EP0051509B1 - Stabilizing compositions for peroxides - Google Patents

Stabilizing compositions for peroxides Download PDF

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Publication number
EP0051509B1
EP0051509B1 EP81401577A EP81401577A EP0051509B1 EP 0051509 B1 EP0051509 B1 EP 0051509B1 EP 81401577 A EP81401577 A EP 81401577A EP 81401577 A EP81401577 A EP 81401577A EP 0051509 B1 EP0051509 B1 EP 0051509B1
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Prior art keywords
stabilizing
composition
compositions
bleaching
magnesium silicate
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German (de)
French (fr)
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EP0051509A1 (en
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Jacques Tourdot
Henry Carron
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Priority to AT81401577T priority Critical patent/ATE6431T1/en
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    • 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 peroxidized 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, which has the effect of improving the elimination of many stains and restoring the linen to its original 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 the bleaching of 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 ° C., 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 tetracarboxylate tetrasodium and H 2 0 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-diphosphonic acid, called HEDP, nitrilotriacetic acid, called NTA, and water-soluble salts and a water-soluble salt such as sulfate. magnesium.
  • French patent 1,420,462 in the name of the applicant, relates to a process for stabilizing compounds peroxidized by magnesium silicate, during their use in the bleaching and bleaching of fibers and textile fabrics, according to which the silicate of magnesium 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 ethylenediaminetotetraacetic acid.
  • stabilizing compositions based on colloidal magnesium silicate are proposed for peroxidized 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 baths in the textile industry.
  • These compositions contain colloidal magnesium silicate associated with diethylenetriaminepentaacetic acid and with diethylenetriaminepentamethylenephosphonic acid.
  • the organophosphonic sequestrant diethylenetriaminepentamethylenephosphonic acid (DTPMP) is in acid or water soluble salt form.
  • the organoacetic sequestrant: diethylenetriaminepentaacetic acid is designated by (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 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 composition. witness # 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 under composition No. 6; it is illustrated in Table 3.
  • Table 3 shows that the sum of the results of compositions 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 No. 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.
  • the pieces 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 Research Institute of St Gall in Switzerland.
  • the degree of polymerization of the cellulose is determined according to the method described in standard AFNOR T 12005.
  • the DP of the fabric “EMPA 301 was, at the start, before the washes, of 1850.
  • Example 5 According to Example 5, Table 3 (6), from French patent 2,140,213, a 36.1% stabilizing solution of 1 mole of NTA, 0.47 mole of magnesium (from a soluble salt such as sulfate) is used. magnesium) and 0.3 moles of HEDP. Or 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 polymerization DP 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 amount of residual active oxygen is 45%, while it is only 5 and 10% in tests n ° 8 and 11.

Abstract

Stabilizing compositions for peroxide products, which contain colloidal magnesium silicate associated with diethylenetriamine pentaacetic acid and diethylenetriaminepentamethylene phosphonic acid. These stabilizing compositions are intended particularly for use in home and industrial laundry powders.

Description

La présente invention concerne des compositions stabilisantes pour produits peroxydés, 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 peroxidized 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, which has the effect of improving the elimination of many stains and restoring the linen to its original whiteness thanks to its whitening effect. Similarly, the textile industry generally uses baths comprising a peroxidized compound, such as hydrogen peroxide or sodium perborate for the bleaching of 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 °C, 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 ° C., 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 rèche, provoque des réserves en teinture par suite du manque d'hydrophilité, et cause des dépôts dans les appareils de blanchiment ou de blanchissage pouvant entraîner 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 US 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 substantial stabilizing agent is added. as 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 these 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 ; ledit complexe de magnésium étant formé à partir d'acides phosphoni- ques.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, constituted, in a concentrated form, by liquid and stable formulations composed of sodium silicate and a magnesium complex; 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 H202, 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 tetracarboxylate tetrasodium and H 2 0 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-diphosphonique, dit HEDP, l'acide nitrilotriacétique, dit NTA, et des sels solubles dans l'eau et un sel soluble dans l'eau telle 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-diphosphonic acid, called HEDP, nitrilotriacetic acid, called NTA, and water-soluble salts and a water-soluble salt such as sulfate. magnesium.

Et le brevet français 1.420.462, au nom de la demanderesse est relatif à un procédé de stabilisation de composés peroxydés 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 éthylènediami- notétracétique.And French patent 1,420,462, in the name of the applicant, relates to a process for stabilizing compounds peroxidized by magnesium silicate, during their use in the bleaching and bleaching of fibers and textile fabrics, according to which the silicate of magnesium is used preformed in the colloidal state. According to an embodiment of the method, the magnesium silicate preformed in the colloidal state is used in combination with small amounts of dimagnesium salt of ethylenediaminetotetraacetic acid.

