EP0206959B1 - Bleaching process for a domestic fabric in a washing cycle - Google Patents
Bleaching process for a domestic fabric in a washing cycle Download PDFInfo
- Publication number
- EP0206959B1 EP0206959B1 EP86420169A EP86420169A EP0206959B1 EP 0206959 B1 EP0206959 B1 EP 0206959B1 EP 86420169 A EP86420169 A EP 86420169A EP 86420169 A EP86420169 A EP 86420169A EP 0206959 B1 EP0206959 B1 EP 0206959B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- activator
- stage
- bleaching
- peroxide
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 28
- 230000008569 process Effects 0.000 title claims description 27
- 238000004061 bleaching Methods 0.000 title claims description 15
- 238000005406 washing Methods 0.000 title claims description 11
- 239000004744 fabric Substances 0.000 title claims description 3
- 239000012190 activator Substances 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000007844 bleaching agent Substances 0.000 claims description 16
- 239000003599 detergent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical group CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 claims description 8
- 229960001922 sodium perborate Drugs 0.000 claims description 7
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 108091005804 Peptidases Proteins 0.000 claims description 3
- 102000035195 Peptidases Human genes 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 108010003855 mesentericopeptidase Proteins 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- UFZOPKFMKMAWLU-UHFFFAOYSA-N ethoxy(methyl)phosphinic acid Chemical compound CCOP(C)(O)=O UFZOPKFMKMAWLU-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 244000038022 Chenopodium capitatum Species 0.000 description 1
- 235000004391 Chenopodium capitatum Nutrition 0.000 description 1
- 241001080024 Telles Species 0.000 description 1
- 241000897276 Termes Species 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MYFXBBAEXORJNB-UHFFFAOYSA-N calcium cyanamide Chemical compound [Ca+2].[N-]=C=[N-] MYFXBBAEXORJNB-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000001609 comparable effect Effects 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- -1 peroxide compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229940045136 urea Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—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
-
- C11D2111/12—
-
- C11D2111/44—
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.
- French Patent No. 2,104,942 describes a process in which a complete perborated formulation is implemented at boiling temperature in the presence of a copper complex with a complexing agent, only after a prewash has been carried out. at low temperature using a detergent formulation free of peroxide bleaching compounds in the presence of a particular derivative of hydroxylamine or hydrazine.
- French Patent No. 2,333,887 recommends forming a complete formulation by adding hydrogen peroxide in aqueous solution with or without an activator to a detergency bath free of peroxide compounds, only when the temperature in this bath reaches the value chosen for the joint action of detergents and bleaches or, better, after this value has been reached. Said value can be between approximately 30 ° C and 95 ° C. The process is considered to have an advantage compared to the direct use of a complete formulation perborated in the absence of an activator.
- the complete formulation is only formed at a temperature at most equal to 60 ° C. using a non-perborated solid detergent composition and hydrogen peroxide in aqueous solution with an activator.
- the process described would then be equivalent to a process consisting in directly using a complete formulation at the same temperature with an activator.
- 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), ⁇ -acetoxy-a-methyl-N, H′-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
- ⁇ -acetoxy-a-methyl-N H′-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 below 70 ° C. in the presence of a activator during a household laundry wash 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 a usual alkaline agent which cannot be oxidized or 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 carried out in the presence of ESPERASE.
- Table 1 collates the results obtained as a function of the temperature and 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.
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.
Par exemple le brevet français n° 2 104 942 décrit un procédé dans lequel une formulation complète perboratée est mise en oeuvre a température d'ébullition en présence d'un complexe du cuivre avec un agent complexant, seulement après qu'un prélavage ait été réalisé à basse température à l'aide d'une formulation détergente exempte de composés de blanchiment peroxydés en présence d'un dérivé particulier de l'hydroxylamine ou de l'hydrazine.For example, French Patent No. 2,104,942 describes a process in which a complete perborated formulation is implemented at boiling temperature in the presence of a copper complex with a complexing agent, only after a prewash has been carried out. at low temperature using a detergent formulation free of peroxide bleaching compounds in the presence of a particular derivative of hydroxylamine or hydrazine.
