EP0246985B1 - Process and composition for bleaching laundry - Google Patents
Process and composition for bleaching laundry Download PDFInfo
- Publication number
- EP0246985B1 EP0246985B1 EP87420124A EP87420124A EP0246985B1 EP 0246985 B1 EP0246985 B1 EP 0246985B1 EP 87420124 A EP87420124 A EP 87420124A EP 87420124 A EP87420124 A EP 87420124A EP 0246985 B1 EP0246985 B1 EP 0246985B1
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- EP
- European Patent Office
- Prior art keywords
- bath
- calcium
- bleaching
- composition
- process 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.)
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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
- C11D3/3942—Inorganic per-compounds
Definitions
- the present invention relates to laundry laundering using a peroxide compound.
- TAED tetra-acetylethylenediamine
- TAGU tetraacetylglycoluryl
- AP 31 ⁇ -acetoxy- ⁇ -methyl-N-N'-diacetylmalonamide
- sodium perborate which is by far the most widely used peroxidized bleaching agent to date, is well known to be the source of pollution caused by the presence of boron in waste water.
- US Pat. No. 3,230,171 describes a bleaching composition comprising calcium peroxide and potassium pyrosulfate in a ratio such that in aqueous media the bleaching is carried out at a pH of between 9.5 and 1.
- the process according to the invention like the compositions which take part in its realization and are another object of the invention, lead to whitening effects superior to those obtained by the peroxide compounds used to date, while avoiding the pollution due to the most used of them, sodium perborate, and the use of complex activators.
- the process according to the invention for bleaching laundry in a bath using a peroxide compound is characterized in that bleaching is carried out at a pH of between 10.5 and 12.5 in the presence, as a peroxide compound, CA02 calcium peroxide introduced in hydrated form or not so that the quantity of calcium per liter of bath is between 3 and 1.10- 1.10- 2 gram atom.
- the bath may also contain, as is most often the case in practice, in kind and in quantity, all or part of the products known to be usually present in a bath with detergent action, other than peroxidized bleaching agents, such as as surfactants and accompanying products: alkylbenzenesulfonates, alkylarylbenzenesulfonates, ethoxylated fatty alcohols, antiredeposition agents, brighteners, perfumes, sequestering agents, alkaline phosphates, etc. .... Examples of known detergents are for example given by Marshall Sittig in DETERGENT MANUFACTURE , Noyes Data Corporation, 1976.
- the sequestering agents of the alkaline-earth ions are chosen for example from the alkaline salts of polyphosphoric acids such as sodium tripolyphosphate designated in the following by TPP, Na, the alkaline salts of acids polyamine carboxylic or polyoxycarboxylic acids such as those of ethylenediaminetetraacetic acid, the pentasodium salt of diethylenetriaminepentaacetic acid, the trisodium salt of nitrilotriacetic acid, or even sodium citrate.
- polyphosphoric acids such as sodium tripolyphosphate designated in the following by TPP, Na
- the alkaline salts of acids polyamine carboxylic or polyoxycarboxylic acids such as those of ethylenediaminetetraacetic acid, the pentasodium salt of diethylenetriaminepentaacetic acid, the trisodium salt of nitrilotriacetic acid, or even sodium citrate.
- TPP Na is well suited in the context of the invention.
- the bleaching effect is particularly improved by applying the process of the invention when the complexing agent of alkaline earth ions is brought into play in an amount at least equal to that allowing the sequestration of calcium ions in solution in the bath.
- a composition according to the invention containing a peroxidized compound for bleaching laundry is characterized in that it contains, as peroxidized compound, calcium peroxide Ca0 2 in hydrated form or not in an amount such that it allows the formation of 'a bath which, at pH between 10.5 and 12.5 contains per liter of 1.10-3 to 1.10-2 gram atoms of calcium in order to carry out the process described above.
