EP0132184B1 - Washing compositions suitable for washing dishes in washing-machines - Google Patents

Washing compositions suitable for washing dishes in washing-machines Download PDF

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Publication number
EP0132184B1
EP0132184B1 EP84401373A EP84401373A EP0132184B1 EP 0132184 B1 EP0132184 B1 EP 0132184B1 EP 84401373 A EP84401373 A EP 84401373A EP 84401373 A EP84401373 A EP 84401373A EP 0132184 B1 EP0132184 B1 EP 0132184B1
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EP
European Patent Office
Prior art keywords
washing
coated
weight
trichloroisocyanuric acid
acid
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EP84401373A
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German (de)
French (fr)
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EP0132184A1 (en
Inventor
Pierre Scotte
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Chimique Des Charbonnages Sa Ste
Orkem SA
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Chimique Des Charbonnages Sa Ste
Chimique des Charbonnages SA
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Priority to AT84401373T priority Critical patent/ATE24015T1/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
    • C11D3/395—Bleaching agents
    • C11D3/3958—Bleaching agents combined with phosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents

Definitions

  • the present invention relates to new detergent compositions suitable for washing dishes in a washing machine, and to a process for their preparation.
  • the disinfecting agent used which releases active chlorine is generally a solid chlorine product, most often a sodium or potassium salt of dichloroisocyanuric acid.
  • an anhydrous sodium dichloroisocyanurate titrating 63% active chlorine has been used in practice, or a sodium dihydrate dichloroisocyanurate titrating 56% active chlorine, or an anhydrous potassium dichloroisocyanurate titrating 59% active chlorine, either a potassium dichloroisocyanurate monohydrate titrating 56% active chlorine, or a calcium dichloroisocyanurate tetrahydrate titrating 56% active chlorine.
  • Active chlorine is defined as the oxidizing power due to positive chlorine.
  • the chlorinated agent which is a chlorinated trione triazine
  • the chlorinated agent is coated with phthalic diester acid or adipinic acid.
  • American patent US Pat. No. 3,703,470 proposes the coating of nonionic and anti-foaming surfactants with synthetic resins in order to avoid their reaction with chlorinated agents.
  • the chlorinated agent which is trichloroisocyanuric acid is stabilized using olefins having a tertiary carbon on a double bond, such as terpenes.
  • Polyethylene waxes have been found to be compatible with trichloroisocyanuric acid. In addition, they allow using relatively low doses to obtain good acid stabilization. Furthermore, they are dispersible under washing conditions, that is to say in aqueous media having a temperature of 50 to 65 ° C.
  • Polyethylene waxes are used in an amount of 0.5 to 10% by weight relative to the trichloroisocyanuric acid and preferably in an amount of 3 to 5% by weight. Beyond 5% of the difficulties for the implementation of the coating appear and it is necessary to adjust the conditions of the coating.
  • the laundry compositions which are the subject of the invention are produced by first coating the trichloroisocyanuric acid with the aid of polyethylene waxes.
  • This coating is carried out in any industrial mixer, such as a drum mixer, preferably a mixer provided with a heating device. It is also possible to use a rotary mixer of the concrete mixer type in which the molten wax is sprayed on the acid heated to a temperature close to 50 ° C. The processing temperature allows a good distribution of polyethylene waxes which solidify on cooling.
  • the wax-coated trichloroisocyanuric acid is then mixed in another mixer with the other constituents of the detergent.
  • the amounts of the various constituents used for the manufacture of the new detergent compositions which are the subject of the invention are used in conventional weight ratios.
  • the softening agent chosen from polyphosphates is used in an amount of 25 to 60% by weight and preferably from 40 to 50% by weight relative to the weight of the composition.
  • the alkanizing agent chosen from sodium salts containing sodium metasilicate is used in an amount of 30 to 70% by weight and preferably from 40 to 60% by weight relative to the weight of the composition.
  • the sodium silicate can be partially replaced by sodium carbonate, sodium sulphate or soda.
  • the nonionic surfactant is used in an amount of 0.5 to 4% by weight and preferably in an amount of 1 to 3% by weight relative to the weight of the composition
  • the trichloroisocyanuric acid coated with the using polyethylene waxes is used in an amount of 0.5 to 5% by weight and preferably 1 to 3% by weight relative to the weight of the composition.
  • the sodium tripolyphosphate is premixed with the nonionic surfactant in a rotary type mixer. After 20 minutes a homogeneous mixture is obtained. The metasilicate is then added to the mixer and after 20 minutes the coated trichloroisocyanuric acid is added. The assembly is then left in the rotating mixer for 20 minutes. The percentage of chlorine dosed by iodometry in the detergent composition is then 1.65%.
  • Table 1 shows the results obtained after 80 days of storage for detergent compositions prepared either from anhydrous sodium metasilicate, or from sodium metasilicate pentahydrate and from trichloroisocyanuric acid coated with waxes. polyethylene used in variable percentages (by weight). Chlorine results remaining are expressed as percentages relative to the initial chlorine.
  • Example 1 is repeated using trichloroisocyanuric acid coated with various quantities of polyethylene waxes and the determination of the remaining chlorine is carried out after 70 days of storage.
  • Table 2 summarizes the results obtained.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Meat, Egg Or Seafood Products (AREA)
  • Table Devices Or Equipment (AREA)
  • Devices For Medical Bathing And Washing (AREA)
  • Seeds, Soups, And Other Foods (AREA)

