EP0051509A1 - Stabilizing compositions for peroxides - Google Patents
Stabilizing compositions for peroxides Download PDFInfo
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- EP0051509A1 EP0051509A1 EP81401577A EP81401577A EP0051509A1 EP 0051509 A1 EP0051509 A1 EP 0051509A1 EP 81401577 A EP81401577 A EP 81401577A EP 81401577 A EP81401577 A EP 81401577A EP 0051509 A1 EP0051509 A1 EP 0051509A1
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- EP
- European Patent Office
- Prior art keywords
- stabilizing
- composition
- bleaching
- magnesium silicate
- compositions
- 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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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 36
- 150000002978 peroxides Chemical class 0.000 title description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 19
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 19
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 19
- 239000003599 detergent Substances 0.000 claims abstract description 9
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims abstract 3
- 229960003330 pentetic acid Drugs 0.000 claims abstract 3
- 239000002253 acid Substances 0.000 claims description 8
- 238000004061 bleaching Methods 0.000 description 20
- 239000004753 textile Substances 0.000 description 13
- 239000003352 sequestering agent Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000004744 fabric Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical group OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- -1 peroxide compound Chemical class 0.000 description 4
- 229960001922 sodium perborate Drugs 0.000 description 4
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- UFZOPKFMKMAWLU-UHFFFAOYSA-N ethoxy(methyl)phosphinic acid Chemical compound CCOP(C)(O)=O UFZOPKFMKMAWLU-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
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
- C11D3/3937—Stabilising agents
Definitions
- the present invention relates to stabilizing compositions for peroxide products, in particular when they are used in the bleaching and bleaching of fibers and textile fabrics. These stabilizing compositions are especially intended for household and industrial detergents.
- Most household detergents contain a peroxidized compound, such as sodium perborate or sodium percarbonate, having the effect of improving the elimination of many stains and restoring the linen to its initial whiteness thanks to its whitening effect.
- a peroxidized compound such as sodium perborate or sodium percarbonate
- the textile industry generally uses baths comprising a peroxidized compound, such as hydrogen peroxide or sodium perborate for bleaching unbleached textiles.
- This stabilizing effect can be obtained by the addition, to the washing bath, of magnesium silicate which slows down the rate of decomposition of the peroxidized compound.
- the magnesium silicate makes it possible to keep in the bleaching bath the maximum of active oxygen beyond a temperature of the order of 60 ° 0, from which the peroxidized compound will reach its full efficiency.
- the magnesium silicate is added to the detergent either preformed or formed “in situ” from sodium silicate and a magnesium salt.
- the "in situ” formation process generally gives a rough feel, causes dye reserves due to the lack of hydrophility, and causes deposits in bleaching or bleaching apparatus which can cause mechanical wear of bleached textile fibers.
- French patent 2,420,593 in the name of Kao Soap, which relates to bleaching compositions which do not alter the color of the treated textiles, proposes to add in particular to sodium percarbonate or to the ethane addition product -1,1,2,2 tetrasarboxylic tetracarboxylate and H 2 O 2 , at least one organoacetic and organophosphonic compound.
- French patent 2,140,213 in the name of Monsanto relates to a stabilizing agent for reducing the decomposition of a peroxidized compound contained in an alkaline aqueous solution.
- This agent is formed by a combination of 1 - hydroxyethylidene -1,1 acid.
- diphosphenic known as HEDP
- nitrilatriacetic acid known as NTA
- water-soluble salts and a water-soluble salt such as magnesium sulfate.
- French patent 1,420,462 in the name of the applicant, relates to a process for stabilizing peroxide compounds by magnesium silicate, during their use in the bleaching and bleaching of fibers and textile fabrics, according to which the magnesium silicate is used preformed in the colloidal state.
- the. Magnesium silicate preformed in the colloidal state is used in combination with small amounts of dimagnesium salt of ethylenediaminetotetracetic acid.
- stabilizing compositions based on colloldal magnesium silicate are proposed, for perogydated products, such as sodium perborate, sodium percarbonate, hydrogen peroxide, etc., intended for the stabilization of laundering baths prepared by means of detergents. household or bleaching industry baths textile.
- perogydated products such as sodium perborate, sodium percarbonate, hydrogen peroxide, etc.
- These compositions contain a low magnesium silicate colloids of al uno associated with content of a sequestering organoacisten type and a low content of a sequestrant such organophosphonic.
- the organophosphonic sequestrant in acid form or in water-soluble salt is a derivative of amino acids (lower alkane) phosphonic such as diethylenetrianine-peatamethylenephonigue (DTPHP)
- the organaacetic sequestrant is a derivative of amino acids (lower alkane) such as diethyetriaminepentaacstic acid (DTPA).
- the stabilizing composition according to the invention makes it possible to obtain a very substantial gain in the degree of polymerization, while the combination proposed in French patent 2,140,213 does not provide any improvement in the protection of the cellulose.
- compositions based on colloidal magnesium silicate were prepared with variable doses of DTPA and DTPMP.
- the doses of DTPA and DTPMP are given as a percentage by weight of pure product.
- Table 1 below indicates the proportions in percent of the different compositions produced.
- Composition No. 1 does not include DTPA or DTPMP: it is a control composition which serves as a reference for measuring the effectiveness of the other compositions.