- compositions may also comprise in nature and in quantity all or part of the products known to be usually present in a bath with detergent action, other than the peroxide bleaching compounds hitherto used, such as those mentioned above.
- It can thus comprise sequestering agents of alkaline earth ions, preferably in quantity at less equal to that corresponding to the sequestration of calcium ions in solution in the bath formed from it.
- Sodium tripolyphosphate is particularly suitable in a composition according to the invention as a sequestering agent of calcium ions.
- a composition of the invention allows the formation of the bleaching bath by simultaneous addition of its constituents.
- the formation of the bath can be carried out anyway by bringing its constituents into contact in any order.
- calcium peroxide in hydrated or non-hydrated form can be added to the other constituents, including the sequestering agent where appropriate, dissolved in water before this addition.
- the calcium peroxide used in hydrated form or not in carrying out the process or the composition of the invention can be prepared in any known manner. Examples of preparation are indicated for example in the NEW TREATY OF MINERAL CHEMISTRY, P. Pascal, volume IV, 1958, pp. 399-400 or in PEROXIDES, SUPEROXIDES, and OZONIDES of ALKALI and ALKALINE EARTH METALS, II'ya Ivanovich Vol'nov, Plenum Press, New-York 1966, pp. 58-60.
- the bleaching operation according to the invention is followed by the rinsing and wringing operations before drying as they are conventionally practiced.
Description
La présente invention concerne le blanchiment de linge au moyen d'un composé peroxydé.The present invention relates to laundry laundering using a peroxide compound.
Le peroxyde d'hydrogène, les persels ou peroxyhydrates tel qu'en particulier le perborate de sodium, sont connus depuis longtemps pour être utilisés dans le domaine de l'invention.Hydrogen peroxide, persalts or peroxyhydrates such as in particular sodium perborate, have been known for a long time to be used in the field of the invention.
Ces composés ont cependant le désavantage de ne plus être suffisamment efficaces à une température inférieure à environ 70°C. Il devient alors nécessaire de leur adjoindre un activeur comme par exemple la tétra-acétyl-éthylènediamine (TAED), le tétraacétylglycoluryle (TAGU) ou l'a-acétoxy-a-mé- thyl-N-N'-diacétylmalonamide (AP 31) décrit dans le brevet français publié sous le numéro 2 363 541.These compounds however have the disadvantage of no longer being sufficiently effective at a temperature below approximately 70 ° C. It then becomes necessary to add an activator to them such as, for example, tetra-acetylethylenediamine (TAED), tetraacetylglycoluryl (TAGU) or α-acetoxy-α-methyl-N-N'-diacetylmalonamide (AP 31) described in the French patent published under the number 2 363 541.
De tels activeurs, dont la synthèse et le mode de présentation sont coûteux, grèvent fortement l'économie du blanchiment.Such activators, the synthesis and presentation of which are costly, greatly strain the economics of money laundering.
Par ailleurs le perborate de sodium, qui est l'agent de blanchiment peroxydé de loin le plus utilisé à ce jour, est bien connu pour être à l'origine d'une pollution causée par la présence de bore dans les eaux de rejet.Furthermore, sodium perborate, which is by far the most widely used peroxidized bleaching agent to date, is well known to be the source of pollution caused by the presence of boron in waste water.
Il a été proposé dans le brevet des Etats-Unis d'Amérique nO3 746 646 de substituer au peroxyde d'hydrogène ou aux persels, des hydroperoxydes organiques, ou plus exactement, à cause de la faible solubilité de ceux-ci certains de leurs dérivés solubles.It has been proposed in patent US Patent No. 3,746,646 of O substitute with hydrogen peroxide or persalts, organic hydroperoxides, or more precisely, because of the low solubility of some of these their soluble derivatives.