Abstract

1. A washing compound suitable for washing crockery in dishwashers, comprising as a percentage by weight relative to composition : - 25 to 60% softening agent selected from polyphosphates, - 30 to 70% alkalinising agent selected from sodium salts containing sodium metasilicate, - 0.5 to 4% non ionic surface-active agent, - 0.5 to 5% coated trichloroisocyanuric acid, characterised in that the trichloroisocyanuric acid is coated using a polyethylene wax in a proportion of 0.5 to 10% by weight relative to the weight of the acid, the said wax having a mean molecular weight of approximately 2 500, a low melting point of less than 70 degrees C, a dripping point of 70 to 80 degrees C with a density of 0.86 to 0.88.

Description

La présente invention concerne de nouvelles compositions de lessive convenant pour le lavage de la vaisselle en machine à laver, et leur procédé de préparation.The present invention relates to new detergent compositions suitable for washing dishes in a washing machine, and to a process for their preparation.

Le lavage de la vaisselle en machine fait intervenir à la fois l'action détergente de la lessive et l'action mécanique de l'eau. En dehors de son action détergente, la lessive doit aussi posséder un pouvoir désinfectant et des propriétés adoucissantes de l'eau, Il est donc nécessaire que la lessive ait une forte détergence mais aussi une composition telle qu'elle ne provoque pas la formation de mousses nuisibles à l'action mécanique de l'eau. C'est pourquoi les compositions de lessive sont constituées de façon connue :

