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EP0206959A2 - Bleaching process for a domestic fabric in a washing cycle - Google Patents

Bleaching process for a domestic fabric in a washing cycle Download PDF

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Publication number
EP0206959A2
EP0206959A2 EP86420169A EP86420169A EP0206959A2 EP 0206959 A2 EP0206959 A2 EP 0206959A2 EP 86420169 A EP86420169 A EP 86420169A EP 86420169 A EP86420169 A EP 86420169A EP 0206959 A2 EP0206959 A2 EP 0206959A2
Authority
EP
European Patent Office
Prior art keywords
carried out
activator
bleaching agent
bleaching
peroxidized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86420169A
Other languages
German (de)
French (fr)
Other versions
EP0206959A3 (en
EP0206959B1 (en
Inventor
Yann Dugenet
Gisèle Landan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Atochem SA, Elf Atochem SA filed Critical Atochem SA
Publication of EP0206959A2 publication Critical patent/EP0206959A2/en
Publication of EP0206959A3 publication Critical patent/EP0206959A3/en
Application granted granted Critical
Publication of EP0206959B1 publication Critical patent/EP0206959B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the present invention relates to the bleaching of household linen in a washing cycle comprising two stages.
  • formulations for washing household linen are essentially marketed, qualified as complete, containing both the agents ensuring detergency and those ensuring bleaching.
  • surfactants sodium polyphosphates such as, in particular, sodium tripolyphosphate.
  • persalts in particular sodium perborate.
  • the activators can be of various chemical nature.
  • the most used industrially and the most commonly cited are however compounds such as for example tetraacetylethylenediamine (TAED), ol-acetoxy-ol-methyl-N, N'-diacetylmalonamide which is the subject of French patents published under the numbers 2,363,541 and 2,363,629, cyanamide and its derivatives which are the subject of the French patent published under the number 2,340,371.
  • TAED tetraacetylethylenediamine
  • ol-acetoxy-ol-methyl-N N'-diacetylmalonamide
  • cyanamide and its derivatives which are the subject of the French patent published under the number 2,340,371.
  • the process of the invention makes it possible to improve the bleaching effect of peroxidized bleaching agents such as persalts but also hydrogen peroxide when they are used at a temperature at most equal to 70 ° C. in the presence of an activator during a household linen washing cycle.
  • the bath of the first stage contains, in kind and in quantity, the detergent products usually present in a conventional prewash currently carried out using a so-called complete detergent composition starting a known cycle, such as for example sodium tripolyphosphate.
  • detergent compositions can also contain, in nature and in quantity, ingredients usually present in such detergent compositions such as for example complexing agents of metal ions, surfactants, brighteners.
  • the bleaching agents present in the bath of the second step are chosen from those commonly used in complete detergent compositions to ensure in them the function of bleaching bleachable stains in household linen, such as for example hydrogen peroxide, persalts or peroxyhydrates such as sodium perborate, sodium percarbonate and urea peroxyhydrate.
  • the concentration of active oxygen resulting from the presence of such peroxidized bleaching agents is generally between 0.004 and 0.03% by weight relative to the weight of the bath.
  • the activator accompanying the bleaching agent in the bath of the second step can be of various nature without being called into question the observation of the improvement caused by the implementation of the invention. High whitening effects are however particularly observed when the activator is of the TAED type or cyanamide such as calcium cyanamide.
  • the molar ratio of peroxidized bleaching agent / activator can vary within fairly wide limits depending in particular on the nature of one or the other compound. Often it is between 1 and 10. When, for example, hydrogen peroxide or sodium perborate are chosen as bleaching agents, the activator being of the cyanamide or TAED type, it may more generally be between 5 and 10.
  • At least one proteolytic enzyme can be used during the first step.
  • detergent compositions comprise compounds of sufficiently alkalizing character so that the pH in the first stage is reached by their mere presence in this stage. Otherwise, an additional alkaline agent such as sodium hydroxide, among others, can be added to them.
  • the pH in the second stage is reached by means of an alca agent usual flax which cannot be oxidized or which cannot be reduced by peroxidized bleaching agents, sodium hydroxide being most frequently chosen for essentially economic and convenience reasons.
  • the preferred pH range in the second step is 9.5 to 12.5.
  • the temperature range, 40 ° C-60 ° C is indicated for carrying out the invention because it only leads, at a temperature below 40 ° C, to an insignificant improvement in the effect of bleaching and results, at a temperature above 60 ° C, in a rapidly prohibitive energy expenditure in comparison with the additional improvement then observed.
  • the cumulative duration of the first and second stages is generally less than 1 hour, each stage not exceeding 0.5 hours most often.
  • the measurements are carried out using an ELREPHO spectrophotometer, filter No. 8, from the company CARL ZEISS.
  • Examples 1 to 8 They relate to the tests carried out when the calcium cyanamide is the activator involved.
  • Examples 1 to 5 are carried out according to the invention, examples 6 to 8 given by way of comparison according to the conditions defined above for the "complete" washing, it being specified that the first step in example 5 and the step unique in Example 8 are performed in the presence of ESPERASE.
  • Table I collates the results obtained as a function of the temperature and of the pH of the bath of the second step of the process of the invention or of the "complete" washing bath.
  • Examples 9 to 13 They relate to the tests carried out when the TAED is the activator used.
  • Table II below collates the results as a function of the temperature and of the pH of the bath of the second step of the process of the invention or of the "complete" washing bath.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Blanchiment de linge domestique dans un cycle de lavage, caractérisé en ce qu'il est effectué en deux étapes à une température comprise entre 40° C et 60° C environ, la première réalisée à un pH compris entre 8 et 12 en présence d'une composition détergente exempte d'agents de blanchiment peroxydés, la seconde réalisée à un pH compris entre 9 et 13 en présence d'un agent de blanchiment peroxydé et d'un activeur en l'absence d'agents détergents, la première comme la seconde étape étant suivies d'opérations classiques de rinçage des cycles connus. La première étape peut être réalisée en présence d'un enzyme protéolytique.Laundering of household laundry in a washing cycle, characterized in that it is carried out in two stages at a temperature between 40 ° C and 60 ° C approximately, the first carried out at a pH between 8 and 12 in the presence of a detergent composition free from peroxidized bleaching agents, the second carried out at a pH between 9 and 13 in the presence of a peroxidized bleaching agent and an activator in the absence of detergents, the first like the second step being followed by conventional rinsing operations of known cycles. The first step can be carried out in the presence of a proteolytic enzyme.