Or, il a été trouvé qu'en présence de silicate de magnésium colloïdal, l'association de l'acide diéthylènetriaminepentaacétique et de l'acide diéthylènetriaminepentaméthylènephosphonique, 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 diethylenetriaminepentaacetic acid and diethylenetriaminepentamethylenephosphonic acid, used in small quantities, has a synergistic effect on the stability of the bleaching bath or laundering; 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 colloïdal, pour produits peroxydés, 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 du silicate de magnésium colloïdal associé à l'acide diéthylènetriaminepentaacétique et à l'acide diéthylènetriaminepentaméthylènephosphonique.According to the invention, stabilizing compositions based on colloidal magnesium silicate are proposed for peroxidized 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 baths in the textile industry. These compositions contain colloidal magnesium silicate associated with diethylenetriaminepentaacetic acid and with diethylenetriaminepentamethylenephosphonic acid.

On obtient des résultats intéressants avec une association stabilisante contenant 1 à 20 % d'acide diéthylènetriaminepentaacétique et 1 à 15 % d'acide triaminepentaméthylènephosphonique, en particulier des teneurs de 1,5 à 8 % en poids du séquestrant du type organoacétique et de 2 à 6 % en poids du séquestrant du type organophosphonique sont avantageuses.Interesting results are obtained with a stabilizing combination containing 1 to 20% of diethylenetriaminepentaacetic acid and 1 to 15% of triaminepentamethylenephosphonic acid, in particular contents of 1.5 to 8% by weight of the sequestrant of the organoacetic type and from 2 to 6% by weight of the organophosphonic type sequestrant are advantageous.

Le séquestrant organophosphonique : le diéthylènetriaminepentaméthylènephosphonique (DTPMP) est sous forme acide ou de sel soluble dans l'eau. Le séquestrant organoacétique : l'acide diéthylènetriaminepentaacétique est désigné par (DTPA).The organophosphonic sequestrant: diethylenetriaminepentamethylenephosphonic acid (DTPMP) is in acid or water soluble salt form. The organoacetic sequestrant: diethylenetriaminepentaacetic acid is designated by (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 peroxydé, caractérisée par le pourcentage d'oxygène actif résiduel.Tests have shown that there is a relationship between the conservation, or even the improvement of the degree of polymerization (DP) of a textile and the stabilization of the peroxidized 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, aux associations binaires du silicate de magnésium colloïdal avec le DTPA d'une part, et le DTPMP d'autre part, et à l'association ternaire selon le brevet français 2.140.213.

Figure imgb0001
Comparative tests carried out under identical conditions have shown the superior effectiveness of the stabilizing composition according to the invention and the synergistic effect of the new combination compared to the colloidal magnesium silicate used alone, with the binary associations of the colloidal magnesium silicate with DTPA on the one hand, and DTPMP on the other, and with the ternary association according to French patent 2,140,213.
Figure imgb0001

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 combination with the sequestering agents NTA + HEDP proposed in the patent referenced above, also constitutes an ineffective association with regard to the protection of the 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.

Exemple 1Example 1

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.

Figure imgb0002
Table 1 below indicates the proportions in percent of the different compositions produced.
Figure imgb0002

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 :

  • - Lessive du commerce (sans peroxyde) : 5 g/l
  • - Perborate de sodium tétrahydraté : 3 g/I
  • -Composition stabilisante : 0,2 g/I
  • - Fe (sel soluble) : 1,5 ppm
  • - Cu (sel soluble) : 1,5 ppm
These stabilizing compositions were tested in a detergent bath of the following formulation:
  • - Commercial detergent (without peroxide): 5 g / l
  • - Sodium perborate tetrahydrate: 3 g / I
  • -Stabilizing composition: 0.2 g / I
  • - Fe (soluble salt): 1.5 ppm
  • - Cu (soluble salt): 1.5 ppm

Le bain lessiviel est maintenu à 90 °C pendant 1 heure ; 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/OA initial en pourcent définit en quelque sorte le pouvoir stabilisant de la composition.The initial residual OA / OA ratio in percent somewhat defines 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 lesdites 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 composition. witness # 1.

