EP0272402A2 - Procédé d'enrobage de granulés d'acides peroxycarboxyliques - Google Patents

Procédé d'enrobage de granulés d'acides peroxycarboxyliques Download PDF

Info

Publication number
EP0272402A2
EP0272402A2 EP87115498A EP87115498A EP0272402A2 EP 0272402 A2 EP0272402 A2 EP 0272402A2 EP 87115498 A EP87115498 A EP 87115498A EP 87115498 A EP87115498 A EP 87115498A EP 0272402 A2 EP0272402 A2 EP 0272402A2
Authority
EP
European Patent Office
Prior art keywords
acid
granules
peracid
further characterized
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87115498A
Other languages
German (de)
English (en)
Other versions
EP0272402B1 (fr
EP0272402A3 (en
Inventor
Jochen Dr. Jacobs
Franz-Josef Dr. Carduck
Eduard Dr. Smulders
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=6312788&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0272402(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 AT87115498T priority Critical patent/ATE61628T1/de
Publication of EP0272402A2 publication Critical patent/EP0272402A2/fr
Publication of EP0272402A3 publication Critical patent/EP0272402A3/de
Application granted granted Critical
Publication of EP0272402B1 publication Critical patent/EP0272402B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the present invention relates to a process for the preparation of bleaching agents in granular form which contain solid peroxycarboxylic acid as the bleaching component, and to the bleaching agents which can be prepared by this process and their use.
  • 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, are required in order to achieve bleaching in a sufficiently short time.
  • 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 their 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, until recently it was still a long way from a percarboxylic acid formulation which met all requirements for safe handling, mechanical and chemical stability, solubility and economical production.
  • the granules of peracids and inorganic salts represent 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 components, but has other disadvantages, such as poor chemical stability with some hydrophilic coating substances or impairment of dissolution in water with hydrophobic coatings or those made from anhydrous surfactants.
  • a particularly stable formulation of solid aliphatic peroxycarboxylic acids is described in the earlier application DE 35 15 712.7. It is a granulate of peracid, hydratable inorganic salt and an organic polymer compound that is soluble in an alkaline-aqueous medium, in which all components are evenly distributed in the individual granules of the granulate and that in water alone has a pH in the weakly acidic range results.
  • 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 a bleaching agent 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 preferred area of application is the bleaching of textiles in the washing process.
  • the invention therefore relates to a process for coating granulated solid peroxycarboxylic acids, which consists in spraying prefabricated peracid granules while moving with the aqueous solution or dispersion of a homo- or copolymer of an unsaturated carboxylic acid containing 3 to 6 carbon atoms which is soluble in an alkaline-aqueous medium and drying simultaneously and / or subsequently.
  • Further objects of the invention are the bleaching agents that can be produced by this method and their use.
  • the new process leads to a granular bleaching agent, the individual parts of which consist of a peracid-containing core with a coherent shell of polymers.
  • Such granules tend to interact to a particularly small extent with surrounding materials and therefore, when mixed with substances sensitive to oxidation, lead to exceptional storage stability. It is particularly remarkable Resistance of substances sensitive to oxidation, especially perfumes, when they are present together with the granules in a mixture with alkaline components, for example in powder detergents.
  • the coating with the polymeric carboxylic acids which are soluble in an alkaline aqueous medium leads to a mechanical solidification of the granulate particles, which is noticeable in reduced abrasion and in this way makes it possible to also use granules for technical purposes previously considered to be insufficiently stable. This is achieved without significantly impairing other advantageous properties of the granules to be coated, in particular their solubility in water or in an aqueous-alkaline medium.