Description

La présente invention concerne le blanchiment de linge domestique dans un cycle de lavage comprenant deux étapes.The present invention relates to the bleaching of household linen in a washing cycle comprising two stages.

Actuellement sont essentiellement commercialisées des formulations pour lavage du linge domestique, qualifiées de complètes, renfermant à la fois les agents assurant la détergence et ceux assurant le blanchiment.Currently, formulations for washing household linen are essentially marketed, qualified as complete, containing both the agents ensuring detergency and those ensuring bleaching.

Parmi les premiers, les plus communs sont les agents tensioactifs, les polyphosphates de sodium comme en particulier le tripolyphosphate de sodium.Among the first, the most common are surfactants, sodium polyphosphates such as, in particular, sodium tripolyphosphate.

Parmi les seconds, les plus couramment utilisés sont les persels, en particulier le perborate de sodium.Among the second, the most commonly used are persalts, in particular sodium perborate.

Ces persels, ou peroxyhydrates, sont des vecteurs de l'oxygène actif relativement coûteux et toute amélioration de leur effet de blanchiment peut se traduire par un gain économique indéniable.These persalts, or peroxyhydrates, are relatively expensive active oxygen carriers and any improvement in their bleaching effect can result in an undeniable economic gain.

Une amélioration est à rechercher particulièrement à basse température, 70°C et moins.An improvement is to be sought particularly at low temperature, 70 ° C and below.

En effet, dans ces conditions, les persels ne sont plus suffisamment actifs et il faut alors leur adjoindre des composés dits activeurs dont le coût réduit en partie le gain attribuable à la diminution de la consommation d'énergie thermique.In fact, under these conditions, the persalts are no longer sufficiently active and it is then necessary to add to them so-called activator compounds whose cost partially reduces the gain attributable to the reduction in the consumption of thermal energy.

Les activeurs peuvent être de nature chimique diverse . Les plus utilisés industriellement et les plus couramment cités sont cependant des composés tels que par exemple la tétraacétyléthylènediamine (TAED), l'ol-acétoxy-ol-méthyl-N,N'-diacétylmalonamide faisant l'objet des brevets français publiés sous les numéros 2 363 541 et 2 363 629, la cyanamide et ses dérivés faisant l'objet du brevet français publié sous le numéro 2 340 371.The activators can be of various chemical nature. The most used industrially and the most commonly cited are however compounds such as for example tetraacetylethylenediamine (TAED), ol-acetoxy-ol-methyl-N, N'-diacetylmalonamide which is the subject of French patents published under the numbers 2,363,541 and 2,363,629, cyanamide and its derivatives which are the subject of the French patent published under the number 2,340,371.