  • - d'un agent adoucissant généralement choisi dans la classe des polyphosphates. Parmi les polyphosphates utilisés, on peut citer le tripolyphosphate de sodium, l'hexamétaphosphate de sodium, le pyrophosphate de sodium, ainsi que les polyphosphates de potassium correspondants.
  • - d'un agent alcalinisant qui est constitué par un sel de sodium contenant un métasilicate de sodium sous sa forme anhydre ou sous sa forme pentahydrate, De façon connue le silicate de sodium peut être partiellement remplacé par du carbonate de soude, du sulfate de sodium, ou de la soude,
  • - d'un agent tensio-actif non moussant du type non ionique choisi parmi les classes de produits suivants : alcools linéaires éthoxylés, condensat d'oxyde d'éthylène sur l'oxyde de propylène, oxyalcoyl amines, polyéthoxyéthers d'alcools gras, alkyl phénols éthoxylés ou esters phosphoriques d'alcools gras. De préférence, pour des raisons d'efficacité, de biodégradabilité et de coûts, on choisit un agent tensio-actif de la classe des alcools linéaires éthoxylés,
  • - et d'un agent de désinfection.
Dishwashing in the machine involves both the detergent action and the mechanical action of water. Apart from its detergent action, the detergent must also have a disinfecting power and softening properties of water. It is therefore necessary that the detergent has a strong detergency but also a composition such that it does not cause foaming. harmful to the mechanical action of water. This is why the detergent compositions are constituted in a known manner:
  • - a softening agent generally chosen from the class of polyphosphates. Among the polyphosphates used, mention may be made of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, as well as the corresponding potassium polyphosphates.
  • - an alkalizing agent which consists of a sodium salt containing a sodium metasilicate in its anhydrous form or in its pentahydrate form, In known manner the sodium silicate can be partially replaced by sodium carbonate, sodium sulfate , or soda,
  • - a non-foaming surfactant of the nonionic type chosen from the following classes of products: ethoxylated linear alcohols, ethylene oxide condensate on propylene oxide, oxyalkyl amines, polyethoxy ethers of fatty alcohols, alkyl ethoxylated phenols or phosphoric esters of fatty alcohols. Preferably, for reasons of efficiency, biodegradability and costs, a surfactant from the class of ethoxylated linear alcohols is chosen,
  • - and a disinfection agent.

L'agent de désinfection utilisé qui libère du chlore actif est généralement un produit chloré solide, le plus souvent un sel de sodium ou de potassium de l'acide dichloroisocyanurique. Jusqu'à présent on utilisait dans la pratique, soit un dichloroisocyanurate de sodium anhydre titrant 63 % de chlore actif, soit un dichloroisocyanurate, de sodium dihydrate titrant 56 % de chlore actif, soit un dichloroisocyanurate de potassium anhydre titrant 59 % de chlore actif, soit un dichloroisocyanurate de potassium monohydrate titrant 56 % de chlore actif, soit un dichloroisocyanurate de calcium tétrahydrate titrant 56 % de chlore actif. Le chlore actif est défini comme étant le pouvoir oxydant dû au chlore positif. Pour mieux comprendre à quoi correspond le chlore positif il faut rappeler que le chlore présent dans les dérivés chlorés décrits ci-dessus est fixé sur l'atome d'azote et s'y trouve sous la forme du degré d'oxydation + 1, c'est-à-dire CI'. Lors du processus d'oxydo-réduction un ion CI+ se combine à deux électrons pour passer au stade Cr (chlorure). Il y a libération de deux équivalents d'oxydants qui correspondent à 71 g de chlore élémentaire bien que la masse atomique ne soit que de 35,5. Ceci veut également dire qu'un atome de CI+ a le même pouvoir oxydant qu'une molécule de chlore élémentaire C12.The disinfecting agent used which releases active chlorine is generally a solid chlorine product, most often a sodium or potassium salt of dichloroisocyanuric acid. Until now, an anhydrous sodium dichloroisocyanurate titrating 63% active chlorine has been used in practice, or a sodium dihydrate dichloroisocyanurate titrating 56% active chlorine, or an anhydrous potassium dichloroisocyanurate titrating 59% active chlorine, either a potassium dichloroisocyanurate monohydrate titrating 56% active chlorine, or a calcium dichloroisocyanurate tetrahydrate titrating 56% active chlorine. Active chlorine is defined as the oxidizing power due to positive chlorine. To better understand what positive chlorine corresponds to, it should be remembered that the chlorine present in the chlorinated derivatives described above is fixed on the nitrogen atom and is there in the form of the degree of oxidation + 1, c 'ie CI'. During the oxidation-reduction process, a CI + ion combines with two electrons to pass to the Cr (chloride) stage. Two equivalents of oxidants are released which correspond to 71 g of elemental chlorine although the atomic mass is only 35.5. This also means that an atom of CI + has the same oxidizing power as a molecule of elementary chlorine C1 2 .