Le gain d'OA résiduel est exprimé en pourcent, par la formule suivante :

  • Gain d'OA résiduel % = Pouvoir stabilisant % ― Pouvoir stabilisant %
  • (Composition stabilisante) (composition n° 1)
The residual OA gain is expressed in percent, by the following formula:
  • Residual OA gain% = Stabilizing power% - Stabilizing power%
  • (Stabilizing composition) (composition n ° 1)

Exemple 2Example 2

Le tableau 2 indique le pouvoir stabilisant et le gain d'OA résiduel des différentes compositions stabilisantes.

Figure imgb0003
Table 2 indicates the stabilizing power and the residual OA gain of the various stabilizing compositions.
Figure imgb0003

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%.

Exemple 3Example 3

L'effet de synergie entre les deux séquestrants est particulièrement marqué sous la composition n° 6 ; il est illustré par le tableau 3.

Figure imgb0004
The synergistic effect between the two sequestrants is particularly marked under composition No. 6; it is illustrated in Table 3.
Figure imgb0004

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 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 n° 6 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 No. 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.

Exemple 4Example 4

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 :

  • On soumet des pièces de tissu à une succession de 10 lavages à 90 °C pendant 40 minutes dans un appareil connu sous la marque commerciale « Terg-o-tometer » ; le bain lessiviel a la composition suivante :
    • - lessive du commerce (sans peroxyde) : 5 g/I
    • - Perborate de sodium tétrahydraté : 3 g/I
    • - Composition stabilisante : 0,2 g/I
    • - Fe (sel soluble) : 1,5 ppm ―Cu (sel soluble) : 1,5 ppm
The tests concerning the reduction in the DP of cotton cellulose were carried out according to the following experimental protocol:
  • Tissue pieces are subjected to a succession of 10 washes at 90 ° C for 40 minutes in an apparatus known under the trade name "Terg-o-tometer"; the detergent bath has the following composition:
    • - commercial detergent (without peroxide): 5 g / I
    • - Sodium perborate tetrahydrate: 3 g / I
    • - Stabilizing composition: 0.2 g / I
    • - Fe (soluble salt): 1.5 ppm ―Cu (soluble salt): 1.5 ppm

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 pieces 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 Research Institute of St Gall 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 standard AFNOR T 12005. The DP of the fabric “EMPA 301 was, at the start, before the washes, of 1850.

Les résultats de cette expérimentation sont rassemblés dans le tableau 4.

Figure imgb0005
The results of this experiment are collated in Table 4.
Figure imgb0005

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 lé 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 preservation 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 %).The synergistic effect is less marked although the composition n ° 6, for example, gives a residual DP of 61.6%, therefore clearly higher than the residual DP given by the composition n ° 2 (52%) and the composition n ° 4 (43.2%).

Exemple 5 (comparatif)Example 5 (comparative)

On a recherché à comparer l'efficacité de diverses compositions stabilisantes pour les produits peroxydés, 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 peroxidized 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 2.140.213 on utilise une solution stabilisante à 36,1 % de 1 mole de NTA, 0,47 mole de magnésium (provenant d'un sel soluble tel 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), from French patent 2,140,213, a 36.1% stabilizing solution of 1 mole of NTA, 0.47 mole of magnesium (from a soluble salt such as sulfate) is used. magnesium) and 0.3 moles of HEDP. Or 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 à 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 "EMPA 301" fabric washes 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 :

  • - Qualité de l'eau : eau distillée
  • - Lessive du commerce sans peroxyde : 5 g/I
  • ―Perborate de sodium tétrahydraté : 3 g/I
  • - Fer (sulfate de fer) : 1,5 ppm
  • ―Cuivre (sulfate de cuivre) : 1,5 ppm
  • -Tissu : 28 g pour 1 litre de bain
On a “Terg-o-tometer” device, the pieces of fabric are subjected to a succession of washes at 90 ° C., for 40 minutes, including the temperature rise time (approximately 30 minutes), in a detergent bath of composition. next :
  • - Water quality: distilled water
  • - Commercial detergent without peroxide: 5 g / I
  • ―Sodium perborate tetrahydrate: 3 g / I
  • - Iron (iron sulfate): 1.5 ppm
  • ―Copper (copper sulfate): 1.5 ppm
  • -Fabric: 28 g for 1 liter of bath

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 polymerization DP 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 2 g/I de composition stabilisante dans un bain contenant 22 g de H2O2 à 35 % par litre.The example cited in French patent 2,140,213 reports a dose of 2 g / I of stabilizing composition in a bath containing 22 g of H 2 O 2 at 35% per liter.

Il n'a été appliqué que 0,2 g/I de ladite 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/I au lieu de 3 600 mg/I dans l'art antérieur.Only 0.2 g / I of said stabilizing composition was applied compared to the same amount for the present invention due to a much lower active oxygen content, ie 300 mg / I instead of 3600 mg / I in the prior art.