Le procédé de l'invention permet d'améliorer l'effet de blanchiment des agents de blanchiment peroxydés tels que les persels mais aussi le peroxyde d'hydrogène lorsqu'ils sont utilisés à une température au plus égale à 70°C en présence d'un activeur au cours d'un cycle de lavage de linge domestique.The process of the invention makes it possible to improve the bleaching effect of peroxidized bleaching agents such as persalts but also hydrogen peroxide when they are used at a temperature at most equal to 70 ° C. in the presence of an activator during a household linen washing cycle.

Il consiste à effectuer un tel cycle en deux étapes à une température comprise entre 40°C et 60°C environ, la première réalisée à un pH de 8 à 12 en présence d'une composition détergente exempte d'agents de blanchiment peroxydés, la seconde réalisée à un pH compris entre 9 et 13 en présence d'au moins un agent de blanchiment peroxydé et d'un activeur, en l'absence d'agents détergents, la première comme la seconde étape étant suivies d'opérations classiques de rinçage des cycles connus.It consists in carrying out such a cycle in two stages at a temperature between approximately 40 ° C. and 60 ° C., the first carried out at a pH of 8 to 12 in the presence of a detergent composition free of peroxidized bleaching agents, the second carried out at a pH between 9 and 13 in the presence of at least one peroxidized bleaching agent and of an activator, in the absence of detergents, the first as the second step being followed by conventional rinsing operations of known cycles.

Le bain de la première étape contient, en nature et en quantité, les produits détergents usuellement présents dans un prélavage classique actuellement réalisé à l'aide d'une composition lessivielle dite complète débutant un cycle connu, tel que par exemple le tripolyphosphate de sodium.The bath of the first stage contains, in kind and in quantity, the detergent products usually present in a conventional prewash currently carried out using a so-called complete detergent composition starting a known cycle, such as for example sodium tripolyphosphate.

Il peut aussi contenir, en nature et en quantité, des ingrédients usuellement présents dans de telles compositions lessivielles comme par exemple des complexants des ions métalliques, des surfactants, des azurants.It can also contain, in nature and in quantity, ingredients usually present in such detergent compositions such as for example complexing agents of metal ions, surfactants, brighteners.

Les agents de blanchiment présents dans le bain de la deuxième étape sont choisis parmi ceux communément mis en oeuvre dans les compositions lessivielles complètes pour assurer en elles la fonction de blanchissage des taches blanchissables du linge domestique, tels que par exemple le peroxyde d'hydrogène, les persels ou peroxyhydrates comme le perborate de sodium, le percarbonate de sodium et le peroxyhydrate d'urée.The bleaching agents present in the bath of the second step are chosen from those commonly used in complete detergent compositions to ensure in them the function of bleaching bleachable stains in household linen, such as for example hydrogen peroxide, persalts or peroxyhydrates such as sodium perborate, sodium percarbonate and urea peroxyhydrate.

La concentration en oxygène actif résultant de la présence de tels agents de blanchiment peroxydés est généralement comprise entre 0,004 et 0,03 % en poids par rapport au poids de bain.The concentration of active oxygen resulting from the presence of such peroxidized bleaching agents is generally between 0.004 and 0.03% by weight relative to the weight of the bath.

L'activeur accompagnant l'agent de blanchiment dans le bain de la deuxième étape peut être de nature diverse sans que soit remis en cause le constat de l'amélioration provoquée par la réalisation de l'invention. Des effets de blanchiment élevés sont cependant particulièrement observés lorsque l'activeur est du type TAED ou cyanamide comme la cyanamide calcique.The activator accompanying the bleaching agent in the bath of the second step can be of various nature without being called into question the observation of the improvement caused by the implementation of the invention. High whitening effects are however particularly observed when the activator is of the TAED type or cyanamide such as calcium cyanamide.

Le rapport molaire agent de blanchiment peroxydé/activeur peut varier dans d'assez larges limites selon en particulier la nature de l'un ou l'autre composé. Souvent il est compris entre 1 et 10. Lorsque, par exemple, le peroxyde d'hydrogène ou le perborate de sodium sont choisis comme agents de blanchiment, l'activeur étant du type cyanamide ou TAED, il pourra être plus généralement compris entre 5 et 10.The molar ratio of peroxidized bleaching agent / activator can vary within fairly wide limits depending in particular on the nature of one or the other compound. Often it is between 1 and 10. When, for example, hydrogen peroxide or sodium perborate are chosen as bleaching agents, the activator being of the cyanamide or TAED type, it may more generally be between 5 and 10.