Parmi les autres agents de désinfection chlorés de la famille des chloroisocyanuriques, il en existe un : l'acide trichloroisocyanurique qui titre près de 91 % de chlore actif. Il serait donc avantageux de pouvoir utiliser ce composé étant donné son pourcentage élevé en chlore actif. Malheureusement, jusqu'à présent son emploi n'était pas possible car il présente une trop grande réactivité vis-à-vis des autres constituants des compositions de lessives en particulier vis-à-vis des agents tensio-actifs, ce qui rend les lessives contenant de l'acide trichloroisocyanurique instables au stockage car elles perdent à la fois des quantités importantes de chlore et de tensio-actifs par destruction mutuelle.Among the other chlorinated disinfectants in the chloroisocyanuric family, there is one: trichloroisocyanuric acid, which contains almost 91% active chlorine. It would therefore be advantageous to be able to use this compound given its high percentage of active chlorine. Unfortunately, until now its use was not possible because it has too great a reactivity with respect to the other constituents of the detergent compositions in particular with respect to the surfactants, which makes the detergents containing trichloroisocyanuric acid unstable on storage as they lose both significant amounts of chlorine and surfactants by mutual destruction.

Différentes méthodes de stabilisation des agents de désinfection chlorés ont été mises au point. Selon la demande de brevet européen 54094, l'agent chloré, qui est une triazine trione chloré est enrobé à l'aide d'acide phtalique diester ou d'acide adipinique. Le brevet américain US-A-3 703 470 propose l'enrobage des agents tensio-actifs non ioniques et antimoussants à l'aide de résines synthétiques afin d'éviter leur réaction avec les agents chlorés. Selon le brevet américain US-A-3 108 078, l'agent chloré qui est l'acide trichloroisocyanurique est stabilisé à l'aide d'oléfines possédant un carbone tertiaire sur une double liaison, tels que les terpènes. De manière différente, le brevet américain US-A-4 126 717 propose un enrobage à l'aide d'un mélange constitué d'un acide gras, d'une cire microcristalline et éventuellement d'un copolymère de polyoxyéthylène-polyoxypropylène, à raison d'au moins 35 % en poids par rapport à la particule d'acide enrobé.Different methods of stabilizing chlorinated disinfectants have been developed. According to European patent application 54094, the chlorinated agent, which is a chlorinated trione triazine, is coated with phthalic diester acid or adipinic acid. American patent US Pat. No. 3,703,470 proposes the coating of nonionic and anti-foaming surfactants with synthetic resins in order to avoid their reaction with chlorinated agents. According to American patent US-A-3 108 078, the chlorinated agent which is trichloroisocyanuric acid is stabilized using olefins having a tertiary carbon on a double bond, such as terpenes. In a different way, American patent US-A-4,126,717 proposes a coating using a mixture consisting of a fatty acid, a microcrystalline wax and possibly a copolymer of polyoxyethylene-polyoxypropylene, at the right rate. at least 35% by weight relative to the particle of coated acid.

On a maintenant trouvé le moyen de stabiliser l'acide trichloroisocyanurique, en particulier de le stabiliser pour la fabrication de compositions de lessives stables au stockage convenant pour le lavage de la vaisselle en machines à laver.We have now found a way to stabilize trichloroisocyanuric acid, in particular to stabilize it for the manufacture of storage stable laundry compositions suitable for washing dishes in washing machines.

La présente invention concerne une nouvelle composition de lessive convenant pour le lavage de la vaisselle en machine à laver, contenant par rapport à la composition :

  • - 25 à 60 % en poids d'un agent adoucissant choisi parmi les polyphosphates,
  • - 30 à 70 % en poids d'un agent alcalinisant choisi parmi les sels de sodium contenant du métasilicate de sodium,
  • - 0,5 à 4 % en poids d'un agent tensio-actif non ionique,
  • - 0,5 à 5 % en poids d'acide trichloroisocyanurique enrobé,