  • Suitable coating substances are polymeric carboxylic acids which are soluble in an aqueous alkaline medium and are prepared by homo- or copolymerization of unsaturated carboxylic acids having 3 to 6 carbon atoms or their anhydrides. Partial salts of these polymeric carboxylic acids are also regarded as such within the scope of the invention, provided that they do not give a pH of not more than 8, preferably not more than 6.5, in 1 percent mixture with water.
  • copolymers of acrylic acid and / or methacrylic acid with maleic acid (molar ratio 1: 5 to 5: 1) and, in particular, polyacrylic acid are very particularly preferred as the coating material.
  • the average molecular weight of the polymeric carboxylic acids is usually above about 1000, preferably above about 5000, and in particular above about 10,000.
  • the upper limit of the molecular weight is determined primarily by the viscosity of the solution and can be above 1,000,000.
  • the molecular weight of the polymers used as coating substances is preferably below about 250,000, in particular below about 100,000.
  • the coating substances can be applied using methods known per se, for example by spraying aqueous solutions or dispersions of the coating substance onto the prefabricated granules while these are being moved on a plate or in a drum. Through a suitable choice of the amount of liquid, the rate of addition and the mechanics, it can be achieved that the particles do not cake together. Drying of the granules, for example by means of an air stream, can begin while the solution is being applied, in which case it may be expedient to keep the granules moving. The degree of dryness can largely be adapted to the later requirements for the granules, but is usually chosen so that the finished granules have approximately the water content that the starting granules also had.
  • a particularly preferred coating method is to spray the aqueous polymer solutions or dispersions onto the granulate particles in a fluidized bed while drying with warm air at the same time.
  • this method is particularly flexible with regard to the variation of almost all ver driving parameters and on the other hand provides a particularly dense coating.
  • processes in the active bed are also considered to be processes in which the fluidized bed is not limited in the conventional sense, but the granulate particles are provided with the shell material essentially in a gas stream.
  • the process according to the invention is carried out at temperatures which do not impair the granules used, for example as a result of melting or decomposition of the peracid.
  • the temperature is therefore preferably controlled such that the granulate particles do not assume temperatures above 45 ° C., in particular not above 40 ° C.
  • the ambient temperature may well be above these limits.
  • the supply air temperature can be up to 70 ° C and even higher, but is preferably kept between 40 and 60 ° C, in particular between 55 and 60 ° C.
  • concentration of the aqueous polymer solution that is sprayed on for coating depends primarily on technical boundary conditions, such as the viscosity of the solution, the tendency of the polymers to stick and the drying rate. Usual concentrations are preferably between 10 and 40% by weight, in particular between 15 and 30% by weight.
  • the amount of wrapping material applied to some extent affects the effectiveness of the wrapper, with thicker layers generally providing greater protection.
  • the objectives of the invention can usually already be fully achieved with an amount of 0.2 to 10% by weight of coating substance, calculated as a dry polymer and based on the finished granulate; Granules which have been coated with 0.5 to 5% by weight of polymers are particularly preferred.
  • peracid granules are suitable as the starting material for the process according to the invention, provided that they are wetted by aqueous polymer solutions. Accordingly, the encasable granules can contain peroxycarboxylic acids of the most varied types, such as aromatic peracids, aliphatic peracids and araliphatic peracids, which can optionally be substituted and which can contain the percarboxyl group -CO3H one or more times in the molecule.
  • peroxycarboxylic acids of the most varied types, such as aromatic peracids, aliphatic peracids and araliphatic peracids, which can optionally be substituted and which can contain the percarboxyl group -CO3H one or more times in the molecule.