S'il en est besoin, au moins un enzyme protéolytique peut être mis en oeuvre au cours de la première étape.If necessary, at least one proteolytic enzyme can be used during the first step.

La majorité des compositions détergentes comprennent des composés de caractère suffisamment alcalinisant pour que le pH dans la première étape soit atteint par leur seule présence dans cette étape. Sinon il peut leur être adjoint un agent alcalin supplémentaire tel que l'hydroxyde de sodium entre autres.The majority of detergent compositions comprise compounds of sufficiently alkalizing character so that the pH in the first stage is reached by their mere presence in this stage. Otherwise, an additional alkaline agent such as sodium hydroxide, among others, can be added to them.

Le pH dans la deuxième étape est atteint au moyen d'un agent alcalin usuel non oxydable ou non réductible par les agents de blanchiment peroxydés, l'hydroxyde de sodium étant le plus fréquemment choisi pour des raisons essentiellement économiques et de commodité.The pH in the second stage is reached by means of an alca agent usual flax which cannot be oxidized or which cannot be reduced by peroxidized bleaching agents, sodium hydroxide being most frequently chosen for essentially economic and convenience reasons.

Bien qu'une amélioration substantielle de l'effet de blanchiment soit encore observée quand le pH dans la deuxième étape est supérieur à 12,5, le risque de dégradation des fibres cellulosiques devient alors non négligeable.Although a substantial improvement in the bleaching effect is still observed when the pH in the second step is greater than 12.5, the risk of degradation of the cellulose fibers then becomes not negligible.

La zone préférée de pH dans la deuxième étape est 9,5 à 12,5.The preferred pH range in the second step is 9.5 to 12.5.

La gamme de température, 40°C-60°C, est indiquée pour la réalisation de l'invention car celle-ci ne conduit, à une température inférieure à 40°C, qu'à une amélioration peu significative de l'efiet de blanchiment et aboutit, à température supérieure à 60°C, à une dépense d'énergie rapidement prohibitive en comparaison de l'amélioration additionnelle alors constatée.The temperature range, 40 ° C-60 ° C, is indicated for carrying out the invention because it only leads, at a temperature below 40 ° C, to an insignificant improvement in the effect of bleaching and results, at a temperature above 60 ° C, in a rapidly prohibitive energy expenditure in comparison with the additional improvement then observed.

La durée cumulée de la première et de la deuxième étape est généralement inférieure à 1 heure, chaque étape ne dépassant pas alors 0,5 heure le plus fréquemment.The cumulative duration of the first and second stages is generally less than 1 hour, each stage not exceeding 0.5 hours most often.

Les exemples ci-dessous, donnés à titre indicatif mais non limitatif, illustrent le procédé de l'invention.The examples below, given as an indication but not limiting, illustrate the process of the invention.

Pour ces exemples :

  • - sous le terme de lessive est désignée dans ce qui suit la lessive normalisée EMPA® en poudre à base de tripolyphosphate de sodium (43,8% en poids).
  • - les deux étapes du procédé sont effectuées dans un bain-marie AHIBA G VI B à agitation verticale et rotative.
  • - le rapport pondéral bain/matière à blanchir est d'environ 20 dans chacune des étapes du procédé de l'invention comme dans l'étape unique des lavages qualifiés de "complets" et décrits à titre comparatif. La valeur relativement élevée de ce rapport est seulement due au type d'équipement utilisé.
  • - la matière a blanchir sont les tissus normalisés EMPA® respectivement tachés de vin, de thé ou de salissures protéiques (lait, sang, encre de Chine). Ces dernières seront désignées par s.p.
  • - les deux étapes sont effectuées à la même température choisie égale soit à 40°C, soit à 60°C et atteinte après une montée de 20 minutes dans le premier cas, de 30 minutes dans le second, à partir de la température ambiante de 20°C environ.
  • - le bain dans la première étape, dont le pH est de 9,6, contient par litre 5,8 g de lessive.
  • - le bain, dans la deuxième étape, dont le pH, atteint à l'aide d'hydroxyde de sodium, est indiqué plus loin cas par cas, renferme par par litre :
  • . 0,09 g d'oxygène actif apporté soit sous forme d'une solution aqueuse de peroxyde d'hydrogène à 35 % en poids, soit sous forme de perborate de sodium,
  • . une quantité de cyanamide calcique ou de TAED telle que le rapport molaire peroxyde d'hydrogène/activeur ou perborate de sodium/activeur soit égal à 8,5,
  • . le cas échéant, 0,0232 g d'un enzyme protéolytique, l'ESPERASE® de la Société NOVO.
  • - les lavages décrits à titre comparatif sont qualifiés de ncomplets". Ils comportent une étape unique effectuée à une température et à un pH indiqués cas par cas, pendant 60 minutes, durée au-delà de laquelle il ne se produit pratiquement plus d'amélioration de l'effet de blanchiment en présence des quantités de lessive, d'agent de blanchiment, d'activeur et, le cas échéant, d'enzyme et autres ingrédients, égales à la réunion de celles présentes dans chacune des deux étapes du mode de réalisation de l'invention auquel ils sont directement comparables, seule la quantité d'hydroxyde de sodium pouvant être adaptée le cas échéant pour que le pH lors du lavage "complet", soit celui dans la deuxième étape du procédé de l'invention.
  • - comme déjà indiqué, le linge traité est rincé d'une façon classique après chaque étape du procédé de l'invention comme après l'étape unique du lavage "complet".
  • - l'effet de blanchiment est défini par la différence entre les indices de blanc après et avant l'application du cycle de lavage, ou variation de blanc, rapportée, en pourcentage, à un blanc maximum de 100, selon la formule :