caractérisé par le fait que l'acide trichloroisocyanurique est enrobé à l'aide d'une cire de polyéthylène utilisée à raison de 0.5 à 10% en poids par rapport au poids d'acide, ladite cire possédant un poids moléculaire moyen d'environ 2 500, un bas point de fusion inférieur à 70 °C. un point de goutte de 70 à 80 °C et une densité de 0,86-0.88.The present invention relates to a new detergent composition suitable for washing dishes in a washing machine, containing with respect to the composition:
  • 25 to 60% by weight of a softening agent chosen from polyphosphates,
  • 30 to 70% by weight of an basifying agent chosen from sodium salts containing sodium metasilicate,
  • - 0.5 to 4% by weight of a nonionic surfactant,
  • - 0.5 to 5% by weight of coated trichloroisocyanuric acid,

characterized in that the trichloroisocyanuric acid is coated using a polyethylene wax used in an amount of 0.5 to 10% by weight relative to the weight of acid, said wax having a weight molecular average of about 2,500, a low melting point below 70 ° C. a drop point of 70 to 80 ° C and a density of 0.86-0.88.

On a trouvé que les cires de polyéthylène étaient compatibles avec l'acide trichloroisocyanurique. De plus, elles permettent en utilisant des doses relativement faibles d'obtenir une bonne stabilisation de l'acide. Par ailleurs, elles sont dispersibles dans les conditions de lavage, c'est-à-dire dans les milieux aqueux ayant une température de 50 à 65 °C.Polyethylene waxes have been found to be compatible with trichloroisocyanuric acid. In addition, they allow using relatively low doses to obtain good acid stabilization. Furthermore, they are dispersible under washing conditions, that is to say in aqueous media having a temperature of 50 to 65 ° C.

Les cires de polyéthylène sont utilisées à raison de 0,5 à 10 % en poids par rapport à l'acide trichloroisocyanurique et de préférence à raison de 3 à 5 % en poids. Au-delà de 5 % des difficultés pour la mise en oeuvre de l'enrobage apparaissent et il est nécessaire d'ajuster les conditions de l'enrobage.Polyethylene waxes are used in an amount of 0.5 to 10% by weight relative to the trichloroisocyanuric acid and preferably in an amount of 3 to 5% by weight. Beyond 5% of the difficulties for the implementation of the coating appear and it is necessary to adjust the conditions of the coating.

La mise en oeuvre de quantités supérieures à 10% n'apporte pas d'amélioration sensible de la stabilité au stockage des compositions de lessive ; l'utilisation de quantités inférieures à 0,5 % conduit à une stabilisation de l'acide non significative.The use of amounts greater than 10% does not bring a significant improvement in the storage stability of the laundry compositions; the use of amounts less than 0.5% leads to an insignificant acid stabilization.

Les compositions de lessive, objet de l'invention sont fabriquées en réalisant préalablement l'enrobage de l'acide trichloroisocyanurique à l'aide des cires de polyéthylène. Cet enrobage est effectué dans n'importe quel mélangeur industriel, tel que mélangeur à tambour, de préférence un mélangeur muni d'un dispositif de chauffage. Il est aussi possible d'utiliser un mélangeur tournant du type bétonnière dans lequel on pulvérise la cire fondue sur l'acide chauffé à une température voisine de 50 °C. La température de mise en oeuvre permet une bonne répartition des cires de polyéthylène qui se solidifient au refroidissement. L'acide trichloroisocyanurique enrobé de cire est ensuite mélangé dans un autre mélangeur avec les autres constituants de la lessive.The laundry compositions which are the subject of the invention are produced by first coating the trichloroisocyanuric acid with the aid of polyethylene waxes. This coating is carried out in any industrial mixer, such as a drum mixer, preferably a mixer provided with a heating device. It is also possible to use a rotary mixer of the concrete mixer type in which the molten wax is sprayed on the acid heated to a temperature close to 50 ° C. The processing temperature allows a good distribution of polyethylene waxes which solidify on cooling. The wax-coated trichloroisocyanuric acid is then mixed in another mixer with the other constituents of the detergent.