- the detergent bath is maintained at 90 ° C for 1 hour; the quantity of active oxygen (OA) residual relative to the quantity of active oxygen initially contained in the bath is then measured.
- OA active oxygen
- the residual OA ratio in percent sort of defines initial OA the stabilizing power of the composition.
- the residual gain in OA provided by said compositions is defined as the difference in the stabilizing power of one of these said compositions minus the stabilizing power of the control composition n ° 1.
- Table 2 indicates the stabilizing power and the residual OA gain of the various stabilizing compositions.
- compositions No. 5, 6 and 8 have the same stabilizing power and the same gain in OA while the sum of the percentages of DTPA and DTPMP are respectively 10.7%, 11.4% and 23 %.
- composition No. 6 The synergistic effect between the two sequestrants is particularly marked for composition No. 6; it is illustrated in Table 3.
- Table 3 shows that the sum of the results of compositions N ° 2 and 4 corresponding to the hypothetical composition (2 + 4)? are significantly lower as stabilizing power and gain of OA, to the results of composition No. 6 which actually contains percentages of DTPA and DTPMP slightly lower than the percentages of DTPA and DTPMP of the hypothetical composition (2 + 4)?
- the synergy of DTPA and DTPMP at relatively low levels is particularly advantageous from an economic point of view because DTPMP is significantly more expensive than DTPA.
- composition N 0 6 which contains only 4.4% of DTPMP has the same stabilizing power and the. same gain in OA as composition No. 5, for example which contains 10.7% of DTPMP.
- Tissue pieces are subjected to a succession of 10 washes at 90 ° C for 40 minutes in a Terg-o-tometer the detergent bath has the following composition:
- EMPA 301 fabric is a reference fabric, made of cotton, used in the textile and bleaching industry; this fabric is supplied by the Federal Laboratory for Materials Testing of the St Gallen Research Institute in SWITZERLAND.
- the degree of polymerization of the cellulose is determined according to the method described in the AFNOR T 12005 standard.
- the DP of the EMPA 301 fabric was, at the start, before the washes, from 1850.
- composition No. 6 for example, gives a residual DP of 61.6%, therefore clearly greater than the residual DP given by composition No. 2 (52%) and composition N ° 4 (43.2%).
- EXAMPLE 5 comparative
- Example 5 According to Example 5, Table 3 (6), of French patent 2140.213, a 36.1% stabilizing solution of 1 mole of NTA 0.47 mole of magnesium is used (coming from a soluble salt, magnesium sulfate and 0 , 3 mole of HEDP, ie a solution which contains by weight 29% of NTA at 90%, 15.8% of MgSO 4 , 7 H 2 O and 14.1% of HEDP at 60%.
- the stabilizing composition consists of 78% colloidal magnesium silicate, 14.5% DTPA in 40% solution (sodium salt) and 7.5% DTPMP in 50% solution.
- the degradation of the cellulose was evaluated by determining the degree of DP polymerization after a succession of 5 washes in the presence of each stabilizing composition.
- test 5 the sodium perborate is better stabilized than in the other tests.
- the quantity of residual active oxygen is 45 whereas it is only 5 and 10% in tests n ° 8 and 11.
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Macromonomer-Based Addition Polymer (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
La présente invention concerne des compositions stabilisantes pour produits peroxydés. Ces compositions stabilisantes contiennent du silicate de magnésium colloïdal associé à l'acide diéthylènetriaminepentaacétique et à l'acide diethylènetriaminepentaméthylène phosphonique. Ces dites compositions stabilisantes sont notamment destinées aux lessives ménagères et industrielles.The present invention relates to stabilizing compositions for peroxidized products. These stabilizing compositions contain colloidal magnesium silicate associated with diethylenetriaminepentaacetic acid and with diethylenetriaminepentamethylene phosphonic acid. These so-called stabilizing compositions are especially intended for household and industrial detergents.
Description
La présente invention concerne des compositions stabilisantes pour produits peroxydes, notamment lors de leur emploi dans le blanchiment et le blanchissage des fibres et des tissus textiles. Ces compositions stabilisantes sont notamment destinées aux lessives ménagères et industrielles.The present invention relates to stabilizing compositions for peroxide products, in particular when they are used in the bleaching and bleaching of fibers and textile fabrics. These stabilizing compositions are especially intended for household and industrial detergents.
La plupart des lessives ménagères contiennent un composé peroxydé, tel perborate de sodium ou percarbonate de sodium, ayant pour effet d'améliorer l'élimination de nombreuses taches et de redonner au linge sa blancheur initiale grâce à son effet de blanchissage. De même, l'industrie textile utilise généralement des bains comportant un composé peroxydé, tel peroxyde d'hydrogène ou' perborate de sodium pour le blanchiment des textiles écrus.Most household detergents contain a peroxidized compound, such as sodium perborate or sodium percarbonate, having the effect of improving the elimination of many stains and restoring the linen to its initial whiteness thanks to its whitening effect. Likewise, the textile industry generally uses baths comprising a peroxidized compound, such as hydrogen peroxide or sodium perborate for bleaching unbleached textiles.