effet de blanchiment variation de blanc - 100 effet de blanchiment = variation de blanc 100-blanc initial x 100 100-blanc initialFor these examples:
  • - In the following, the term detergent is designated the standard EMPA® detergent powder based on sodium tripolyphosphate (43.8% by weight).
  • - the two stages of the process are carried out in an AHIBA G VI B water bath with vertical and rotary agitation.
  • - The weight ratio bath / material to be bleached is approximately 20 in each of the steps of the process of the invention as in the single step of washes described as "complete" and described for comparison. The relatively high value of this ratio is only due to the type of equipment used.
  • - the material to be bleached are EMPA® standardized fabrics, respectively stained with wine, tea or protein soiling (milk, blood, Indian ink). These will be designated by sp
  • - the two stages are carried out at the same chosen temperature equal to either 40 ° C or 60 ° C and reached after a rise of 20 minutes in the first case, 30 minutes in the second, from the ambient temperature of About 20 ° C.
  • - the bath in the first stage, whose pH is 9.6, contains 5.8 g of detergent per liter.
  • - the bath, in the second stage, the pH of which, reached using sodium hydroxide, is indicated below case by case, contains per per liter:
  • . 0.09 g of active oxygen supplied either in the form of an aqueous solution of hydrogen peroxide at 35% by weight, or in the form of sodium perborate,
  • . an amount of calcium cyanamide or TAED such that the molar ratio of hydrogen peroxide / activator or sodium perborate / activator is equal to 8.5,
  • . if necessary, 0.0232 g of a proteolytic enzyme, ESPERASE® from the company NOVO.
  • - washes described for comparison are called complete n "They have a single step performed at a temperature and pH indicated case by case, for 60 minutes duration beyond which there occurs practically more. improvement of the bleaching effect in the presence of the amounts of detergent, bleaching agent, activator and, where appropriate, enzyme and other ingredients, equal to the combination of those present in each of the two stages of the mode of carrying out the invention to which they are directly comparable, only the quantity of sodium hydroxide can be adapted if necessary so that the pH during the "complete" washing, is that in the second step of the process of the invention.
  • - As already indicated, the treated linen is rinsed in a conventional manner after each stage of the process of the invention as after the single stage of "complete" washing.
  • - the whitening effect is defined by the difference between the whiteness indices after and before the application of the washing cycle, or variation of whiteness, referred, in percentage, to a maximum whitespace of 100, according to the formula:

whitening effect white variation - 100 whitening effect = white variation initial 100-white x 100 initial white-100

Les mesures sont effectuées à l'aide d'un spectrophotomètre ELREPHO, filtre n°8, de la Société CARL ZEISS.The measurements are carried out using an ELREPHO spectrophotometer, filter No. 8, from the company CARL ZEISS.

Exemples 1 à 8 : Ils concernent les essais effectués lorsque la cyanamide calcique est l'activeur mis en jeu.Examples 1 to 8: They relate to the tests carried out when the calcium cyanamide is the activator involved.