Les quantités des différents constituants utilisés pour la fabrication des nouvelles compositions de lessive, objet de l'invention, sont utilisées dans des rapports pondéraux classiques. L'agent adoucissant choisi parmi les polyphosphates est utilisé à raison de 25 à 60 % en poids et de préférence de 40 à 50 % en poids par rapport au poids de la composition. L'agent alcanisant choisi parmi les sels de sodium contenant du métasilicate de sodium est utilisé à raison de 30 à 70 % en poids et de préférence de 40 à 60 % en poids par rapport au poids de la composition. De façon connue le silicate de sodium peut être partiellement remplacé par du carbonate de soude, du sulfate de sodium ou de la soude. L'agent tensio-actif non ionique est mis en oeuvre à raison de 0,5 à 4 % en poids et de préférence à raison de 1 à 3 % en poids par rapport au poids de la composition, L'acide trichloroisocyanurique enrobé à l'aide de cires de polyéthylènes est employé à raison de 0,5 à 5 % en poids et de préférence 1 à 3 % en poids par rapport au poids de la composition.The amounts of the various constituents used for the manufacture of the new detergent compositions which are the subject of the invention are used in conventional weight ratios. The softening agent chosen from polyphosphates is used in an amount of 25 to 60% by weight and preferably from 40 to 50% by weight relative to the weight of the composition. The alkanizing agent chosen from sodium salts containing sodium metasilicate is used in an amount of 30 to 70% by weight and preferably from 40 to 60% by weight relative to the weight of the composition. In known manner, the sodium silicate can be partially replaced by sodium carbonate, sodium sulphate or soda. The nonionic surfactant is used in an amount of 0.5 to 4% by weight and preferably in an amount of 1 to 3% by weight relative to the weight of the composition, the trichloroisocyanuric acid coated with the using polyethylene waxes is used in an amount of 0.5 to 5% by weight and preferably 1 to 3% by weight relative to the weight of the composition.

Les exemples suivants illustrent la présente invention.The following examples illustrate the present invention.

Exemple 1Example 1

On stabilise au préalable de l'acide trichloroisocyanurique à l'aide de cires de polyéthylène de la façon suivante :

  • L'acide est chauffé à une température de 50 °C puis est mis dans un mélangeur tournant. Durant la rotation du mélangeur, on pulvérise dessus à l'aide d'un pistolet des cires de polyéthylène. La température de mise en oeuvre permet une bonne répartition des cires qui se solidifient au refroidissement. Les cires de polyéthylène utilisées ont un point de fusion inférieur à 70 °C, un point de gouttes de 70 à 80 °C et une densité de 0,86 à 0,88. On réalise divers mélanges d'acide et de cires en mettant en oeuvre des pourcentages variables de cires de polyéthylène. Les mélanges ainsi obtenus sont utilisés pour la fabrication de compositions de lessive.
Trichloroisocyanuric acid is stabilized beforehand using polyethylene waxes as follows:
  • The acid is heated to a temperature of 50 ° C and then put into a rotating mixer. During the rotation of the mixer, polyethylene waxes are sprayed on it with a gun. The processing temperature allows a good distribution of the waxes which solidify on cooling. The polyethylene waxes used have a melting point below 70 ° C, a drop point of 70 to 80 ° C and a density of 0.86 to 0.88. Various mixtures of acid and waxes are produced using variable percentages of polyethylene waxes. The mixtures thus obtained are used for the manufacture of laundry compositions.

On prépare des lessives ayant la composition suivante (les parties sont exprimées en parties en poids) :

  • - tripolyphosphate de sodium : 50 parties.
  • - métasilicate de sodium (anhydre ou hydraté 5 H20) : 50 parties
  • - un tensio-actif non ionique éthoxylé fabriqué par la Société PCUK, de dénomination commerciale PLURAFAC RA 43: 2 parties,
  • - acide trichloroisocyanurique enrobé de cires de polyéthylène : 2 parties.
Detergents are prepared having the following composition (the parts are expressed in parts by weight):
  • - sodium tripolyphosphate: 50 parts.
  • - sodium metasilicate (anhydrous or hydrated 5 H 2 0): 50 parts
  • an ethoxylated nonionic surfactant manufactured by the company PCUK, with the commercial name PLURAFAC RA 43: 2 parts,
  • - trichloroisocyanuric acid coated with polyethylene waxes: 2 parts.