La demande de brevet français publiée sous le numéro 2 552 123 propose de son côté l'usage d'amino- peroxydes dont la synthèse, décrite notamment dans l'article de E.G.E. HAWKINS, J. Chem. Soc., (1969), 191, pp.2678-2681, reste délicate et coûteuse.The French patent application published under number 2,552,123 proposes the use of amino peroxides, the synthesis of which, described in particular in the article by E.G.E. HAWKINS, J. Chem. Soc., (1969), 191, pp. 2678-2681, remains delicate and costly.
Le brevet US-A 3 230 171 décrit une composition de blanchiment comprenant du peroxde de calcium et du pyrosulfate de potassium dans un rapport tel qu'en milieux aqueux le blanchiment soit réalisé à un pH compris entre 9,5 et 1.US Pat. No. 3,230,171 describes a bleaching composition comprising calcium peroxide and potassium pyrosulfate in a ratio such that in aqueous media the bleaching is carried out at a pH of between 9.5 and 1.
Le procédé selon l'invention, comme les compositions qui participent à sa réalisation et sont un autre objet de l'invention, conduisent à des effets de blanchiment supérieurs à ceux procurés par les composés peroxydés mis en oeuvre à ce jour, tout en évitant la pollution due au plus utilisé d'entre eux, le perborate de sodium, et l'usage d'activeurs complexes.The process according to the invention, like the compositions which take part in its realization and are another object of the invention, lead to whitening effects superior to those obtained by the peroxide compounds used to date, while avoiding the pollution due to the most used of them, sodium perborate, and the use of complex activators.
Le procédé conforme à l'invention pour le blanchiment de linge dans un bain au moyen d'un composé peroxydé est caractérisé en ce que le blanchiment est réalisé à un pH compris entre 10,5 et 12,5 en présence, comme composé peroxydé, de peroxyde de calcium Ca02 introduit sous forme hydratée ou non de façon à ce que la quantité de calcium par litre de bain soit comprise entre 1.10-3 et 1.10-2 atome-gramme.The process according to the invention for bleaching laundry in a bath using a peroxide compound is characterized in that bleaching is carried out at a pH of between 10.5 and 12.5 in the presence, as a peroxide compound, CA02 calcium peroxide introduced in hydrated form or not so that the quantity of calcium per liter of bath is between 3 and 1.10- 1.10- 2 gram atom.
Les résultats les plus intéressants sur le plan économique ou sur le plan de la sureté du procédé sont obtenus à une température du bain préférentiellement comprise entre environ 30°C et 70°C, à un pH limité au plus à 11,5, ces deux paramètres étant pris isolément ou en combinaison.The most interesting results from the economic point of view or from the point of view of the safety of the process are obtained at a bath temperature preferably between approximately 30 ° C. and 70 ° C., at a pH limited at most to 11.5, these two parameters being taken individually or in combination.
Au-dessous de 30°C, l'amélioration constatée de l'effet de blanchiment, bien que sensible encore à 20°C se réduit toutefois. Au-dessus de 70°C la dépense en énergie arrive à s'opposer à l'intérêt industriel du procédé.Below 30 ° C, the improvement observed in the bleaching effect, although still noticeable at 20 ° C, is however reduced. Above 70 ° C the energy expenditure comes to oppose the industrial interest of the process.
Au-delà d'un pH de 11,5 environ, le risque de dégradation de la fibre cellulosique peut devenir non négligeable.Above a pH of around 11.5, the risk of degradation of the cellulosic fiber can become significant.
