EP0200163A2 - Agent de blanchiment, sa préparation et son utilisation - Google Patents

Agent de blanchiment, sa préparation et son utilisation Download PDF

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Publication number
EP0200163A2
EP0200163A2 EP86105669A EP86105669A EP0200163A2 EP 0200163 A2 EP0200163 A2 EP 0200163A2 EP 86105669 A EP86105669 A EP 86105669A EP 86105669 A EP86105669 A EP 86105669A EP 0200163 A2 EP0200163 A2 EP 0200163A2
Authority
EP
European Patent Office
Prior art keywords
acid
weight
granules
bleaching agent
agent according
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
EP86105669A
Other languages
German (de)
English (en)
Other versions
EP0200163A3 (en
EP0200163B1 (fr
Inventor
Jochen Dr. Jacobs
Edgar Dr. Köppelmann
Martin Dr. Witthaus
Manfred Dr. Dankowski
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6269591&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0200163(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86105669T priority Critical patent/ATE46916T1/de
Publication of EP0200163A2 publication Critical patent/EP0200163A2/fr
Publication of EP0200163A3 publication Critical patent/EP0200163A3/de
Application granted granted Critical
Publication of EP0200163B1 publication Critical patent/EP0200163B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • the present invention relates to bleaching agents in granular form which contain solid aliphatic peroxycarboxylic acid as the bleaching component.
  • Bleaching agents based on peroxygen compounds are widely used in the field of textile bleaching.
  • hydrogen peroxide and its inorganic derivatives such as sodium perborate and sodium percarbonate
  • they are very safe to handle, mild oxidizing agents and on the other hand they have a good bleaching capacity at sufficiently high temperatures.
  • stronger oxidizing agents such as peroxycarboxylic acids
  • peroxycarboxylic acids also called percarboxylic acids or simply peracids, are very aggressive oxidizing agents that tend to exothermic decomposition and explosion, and cannot be handled in pure form without protective measures.
  • Belgian patent 560 389 describes the stabilization of solid peroxycarboxylic acids with the aid of hydratable inorganic salts, whereby granulation is also possible.
  • the conversion into the granulated form is particularly desirable when the percarboxylic acids are to be mixed with other components, but which, for. B. may not come into direct contact with the peracids because of their oxidation sensitivity.
  • German Offenlegungsschrift 2,422,691 mentions a special embodiment of the stabilization with salts, in which mixtures of magnesium sulfate with little sodium or potassium sulfate are used.
  • the measures described have solved a number of problems with the use of peroxycarboxylic acids, it has so far been far from a percarboxylic acid formulation which meets all requirements for safe handling, mechanical and chemical stability, solubility and economical production.
  • the granules made from peracids and inorganic salts are sufficiently desensitized. Forms; however, they are only slightly resistant to abrasion, so that in many cases it is not possible to prevent the release of the peroxycarboxylic acids from the granules during storage and thus the oxidation of other sensitive components of the bleaching preparations which contain these granules.
  • coating substances improves the mechanical properties of the granules and reduces the interaction with other comporents, but has other disadvantages, such as poor chemical stability with some hydrophilic coating substances or hinders the dissolution in water with hydrophobic coatings or those made from anhydrous surfactants.
  • the object of the present invention was to find a preparation form of solid aliphatic peroxycarboxylic acids which is improved compared to the prior art.
  • a bleaching agent in the form of a uniformly composed granulate which contains solid aliphatic peroxycarboxylic acid and hydratable inorganic salt and which is characterized in that it contains an organic polymer compound which is soluble in an alkaline aqueous medium as the granulating auxiliary, all components uniformly in the individual granules of the granules are distributed and the granules in water alone give a pH in the weakly acidic range.
  • This peroxycarboxylic acid formulation is a sufficiently desensitized, abrasion-resistant and dust-free and therefore easy to handle form of the solid aliphatic peracids.
  • the granules quickly dissolve in water or an alkaline aqueous medium, so that the peracids contained without delay as bleaching agents in the Fleet are available.
  • the peracids are chemically unusually stable in this form and can therefore be stored for a long time even under unfavorable conditions.
  • the granules can be produced in a simple manner by means of build-up granulation in a one-step process.
  • the peracid granules according to the invention can generally be used wherever the percarboxylic acids contained can advantageously be used as oxidizing agents, bleaching agents or disinfectants.
  • the preferred field of application is fiber and textile bleaching, and here in particular the bleaching of textiles in the washing process.