Pour obtenir un effet maximum de blanchiment ou de blanchissage, il est nécessaire de bien stabiliser le composé peroxydé. Cet effet stabilisant peut être obtenu par l'addition, au bain de lavage, de silicate de magnésium qui ralentit la vitesse de décomposition du composé peroxydé. Le silicate de magnésium permet de conserver dans le bain de blanchiment le maximum d'oxygène actif au-delà d'une température de l'ordre de 60°0, à partir de laquelle le composé peroxydé atteindra sa pleine efficacité.To obtain a maximum bleaching or bleaching effect, it is necessary to stabilize the peroxide compound well. This stabilizing effect can be obtained by the addition, to the washing bath, of magnesium silicate which slows down the rate of decomposition of the peroxidized compound. The magnesium silicate makes it possible to keep in the bleaching bath the maximum of active oxygen beyond a temperature of the order of 60 ° 0, from which the peroxidized compound will reach its full efficiency.
Le silicate de magnésium est additionné à la lessive soit préformé, soit formé "in situ" à partir de silicate de sodium et d'un sel de magnésium. Le procédé de formation "in situ" donne généralement un toucher rêche, provoque des réserves en teinture par suite du manque d'hydrophilité, et cause des dépôts dans les appareils de blanchiment ou de blanchissage pouvant entrainer l'usure mécanique des fibres textiles blanchies.The magnesium silicate is added to the detergent either preformed or formed "in situ" from sodium silicate and a magnesium salt. The "in situ" formation process generally gives a rough feel, causes dye reserves due to the lack of hydrophility, and causes deposits in bleaching or bleaching apparatus which can cause mechanical wear of bleached textile fibers.
Selon le brevet américain 3.860.391, de la Société Benkiser-Knapsak, il a été proposé un procédé de blanchiment de fibres textiles dans un bain sans silicate, dont le pH est ajusté- entre 9 et 12, dans lequel on additionne un agent stabilisant consistant en un mélange d'un composé hydroxyaliphatique contenant 2 à 6 atomes de carbone et d'un acide phosphonique choisi parmi le groupe consistant en un amino acide alkylène phosphonique, un acide hydroxyalcane phosphonique, un sel soluble de ces acides et des mélanges de ceux-ci; le composé peroxydé étant le peroxyde d'hydrogène.According to American patent 3,860,391, from the Benkiser-Knapsak Company, a process has been proposed for bleaching textile fibers in a silicate-free bath, the pH of which is adjusted between 9 and 12, in which a stabilizing agent is added consisting of a mixture of a hydroxyaliphatic compound containing 2 to 6 carbon atoms and of a phosphonic acid chosen from the group consisting of an amino alkylene phosphonic acid, a hydroxyalkane phosphonic acid, a soluble salt of these acids and mixtures of those -this; the peroxidized compound being hydrogen peroxide.
Le brevet français 2.396.114, au nom de la Société dite Manufacture de produits chimiques Protex, a proposé des compositions destinées à la stabilisation des bains de peroxyde d'hydrogène, constituées, sous une forme concentrée, par des formulations liquides et stables composées de silicate de sodium et d'un complexe de magnésium ; le dit complexe de magnésium étant formé à partir d'acides phosphoniques.French patent 2,396,114, in the name of the so-called Protex chemical manufacturing company, proposed compositions intended for the stabilization of hydrogen peroxide baths, made up, in a concentrated form, by liquid and stable formulations composed of sodium silicate and a magnesium complex; the said magnesium complex being formed from phosphonic acids.
Le brevet français 2.420.593, au nom de Kao Soap, qui a pour objet des compositions de blanchiment qui n'altèrent pas la couleur des textiles traités, propose d'ajouter notamment au percarbonate de sodium ou au produit d'addition d'éthane -1,1,2,2 tétracarboxylate tétrasodique et de H2O2, au moins un composé organoacétique et organophosphonique.French patent 2,420,593, in the name of Kao Soap, which relates to bleaching compositions which do not alter the color of the treated textiles, proposes to add in particular to sodium percarbonate or to the ethane addition product -1,1,2,2 tetrasarboxylic tetracarboxylate and H 2 O 2 , at least one organoacetic and organophosphonic compound.
D'autre part, le brevet français 2.140.213 au nom de Monsanto, concerne un agent de stabilisation pour réduire la décomposition d'un composé peroxydé contenu dans une solution aqueuse alcaline. Cet agent est formé par une combinaison de l'acide 1 - hydroxyéthylidène -1,1. diphosphenique, dit HEDP, l'acide nitrilatriacétique, dit NTA, et des sels solubles dans l'eau et un sel soluble dans l'eau tel le sulfate- de magnésium.On the other hand, French patent 2,140,213 in the name of Monsanto, relates to a stabilizing agent for reducing the decomposition of a peroxidized compound contained in an alkaline aqueous solution. This agent is formed by a combination of 1 - hydroxyethylidene -1,1 acid. diphosphenic, known as HEDP, nitrilatriacetic acid, known as NTA, and water-soluble salts and a water-soluble salt such as magnesium sulfate.