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.
Par exemple le brevet français n° 2 333 887 préconise de ne former une formulation complète par addition de peroxyde d'hydrogène en solution aqueuse avec ou non un activeur à un bain de détergence exempt de composés peroxydés, que lorsque la température dans ce bain atteint la valeur choisie pour l'action conjointe des agents de détergence et de blanchiment ou, mieux, après que cette valeur ait été atteinte. Ladite valeur peut être comprise entre environ 30°C et 95°C. Le procédé est considéré comme présentant un avantage par rapport à l'utilisation directe d'une formulation complète perboratée en l'absence d'activeur.For example, French Patent No. 2,333,887 recommends forming a complete formulation by adding hydrogen peroxide in aqueous solution with or without an activator to a detergency bath free of peroxide compounds, only when the temperature in this bath reaches the value chosen for the joint action of detergents and bleaches or, better, after this value has been reached. Said value can be between approximately 30 ° C and 95 ° C. The process is considered to have an advantage compared to the direct use of a complete formulation perborated in the absence of an activator.
Enfin le brevet français n° 2 388 924 reprend en le simplifiant le brevet précédant.Finally the French patent n ° 2 388 924 resumes by simplifying the preceding patent.
La formulation complète n'est formée qu'à température au plus égale à 60°C à l'aide d'une composition détergente solide non perboratée et de peroxyde d'hydrogène en solution aqueuse avec un activeur. Le procédé décrit serait équivalent alors à un procédé consistant à utiliser directement une formulation complète à la même température avec un activeur.The complete formulation is only formed at a temperature at most equal to 60 ° C. using a non-perborated solid detergent composition and hydrogen peroxide in aqueous solution with an activator. The process described would then be equivalent to a process consisting in directly using a complete formulation at the same temperature with an activator.
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), 1'a-acétoxy-a-méthyl-N,H'-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), α-acetoxy-a-methyl-N, H′-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 dessous de 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 below 70 ° C. in the presence of a activator during a household laundry wash 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 stage being followed by conventional rinsing operations 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 a usual alkaline agent which cannot be oxidized or 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 stage 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'effet 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 EMPAE 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 à 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 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'ESPERASEO de la Société NOVO.
- - les lavages décrits à titre comparatif sont qualifiés de "complets". 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:
- - In the following, the term detergent is designated the standard detergent EMPA E 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, of 30 minutes in the second, starting 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 step, whose pH, reached using sodium hydroxide, is indicated below case by case, contains 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 O from the company NOVO.
- - the washes described for comparison are qualified as "complete". They comprise a single step carried out at a temperature and at a pH indicated case by case, for 60 minutes, duration beyond which there is practically no more improvement in the bleaching effect in the presence of the amounts of detergent, bleach, activator and, where appropriate, enzyme and other ingredients, equal to the combination of those present in each of the two stages of the embodiment of the invention to which they are directly comparable, only the quantity of sodium hydroxide which can be adapted if necessary so that the pH during the "complete" washing, is that in the second stage 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:
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 jeuExamples 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 carried out in the presence of ESPERASE.
Le tableau 1 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".
Les exemples 9 à 11 sont réalisés selon l'invention, les exemples 12 et 13, donnés à titre comparatif, selon les conditions définies cidessus 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 Il 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".