  • a particular advantage of the granules is their compatibility with other detergent constituents, in particular alkaline substances and components sensitive to oxidation, which makes it possible to mix the peracids with the detergents without further measures and to store them in this form.
  • Diperoxycarboxylic acids with 6 - 22 C atoms of which in turn the unbranched ⁇ , ⁇ -diperoxydicarboxylic acids with 9-13 C atoms are of outstanding importance because of their particularly good bleaching action.
  • the peroxycarboxylic acids should be solid as pure compounds at room temperature, in particular up to 50 ° C. Those peracids which are also of technical quality, ie. i.e. are solid with a clear content of the underlying carboxylic acid up to 50 ° C.
  • the content of peracids in the granules is 3 to 50% by weight, preferably 5 to 30% by weight, and in particular 7 to 20% by weight.
  • Suitable hydratable inorganic salts for the granules according to the invention are salts of sodium, potassium, magnesium, calcium and aluminum with oxidation-stable anions of mineral acids, insofar as these salts can form defined hydrates and do not react alkaline in water.
  • Examples of such salts are NaH PC L and KAl (SO 4 ) 2 .
  • Sodium sulfate and magnesium sulfate are preferably used; a mixture of sodium sulfate and magnesium sulfate in a ratio of 2: 1 to 40: 1, preferably 5: 1 to 25: 1 (based on the anhydrous forms) is particularly preferred.
  • the content of inorganic salt in the granules is 40-95 percent by weight, preferably 70-92 percent by weight, but in particular 75-90 percent by weight, also based on the anhydrous form of the salt.
  • the granulation aid is of particular importance.
  • Organic polymer compounds which are soluble in an alkaline aqueous medium such as soluble cellulose or starch derivatives or soluble, fully synthetic polymers, are suitable. Examples include methyl cellulose, solid polyethylene oxides, polyvinyl pyrrolidone and polymeric carboxylic acids.
  • the homopolymers of acrylic acid, maleic acid and crotonic acid and their copolymers are preferably used with one another and with other monomers, in particular polyacrylic acid, maleic acid.
  • Polymers containing carboxyl groups are preferably in the acid form, but can also be used partially as salts, provided that these do not react in an alkaline manner.
  • the amount of polymeric granulation aid is preferably 0.2-10 percent by weight and in particular 0.5-4 percent by weight of the finished bleaching agent.
  • the granulation auxiliaries in the amounts used do not impair the chemical stability of the peracids, so that the bleaching activity of the products is largely retained even when stored for a long time.
  • various additives however, it is often still possible to increase stability.
  • chelating agents for heavy metals in particular in amounts of up to 2 percent by weight, preferably 0.1-1 percent by weight, can have an advantageous effect on the maintenance of the active oxygen during storage and / or during the bleaching process in solution.
  • polyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, and their salts are used.
  • surfactants do not adversely affect the storage stability of the granules even if they are incorporated evenly into the grains.
  • These are certain anionic surfactants, namely the salts of long-chain monoalkylsulfuric acid esters (alcohol sulfates), in particular the fatty alcohol sulfates and the salts of sulfuric acid semiesters of the reaction products from long-chain alcohols, in particular from fatty alcohols, with ethylene oxide (ether sulfates).
  • these surfactants seem to improve storage stability in some cases and have a positive effect on the bleaching results that can be achieved with the granules.
  • the proportion of these surfactants in the granules can be up to 10 percent by weight; it is preferably between 1 and 5 percent by weight.
  • the finished granulated bleaching agents contain water in amounts of up to 20 percent by weight, preferably in amounts between 0.5 and 5 percent by weight.
  • the amount of water contained is always smaller than the amount that can be calculated as the maximum possible hydrate water content from the salt content of the granules.
  • the water content of the granules is due to the manufacturing process. The presence of water has a beneficial effect on the phlegmatization of peracids, but it is not absolutely necessary for this purpose.
  • constituents can also be incorporated into the granules, provided that they do not negatively influence the positive properties of the basic composition.
  • additional desensitizing agents substances for modifying the flowability or solubility and buffer substances, In any case, it must be ensured that no alkaline materials are used and that the granules react weakly acidic. They should have a pH in water (0.5% lg) of between 3 and 7, preferably between 4 and 6. Compliance with these requirements is essential for the chemical stability of the granules.
  • Granulation processes are suitable for the production of the granules, in which strong thermal and mechanical loads which could lead to the decomposition of the peracids are avoided.