Et le brevet français 1.420.462, au nom de la demanderesse est relatif à un procédé de stabilisation de composés peroxydes par le silicate-de magnésium, lors de leur emploi dans le blanchiment et le blanchissage des fibres et des tissus textiles, selon lequel le silicate de magnésium est utilisé préformé à l'état colloïdal. Selon un mode de mise en oeuvre du procédé, le. silicate de magnésium préformé à l'état colloïdal est utilisé en association avec de petites quantités de sel dimagnésien de l'acide éthylènediaminotétracétique.And French patent 1,420,462, in the name of the applicant, relates to a process for stabilizing peroxide compounds by magnesium silicate, during their use in the bleaching and bleaching of fibers and textile fabrics, according to which the magnesium silicate is used preformed in the colloidal state. According to one embodiment of the method, the. Magnesium silicate preformed in the colloidal state is used in combination with small amounts of dimagnesium salt of ethylenediaminetotetracetic acid.
Or, il a été trouvé qu'en présence de silicate de magnésium colloïdal, l'association d'un séquestrant organoacétique et d'un séquestrant organophosphonique, utilisés en petite quantité, possède un . effet de synergie sur la stabilité du bain de blanchiment ou de blanchissage ; la diminution de la dégradation du degré de polymérisation de la fibre textile restant par ailleurs satisfaisante.However, it has been found that in the presence of colloidal magnesium silicate, the combination of an organoacetic sequestrant and an organophosphonic sequestrant, used in small quantities, has a. synergistic effect on the stability of the bleaching or bleaching bath; the reduction in the degradation of the degree of polymerization of the textile fiber also remains satisfactory.
Cet effet de synergie est particulièrement marqué lorsque le bain de blanchiment ou de blanchissage contient à la fois des traces de cuivre et de fer.This synergistic effect is particularly marked when the bleaching or bleaching bath contains both traces of copper and iron.
Selon l'invention, on propose des compositions stabilisantes à base de silicate de magnésium colloldal, pour produits perogydés, tels perborate de sodium, percarbonate de sodium, peroxyde d'hydrogène etc, destinées à la stabilisation des bains de blanchissage préparés au moyen de lessives ménagères ou de bains de blanchiment de l'industrie textile. Ces compositions contiennent un silicate de magnésium colloï- dal associé à uno faible teneur d'un séquestrant du type organoacétique et à une faible teneur d'un séquestrant du type organophosphonique.According to the invention, stabilizing compositions based on colloldal magnesium silicate are proposed, for perogydated products, such as sodium perborate, sodium percarbonate, hydrogen peroxide, etc., intended for the stabilization of laundering baths prepared by means of detergents. household or bleaching industry baths textile. These compositions contain a low magnesium silicate colloids of al uno associated with content of a sequestering organoacétique type and a low content of a sequestrant such organophosphonic.
On obtient des résultats intéressants avec une association stabilisante contenant 1 à 15 % en poids de séquestrant du type orgaaophosphonique et 1 à 20 % en poids de séquestrant du type organoacétique : en particulier des teneurs de 2 à 6 % en poids de séquestrant du type organophosphoniqus et 1,5 à 8 % en poids de séquestrant du type organoacétique.Interesting results are obtained with a stabilizing combination containing 1 to 15% by weight of sequestering agent of the organophosphonic type and 1 to 20% by weight of sequestering agent of the organoacetic type: in particular contents of 2 to 6% by weight of sequestering agent of the organophosphonic type. and 1.5 to 8% by weight of sequestrant of the organoacetic type.
Le séquestrant organophosphonique sous forme acide ou de sel soluble dans l'eau est un dérivé des acides amino (alcane inférieur) phosphoniques tel le diéthylènetrianine-peatàméthylénephonigue (DTPHP) Le séquestrant organaacétique est un dérivé des acides amino (alcane inférieur) acétiques tel l'acide diéthyiènetriaminepentaacstique (DTPA).The organophosphonic sequestrant in acid form or in water-soluble salt is a derivative of amino acids (lower alkane) phosphonic such as diethylenetrianine-peatamethylenephonigue (DTPHP) The organaacetic sequestrant is a derivative of amino acids (lower alkane) such as diethyetriaminepentaacstic acid (DTPA).
Des essais ont montré qu'il existe une relation entre la conservation voire l'amélioration du degré de polymérisation (DP) d'un textile et la stabilisation du composé peroxyde, caractérisée par le pourcentage d'oxygène actif résiduel.Tests have shown that there is a relationship between preserving or even improving the degree of polymerization (DP) of a textile and the stabilization of the peroxide compound, characterized by the percentage of residual active oxygen.
Des essais comparatifs conduits dans des conditions identiques ont montré l'efficacité supérieure de la composition stabilisante selon l'invention et l'effet de synergie de la nouvelle association par rapport au silicate de magnésium colloïdal employé seul, aur associations binaires du silicate de magnésium colloïdal avec la DTPA d'une part, et le DTPMP d'autre part, et à l'association ternaira selon le brevet français 2.140.213. DP Gain
On constate que la composition stabilisante selon l'invention permet d'obtenir un gain très substantiel du degré de polymérisation, alors que l'association proposée dans le brevet français 2.140.213 ne procure aucune amélioration de la protection de la cellulose.It is found that the stabilizing composition according to the invention makes it possible to obtain a very substantial gain in the degree of polymerization, while the combination proposed in French patent 2,140,213 does not provide any improvement in the protection of the cellulose.