Le bain peut encore contenir, comme c'est le plus souvent le cas en pratique, en nature et en quantité, tout ou partie des produits connus pour être usuellement présents dans un bain à action détergente, autres que les agents de blanchiment peroxydés, tels que les surfactants et produits d'accompagnement : alkylbenzènesulfonates, alkylarylbenzènesulfonates, alcools gras éthoxylés, agents antiredéposition, azurants, parfums, agents séquestrants, phosphates alcalins, etc.... Des exemples de détergents connus sont par exemple donnés par Marshall Sittig dans DETERGENT MANUFACTURE, Noyes Data Corporation, 1976.The bath may also contain, as is most often the case in practice, in kind and in quantity, all or part of the products known to be usually present in a bath with detergent action, other than peroxidized bleaching agents, such as as surfactants and accompanying products: alkylbenzenesulfonates, alkylarylbenzenesulfonates, ethoxylated fatty alcohols, antiredeposition agents, brighteners, perfumes, sequestering agents, alkaline phosphates, etc. .... Examples of known detergents are for example given by Marshall Sittig in DETERGENT MANUFACTURE , Noyes Data Corporation, 1976.
Les séquestrants des ions alcalino-terreux dont la présence dans le bain est facultative mais cependant préférée, sont choisis par exemple parmi les sels alcalins des acides polyphosphoriques comme le tripolyphosphate de sodium désigné dans ce qui suit par TPP, Na, les sels alcalins des acides polyamine- carboxyliques ou des acides polyoxycarboxyliques comme ceux de l'acide éthylènediaminetétraacétique, le sel pentasodique de l'acide diéthylènetriaminepentaacétique, le sel trisodique de l'acide nitrilotriacéti- que, ou encore le citrate de sodium.The sequestering agents of the alkaline-earth ions, the presence of which in the bath is optional but nevertheless preferred, are chosen for example from the alkaline salts of polyphosphoric acids such as sodium tripolyphosphate designated in the following by TPP, Na, the alkaline salts of acids polyamine carboxylic or polyoxycarboxylic acids such as those of ethylenediaminetetraacetic acid, the pentasodium salt of diethylenetriaminepentaacetic acid, the trisodium salt of nitrilotriacetic acid, or even sodium citrate.
Le TPP, Na convient bien dans le cadre de l'invention.TPP, Na is well suited in the context of the invention.
L'effet de blanchiment est particulièrement amélioré par application du procédé de l'invention lorsque le complexant des ions alcalinoterreux est mis en jeu en quantité au moins égale à celle permettant la séquestration des ions calcium en solution dans le bain.The bleaching effect is particularly improved by applying the process of the invention when the complexing agent of alkaline earth ions is brought into play in an amount at least equal to that allowing the sequestration of calcium ions in solution in the bath.
Une composition conforme à l'invention contenant un composé peroxydé pour le blanchiment de linge est caractérisé en ce qu'elle renferme, comme composé peroxydé, du peroxyde de calcium Ca02 sous forme hydratée ou non en quantité telle qu'elle permette la formation d'un bain qui, à pH compris entre 10,5 et 12,5 contient par litre de 1.10-3 à 1.10-2 atome-gramme de calcium en vue de réaliser le procédé décrit plus haut.A composition according to the invention containing a peroxidized compound for bleaching laundry is characterized in that it contains, as peroxidized compound, calcium peroxide Ca0 2 in hydrated form or not in an amount such that it allows the formation of 'a bath which, at pH between 10.5 and 12.5 contains per liter of 1.10-3 to 1.10-2 gram atoms of calcium in order to carry out the process described above.
Une telle composition peut encore comprendre en nature et en quantité tout ou partie des produits connus pour être usuellement présents dans un bain à action détergente, autres que les composés de blanchiment peroxydés jusqu'alors utilisés, tels que ceux mentionnés plus haut.Such a composition may also comprise in nature and in quantity all or part of the products known to be usually present in a bath with detergent action, other than the peroxide bleaching compounds hitherto used, such as those mentioned above.
Elle peut ainsi comprendre des séquestrants des ions alcalinoterreux, de préférence en quantité au moins égale à celle correspondant à la séquestration des ions calcium en solution dans le bain formé à partir d'elle. Le tripolyphosphate de sodium convient bien en particulier dans une composition selon l'invention comme séquestrant des ions calcium.It can thus comprise sequestering agents of alkaline earth ions, preferably in quantity at less equal to that corresponding to the sequestration of calcium ions in solution in the bath formed from it. Sodium tripolyphosphate is particularly suitable in a composition according to the invention as a sequestering agent of calcium ions.