On réalise d'abord le pré-mélange du tripolyphosphate de sodium avec le tensio-actif non ionique dans un mélangeur de type tournant. Au bout de 20 minutes on obtient un mélange homogène. On ajoute ensuite le métasilicate dans le mélangeur et au bout de 20 minutes on ajoute l'acide trichloroisocyanurique enrobé. L'ensemble est alors laissé dans le mélangeur tournant pendant 20 minutes. Le pourcentage de chlore dosé par iodométrie dans la composition de lessive est alors de 1,65 %.First, the sodium tripolyphosphate is premixed with the nonionic surfactant in a rotary type mixer. After 20 minutes a homogeneous mixture is obtained. The metasilicate is then added to the mixer and after 20 minutes the coated trichloroisocyanuric acid is added. The assembly is then left in the rotating mixer for 20 minutes. The percentage of chlorine dosed by iodometry in the detergent composition is then 1.65%.

La composition de lessive ainsi obtenue est mise dans des sacs plastiques fermés par un lien non hermétique. Les sacs sont stockés dans une étuve à ambiance contrôlée dans les conditions suivantes :

  • - température : 42 °C,
  • - humidité relative : 85 %.
The composition of detergent thus obtained is put in plastic bags closed by a non-hermetic link. The bags are stored in a controlled atmosphere oven under the following conditions:
  • - temperature: 42 ° C,
  • - relative humidity: 85%.

Des échantillons sont prélevés après une durée de stockage comprise entre 2 et 3 mois et le chlore restant est analysé par iodométrie. Le tableau 1 indique les résultats obtenus après 80 jours de stockage pour des compositions de lessive préparés soit à partir de métasilicate de sodium anhydre, soit à partir de métasilicate de sodium pentahydrate et à partir d'acide trichloroisocyanurique enrobé à l'aide de cires de polyéthylène utilisées dans des pourcentages (en poids) variables. Les résultats concernant le chlore restant sont exprimés en pourcentages par rapport au chlore initial.

Figure imgb0001
Samples are taken after a storage period of between 2 and 3 months and the remaining chlorine is analyzed by iodometry. Table 1 shows the results obtained after 80 days of storage for detergent compositions prepared either from anhydrous sodium metasilicate, or from sodium metasilicate pentahydrate and from trichloroisocyanuric acid coated with waxes. polyethylene used in variable percentages (by weight). Chlorine results remaining are expressed as percentages relative to the initial chlorine.
Figure imgb0001

Exemple 2Example 2

L'exemple 1 est répété en mettant en oeuvre de l'acide trichloroisocyanurique enrobé avec diverses quantités de cires de polyéthylène et le dosage du chlore restant est réalisé après 70 jours de stockage. Le tableau 2 résume les résultats obtenus.

Figure imgb0002
Example 1 is repeated using trichloroisocyanuric acid coated with various quantities of polyethylene waxes and the determination of the remaining chlorine is carried out after 70 days of storage. Table 2 summarizes the results obtained.
Figure imgb0002

Claims (4)

1. A washing compound suitable for washing crockery in dishwashers, comprising as a percentage by weight relative to composition :
- 25 to 60 % softening agent selected from polyphosphates,
- 30 to 70 % alkalinising agent selected from sodium salts containing sodium metasilicate,
- 0.5 to 4 % non ionic surface-active agent,
- 0.5 to 5 % coated trichloroisocyanuric acid,