Les exemples 1 à 5 sont réalisés selon l'invention, les exemples 6 à 8 donnés à titre comparatif selon les conditions définies ci-dessus pour le lavage "complet", étant précisé que la première étape dans l'exemple 5 et l'étape unique dans l'exemple 8 sont réalisées en présence d'ESPERASE.Examples 1 to 5 are carried out according to the invention, examples 6 to 8 given by way of comparison according to the conditions defined above for the "complete" washing, it being specified that the first step in example 5 and the step unique in Example 8 are performed in the presence of ESPERASE.

Le tableau I ci-dessous rassemble les résultats obtenus en fonction de la température et du pH du bain de la second étape du procédé de l'invention ou du bain de lavage "complet".

Figure imgb0001
Table I below collates the results obtained as a function of the temperature and of the pH of the bath of the second step of the process of the invention or of the "complete" washing bath.
Figure imgb0001

Exemples 9 à 13 : Ils concernent les essais effectués lorsque le TAED est l'activeur mis en oeuvre.Examples 9 to 13: They relate to the tests carried out when the TAED is the activator used.

Les exemples 9 à 11 sont réalisés selon l'invention, les exemples 12 et 13, donnés à titre comparatif, selon les conditions définies ci-dessus pour le lavage "complet".Examples 9 to 11 are carried out according to the invention, examples 12 and 13, given by way of comparison, according to the conditions defined above for the "complete" washing.

Le tableau II ci-après rassemble les résultats en fonction de la température et du pH du bain de la seconde étape du procédé de l'invention ou du bain de lavage "complet".

Figure imgb0002
Table II below collates the results as a function of the temperature and of the pH of the bath of the second step of the process of the invention or of the "complete" washing bath.
Figure imgb0002

Des tableaux I et II, certaines comparaisons mettent en lumière des avantages du procédé de l'invention.Tables I and II, certain comparisons highlight advantages of the process of the invention.

En particulier, de la comparaison des essais 6 et 2, des essais 7 et 3, des essais 12 et 10 et des essais 8 et 5, il ressort que le procédé de l'invention procure, à une température et à un pH donnés, un accroissement substantiel de l'effet de blanchiment. Cet effet est ici multiplié par 1,2 environ dans le cas du vin, par 1,2 et jusqu'à 1,6 dans le cas du thé et par 1,3 dans le cas des taches protéiques.In particular, from the comparison of tests 6 and 2, tests 7 and 3, tests 12 and 10 and tests 8 and 5, it emerges that the process of the invention provides, at a given temperature and at a given pH, a substantial increase in the bleaching effect. This effect is here multiplied by approximately 1.2 in the case of wine, by 1.2 and up to 1.6 in the case of tea and by 1.3 in the case of protein stains.

La comparaison des essais 6 et 1, des essais 13 et 9 fait clairement apparaître, qu'à une température donnée, l'invention permet d'attein- dre un effet de blanchiment donné à une valeur de pH inférieure de plus de 2 unités à celle nécessitée par le procédé connu.The comparison of tests 6 and 1, of tests 13 and 9 clearly shows that, at a given temperature, the invention makes it possible to achieve a given bleaching effect at a pH value lower by more than 2 units at that required by the known method.

Outre le fait que, toute autre condition restant semblable, le procédé de l'invention écourte généralement la durée globale de l'opération, la comparaison des essais 6 et 4 montre qu'un résultat obtenu à 60°C dans le cadre du procédé connu peut pratiquement l'être dès 40°C en opérant selon l'invention.In addition to the fact that, any other condition remaining similar, the process of the invention generally shortens the overall duration of the operation, the comparison of tests 6 and 4 shows that a result obtained at 60 ° C. within the framework of the known process can practically be from 40 ° C by operating according to the invention.

Des résultats très proches bien que généralement légèrement inférieurs sont obtenus lorsque les exemples ci-dessus sont répétés en remplaçant le peroxyde d'hydrogène par le perborate de sodium.Very similar results, although generally slightly lower, are obtained when the above examples are repeated, replacing the hydrogen peroxide with sodium perborate.

Claims (10)

