions, although it should be appreciated that its use in other detergent compositions is not excluded.
  • the invention provides a detergent bleach composition which is substantially free of phosphorus-containing material, comprising:
  • the effective amount of the detergent active compound or compounds used in the composition is generally in the range from 5 to 40% by weight, preferably not more than 30% by weight of the composition.
  • a second essential ingredient of the composition is a non-phosphorus-containing detergency builder which may be present in an amount of from 5-80% by weight of the composition.
  • Preferred non-phosphorus-containing detergency builders are:
  • Groups of other non-phosphorus detergency builders are known in the art and described in a number of patent publications, such as the sodium carboxy methyloxy disuccinates; citric acid; mellitic acid; benzene polycarboxylic acids; and the polyacetalcarboxylates as disclosed in US Patent Specification 4,144,226.
  • a soap is used as a detergent active material, it may be present in such a quantity that it will also contribute as an additional builder.
  • the amount of peroxygen bleaching agent used in the compositions of the invention will generally be from 5% to 30% by weight, preferably from 7% to 25% by weight.
  • the amount of non-phosphorus bleach activator granules incorporated in the compositions will depend on the bleach activator content of the granule composition and should be from 0.5% to 15% by weight, more preferably from 1.5% to 10% by weight, calculated as pure bleach activator.
  • bleach activator As used in preparing the granular bleach activator compositions, it is preferred that its particle size should be less than 200 micrometre, more preferably 150 micrometre. Bleach activators having a major proportion of particle size of between 50 micrometre to 150 micrometre as described in GB Patent Specification 2,053,998 are particularly suitable.
  • the detergent compositions in which the granular non­phosphorus bleach activator compositions are incor­porated can optionally contain any of the conventional ingredients in the amounts in which such ingredients are normally employed in fabric washing detergent compositions.
  • One such optional ingredient is an alkalimetal silicate, particularly sodium, neutral, alkaline, meta­or orthosilicate.
  • a low level of silicate for example 2-10% by weight, is usually advantageous in decreasing the corrosion of metal parts in fabric washing machines and it may give processing benefits. If higher levels of silicate are used up to a practical maximum of 30%, for example from 10% to 20% by weight, there can be a more noticeable improvement in detergency, which may permit some decrease in the water-soluble carbonate material content. This effect appears to be particularly beneficial when the wash liquor is used in water with appreciable levels of magnesium hardness.
  • the amount of silicate can also be used to some extent to control the equilibrium pH of the wash liquor, which is generally within the range of 9-11, preferably 10-11, for an aqueous solution of the composition at the recommended concentration. It should be noted that a higher pH (i.e. over pH 10.5) tends to be more efficient as regards detergency, but it may be less desirable for domestic safety.
  • Sodium silicate is commonly supplied in concentrated aqueous solution or in concentrated powder form, but the amounts are calculated on an anhydrous basis.
  • Examples of other optional ingredients include the lather boosters, such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids, lather depressants, fabric softening agents, inorganic salts, such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes, such as proteases and amylases, germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids
  • lather depressants such as the lather depressants
  • fabric softening agents such as sodium sulphate
  • fluorescent agents such as sodium sulphate
  • perfumes such as acetylases
  • germicides and colourants particularly when the composition does not contain an anionic detergent active material, it can be beneficial to include an anti-ashing material to reduce the deposition of calcium carbonate on to fabrics.
  • the detergent compsitions may be produced by any of the techniques commonly employed in the manufacture of fabric washing detergent compositions, including particularly slurry-making and spray-drying processes for the manufacture of detergent powders.
  • a solid feed consisting of a mixture of 90% TAED and 10% sodium sulphate was sprayed with the proper amount of an aqueous mixture consisting of 5% Gantrez AN 119, 10% kaolin and 85% water in a Schugi Flexomix 160 Apparatus.
  • the product was aerated to dry and obtain a product of the above composition with the following properties:

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Detergent Compositions (AREA)
EP87200466A 1986-03-25 1987-03-12 Compositions d'activateurs de blanchiment, granulaires, libres de phosphore et leur utilisation dans des compositions détergentes de blanchiment granulaires Expired - Lifetime EP0240057B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8607388 1986-03-25
GB868607388A GB8607388D0 (en) 1986-03-25 1986-03-25 Activator compositions

Publications (3)

Publication Number Publication Date
EP0240057A1 true EP0240057A1 (fr) 1987-10-07
EP0240057B1 EP0240057B1 (fr) 1989-03-01
EP0240057B2 EP0240057B2 (fr) 1993-09-22