De plus, on a observé que le remplacement de sulfate de magnésium par du silicate de magnésium en association avec les séquestrants NTA + HEDP proposés dans le brevet ci-dessus référencé, constitue également une association inefficace vis à vis de la protection de la cellulose.In addition, it has been observed that the replacement of magnesium sulphate by magnesium silicate in association with the sequestering agents NTA + HEDP proposed in the patent referenced above, also constitutes an ineffective association with respect to the protection of cellulose.
Il est donné ci-après des exemples qui illustrent l'invention à titre non limitatif.Examples are given below which illustrate the invention without implied limitation.
Des compositions à base de silicate de magnésium colloïdal ont été préparées avec des doses variables de DTPA et de DTPMP. Les doses de DTPA et de DTPMP sont données en pourcentage en poids de produit pur.Compositions based on colloidal magnesium silicate were prepared with variable doses of DTPA and DTPMP. The doses of DTPA and DTPMP are given as a percentage by weight of pure product.
Le tableau 1 ci-dessous indique les proportions en pourcent des différentes compositions réalisées.
La composition N°1 ne comprend ni DTPA ni DTPMP : il s'agit d'une composition témoin qui sert de référence pour mesurer l'efficacité des autres compositions.Composition No. 1 does not include DTPA or DTPMP: it is a control composition which serves as a reference for measuring the effectiveness of the other compositions.
Ces compositions stabilisantes ont été essayées dans un bain lessiviel de formulation suivante :
Le bain lessiviel est maintenu à 90°C pendant 1heure; on procède ensuite au dosage de la quantité d'oxygène actif (OA) résiduel rapport à la quantité d'oxygène actif contenu initialement dans le bain.The detergent bath is maintained at 90 ° C for 1 hour; the quantity of active oxygen (OA) residual relative to the quantity of active oxygen initially contained in the bath is then measured.
Le rapport OA résiduel en pourcent définit en quelque sorte OA initial
le pouvoir stabilisant de la composition.The residual OA ratio in percent sort of defines initial OA
the stabilizing power of the composition.
D'autre part, pour mieux mettre en évidence les avantages des compositions nouvelles, le gain d'OA résiduel, apporté par les dites compositions, est défini comme la différence du pouvoir stabilisant d'une de ces dites compositions moins le pouvoir stabilisant de la composition témoin n°1.On the other hand, to better highlight the advantages of the new compositions, the residual gain in OA provided by said compositions is defined as the difference in the stabilizing power of one of these said compositions minus the stabilizing power of the control composition n ° 1.
Le gain d'OA résiduel est exprimé en pourcent, par la formule suivante :
- Gain d'OA résiduel % = Pouvoir stabilisant % - Pouvoir stabilisant % (composition stabi- (composition N°1) sante)
- Residual OA gain% = Stabilizing power% - Stabilizing power% (stabilizing composition (composition N ° 1) healthy)
Le tableau 2 indique le pouvoir stabilisant et le gain d'OA résiduel des différentes compositions stabilisantes.
Les résultats du tableau 2 montrent que le pouvoir stabilisant et le gain d'OA n'augmentent pas d'une manière continue en fonction de l'augmentation du DTPA et du DTPMP dans la composition.The results of Table 2 show that the stabilizing power and the gain of OA do not increase continuously as a function of the increase in DTPA and DTPMP in the composition.
On remarque par exemple que les compositions N°5, 6 et 8 ont le même pouvoir stabilisant et le même gain d'OA alors que la somme des pourcentages de DTPA et DTPMP sont respectivement de 10,7 %, 11,4 % et 23 %.We note, for example, that compositions No. 5, 6 and 8 have the same stabilizing power and the same gain in OA while the sum of the percentages of DTPA and DTPMP are respectively 10.7%, 11.4% and 23 %.
L'effet de synergie entre les deux séquestrants est particulièrement marqué pour la composition N°6; il est illustré par le tableau 3.
Le tableau 3 montre que la somme des résultats des compositions N°2 et 4 correspondant à la composition hypothétique (2 + 4) ? sont nettement inférieures en tant que pouvoir stabilisant et gain d'OA, aux résultats de la composition N°6 qui contient réellement des pourcentages de DTPA et DTPMP légèrement inférieurs aux pourcentages de DTPA et DTPMP de la composition hypothétique (2+4) ?Table 3 shows that the sum of the results of compositions N ° 2 and 4 corresponding to the hypothetical composition (2 + 4)? are significantly lower as stabilizing power and gain of OA, to the results of composition No. 6 which actually contains percentages of DTPA and DTPMP slightly lower than the percentages of DTPA and DTPMP of the hypothetical composition (2 + 4)?
La synergie du DTPA et du DTPMP à des teneurs relativement faibles est particulièrement avantageuse sur le plan économique car le DTPMP est nettement plus cher que le DTPA.The synergy of DTPA and DTPMP at relatively low levels is particularly advantageous from an economic point of view because DTPMP is significantly more expensive than DTPA.
La composition N06 qui ne contient que 4,4 % de DTPMP a le même pouvoir stabilisant et le. même gain d'OA que la composition N°5, par exemple qui contient 10,7 % de DTPMP.Composition N 0 6 which contains only 4.4% of DTPMP has the same stabilizing power and the. same gain in OA as composition No. 5, for example which contains 10.7% of DTPMP.