  • the granules suitable as starting material generally contain at least one desensitizing agent, for example inorganic salt or boric acid, in addition, if appropriate, water, granulating auxiliaries, complexing agents for heavy metals and buffer substances or acids, and other additives, such as surfactants and Solubility modification substances.
  • desensitizing agent for example inorganic salt or boric acid
  • water granulating auxiliaries, complexing agents for heavy metals and buffer substances or acids, and other additives, such as surfactants and Solubility modification substances.
  • preferred starting granules are those which already have a high storage stability and desensitization without the coating according to the invention.
  • the granules of solid aliphatic peroxycarboxylic acids described in the earlier application DE 35 15 712 are therefore particularly preferred as starting granules.
  • the teaching of this application is therefore expressly made part of the subject matter of the present disclosure of the invention.
  • the granules according to the invention preferably contain at their core solid aliphatic peroxycarboxylic acids having 4 to 36 carbon atoms, which have one or more carbon atoms in the molecule and contain the group -CO3H.
  • 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.
  • the granules of DE 35 15 712 preferred as the starting material contain inorganic salts as desensitizing agents and a polymer compound which is soluble in an alkaline aqueous medium as granulation aids, and, if appropriate, water, surfactants, complexing agents and other additives.
  • inorganic salts as desensitizing agents and a polymer compound which is soluble in an alkaline aqueous medium as granulation aids, and, if appropriate, water, surfactants, complexing agents and other additives.
  • the process according to the invention is preferably carried out in such a way that the individual particles of the prefabricated granules do not agglomerate or only agglomerate to a small extent.
  • the grain size and the grain size distribution of the granules used are essentially retained.
  • the bulk density is also changed insignificantly at most.
  • the grain size and bulk density of the starting granulate are of no importance for the successful implementation of the process; it can be used, for example, on fine granules of 0.1 mm particle diameter as well as on coarse types of 5 mm particle diameter, so that the grain size and the Bulk weight can be fully adapted to the particular application of the granules.
  • the range from 0.1 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 g / l, preferably between 500 and 1100 g / l.
  • 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.
  • 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 in a uniform form, ie without further admixtures, but they are preferably made up as scatterable 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 optionally other bleaching agents, such as perborate, as further active ingredients.
  • a combined detergent and bleaching agent furthermore, in particular surfactants, builders, foam-suppressing substances, optical brighteners and perfume are to be mentioned as active ingredients. It works in these ready-made forms extremely low tendency of the granules to interact with components of the mixture which are capable of oxidation, is particularly advantageous.
  • the detergent was mixed with an amount of the respective granules, which corresponded to 0.05% by weight of pure peracid, based on the weight of the peracid-free detergent, and mixed thoroughly.
  • the storage took place at 30 ° C and 80% relative humidity in non-laminated cardboard boxes. After each week, the strength and quality of the odor was assessed by trained perfumers compared to the peracid-free detergent, which was stored under the same conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Glanulating (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cyclones (AREA)
  • Disintegrating Or Milling (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Medicinal Preparation (AREA)
EP87115498A 1986-10-30 1987-10-22 Procédé d'enrobage de granulés d'acides peroxycarboxyliques Expired - Lifetime EP0272402B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87115498T ATE61628T1 (de) 1986-10-30 1987-10-22 Verfahren zur umhuellung von peroxycarbonsaeuregranulaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3636904 1986-10-30
DE19863636904 DE3636904A1 (de) 1986-10-30 1986-10-30 Verfahren zur umhuellung von persaeuregranulaten