Une composition de l'invention permet la formation du bain de blanchiment par addition simultanée de ses constituants.A composition of the invention allows the formation of the bleaching bath by simultaneous addition of its constituents.
La formation du bain peut être réalisée de toute manière en mettant en contact ses constituants dans un ordre quelconque. Par exemple, le peroxyde de calcium sous forme hydratée ou non peut être ajouté aux autres constituants, dont le séquestrant le cas échéant, solubilisés dans l'eau préalablement à cette addition.The formation of the bath can be carried out anyway by bringing its constituents into contact in any order. For example, calcium peroxide in hydrated or non-hydrated form can be added to the other constituents, including the sequestering agent where appropriate, dissolved in water before this addition.
Le peroxyde de calcium utilisé sous forme hydratée ou non dans la réalisation du procédé ou la composition de l'invention, peut être préparé de toute manière connue. Des exemples de préparation sont indiqués par exemple dans le NOUVEAU TRAITE DE CHIMIE MINERALE, P. Pascal, tome IV, 1958, pp. 399-400 ou dans PEROXIDES, SUPEROXIDES, and OZONIDES of ALKALI and ALKALINE EARTH METALS, II'ya Ivanovich Vol'nov, Plenum Press, New-York 1966, pp. 58-60.The calcium peroxide used in hydrated form or not in carrying out the process or the composition of the invention can be prepared in any known manner. Examples of preparation are indicated for example in the NEW TREATY OF MINERAL CHEMISTRY, P. Pascal, volume IV, 1958, pp. 399-400 or in PEROXIDES, SUPEROXIDES, and OZONIDES of ALKALI and ALKALINE EARTH METALS, II'ya Ivanovich Vol'nov, Plenum Press, New-York 1966, pp. 58-60.
Il est particulièrement intéressant d'utiliser une forme de peroxyde de calcium de solubilité la meilleure dans les conditions d'exécution du procédé de l'invention.It is particularly advantageous to use a form of calcium peroxide with the best solubility under the conditions for carrying out the process of the invention.
L'opération de blanchiment selon l'invention est suivie des opérations de rinçage et d'essorage avant séchage telles qu'elles sont classiquement pratiquées.The bleaching operation according to the invention is followed by the rinsing and wringing operations before drying as they are conventionally practiced.
Les exemples ci-dessous, donnés à titre indicatif mais non limitatif, permettent d'apprécier l'avantage de l'invention.The examples below, given as an indication but not limiting, make it possible to appreciate the advantage of the invention.
Dans ces exemples :
- - sous le terme de lessive est désignée la lessive normalisée en poudre EMPA@ renfermant, en poids, 14 % de surfactants, 30,4 % de tripolyphosphate de sodium, le complément à 100 % étant assuré par du pyrophosphate de sodium, de l'orthophosphate de sodium et d'autres sels de sodium, ainsi que par des azurants, composés divers et 18,9 % d'eau,
- - le procédé de l'invention est réalisé en cuve cylindrique en verre agitée, munie d'un moyen de chauffage et renfermant le bain et un tissu normalisé EMPAo taché de vin dans un rapport pondéral bain/tissu égal à 100. Un rapport aussi élevé n'a été choisi que par raison de commodité. C'est un paramètre qui n'a pas d'incidence pratique sur le résultat du procédé,
- - l'opération de détergence-blanchiment comporte un palier en température de 15 minutes. Seule la valeur de cette température sera indiquée ci-après. La vitesse de montée en température du bain jusqu'à la température de palier à partir de la température ambiante de 20°C environ est de 10°C par minute. En fin d'opération le tissu traité est classiquement séparé du bain, égoutté et rincé à l'eau à température ambiante avant séchage,
- - le pH du bain est chaque fois compris entre 10,5 et 12,5,
- - le degré de blanc du tissu est mesuré à l'aide d'un spectrophotomètre ERICHSEN GLOSSMASTER n° 507 étallonné à un degré de blanc égal à 90 pour l'oxyde de magnésium fourni comme référence avec l'appareil,
- - le tissu à traiter a un degré de blanc mesuré égal à 41,
- - le peroxyde de calcium a été engagé sous forme d'octahydrate.