Si l'on considère la dégradation de la fibre textile au cours des lavages successifs et plus particulièrement la diminution du degré de polymérisation (D.P.) de la cellulose du coton, on ne retrouve pas un effet de synergie aussi net mais les résultats montrent cependant que l'association du DTPA et du DTPMP, à faibles teneurs et dans des proportions bien déterminées, procurent des résultats satisfaisants.If we consider the degradation of the textile fiber during successive washings and more particularly the decrease in the degree of polymerization (DP) of cotton cellulose, we do not find such a synergistic effect but the results show however that the combination of DTPA and DTPMP, at low contents and in well-defined proportions, give satisfactory results.
Les essais concernant la diminution du DP de la cellulose du coton ont été réalisés selon le protocole expérimental suivant :The tests concerning the reduction in the DP of cotton cellulose were carried out according to the following experimental protocol:
On soumet des pièces de tissu à une succession de 10 lavages à 90°C pendant 40 minutes dans un appareil Terg-o-tometer le bain lessiviel a la composition suivante :
Les pièces testées sont en tissu EMPA 301 : il s'agit d'un tissu de référence, en coton, utilisé dans l'industrie textile et du blanchiment ; ce tissu est fourni par le Laboratoire Fédéral d'Essais des Matériaux de l'Institut de Recherches de St Gall en SUISSE.The parts tested are made of EMPA 301 fabric: it is a reference fabric, made of cotton, used in the textile and bleaching industry; this fabric is supplied by the Federal Laboratory for Materials Testing of the St Gallen Research Institute in SWITZERLAND.
D'autre part, le degré de polymérisation de la cellulose est déterminé selon la méthode décrite dans la norme AFNOR T 12005. Le DP du tissu EMPA 301 était, au départ, avant les lavages, de 1850.On the other hand, the degree of polymerization of the cellulose is determined according to the method described in the AFNOR T 12005 standard. The DP of the EMPA 301 fabric was, at the start, before the washes, from 1850.
Les résultats de cette expérimentation sont rassemblés dans le tableau 4
Les résultats du tableau 4 montrent que le DP résiduel dépend généralement de la quantité globale de séquestrant DTPA et DTPMP présente dans la composition. Le DTPMP a un effet plus accentué que le DTPA sur la conservation du DP.The results in Table 4 show that the residual DP generally depends on the overall amount of DTPA and DTPMP sequestrant present in the composition. DTPMP has a more pronounced effect than DTPA on the storage of DP.
L'effet de synergie est moins marqué bien que la composition N°6, par exemple, donne un DP résiduel de 61,6 %, donc nettement supérieur au DP résiduel donné par la composition N°2 (52%) et la composition N°4 (43,2 %). EXEMPLE 5 (comparatif)The synergistic effect is less marked although composition No. 6, for example, gives a residual DP of 61.6%, therefore clearly greater than the residual DP given by composition No. 2 (52%) and composition N ° 4 (43.2%). EXAMPLE 5 (comparative)
On a recherché à comparer l'efficacité de diverses compositions stabilisantes pour les produits peroacydés, notamment lors de leur emploi dans le blanchiment et le blanchissage des fibres et tissus textiles.Attempts have been made to compare the effectiveness of various stabilizing compositions for peroacid products, in particular when they are used in the bleaching and bleaching of textile fibers and fabrics.
Selon l'exemple 5, tableau 3 (6), du brevet français 2140.213 on utilise une solution stabilisante à 36,1 % de 1 mole de NTA 0,47 mole de magnésium (provenant d'un sel soluble le sulfate de magnésium et 0,3 mole de HEDP. Soit une solution qui contient en poids 29 % de NTA à 90%, 15,8 % de MgSO4, 7 H2O et 14,1 % de HEDP à 60 %.According to Example 5, Table 3 (6), of French patent 2140.213, a 36.1% stabilizing solution of 1 mole of NTA 0.47 mole of magnesium is used (coming from a soluble salt, magnesium sulfate and 0 , 3 mole of HEDP, ie a solution which contains by weight 29% of NTA at 90%, 15.8% of MgSO 4 , 7 H 2 O and 14.1% of HEDP at 60%.
Selon la présente invention la composition stabilisante est constituée par 78 % de silicate de magnésium colloïdal, 14,5 % de DTPA en solution 40 % (sel de sodium) et 7,5 % de DTPMP en solution à 50 %.According to the present invention, the stabilizing composition consists of 78% colloidal magnesium silicate, 14.5% DTPA in 40% solution (sodium salt) and 7.5% DTPMP in 50% solution.
Pour vérifier l'efficacité des différentes compositions stabilisantes, on a réalisé des successions de lavages de tissus EMPA 301 en présence de fer et de cuivre.To verify the effectiveness of the various stabilizing compositions, successions of washing of EMPA 301 fabrics were carried out in the presence of iron and copper.
Sur appareil "Terg-O-tometer", on soumet les pièces de tissu à une succession de lavages à 90°C, pendant 40 minutes, y compris le temps de montée en température (environ 30 minutes), dans un bain lessiviel de composition suivante :
La dégradation de la cellulose a été évaluée par détermination du degré de polymérisation DP après une succession de 5 lavages en présence de chaque composition stabilisante.The degradation of the cellulose was evaluated by determining the degree of DP polymerization after a succession of 5 washes in the presence of each stabilizing composition.