  • Build-up granulation methods such as fluidized bed granulation, roll granulation in rotating drums or on granulation plates and mixed granulation, of which in turn the mixed granulation method, in particular in mixers with rotating tools, such as e.g. B. the Patterson-Kelly mixer, the Lödige mixer and the Forberg mixer, are particularly preferred.
  • premixes which can be handled safely, such as those obtained in the production of the percarboxylic acids, for example in accordance with German Offenlegungsschrift 29 30 546.
  • Such premixes contain, based on dry matter, about 10 to 90 percent by weight of the solid aliphatic peroxycarboxylic acid, in addition to it portions of the underlying carboxylic acid (due to insufficient conversion during conversion into the peracid), traces of hydrogen peroxide and inorganic salts, in particular Na 2 SO 4 and MgSO 4 .
  • a particular advantage is that the granules according to the invention are used to produce them
  • Peracid premixes do not have to be dried, but can be used in a moist form, such as is initially obtained during production.
  • the water content of the premixes can also be above the maximum amount that can be fixed in the salts as water of hydration.
  • the solid peracid or, preferably, the peracid premix with other solid constituents of the granules are introduced into the granulation apparatus, for example a Patterson-Kelly V mixer or a Lödige ploughshare mixer, and premixed intensively.
  • Water or a solution or suspension of granulate constituents in water, preferably an aqueous solution of the granulating aid is then introduced in finely divided form with constant movement and the movement of the apparatus is continued until a uniform distribution of all constituents has occurred and the desired particle size range of the granules has formed Has.
  • the amount of water is preferably chosen so that the wet granules primarily formed have between 8 and 30 percent by weight water.
  • the starting materials already contain enough water metering in during the course of the granulation can also be dispensed with.
  • the mixed granulation described can take place at room temperature, but also at a slightly elevated temperature of up to about 45 ° C., preferably between 32 and 40 ° C.
  • the granulation can be followed by drying of the granules, which can optionally be carried out in the same apparatus, but also with the aid of other gentle processes, for example in a fluidized bed process. Post-dried granules are particularly preferred when the ballast-free peracid formulation is important. If the granules are obtained by a process which provides a very wide particle size distribution, screening of the finished material and recycling of the undesired particle sizes, if appropriate after grinding, may be appropriate.
  • the resulting peracid granules are characterized by high mechanical stability, in particular by resistance to abrasion. They can be produced in various grain sizes, especially in the range 0.1 to 5 mm. The range from 0.4 to 1.6 mm is of particular importance for incorporation into detergent, while coarser granules with grain sizes in the range from 1.6 to 4 mm can also be preferred for independently used special products.
  • the granules according to the invention generally have bulk densities between 400 and 1200 grams per liter, preferably between 500 and 1000 g / l.
  • a particularly preferred area of application of the bleaching agents according to the invention is the bleaching of textiles in connection with a washing treatment.
  • the granules can be used for this purpose in a uniform form, i.e. without further admixtures, but they are preferably made up as sprinkle-free mixtures with other solid active substances which are necessary for textile treatment.
  • a bleaching agent based on the granules according to the invention can contain, for example, alkalizing agents, peracid activators and possibly other bleaching agents, such as perborate, as further active ingredients.
  • furthermore, in particular surfactants, builders, foam-suppressing substances and optical brighteners should be mentioned as active ingredients.
  • the excellent mechanical and chemical stability of the granules and their compatibility with the surrounding materials have a particularly advantageous effect, in particular on the storage stability of the finished products.
  • Example 2 In the same mixer as in Example 1, 1.655 kg of dry desensitized. Diperoxybrassylic acid (content in% by weight: peracid 26.7; Na 2 SO 4 70.8; brassylic acid 2.5), 2.56 kg of anhydrous Na 2 SO 4 and 0.26 kg MgSO 4 'H 2 0 (water content 30%) for 3 min. mixed at about 20 rpm. The spray wave was then over a period of 0.5 min. 0.42 kg of a solution of polyacrylic acid (19% by weight in H 2 O) are injected. After a post-mixing time of 1.5 min. a wet granulate had formed, which was then 20 min.
  • the bleaching tests were carried out in household drum washing machines at a liquor temperature of up to 30 ° C. and a washing time of 15 minutes. carried out, so that differences in the dissolution behavior of the granules were particularly evident.
  • the wash liquor (20 l per machine) contained 120 g of a detergent of the following composition:

Landscapes

  • 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)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Glanulating (AREA)
EP86105669A 1985-05-02 1986-04-24 Agent de blanchiment, sa préparation et son utilisation Expired EP0200163B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86105669T ATE46916T1 (de) 1985-05-02 1986-04-24 Bleichwirkstoff, seine herstellung und seine verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853515712 DE3515712A1 (de) 1985-05-02 1985-05-02 Bleichwirkstoff, seine herstellung und seine verwendung
DE3515712 1985-05-02

Publications (3)

Publication Number Publication Date
EP0200163A2 true EP0200163A2 (fr) 1986-11-05
EP0200163A3 EP0200163A3 (en) 1987-09-16
EP0200163B1 EP0200163B1 (fr) 1989-10-04

Family

ID=6269591

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86105669A Expired EP0200163B1 (fr) 1985-05-02 1986-04-24 Agent de blanchiment, sa préparation et son utilisation

Country Status (6)

Country Link
US (1) US5091106A (fr)
EP (1) EP0200163B1 (fr)
JP (1) JPS61258072A (fr)
AT (1) ATE46916T1 (fr)
DE (2) DE3515712A1 (fr)
ES (1) ES8704566A1 (fr)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0273334A1 (fr) * 1986-12-27 1988-07-06 Henkel Kommanditgesellschaft auf Aktien Procédé pour la production de concentrés de peracides s'écoulant librement, stable à partir de granulation à rendre compact
EP0256443A3 (fr) * 1986-08-15 1988-12-14 Unilever N.V. Composition à base d'acide peroxydé et son utilisation dans des compositions détergentes
EP0212976A3 (en) * 1985-08-21 1988-12-21 The Clorox Company Stable peracid bleaching composition
EP0214789A3 (en) * 1985-08-21 1989-04-26 The Clorox Company Dry peracid based bleaching product
US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
EP0347988A1 (fr) * 1988-06-22 1989-12-27 Akzo N.V. Compositions de blanchiment aqueuses et stables pouvant être versées, comprenant un péroxide d'acide organique solide à au moins deux polymères
EP0376360A1 (fr) * 1988-11-25 1990-07-04 Akzo Nobel N.V. Procédé pour la préparation d'agents de blanchiment granulés
EP0340847A3 (fr) * 1988-05-05 1990-10-03 Unilever N.V. Procédé de préparation de corps contenant un composé d'un peroxyacide et compositions comprenant les dits corps
EP0360323A3 (fr) * 1988-09-20 1990-11-07 Unilever N.V. Compositions de blanchiment et procédé de préparation
US5030381A (en) * 1988-07-06 1991-07-09 Huels Aktiengesellschaft Process for the preparation of stabilized aliphatic diperoxydicarboxylic acids
US5055218A (en) * 1990-04-13 1991-10-08 The Procter & Gamble Company Bleach granules containing an amidoperoxyacid
EP0421664A3 (en) * 1989-10-02 1991-12-18 Rohm And Haas Company Polymer-containing granulates
EP0396341A3 (fr) * 1989-05-01 1992-01-22 The Procter & Gamble Company Granulé de blanchiment aggloméré à base de peroxyacide et procédé de préparation
US5093021A (en) * 1985-08-21 1992-03-03 The Clorox Company Encapsulated enzyme in dry bleach composition
US5126066A (en) * 1988-06-22 1992-06-30 Akzo N.V. Stable, pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
EP0468824A3 (en) * 1990-07-27 1992-07-01 Warwick International Group Plc Granular compositions
EP0453970A3 (en) * 1990-04-21 1992-08-05 Hoechst Aktiengesellschaft Stable granulates of peroxycarbonic acids
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
TR25837A (tr) * 1990-05-31 1993-09-01 Procter & Gamble KüLCELENDIRILMIS PEROKSIASIT AGARTICI GRANüLü VE BUNU YAPMAYA MAHSUS YÖNTEM.
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
US5279757A (en) * 1990-04-06 1994-01-18 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof
US5296156A (en) * 1988-11-25 1994-03-22 Akzo N.V. Bleaching granules
US5358654A (en) * 1988-06-22 1994-10-25 Akzo Nobel N.V. Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
US5518650A (en) * 1991-05-04 1996-05-21 Hoechst Aktiengesellschaft Imidocarboxylic acid activators and sulfimidocarboxylic acid activators, processes for their preparation and their use
WO2015118357A3 (fr) * 2014-02-10 2015-12-03 Revolymer (U.K) Limited Nouvelle particule contenant un peracide