- - under the term of detergent is designated the standard detergent in powder EMPA @ containing, by weight, 14% of surfactants, 30.4% of sodium tripolyphosphate, the complement to 100% being ensured by sodium pyrophosphate, sodium orthophosphate and other sodium salts, as well as by brighteners, various compounds and 18.9% water,
- - The process of the invention is carried out in a cylindrical tank made of stirred glass, provided with a heating means and containing the bath and a standardized EMPAo fabric stained with wine in a weight ratio bath / fabric equal to 100. Such a high ratio was chosen for convenience only. This is a parameter which has no practical impact on the result of the process,
- - the detergency-bleaching operation includes a temperature plateau of 15 minutes. Only the value of this temperature will be indicated below. The rate of temperature rise from the bath to the plateau temperature from the ambient temperature of approximately 20 ° C. is 10 ° C. per minute. At the end of the operation, the treated fabric is conventionally separated from the bath, drained and rinsed with water at room temperature before drying,
- - the pH of the bath is each between 10.5 and 12.5,
- the degree of white of the tissue is measured using an ERICHSEN GLOSSMASTER spectrophotometer n ° 507 calibrated to a degree of white equal to 90 for the magnesium oxide supplied as reference with the apparatus,
- - the fabric to be treated has a measured degree of white equal to 41,
- - calcium peroxide has been used in the form of an octahydrate.
Les caractéristiques des exemples et les résultats obtenus pour chacun d'eux sont rassemblés dans le tableau 1 ci-dessous.
Les exemples 3, 6, 7 et 11 sont donnés à titre comparatif.Examples 3, 6, 7 and 11 are given for comparison.
De la comparaison entre eux des exemples 2 et 3, 5 et 6, 8 et 7, 10 et 11 respectivement, il ressort que l'invention permet d'accroître le degré de blanc de plus de 15 % en moyenne.From the comparison between them of Examples 2 and 3, 5 and 6, 8 and 7, 10 and 11 respectively, it appears that the invention makes it possible to increase the degree of whiteness by more than 15% on average.
De la comparaison des exemples 9 et 7 il ressort qu'en engageant selon l'invention une quantité d'agent peroxydé exprimée en oxygène actif 4 fois plus faible que dans un procédé connu, il est possible d'atteindre un degré de blanc au moins aussi élevé que celui procuré par ce dernier.From the comparison of Examples 9 and 7, it appears that by using, according to the invention, a quantity of peroxidized agent expressed in active oxygen 4 times lower than in a known process, it is possible to achieve a degree of white at least as high as that provided by the latter.
De la comparaison des exemples 1 et 11 il est permis de constater qu'un même degré de blanc peut être attendu d'un procédé n'incorporant pas l'invention ou l'incorporant mais dans ce dernier cas à une température inférieure de 20°C à 30°C.From the comparison of Examples 1 and 11, it can be seen that the same degree of white can be expected from a process which does not incorporate the invention or incorporate it, but in the latter case at a temperature below 20 °. C at 30 ° C.