L'exemple cité dans le brevet français 2.140.213 fait état d'une dose de 2g/l de composition stabilisante dans un bain contenant 22g de H202 à 35 % par litre.The example cited in French patent 2,140,213 reports a dose of 2 g / l of stabilizing composition in a bath containing 22 g of H 2 0 2 at 35% per liter.
II n'a été appliqué que 0,2 g/l de la dite composition stabilisante comparativement à la même quantité pour la présente invention en raison d'une teneur en oxygène actif beaucoup plus faible soit 300 mg/l au lieu de 3600 mg/l dans l'art antérieur.It was applied only 0.2 g / l of said stabilizing composition compared to the same amount for the present invention due to a much lower active oxygen content is 300 mg / l instead of 3600 mg / l in the prior art.
Les résultats obtenus sont consignés dans le tableau 5
La lecture des résultats figurant dans ce tableau démontre l'effet de synergie de l'association de la composition de l'essai n°5, selon l'invention : silicate de magnésium colloidal+DTPA + DTPMP, alors qu'aucune amélioration de la protection de la cellulose n'est obtenue dans les essais n°8 et 11 : respectivement relatifs aux associations silicate de magnésium colloïdal ÷NTA + HEDP et sulfate de magnésium + NTA + HEDP.Reading the results in this table demonstrates the synergistic effect of the combination of the composition of test No. 5, according to the invention: colloidal magnesium silicate + DTPA + DTPMP, while no improvement in the Cellulose protection is not obtained in tests 8 and 11: respectively relating to the associations of colloidal magnesium silicate ÷ NTA + HEDP and magnesium sulfate + NTA + HEDP.
De plus on constate que dans les conditions de l'essai 5, le perborate de sodium est mieux stabilisé que dans les autres essais. Dans l'essai 5 la quantité d'oxygène actif résiduel est de 45 alors qu'elle n'est que de 5 et 10 % dans les essais n° 8 et 11.Furthermore, it is found that under the conditions of test 5, the sodium perborate is better stabilized than in the other tests. In test 5 the quantity of residual active oxygen is 45 whereas it is only 5 and 10% in tests n ° 8 and 11.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81401577T ATE6431T1 (en) | 1980-11-04 | 1981-10-13 | STABILIZER COMPOSITIONS FOR PEROXIDES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8023524 | 1980-11-04 | ||
| FR8023524A FR2493294A1 (en) | 1980-11-04 | 1980-11-04 | STABILIZING COMPOSITIONS FOR PEROXIDE PRODUCTS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0051509A1 true EP0051509A1 (en) | 1982-05-12 |
| EP0051509B1 EP0051509B1 (en) | 1984-02-29 |
Family
ID=9247659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81401577A Expired EP0051509B1 (en) | 1980-11-04 | 1981-10-13 | Stabilizing compositions for peroxides |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4384970A (en) |
| EP (1) | EP0051509B1 (en) |
| JP (1) | JPS57105499A (en) |
| AT (1) | ATE6431T1 (en) |
| CA (1) | CA1166406A (en) |
| DE (1) | DE3162441D1 (en) |
| DK (1) | DK149338C (en) |
| ES (1) | ES506799A0 (en) |
| FI (1) | FI66820C (en) |
| FR (1) | FR2493294A1 (en) |
| GR (1) | GR75357B (en) |
| NO (1) | NO154343C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0072166A1 (en) * | 1981-08-08 | 1983-02-16 | THE PROCTER & GAMBLE COMPANY | Bleach catalyst compositons, use thereof in laundry bleaching and detergent compositions, and process of bleaching therewith |
| FR2518115A1 (en) * | 1981-12-10 | 1983-06-17 | Colgate Palmolive Co | PEROXYGEN BLEACHING COMPOSITION AND PROCESS FOR PREPARING THE SAME |
| EP0210952A1 (en) * | 1985-07-19 | 1987-02-04 | Ciba-Geigy Ag | Aqueous, alkaline, silicate-containing composition for the bleaching of cellulosic fibres in the presence of percompounds |
| EP0750661A1 (en) * | 1994-03-14 | 1997-01-02 | The Procter & Gamble Company | Granular bleaching compositions |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60201388A (en) * | 1984-03-26 | 1985-10-11 | 日本板硝子株式会社 | Flash control for crt display |
| JPS6236498A (en) * | 1985-08-09 | 1987-02-17 | ル・エ−ル・リクイツド・ソシエテ・アノニム・プ−ル・ル・エチユド・エ・ル・エクスプルワテシヨン・デ・プロセデ・ジエオルジエ・クロ−ド | Cellulose protecting agent |
| GB8904007D0 (en) * | 1989-02-22 | 1989-04-05 | Procter & Gamble | Stabilized,bleach containing,liquid detergent compositions |