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5234617A (en) * 1992-04-20 1993-08-10 Kathleen B. Hunter Aqueous liquid bleach compositions with fluorescent whitening agent and polyvinyl pyrrolidone or polyvinyl alcohol
EP0592033A1 (fr) * 1992-10-07 1994-04-13 The Procter & Gamble Company Procédé pour fabriquer des particules contenant des peroxyacides
US5409632A (en) * 1992-11-16 1995-04-25 The Procter & Gamble Company Cleaning and bleaching composition with amidoperoxyacid
US5932532A (en) * 1993-10-14 1999-08-03 Procter & Gamble Company Bleach compositions comprising protease enzyme
AU3686895A (en) * 1994-09-26 1996-04-19 Fmc Corporation Stable peracid sols, gels and solids and a process therefor
US6017865A (en) * 1995-12-06 2000-01-25 The Procter & Gamble Company Perfume laundry detergent compositions which comprise a hydrophobic bleaching system
AU2075097A (en) * 1996-03-15 1997-10-01 Amway Corporation Discrete whitening agent particles, method of making, and powder detergent containing same
WO1997033957A1 (fr) * 1996-03-15 1997-09-18 Amway Corporation Composition detergente en poudre presentant une solubilite amelioree
US5714450A (en) * 1996-03-15 1998-02-03 Amway Corporation Detergent composition containing discrete whitening agent particles
US5714451A (en) * 1996-03-15 1998-02-03 Amway Corporation Powder detergent composition and method of making
US6177397B1 (en) 1997-03-10 2001-01-23 Amway Corporation Free-flowing agglomerated nonionic surfactant detergent composition and process for making same
GB2345701A (en) * 1999-01-12 2000-07-19 Procter & Gamble Particulate bleaching components
EP1187906A1 (fr) * 1999-06-21 2002-03-20 The Procter & Gamble Company Compositions de detergent
DE10361100A1 (de) * 2003-06-13 2005-01-05 Henkel Kgaa Lagerstabile Kapseln auf Basis von Peroxycarbonsäuren
US8034759B2 (en) * 2008-10-31 2011-10-11 Ecolab Usa Inc. Enhanced stability peracid compositions