Claims (14)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8607151A FR2598728B1 (en) | 1986-05-15 | 1986-05-15 | METHOD AND COMPOSITION FOR THE BLEACHING OF DOMESTIC LAUNDRY |
| FR8607151 | 1986-05-15 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0246985A2 EP0246985A2 (en) | 1987-11-25 |
| EP0246985A3 EP0246985A3 (en) | 1988-02-24 |
| EP0246985B1 true EP0246985B1 (en) | 1989-10-25 |
Family
ID=9335378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87420124A Expired EP0246985B1 (en) | 1986-05-15 | 1987-05-12 | Process and composition for bleaching laundry |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4784787A (en) |
| EP (1) | EP0246985B1 (en) |
| JP (1) | JPS62299563A (en) |
| CN (1) | CN1005637B (en) |
| AU (1) | AU603100B2 (en) |
| CA (1) | CA1312179C (en) |
| DE (2) | DE3760878D1 (en) |
| ES (1) | ES2000631B3 (en) |
| FR (1) | FR2598728B1 (en) |
| GR (2) | GR880300020T1 (en) |
| PT (1) | PT84867B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5019289A (en) * | 1988-11-25 | 1991-05-28 | The Clorox Company | Stable liquid detergent containing insoluble oxidant |
| US4891147A (en) * | 1988-11-25 | 1990-01-02 | The Clorox Company | Stable liquid detergent containing insoluble oxidant |
| DE4035813A1 (en) * | 1990-11-10 | 1992-05-14 | Akzo Gmbh | OXYGEN BLEACHING |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3230171A (en) * | 1963-03-04 | 1966-01-18 | Dow Chemical Co | Bleaching composition |
| JPS5122984B2 (en) * | 1972-07-29 | 1976-07-14 | ||
| US4120650A (en) * | 1977-12-05 | 1978-10-17 | Basf Wyandotte Corporation | Laundering process for dual bleaching stained fabrics |
-
1986
- 1986-05-15 FR FR8607151A patent/FR2598728B1/en not_active Expired - Lifetime
-
1987
- 1987-05-12 DE DE8787420124T patent/DE3760878D1/en not_active Expired
- 1987-05-12 EP EP87420124A patent/EP0246985B1/en not_active Expired
- 1987-05-12 ES ES87420124T patent/ES2000631B3/en not_active Expired - Lifetime
- 1987-05-12 DE DE198787420124T patent/DE246985T1/en active Pending
- 1987-05-12 US US07/049,128 patent/US4784787A/en not_active Expired - Fee Related
- 1987-05-14 PT PT84867A patent/PT84867B/en not_active IP Right Cessation
- 1987-05-14 CA CA000537105A patent/CA1312179C/en not_active Expired - Fee Related
- 1987-05-14 JP JP62118088A patent/JPS62299563A/en active Granted
- 1987-05-14 AU AU72925/87A patent/AU603100B2/en not_active Ceased
- 1987-05-15 CN CN87103609.6A patent/CN1005637B/en not_active Expired
-
1988
- 1988-05-20 GR GR88300020T patent/GR880300020T1/en unknown
-
1989
- 1989-10-31 GR GR89400222T patent/GR3000201T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2598728B1 (en) | 1991-04-19 |
| ES2000631B3 (en) | 1990-02-16 |
| AU603100B2 (en) | 1990-11-08 |
| EP0246985A3 (en) | 1988-02-24 |
| CA1312179C (en) | 1993-01-05 |
| FR2598728A1 (en) | 1987-11-20 |
| CN1005637B (en) | 1989-11-01 |
| AU7292587A (en) | 1987-11-19 |
| DE3760878D1 (en) | 1989-11-30 |
| JPH0219226B2 (en) | 1990-05-01 |
| ES2000631A4 (en) | 1988-03-16 |
| GR3000201T3 (en) | 1990-12-31 |
| CN87103609A (en) | 1987-11-25 |
| PT84867A (en) | 1987-06-01 |
| PT84867B (en) | 1990-02-08 |
| GR880300020T1 (en) | 1988-10-18 |
| US4784787A (en) | 1988-11-15 |
| EP0246985A2 (en) | 1987-11-25 |
| JPS62299563A (en) | 1987-12-26 |
| DE246985T1 (en) | 1988-04-28 |
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