| DE4035813A1 (en) * | 1990-11-10 | 1992-05-14 | Akzo Gmbh | OXYGEN BLEACHING |
| EP0678572A1 (en) * | 1994-04-20 | 1995-10-25 | The Procter & Gamble Company | Detergent powder compositions |
| US5780419A (en) * | 1994-04-20 | 1998-07-14 | The Procter & Gamble Company | Detergent powder compositions comprising metal ion-chelant complex and anionic functional polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2140213A1 (en) * | 1971-06-03 | 1973-01-12 | Monsanto Co | |
| FR2396114A1 (en) * | 1977-06-29 | 1979-01-26 | Protex Manuf Prod Chimiq | Stabiliser compsn. for hydrogen peroxide fibre-bleaching baths - contains sodium silicate and magnesium complex prepd. esp. from phosphonic acid derivs. |
| FR2420593A1 (en) * | 1978-03-20 | 1979-10-19 | Kao Corp | BLEACHING COMPOSITION |
| FR2453212A1 (en) * | 1979-04-06 | 1980-10-31 | Unilever Nv | BLEACHING AND CLEANING COMPOSITIONS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1420462A (en) | 1964-10-22 | 1965-12-10 | Air Liquide | Stabilization process for peroxygen compounds |
| BE795085A (en) * | 1972-03-10 | 1973-05-29 | Benckiser Knapsack Gmbh | PROCESS FOR BLEACHING CELLULOSIC FIBERS SINGLE OR IN MIXTURE WITH SYNTHETIC FIBERS |
| FI64639C (en) * | 1978-09-27 | 1983-12-12 | Unilever Nv | BLEKNINGS- OCH RENGOERINGSKOMPOSITION |
-
1980
- 1980-11-04 FR FR8023524A patent/FR2493294A1/en active Granted
-
1981
- 1981-10-13 DE DE8181401577T patent/DE3162441D1/en not_active Expired
- 1981-10-13 EP EP81401577A patent/EP0051509B1/en not_active Expired
- 1981-10-13 AT AT81401577T patent/ATE6431T1/en not_active IP Right Cessation
- 1981-10-28 US US06/316,052 patent/US4384970A/en not_active Expired - Lifetime
- 1981-10-29 CA CA000388971A patent/CA1166406A/en not_active Expired
- 1981-10-29 GR GR66387A patent/GR75357B/el unknown
- 1981-11-03 NO NO813714A patent/NO154343C/en unknown
- 1981-11-03 FI FI813452A patent/FI66820C/en not_active IP Right Cessation
- 1981-11-03 ES ES506799A patent/ES506799A0/en active Granted
- 1981-11-03 DK DK485481A patent/DK149338C/en not_active IP Right Cessation
- 1981-11-04 JP JP56175869A patent/JPS57105499A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2140213A1 (en) * | 1971-06-03 | 1973-01-12 | Monsanto Co | |
| FR2396114A1 (en) * | 1977-06-29 | 1979-01-26 | Protex Manuf Prod Chimiq | Stabiliser compsn. for hydrogen peroxide fibre-bleaching baths - contains sodium silicate and magnesium complex prepd. esp. from phosphonic acid derivs. |
| FR2420593A1 (en) * | 1978-03-20 | 1979-10-19 | Kao Corp | BLEACHING COMPOSITION |
| FR2453212A1 (en) * | 1979-04-06 | 1980-10-31 | Unilever Nv | BLEACHING AND CLEANING COMPOSITIONS |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0072166A1 (en) * | 1981-08-08 | 1983-02-16 | THE PROCTER & GAMBLE COMPANY | Bleach catalyst compositons, use thereof in laundry bleaching and detergent compositions, and process of bleaching therewith |
| FR2518115A1 (en) * | 1981-12-10 | 1983-06-17 | Colgate Palmolive Co | PEROXYGEN BLEACHING COMPOSITION AND PROCESS FOR PREPARING THE SAME |
| EP0210952A1 (en) * | 1985-07-19 | 1987-02-04 | Ciba-Geigy Ag | Aqueous, alkaline, silicate-containing composition for the bleaching of cellulosic fibres in the presence of percompounds |
| EP0750661A1 (en) * | 1994-03-14 | 1997-01-02 | The Procter & Gamble Company | Granular bleaching compositions |
| EP0750661A4 (en) * | 1994-03-14 | 1998-10-07 | Procter & Gamble | Granular bleaching compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| FI813452L (en) | 1982-05-05 |
| ES8307660A1 (en) | 1983-07-01 |
| DK149338B (en) | 1986-05-05 |
| GR75357B (en) | 1984-07-13 |
| EP0051509B1 (en) | 1984-02-29 |
| FI66820C (en) | 1984-12-10 |
| FI66820B (en) | 1984-08-31 |
| FR2493294A1 (en) | 1982-05-07 |
| NO154343C (en) | 1986-09-03 |
| DE3162441D1 (en) | 1984-04-05 |
| DK149338C (en) | 1987-02-02 |
| US4384970A (en) | 1983-05-24 |
| ES506799A0 (en) | 1983-07-01 |
| JPS57105499A (en) | 1982-06-30 |
| CA1166406A (en) | 1984-05-01 |
| DK485481A (en) | 1982-05-05 |
| NO813714L (en) | 1982-05-05 |
| JPH0227399B2 (en) | 1990-06-15 |
| NO154343B (en) | 1986-05-26 |
| FR2493294B1 (en) | 1985-02-22 |
| ATE6431T1 (en) | 1984-03-15 |
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