Publications (3)

Publication Number Publication Date
EP0272402A2 true EP0272402A2 (fr) 1988-06-29
EP0272402A3 EP0272402A3 (en) 1988-12-28
EP0272402B1 EP0272402B1 (fr) 1991-03-13

Family

ID=6312788

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87115498A Expired - Lifetime EP0272402B1 (fr) 1986-10-30 1987-10-22 Procédé d'enrobage de granulés d'acides peroxycarboxyliques

Country Status (6)

Country Link
EP (1) EP0272402B1 (fr)
JP (1) JPS63122798A (fr)
AT (1) ATE61628T1 (fr)
DE (2) DE3636904A1 (fr)
DK (1) DK567587A (fr)
ES (1) ES2020988B3 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0454881A1 (fr) * 1987-03-26 1991-11-06 The Dow Chemical Company Compositions pour la libération contrôlée d'acides
EP0450587A3 (en) * 1990-04-06 1991-12-18 Hoechst Aktiengesellschaft Stable granules of peroxycarboxylic acid
EP0468824A3 (en) * 1990-07-27 1992-07-01 Warwick International Group Plc Granular compositions
US5419846A (en) * 1992-08-18 1995-05-30 Hoechst Ag Stable granules for detergents, cleaning agents and disinfectants
WO2004110613A1 (fr) * 2003-06-13 2004-12-23 Henkel Kommanditgesellschaft Auf Aktien Systeme de capsule polyelectrolytique a base d'acides peroxycarboniques presentant une bonne stabilite au stockage
WO2004110612A1 (fr) * 2003-06-13 2004-12-23 Henkel Kommanditgesellschaft Auf Aktien Capsules a base d'acides peroxycarboniques presentant une bonne stabilite au stockage
DE102004030900A1 (de) * 2004-06-25 2006-01-26 Henkel Kgaa Herstellung teilchenförmiger Peroxycarbonsäurezusammensetzungen
US7531498B2 (en) 2003-06-13 2009-05-12 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Peroxycarboxylic acid-based bleach compositions having a long shelf life

Families Citing this family (7)

* 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
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
EP0373691A3 (fr) * 1988-12-16 1991-05-15 Unilever N.V. Compositions granulaires de blanchiment stabilisées
US5279757A (en) * 1990-04-06 1994-01-18 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof
DE10260833B4 (de) * 2002-12-23 2007-08-16 Henkel Kgaa Verfahren zur Verarbeitung von Wasch- oder Reinigungsmitteln
EP1760141A1 (fr) * 2005-09-06 2007-03-07 SOLVAY (Société Anonyme) Peroxycarboxylique acide granulé enveloppé, procédé de préparation et utilisation dans la blanchissage, le blanchiment et la désinfection

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3639285A (en) 1969-07-23 1972-02-01 Ppg Industries Inc Novel bleaching compositions and use thereof
EP0074730A1 (fr) 1981-09-08 1983-03-23 Interox Chemicals Limited Granulation

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770816A (en) * 1969-07-23 1973-11-06 Ppg Industries Inc Diperisophthalic acid compositions
GB1569258A (en) * 1975-11-18 1980-06-11 Interox Chemicals Ltd Bleaching compositions and processes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3639285A (en) 1969-07-23 1972-02-01 Ppg Industries Inc Novel bleaching compositions and use thereof
EP0074730A1 (fr) 1981-09-08 1983-03-23 Interox Chemicals Limited Granulation

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0454881A1 (fr) * 1987-03-26 1991-11-06 The Dow Chemical Company Compositions pour la libération contrôlée d'acides
EP0450587A3 (en) * 1990-04-06 1991-12-18 Hoechst Aktiengesellschaft Stable granules of peroxycarboxylic acid
EP0468824A3 (en) * 1990-07-27 1992-07-01 Warwick International Group Plc Granular compositions
US5419846A (en) * 1992-08-18 1995-05-30 Hoechst Ag Stable granules for detergents, cleaning agents and disinfectants
WO2004110613A1 (fr) * 2003-06-13 2004-12-23 Henkel Kommanditgesellschaft Auf Aktien Systeme de capsule polyelectrolytique a base d'acides peroxycarboniques presentant une bonne stabilite au stockage
WO2004110612A1 (fr) * 2003-06-13 2004-12-23 Henkel Kommanditgesellschaft Auf Aktien Capsules a base d'acides peroxycarboniques presentant une bonne stabilite au stockage
US7531498B2 (en) 2003-06-13 2009-05-12 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Peroxycarboxylic acid-based bleach compositions having a long shelf life
DE102004030900A1 (de) * 2004-06-25 2006-01-26 Henkel Kgaa Herstellung teilchenförmiger Peroxycarbonsäurezusammensetzungen