1) Procédé de blanchiment de linge domestique dans un cycle de lavage caractérisé en ce qu'il est effectué en deux étapes à une température comprise entre 40°C et 60°C environ, la première réalisée à un pH compris entre 8 et 12 en présence d'une composition détergente exempte d'agents de blanchiment peroxydés, la seconde réalisée à un pH compris entre 9 et 13 en présence d'au moins un agent de blanchiment peroxydé et d'un activeur en l'absence d'agents détergents, la première comme la seconde étape étant suivies d'opérations classiques de rinçage des cycles connus.1) Process for bleaching household linen in a washing cycle characterized in that it is carried out in two stages at a temperature between 40 ° C and 60 ° C approximately, the first carried out at a pH between 8 and 12 in presence of a detergent composition free of peroxide bleaches, the second carried out at a pH between 9 and 13 in the presence of at least one peroxide bleach and an activator in the absence of detergent agents, the first as the second step being followed by conventional rinsing operations of known cycles. 2) Procédé selon la revendication 1 caractérisé en ce que la deuxième étape est réalisée à un pH de préférence compris entre 9,5 et 12,5.2) Method according to claim 1 characterized in that the second step is carried out at a pH preferably between 9.5 and 12.5. 3) Procédé selon l'une des revendications 1 et 2, caractérisé en ce que la composition détergente est à base de tripolyphosphate de sodium.3) Method according to one of claims 1 and 2, characterized in that the detergent composition is based on sodium tripolyphosphate. 4) Procédé selon l'une des revendications 1 à 3 caractérisé en ce que la deuxième étape est réalisée en présence d'au moins un agent de blanchiment peroxydé choisi parmi le peroxyde d'hydrogène, le perborate de sodium, le peroxyhydrate d'urée.4) Method according to one of claims 1 to 3 characterized in that the second step is carried out in the presence of at least one peroxidized bleaching agent chosen from hydrogen peroxide, sodium perborate, urea peroxyhydrate . 5) Procédé selon l'une des revendications 1 à 4 caractérisé en ce que la quantité d'agent de blanchiment peroxydé équivaut à une concentration en oxygène actif comprise entre 0,004 et 0,03 % en poids dans la deuxième étape.5) Method according to one of claims 1 to 4 characterized in that the amount of peroxidized bleaching agent is equivalent to an active oxygen concentration between 0.004 and 0.03% by weight in the second step. 6) Procédé selon l'une des revendications 1 à 5 caractérisé en ce que le rapport molaire agent de blanchiment peroxydé/activeur est compris entre 1 et 10.6) Method according to one of claims 1 to 5 characterized in that the molar ratio of peroxide bleaching agent / activator is between 1 and 10. 7) Procédé selon l'une des revendications 1 à 6 caractérisé en ce que l'activeur est la cyanamide calcique.7) Method according to one of claims 1 to 6 characterized in that the activator is calcium cyanamide. 8) Procédé selon l'une des revendications 1 à 7 caractérisé en ce que l'activeur est la tétraacétyléthylènediamine.8) Method according to one of claims 1 to 7 characterized in that the activator is tetraacetylethylenediamine. 9) Procédé selon l'une des revendications et 8 caractérisé en ce que le rapport molaire agent de blanchiment peroxydé/activeur est compris entre 5 et 10.9) Method according to one of claims and 8 characterized in that the molar ratio of peroxidized bleaching agent / activator is between 5 and 10. 10) Procédé selon l'une des revendications 1 à 9 caractérisé en ce que la première étape est réalisée en présence d'au moins un enzyme protéolytique.10) Method according to one of claims 1 to 9 characterized in that the first step is carried out in the presence of at least one proteolytic enzyme.
EP86420169A 1985-06-28 1986-06-26 Bleaching process for a domestic fabric in a washing cycle Expired EP0206959B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8510121A FR2584109B1 (en) 1985-06-28 1985-06-28 HOUSEHOLD LAUNDRY LAUNDRY PROCESS IN A WASHING CYCLE
FR8510121 1985-06-28

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EP0206959A2 true EP0206959A2 (en) 1986-12-30
EP0206959A3 EP0206959A3 (en) 1987-08-12
EP0206959B1 EP0206959B1 (en) 1989-04-19

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US (1) US4775382A (en)
EP (1) EP0206959B1 (en)
JP (1) JPS626972A (en)
CA (1) CA1278152C (en)
DE (2) DE206959T1 (en)
DK (1) DK162944C (en)
ES (1) ES2000053A6 (en)
FI (1) FI80914C (en)
FR (1) FR2584109B1 (en)
NO (1) NO164115C (en)

Cited By (2)

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WO1996026261A1 (en) * 1995-02-18 1996-08-29 Albright & Wilson Uk Limited Enzyme detergents
EP0913515A1 (en) * 1997-10-31 1999-05-06 The Procter & Gamble Company Process of bleaching fabrics

Families Citing this family (5)