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ID=10595210

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87200466A Expired - Lifetime EP0240057B2 (fr) 1986-03-25 1987-03-12 Compositions d'activateurs de blanchiment, granulaires, libres de phosphore et leur utilisation dans des compositions détergentes de blanchiment granulaires

Country Status (9)

Country Link
EP (1) EP0240057B2 (fr)
JP (1) JPH0645800B2 (fr)
AU (1) AU587315B2 (fr)
CA (1) CA1299460C (fr)
DE (1) DE3760055D1 (fr)
ES (1) ES2008046T5 (fr)
GB (1) GB8607388D0 (fr)
TR (1) TR24553A (fr)
ZA (1) ZA872199B (fr)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299575A1 (fr) * 1987-07-14 1989-01-18 The Procter & Gamble Company Compositions détergentes
EP0268170A3 (en) * 1986-11-15 1990-01-31 Henkel Kommanditgesellschaft Auf Aktien Bleaching composition with a constant shelf-life and with improved solution ability
EP0415472A3 (en) * 1989-08-21 1991-04-03 Unilever Nv Granulated bleach activator particles
EP0373743A3 (fr) * 1988-10-14 1991-07-17 The Clorox Company Détergent contenant des granulés stables d'activateur de blanchiment
EP0482806A1 (fr) * 1990-10-23 1992-04-29 WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) Formulations d'activateur de blanchiment
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
WO1993025651A1 (fr) * 1992-06-18 1993-12-23 Unilever N.V. Composition pour le lavage de la vaisselle en machine
US5286401A (en) * 1989-11-21 1994-02-15 Basf Aktiengesellschaft Use of heterocyclic compounds as bleach activators or optical brighteners in washing and cleaning agents
GB2294707A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching composition
EP0710716A2 (fr) 1994-11-02 1996-05-08 Hoechst Aktiengesellschaft Activateurs de blanchiment sous forme granulaire et leur production
EP0790244A1 (fr) 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
EP0713910A3 (fr) * 1994-11-05 1998-02-25 The Procter & Gamble Company Compositions détergentes
WO1999014302A1 (fr) * 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment sous forme de granules
WO1999014306A3 (fr) * 1997-09-16 1999-05-14 Clariant Gmbh Activateurs de blanchiment sous forme de granules stables au stockage
EP0794988A4 (fr) * 1994-11-29 1999-08-04 Procter & Gamble Compositions comportant un precurseur d'agent de blanchiment a base de peroxyacde
US5969171A (en) * 1997-07-01 1999-10-19 Clariant Gmbh Metal complexes as bleach activators
US5998645A (en) * 1997-05-07 1999-12-07 Clariant Gmbh Bleaching-active metal complexes
US6214785B1 (en) 1998-09-09 2001-04-10 Clariant Gmbh Bleach activator granules
US6365562B1 (en) 2000-04-20 2002-04-02 Clariant Gmbh Laundry detergents and cleaners comprising bleaching-active dendrimer ligands and metal complexes thereof
US6545147B1 (en) 1999-09-10 2003-04-08 Clariant Gmbh Bleaching-active metal complexes

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8607387D0 (en) * 1986-03-25 1986-04-30 Unilever Plc Activator compositions
GB8810630D0 (en) * 1988-05-05 1988-06-08 Unilever Plc Process for preparing bodies containing peroxyacid & compositions comprising said bodies
EP1894993A1 (fr) * 2006-08-28 2008-03-05 Süd-Chemie Ag Additif détergent au base de minéraux d'argile et des copolymers contenant du PVP

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051987A1 (fr) * 1980-11-06 1982-05-19 THE PROCTER & GAMBLE COMPANY Compositions d'activeurs pour blanchiment, leur préparation et leur application dans des compositions détergentes granuleuses
FR2500475A1 (fr) * 1981-02-26 1982-08-27 Colgate Palmolive Co Perles de base destinees a la fabrication de compositions detergentes, procede et melanges pour leur fabrication et compositions detergentes les contenant
EP0075818A2 (fr) * 1981-09-28 1983-04-06 BASF Aktiengesellschaft Activateur de blanchiment granulaire
EP0098108A1 (fr) * 1982-06-25 1984-01-11 Unilever Plc Composition détergente

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
GB8328017D0 (en) * 1983-10-19 1983-11-23 Unilever Plc Detergent powders
CA1275019A (fr) * 1985-10-09 1990-10-09 The Procter & Gamble Company Compositions detergentes granulees a solubilite accrue