Also Published As

Publication number Publication date
DE3768627D1 (de) 1991-04-18
ES2020988B3 (es) 1991-10-16
DK567587D0 (da) 1987-10-29
EP0272402B1 (fr) 1991-03-13
DE3636904A1 (de) 1988-05-05
JPS63122798A (ja) 1988-05-26
EP0272402A3 (en) 1988-12-28
DK567587A (da) 1988-05-01
ATE61628T1 (de) 1991-03-15

Similar Documents

Publication Publication Date Title
EP0200163B1 (fr) Agent de blanchiment, sa préparation et son utilisation
EP0272402B1 (fr) Procédé d'enrobage de granulés d'acides peroxycarboxyliques
DE2622610C2 (de) Verfahren zum Stabilisieren von teilchenförmigen Alkalimetallperoxosalzen
DE2800916C2 (de) Verfahren zur Stabilisierung von Teilchen von Peroxidverbindungen, die hierbei erhaltenen Teilchen und sie enthaltende Mittel
EP1475350B1 (fr) Granules de percarbonate de sodium enrobés avec une stabilité de stockage améliorée
EP1633471B1 (fr) Systeme de capsule polyelectrolytique a base d'acides peroxycarboniques presentant une bonne stabilite au stockage
DE69404543T2 (de) Stabilisiertes Natriumpercarbonatteilchen
DE4012769A1 (de) Stabile peroxicarbonsaeuregranulate
EP0710215B1 (fr) Particules enrobees de percarbonate de sodium, leur procede de fabrication et leur utilisation
EP0592969B2 (fr) Percarbonate de sodium stabilisé par revêtement
DE19544293A1 (de) Umhüllte Natriumpercarbonatpartikel, Verfahren zu ihrer Herstellung und deren Verwendung
EP0868396B1 (fr) Composes peroxo et peroxy stabilises par revetement
DE10361100A1 (de) Lagerstabile Kapseln auf Basis von Peroxycarbonsäuren
DE69403207T2 (de) Wirbelbett beschichtete amidoperoxysäure enthaltende bleichmittel zusammentzung
EP0583744B1 (fr) Granulats stables pour compositions détergentes, nettoyantes et désinfectantes
DE69104124T2 (de) Verfahren zur Herstellung von stabilisiertem Natriumperkarbonat.
DE2811554C2 (fr)
DE4040654A1 (de) Granulat mit umhuelltem bleichaktivator
DE69815077T2 (de) Stabilisierte natriumcarbonat-peroxyhydrate
EP1232239B1 (fr) Procede pour la production de detergents ou de nettoyants particulaires
DE68921957T2 (de) Teilchenförmige Zusammensetzung mit Bleichmittel und optischem Aufheller und deren Herstellung.
WO1992017400A1 (fr) Percarbonate de sodium particulaire enrobe a longue duree de conservation et son procede de fabrication
DE2535183A1 (de) Verfahren zum umhuellen und granulieren von tetraacetylglycoluril und tetraacetylaethylendiamin
DE4011185A1 (de) Stabile peroxicarbonsaeuregranulate
DE2402392C2 (de) Stabilisierte teilchenförmige Peroxyverbindungen, Verfahren zu deren Herstellung und ihre Verwendung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19890607

17Q First examination report despatched

Effective date: 19900119

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 61628

Country of ref document: AT

Date of ref document: 19910315

Kind code of ref document: T

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3768627

Country of ref document: DE

Date of ref document: 19910418

ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19911022

Ref country code: AT

Effective date: 19911022

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19911023

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19911023

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19911031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19911031

Ref country code: BE

Effective date: 19911031

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: HOECHST AKTIENGESELLSCHAFT ZENTRALE PATENTABTEILUN

Effective date: 19911213

NLR1 Nl: opposition has been filed with the epo

Opponent name: HOECHST AG.

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19911031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19920501

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19920630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19920701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 19920817

EUG Se: european patent has lapsed

Ref document number: 87115498.5

Effective date: 19920510