characterised in that the trichloroisocyanuric acid is coated using a polyethylene wax in a proportion of 0.5 to 10 % by weight relative to the weight of the acid, the said wax having a mean molecular weight of approximately 2 500, a low melting point of less than 70 °C, a dripping point of 70 to 80 °C with a density of 0.86 to 0.88.
2. A compound according to claim 1, characterised in that the trichloroisocyanuric acid is coated using polyethylene wax in a proportion of 3 to 5 % by weight.
3. A method for preparing compounds suitable for washing crockery in dishwashers according to claim 1, characterised in that the trichloroisocyanuric acid is coated in advance using polyethylene waxes and the coated trichloroisocyanuric acid is then mixed with the other constituents of the washing powder.
4. A method for preparing washing compounds according to claim 3, characterised in that the melted wax is then sprayed onto the trichloroisocyanuric acid which is heated to 50 °C.
EP84401373A 1983-07-08 1984-06-28 Washing compositions suitable for washing dishes in washing-machines Expired EP0132184B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84401373T ATE24015T1 (en) 1983-07-08 1984-06-28 DETERGENT COMPOSITIONS SUITABLE FOR CLEANING DISHES IN WASHING MACHINES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8311426 1983-07-08
FR8311426A FR2548683B1 (en) 1983-07-08 1983-07-08 NEW LAUNDRY COMPOSITIONS SUITABLE FOR WASHING DISHWASHER IN A WASHING MACHINE

Publications (2)

Publication Number Publication Date
EP0132184A1 EP0132184A1 (en) 1985-01-23
EP0132184B1 true EP0132184B1 (en) 1986-12-03

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EP (1) EP0132184B1 (en)
JP (1) JPS6036598A (en)
AT (1) ATE24015T1 (en)
BR (1) BR8403372A (en)
CA (1) CA1235975A (en)
DE (1) DE3461546D1 (en)
DK (1) DK161204C (en)
FR (1) FR2548683B1 (en)
NO (1) NO842756L (en)
ZA (1) ZA845038B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4762637A (en) * 1986-11-14 1988-08-09 Lever Brothers Company Encapsulated bleach particles for machine dishwashing compositions
US4919841A (en) * 1988-06-06 1990-04-24 Lever Brothers Company Wax encapsulated actives and emulsion process for their production
US5258132A (en) * 1989-11-15 1993-11-02 Lever Brothers Company, Division Of Conopco, Inc. Wax-encapsulated particles
US5200236A (en) * 1989-11-15 1993-04-06 Lever Brothers Company, Division Of Conopco, Inc. Method for wax encapsulating particles
US5834414A (en) * 1996-10-17 1998-11-10 Ecolab Inc. Detergent composition having improved chlorine stability characteristics, novel chlorine containing product format and method of making chlorine stable composition
WO2013093877A2 (en) 2011-12-23 2013-06-27 Koninklijke Philips Electronics N.V. Encapsulation system for controlled release of a bleaching agent
WO2013128328A2 (en) 2012-02-28 2013-09-06 Koninklijke Philips N.V. System and method for whitening teeth
WO2014097053A1 (en) 2012-12-18 2014-06-26 Koninklijke Philips N.V. Enhanced tooth whitening method combining sustained release varnish with light activation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3108078A (en) * 1958-04-14 1963-10-22 Colgate Palmolive Co Stabilized trichlorocyanuric acid and compositions containing same
US3703470A (en) * 1970-10-06 1972-11-21 Chemed Corp Storage stable detergent composition
US4078099A (en) * 1976-08-25 1978-03-07 Lever Brothers Company Encapsulated bleaches and methods for their preparation
EP0054094B1 (en) * 1980-12-11 1985-07-24 Eka Ab Detergent compositions stable to chlorine separation, and agents for producing same

Also Published As

Publication number Publication date
EP0132184A1 (en) 1985-01-23
BR8403372A (en) 1985-06-18
ZA845038B (en) 1985-03-27
JPS6036598A (en) 1985-02-25
FR2548683A1 (en) 1985-01-11
NO842756L (en) 1985-01-09
ATE24015T1 (en) 1986-12-15
DK335484D0 (en) 1984-07-06
FR2548683B1 (en) 1986-02-21
DK335484A (en) 1985-01-09
DK161204C (en) 1991-11-25
CA1235975A (en) 1988-05-03
DE3461546D1 (en) 1987-01-15
DK161204B (en) 1991-06-10

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