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA651777A (en) * 1962-11-06 Unilever Limited Bleaching compositions
DE1240508B (de) * 1963-04-01 1967-05-18 Degussa Verfahren zur Granulierung von Perborat
US3639285A (en) * 1969-07-23 1972-02-01 Ppg Industries Inc Novel bleaching compositions and use thereof
US3770816A (en) * 1969-07-23 1973-11-06 Ppg Industries Inc Diperisophthalic acid compositions
US3664961A (en) * 1970-03-31 1972-05-23 Procter & Gamble Enzyme detergent composition containing coagglomerated perborate bleaching agent
GB1387167A (en) * 1972-09-28 1975-03-12 Procter & Gamble Ltd Bleaching agent
DE2422691A1 (de) * 1973-05-14 1974-12-05 Procter & Gamble Stabile bleichmittel
CA1029153A (fr) * 1973-05-14 1978-04-11 Thomas W. Gougeon Compose de blanchiment et mode d'emploi
CA1001361A (en) * 1973-05-16 1976-12-14 Ppg Industries, Inc. Bleaching formulation
DE2413561A1 (de) * 1974-03-21 1975-10-02 Henkel & Cie Gmbh Lagerbestaendiger, leichtloeslicher waschmittelzusatz und verfahren zu dessen herstellung
LU70331A1 (fr) * 1974-06-17 1976-05-31
GB1534261A (en) * 1974-11-08 1978-11-29 Reckitt & Colmann Prod Ltd Cleaning composition
US4013581A (en) * 1975-07-10 1977-03-22 The Procter & Gamble Company Bleach tablet composition
GB1568358A (en) * 1975-11-18 1980-05-29 Interox Chemicals Ltd Aromatic peroxyacids and their use in bleaching processes
GB1569258A (en) * 1975-11-18 1980-06-11 Interox Chemicals Ltd Bleaching compositions and processes
DE2622463C3 (de) * 1976-05-20 1985-06-05 Basf Ag, 6700 Ludwigshafen Verfahren zur Reinigung von crotonsäurehaltigen Copolymerisaten
US4126573A (en) * 1976-08-27 1978-11-21 The Procter & Gamble Company Peroxyacid bleach compositions having increased solubility
US4170453A (en) * 1977-06-03 1979-10-09 The Procter & Gamble Company Peroxyacid bleach composition
US4287135A (en) * 1978-10-25 1981-09-01 Reinhard Stober Stabilized diperoxyalkanedioic acids and aromatic peroxycarboxylic acids
DE3064301D1 (en) * 1979-10-18 1983-08-25 Interox Chemicals Ltd Magnesium salts of peroxycarboxylic acids, processes for their preparation and their use as bleaching agents in washing compositions, and processes
US4259201A (en) * 1979-11-09 1981-03-31 The Procter & Gamble Company Detergent composition containing organic peracids buffered for optimum performance
ATE15771T1 (de) * 1981-09-08 1985-10-15 Interox Chemicals Ltd Granulierung.
US4497757A (en) * 1983-01-31 1985-02-05 The Procter & Gamble Company Energy efficient hydration process
DE3305637A1 (de) * 1983-02-18 1984-08-23 Basf Ag, 6700 Ludwigshafen Copolymerisate, ihre herstellung und ihre verwendung als hilfsmittel in wasch- und reinigungsmitteln
JPS6060905A (ja) * 1983-09-08 1985-04-08 Nippon Peroxide Co Ltd 水中崩壊性の優れた過炭酸ソーダ顆粒の製造方法
GB8332682D0 (en) * 1983-12-07 1984-01-11 Procter & Gamble Laundry additive products
EP0212976B2 (fr) * 1985-08-21 1995-03-15 The Clorox Company Composition de blanchiment stable, à base de peracide