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051987A1 (fr) * 1980-11-06 1982-05-19 THE PROCTER & GAMBLE COMPANY Compositions d'activeurs pour blanchiment, leur préparation et leur application dans des compositions détergentes granuleuses
FR2500475A1 (fr) * 1981-02-26 1982-08-27 Colgate Palmolive Co Perles de base destinees a la fabrication de compositions detergentes, procede et melanges pour leur fabrication et compositions detergentes les contenant
EP0075818A2 (fr) * 1981-09-28 1983-04-06 BASF Aktiengesellschaft Activateur de blanchiment granulaire
EP0098108A1 (fr) * 1982-06-25 1984-01-11 Unilever Plc Composition détergente

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0268170A3 (en) * 1986-11-15 1990-01-31 Henkel Kommanditgesellschaft Auf Aktien Bleaching composition with a constant shelf-life and with improved solution ability
EP0299575A1 (fr) * 1987-07-14 1989-01-18 The Procter & Gamble Company Compositions détergentes
EP0373743A3 (fr) * 1988-10-14 1991-07-17 The Clorox Company Détergent contenant des granulés stables d'activateur de blanchiment
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
EP0415472A3 (en) * 1989-08-21 1991-04-03 Unilever Nv Granulated bleach activator particles
AU630999B2 (en) * 1989-08-21 1992-11-12 Unilever Plc Granulated bleach activator particles
US5286401A (en) * 1989-11-21 1994-02-15 Basf Aktiengesellschaft Use of heterocyclic compounds as bleach activators or optical brighteners in washing and cleaning agents
EP0482806A1 (fr) * 1990-10-23 1992-04-29 WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) Formulations d'activateur de blanchiment
WO1993025651A1 (fr) * 1992-06-18 1993-12-23 Unilever N.V. Composition pour le lavage de la vaisselle en machine
US5716569A (en) * 1994-11-02 1998-02-10 Hoechst Aktiengesellschaft Granulated bleaching activators and their preparation
EP0710716A3 (fr) * 1994-11-02 1998-07-08 Clariant GmbH Activateurs de blanchiment sous forme granulaire et leur production
EP0710716A2 (fr) 1994-11-02 1996-05-08 Hoechst Aktiengesellschaft Activateurs de blanchiment sous forme granulaire et leur production
GB2294707A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching composition
EP0713910A3 (fr) * 1994-11-05 1998-02-25 The Procter & Gamble Company Compositions détergentes
EP0794988A4 (fr) * 1994-11-29 1999-08-04 Procter & Gamble Compositions comportant un precurseur d'agent de blanchiment a base de peroxyacde
EP0790244A1 (fr) 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
US5998645A (en) * 1997-05-07 1999-12-07 Clariant Gmbh Bleaching-active metal complexes
US5969171A (en) * 1997-07-01 1999-10-19 Clariant Gmbh Metal complexes as bleach activators
WO1999014306A3 (fr) * 1997-09-16 1999-05-14 Clariant Gmbh Activateurs de blanchiment sous forme de granules stables au stockage
WO1999014302A1 (fr) * 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment sous forme de granules
US6063750A (en) * 1997-09-16 2000-05-16 Clariant Gmbh Bleach activator granules
US6270690B1 (en) 1997-09-16 2001-08-07 Clariant Gmbh Storage stable bleach activator granules
US6214785B1 (en) 1998-09-09 2001-04-10 Clariant Gmbh Bleach activator granules
US6545147B1 (en) 1999-09-10 2003-04-08 Clariant Gmbh Bleaching-active metal complexes
US6365562B1 (en) 2000-04-20 2002-04-02 Clariant Gmbh Laundry detergents and cleaners comprising bleaching-active dendrimer ligands and metal complexes thereof

Also Published As

Publication number Publication date
AU7050787A (en) 1987-10-01
DE3760055D1 (en) 1989-04-06
GB8607388D0 (en) 1986-04-30
ES2008046T5 (es) 1995-08-01
TR24553A (tr) 1991-11-21
JPS62240395A (ja) 1987-10-21
ZA872199B (en) 1988-11-30
JPH0645800B2 (ja) 1994-06-15
ES2008046B3 (es) 1989-07-01
AU587315B2 (en) 1989-08-10
EP0240057B1 (fr) 1989-03-01
EP0240057B2 (fr) 1993-09-22
CA1299460C (fr) 1992-04-28

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