Les résultats obtenus sont consignés dans le tableau 5

Figure imgb0006
The results obtained are shown in Table 5
Figure imgb0006

DP = degré de polymérisation OA % oxygène actif résiduel.DP = degree of polymerization OA% residual active oxygen.

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 colloïdal + 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 colloïdale + 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 was 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 amount of residual active oxygen is 45%, while it is only 5 and 10% in tests n ° 8 and 11.

Claims (4)

1. Stabilizing composition based on colloidal magnesium silicate for peroxide products, characterized in that it contains colloidal magnesium silicate in combination with diethylene triamine pentaacetic acid and diethylene triamine pentamethylene phosphonic acid.
2. Stabilizing composition according to claim 1, characterized in that the diethylene triamine pentaacetic acid is present In the combination in a ratio of 1 to 20 percent by weight and the diethylene triamine pentamethylene phosphonic acid in a ratio of 1 to 15 percent by weight.
3. Stabilizing composition according to claim 1, characterized in that the composition contains 1.5 to 8 percent by weight of diethylene triamine pentaacetic acid and 2 to 6 percent by weight of diethylene triamine pentamethylene phosphonic acid.
4. Use of the stabilizing composition according to one of the claims 1 to 3 for household and industrial washing agents.
EP81401577A 1980-11-04 1981-10-13 Stabilizing compositions for peroxides Expired EP0051509B1 (en)

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
FR8023524A FR2493294A1 (en) 1980-11-04 1980-11-04 STABILIZING COMPOSITIONS FOR PEROXIDE PRODUCTS
FR8023524 1980-11-04

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EP0051509A1 EP0051509A1 (en) 1982-05-12
EP0051509B1 true EP0051509B1 (en) 1984-02-29

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JP (1) JPS57105499A (en)
AT (1) ATE6431T1 (en)
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DE (1) DE3162441D1 (en)
DK (1) DK149338C (en)
ES (1) ES8307660A1 (en)
FI (1) FI66820C (en)
FR (1) FR2493294A1 (en)
GR (1) GR75357B (en)
NO (1) NO154343C (en)

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GR76237B (en) * 1981-08-08 1984-08-04 Procter & Gamble
US4378300A (en) * 1981-12-10 1983-03-29 Colgate-Palmolive Company Peroxygen bleaching composition
JPS60201388A (en) * 1984-03-26 1985-10-11 日本板硝子株式会社 Flash control for crt display
US4725281A (en) * 1985-07-19 1988-02-16 Ciba-Geigy Corporation Aqueous alkaline, silicate-containing composition and the use thereof for bleaching cellulosic fiber materials in the presence of per compounds
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
ES2190450T3 (en) * 1994-03-14 2003-08-01 Procter & Gamble GRANULAR WHITENING COMPOSITIONS.
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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1420462A (en) 1964-10-22 1965-12-10 Air Liquide Stabilization process for peroxygen compounds
US3766078A (en) * 1971-06-03 1973-10-16 Monsanto Co Processes for stabilizing peroxy solutions
BE795085A (en) * 1972-03-10 1973-05-29 Benckiser Knapsack Gmbh PROCESS FOR BLEACHING CELLULOSIC FIBERS SINGLE OR IN MIXTURE WITH SYNTHETIC FIBERS
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.
US4279769A (en) * 1978-03-20 1981-07-21 Kao Soap Co., Ltd. Bleaching composition
FI64639C (en) * 1978-09-27 1983-12-12 Unilever Nv BLEKNINGS- OCH RENGOERINGSKOMPOSITION
CH642678A5 (en) * 1979-04-06 1984-04-30 Unilever Nv Bleach and detergent.

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US4384970A (en) 1983-05-24
JPH0227399B2 (en) 1990-06-15
GR75357B (en) 1984-07-13
ES506799A0 (en) 1983-07-01
NO154343C (en) 1986-09-03
DK149338B (en) 1986-05-05
FR2493294A1 (en) 1982-05-07
DE3162441D1 (en) 1984-04-05
FI66820B (en) 1984-08-31
EP0051509A1 (en) 1982-05-12
NO154343B (en) 1986-05-26
DK149338C (en) 1987-02-02
FI66820C (en) 1984-12-10
DK485481A (en) 1982-05-05
NO813714L (en) 1982-05-05
CA1166406A (en) 1984-05-01
JPS57105499A (en) 1982-06-30
ATE6431T1 (en) 1984-03-15
ES8307660A1 (en) 1983-07-01
FI813452L (en) 1982-05-05

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