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
EP0212976A3 (en) * 1985-08-21 1988-12-21 The Clorox Company Stable peracid bleaching composition
EP0214789A3 (en) * 1985-08-21 1989-04-26 The Clorox Company Dry peracid based bleaching product
US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
US4865759A (en) * 1985-08-21 1989-09-12 The Clorox Company Dry peracid based bleaching product
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
US5089167A (en) * 1985-08-21 1992-02-18 The Clorox Company Stable peracid bleaching compositions: organic peracid, magnesium sulfate and controlled amounts of water
US5093021A (en) * 1985-08-21 1992-03-03 The Clorox Company Encapsulated enzyme in dry bleach composition
EP0256443A3 (fr) * 1986-08-15 1988-12-14 Unilever N.V. Composition à base d'acide peroxydé et son utilisation dans des compositions détergentes
AU600503B2 (en) * 1986-08-15 1990-08-16 Unilever Plc Peroxyacid bleach composition and its use in detergent bleach compositions
EP0273334A1 (fr) * 1986-12-27 1988-07-06 Henkel Kommanditgesellschaft auf Aktien Procédé pour la production de concentrés de peracides s'écoulant librement, stable à partir de granulation à rendre compact
EP0340847A3 (fr) * 1988-05-05 1990-10-03 Unilever N.V. Procédé de préparation de corps contenant un composé d'un peroxyacide et compositions comprenant les dits corps
EP0347988A1 (fr) * 1988-06-22 1989-12-27 Akzo N.V. Compositions de blanchiment aqueuses et stables pouvant être versées, comprenant un péroxide d'acide organique solide à au moins deux polymères
US5358654A (en) * 1988-06-22 1994-10-25 Akzo Nobel N.V. Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
US5126066A (en) * 1988-06-22 1992-06-30 Akzo N.V. Stable, pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
US5030381A (en) * 1988-07-06 1991-07-09 Huels Aktiengesellschaft Process for the preparation of stabilized aliphatic diperoxydicarboxylic acids
EP0360323A3 (fr) * 1988-09-20 1990-11-07 Unilever N.V. Compositions de blanchiment et procédé de préparation
US5296156A (en) * 1988-11-25 1994-03-22 Akzo N.V. Bleaching granules
US5049298A (en) * 1988-11-25 1991-09-17 Akzo Nv Process for the preparation of bleaching granules
EP0376360A1 (fr) * 1988-11-25 1990-07-04 Akzo Nobel N.V. Procédé pour la préparation d'agents de blanchiment granulés
EP0396341A3 (fr) * 1989-05-01 1992-01-22 The Procter & Gamble Company Granulé de blanchiment aggloméré à base de peroxyacide et procédé de préparation
AU643206B2 (en) * 1989-05-01 1993-11-11 Procter & Gamble Company, The Agglomerated peroxyacid bleach granule and process for making same
AU645501B2 (en) * 1989-10-02 1994-01-20 Rohm And Haas Company Polymer-containing granulates
EP0421664A3 (en) * 1989-10-02 1991-12-18 Rohm And Haas Company Polymer-containing granulates
US5279757A (en) * 1990-04-06 1994-01-18 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof
US5055218A (en) * 1990-04-13 1991-10-08 The Procter & Gamble Company Bleach granules containing an amidoperoxyacid
US5246620A (en) * 1990-04-21 1993-09-21 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granules
EP0453970A3 (en) * 1990-04-21 1992-08-05 Hoechst Aktiengesellschaft Stable granulates of peroxycarbonic acids
TR25837A (tr) * 1990-05-31 1993-09-01 Procter & Gamble KüLCELENDIRILMIS PEROKSIASIT AGARTICI GRANüLü VE BUNU YAPMAYA MAHSUS YÖNTEM.
EP0468824A3 (en) * 1990-07-27 1992-07-01 Warwick International Group Plc Granular compositions
US5518650A (en) * 1991-05-04 1996-05-21 Hoechst Aktiengesellschaft Imidocarboxylic acid activators and sulfimidocarboxylic acid activators, processes for their preparation and their use
US5610318A (en) * 1991-05-04 1997-03-11 Hoechst Aktiengesellschaft Imidocarboxylic acid activators and sulfimidocarboxylic acid activators processes for their preparation and their use
WO2015118357A3 (fr) * 2014-02-10 2015-12-03 Revolymer (U.K) Limited Nouvelle particule contenant un peracide
US10870817B2 (en) 2014-02-10 2020-12-22 Societa Chimica Bussi S.P.A. Peracid-containing particle

Also Published As

Publication number Publication date
DE3666048D1 (en) 1989-11-09
EP0200163A3 (en) 1987-09-16
EP0200163B1 (fr) 1989-10-04
ATE46916T1 (de) 1989-10-15
DE3515712A1 (de) 1986-11-06
ES554586A0 (es) 1987-04-01
ES8704566A1 (es) 1987-04-01
JPS61258072A (ja) 1986-11-15
US5091106A (en) 1992-02-25

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