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JP3001936B2 (en) * 1990-06-29 2000-01-24 ポリプラスチックス株式会社 Polyester resin for molding with high melting heat stability and molded article thereof
KR19990084114A (en) * 1999-09-15 1999-12-06 강철수 The Bleaching Method for Cotton Fabrics
JP5236369B2 (en) * 2008-07-03 2013-07-17 第一工業製薬株式会社 Washing method
CN103189493A (en) * 2010-08-30 2013-07-03 诺维信公司 A concentrated soak wash
WO2020123113A1 (en) * 2018-12-13 2020-06-18 The Procter & Gamble Company Method for treating fabrics with a varying ph profile during wash and rinse cycles

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FR1457677A (en) * 1965-09-23 1966-01-24 Colgate Palmolive Co Laundry washing process
FR2104942A1 (en) * 1970-09-09 1972-04-28 Colgate Palmolive Co Detergent compsns - for presoaking and washing stained materials
FR2333887A1 (en) * 1975-12-04 1977-07-01 Huels Chemische Werke Ag WASHING PROCESS FOR USE IN AN AUTOMATIC WASHING MACHINE FOR TEXTILES, WORKING AGENT AND DEVICE FOR ITS IMPLEMENTATION
FR2388924A1 (en) * 1977-04-29 1978-11-24 Bosch Siemens Hausgeraete WASHING PROCESS, LAUNDRY PRODUCTS USED AND AUTOMATIC WASHING MACHINE FOR THE IMPLEMENTATION OF THE SAID WASHING PROCESS
GB2053998A (en) * 1979-07-06 1981-02-11 Unilever Ltd Particulate bleach composition
AU538580B2 (en) * 1976-02-09 1984-08-23 Shell Internationale Research Maatschappij B.V. Bleach compositions

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FR2340371A1 (en) * 1976-02-09 1977-09-02 Shell Int Research PROCESS FOR ACTIVATION OF BLEACHING AGENTS BASED ON PEROXIDES AND BLEACHING AND WASHING COMPOSITIONS
IE49996B1 (en) * 1979-07-06 1986-01-22 Unilever Ltd Particulate bleach compositions
JPS5914587A (en) * 1982-07-15 1984-01-25 カヤバ工業株式会社 Hydraulic shock absorber for two-wheel barrow

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Publication number Priority date Publication date Assignee Title
FR1457677A (en) * 1965-09-23 1966-01-24 Colgate Palmolive Co Laundry washing process
FR2104942A1 (en) * 1970-09-09 1972-04-28 Colgate Palmolive Co Detergent compsns - for presoaking and washing stained materials
FR2333887A1 (en) * 1975-12-04 1977-07-01 Huels Chemische Werke Ag WASHING PROCESS FOR USE IN AN AUTOMATIC WASHING MACHINE FOR TEXTILES, WORKING AGENT AND DEVICE FOR ITS IMPLEMENTATION
AU538580B2 (en) * 1976-02-09 1984-08-23 Shell Internationale Research Maatschappij B.V. Bleach compositions
FR2388924A1 (en) * 1977-04-29 1978-11-24 Bosch Siemens Hausgeraete WASHING PROCESS, LAUNDRY PRODUCTS USED AND AUTOMATIC WASHING MACHINE FOR THE IMPLEMENTATION OF THE SAID WASHING PROCESS
GB2053998A (en) * 1979-07-06 1981-02-11 Unilever Ltd Particulate bleach composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996026261A1 (en) * 1995-02-18 1996-08-29 Albright & Wilson Uk Limited Enzyme detergents
EP0913515A1 (en) * 1997-10-31 1999-05-06 The Procter & Gamble Company Process of bleaching fabrics
WO1999023294A1 (en) * 1997-10-31 1999-05-14 The Procter & Gamble Company Processes of bleaching fabrics

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DE206959T1 (en) 1987-04-30
EP0206959A3 (en) 1987-08-12
EP0206959B1 (en) 1989-04-19
DE3662913D1 (en) 1989-05-24
ES2000053A6 (en) 1987-11-16
US4775382A (en) 1988-10-04
DK306186A (en) 1986-12-29
DK306186D0 (en) 1986-06-27
NO862607L (en) 1986-12-29
FR2584109A1 (en) 1987-01-02
FI80914B (en) 1990-04-30
FR2584109B1 (en) 1988-03-18
FI862729A0 (en) 1986-06-26
NO164115B (en) 1990-05-21
DK162944B (en) 1991-12-30
FI862729A (en) 1986-12-29
CA1278152C (en) 1990-12-27
DK162944C (en) 1992-05-25
NO164115C (en) 1990-08-29
JPS6344861B2 (en) 1988-09-07
JPS626972A (en) 1987-01-13
FI80914C (en) 1990-08-10
NO862607D0 (en) 1986-06-27

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