Des tableaux et II, certaines comparaisons mettent en lumière des avantages du procédé de l'invention.Tables 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'invéntion 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 appears 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'atteindre 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 than 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. in the context 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)
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 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0206959A2 EP0206959A2 (en) | 1986-12-30 |
EP0206959A3 EP0206959A3 (en) | 1987-08-12 |
EP0206959B1 true EP0206959B1 (en) | 1989-04-19 |
Family
ID=9320905
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86420169A Expired EP0206959B1 (en) | 1985-06-28 | 1986-06-26 | Bleaching process for a domestic fabric in a washing cycle |
Country Status (10)
Country | Link |
---|---|
US (1) | US4775382A (en) |
EP (1) | EP0206959B1 (en) |
JP (1) | JPS626972A (en) |
CA (1) | CA1278152C (en) |
DE (2) | DE3662913D1 (en) |
DK (1) | DK162944C (en) |
ES (1) | ES2000053A6 (en) |
FI (1) | FI80914C (en) |
FR (1) | FR2584109B1 (en) |
NO (1) | NO164115C (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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 |
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 |
EP2611898A1 (en) * | 2010-08-30 | 2013-07-10 | Novozymes A/S | A concentrated soak wash |
CA3118154A1 (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 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (9)
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 |
GB1538744A (en) * | 1975-05-13 | 1979-01-24 | Interox Chemicals Ltd | Bleaching composition containing diacyl peroxides |
AU538580B2 (en) * | 1976-02-09 | 1984-08-23 | Shell Internationale Research Maatschappij B.V. | Bleach compositions |
NL186920C (en) * | 1976-02-09 | 1991-04-02 | Shell Int Research | METHOD FOR PREPARING A PEROXIDE BASED BLEACH PREPARATION AND METHOD FOR PREPARING SOLID BLEACH CONCENTRATES |
DE2719235B2 (en) * | 1977-04-29 | 1980-07-17 | Bosch-Siemens Hausgeraete Gmbh, 7000 Stuttgart | Washing process and automatic washing machine to carry out the washing process |
IE49996B1 (en) * | 1979-07-06 | 1986-01-22 | Unilever Ltd | Particulate bleach compositions |
GB2053998B (en) * | 1979-07-06 | 1983-04-20 | Unilever Ltd | Particulate bleach composition |
JPS5914587A (en) * | 1982-07-15 | 1984-01-25 | カヤバ工業株式会社 | Hydraulic shock absorber for two-wheel barrow |
-
1985
- 1985-06-28 FR FR8510121A patent/FR2584109B1/en not_active Expired
-
1986
- 1986-06-12 US US06/873,418 patent/US4775382A/en not_active Expired - Fee Related
- 1986-06-26 FI FI862729A patent/FI80914C/en not_active IP Right Cessation
- 1986-06-26 EP EP86420169A patent/EP0206959B1/en not_active Expired
- 1986-06-26 DE DE8686420169T patent/DE3662913D1/en not_active Expired
- 1986-06-26 DE DE198686420169T patent/DE206959T1/en active Pending
- 1986-06-27 ES ES8600017A patent/ES2000053A6/en not_active Expired
- 1986-06-27 DK DK306186A patent/DK162944C/en not_active IP Right Cessation
- 1986-06-27 JP JP61151337A patent/JPS626972A/en active Granted
- 1986-06-27 NO NO862607A patent/NO164115C/en unknown
- 1986-06-27 CA CA000512704A patent/CA1278152C/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Also Published As
Publication number | Publication date |
---|---|
DK162944B (en) | 1991-12-30 |
JPS6344861B2 (en) | 1988-09-07 |
FI862729A (en) | 1986-12-29 |
US4775382A (en) | 1988-10-04 |
CA1278152C (en) | 1990-12-27 |
DE3662913D1 (en) | 1989-05-24 |
DK306186A (en) | 1986-12-29 |
JPS626972A (en) | 1987-01-13 |
EP0206959A2 (en) | 1986-12-30 |
FI862729A0 (en) | 1986-06-26 |
NO862607L (en) | 1986-12-29 |
ES2000053A6 (en) | 1987-11-16 |
FI80914B (en) | 1990-04-30 |
DK162944C (en) | 1992-05-25 |
NO164115B (en) | 1990-05-21 |
DE206959T1 (en) | 1987-04-30 |
FR2584109B1 (en) | 1988-03-18 |
NO862607D0 (en) | 1986-06-27 |
FR2584109A1 (en) | 1987-01-02 |
FI80914C (en) | 1990-08-10 |
NO164115C (en) | 1990-08-29 |
EP0206959A3 (en) | 1987-08-12 |
DK306186D0 (en) | 1986-06-27 |
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