EP0414581A1 - Textile bleaching compositions effective at low temperatures - Google Patents
Textile bleaching compositions effective at low temperatures Download PDFInfo
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- EP0414581A1 EP0414581A1 EP90401635A EP90401635A EP0414581A1 EP 0414581 A1 EP0414581 A1 EP 0414581A1 EP 90401635 A EP90401635 A EP 90401635A EP 90401635 A EP90401635 A EP 90401635A EP 0414581 A1 EP0414581 A1 EP 0414581A1
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- bleaching
- catalytic
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- detergent
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
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- the present invention relates to detergent compositions having a bleaching effect on textiles, suitable for containing a bleaching system based on peroxide compounds and divalent metal complexes with atomic number between 25 and 29 (or their precursors), which have, under the washing conditions, a positive net charge and act as catalysts for the decomposition of peroxides, increasing the bleaching efficiency of detergent compositions at low temperatures.
- peroxidized compounds in compositions for washing clothes and other compositions intended for domestic or industrial use has been known for a long time, these compounds being particularly useful for removing stains having a significant content of colored materials, such as stains from coffee, tea, fruit, wine and cosmetics.
- peroxides such as hydrogen peroxide, mineral persalts such as perborates, percarbonates, persulfates, perphosphates and the like, and organic percarboxylic acids.
- Another solution described to improve the behavior of detergents with peroxidized bleaching agents consists in incorporating into the formulation of small quantities of metal cations in the form of coordination complexes, so that the intrinsic capacity of metal cations to decompose peroxides remains controlled, which allows to obtain a beneficial effect on the effectiveness of the peroxide bleaching as described in, e.g., British patent No. 984,459 and US patent No. 3,156,654.
- Said complexes do not act by regulating the amount of free metal so that the latter is that which effectively catalyzes the decomposition; instead, it is the complexes themselves, or the complex species they produce in solution, that catalyze this decomposition on the substrates to be bleached, so that bleaching efficiency can be obtained at low temperatures higher than that obtained with catalysis by free metal.
- the problem of making reactive additives compatible in finished formulations is not limited to ensuring the stability of the formulations; it is also a question of obtaining the stability of the various constituents in the washing bath, where they are in much more intimate contact because they are dissolved there.
- the object of the present invention is thus to produce a stable detergent and bleaching composition which contains a bleaching system consisting of a peroxidized compound and a soluble salt of a divalent heavy metal cation with atomic number between 25 and 29 and a sequestering agent capable of forming, with the metal salt, in the washing bath, a catalytic complex comprising a positive residual charge, and which is ca able to provide maximum bleaching efficiency in hard water and at low temperatures.
- the metal cation salt and the sequestering agent can be incorporated into the detergent and bleaching compositions as such or in the form of the preformed complex.
- detergent compositions which contain a bleaching system based on a peroxide compound and on a catalytic metal complex or its precursors, according to what has been described in the above paragraph, and which are suitable for enhancing the efficiency of the bleaching system in the washing operation.
- anionic surfactants which are another of the key ingredients in the majority of detergent formulations, can also impede the catalytic activity of the bleaching catalysts described above.
- the content of alkaline earth cations in the washing bath which is usually designated by the term "hardness” also has a negative influence on the catalytic bleaching activity. This fact worsens because of the impossibility of adding large quantities of powerful sequestering agents to the detergent compositions in question, since said sequestering agents destroy the catalytic complexes by competing with the ligands of which they are made up.
- the detergent compositions which are suitable for containing the catalysts described above, and which improve the behavior of the latter in hard water, have a combination of characteristics which make them suitable for ensuring the effectiveness of the catalysts which they contain. These characteristics are described below:
- mineral phosphates typically contain a reduced amount of mineral phosphates, specifically less than 1% by weight of the composition. These amounts of mineral phosphates ensure that, in the concentrations of detergent that are usually used in washing, the phosphate concentration of the bath does not exceed 10 ⁇ 4 molar. Higher phosphate concentrations in the wash bath partially inhibit the whitening enhancement effect of the catalysts.
- Zeolites contain zeolites, replacing mineral phosphates, as detergency builders. Zeolites have a good detergency builder power without having a sequestering power which would allow them to compete with the ligands of the catalytic complex, inactivating the latter.
- zeolites have the additional beneficial effect, when used to absorb the bleach catalyst on themselves, thereby incorporating it into detergent compositions.
- Said additional beneficial effect consists in a reduction in the rate of decomposition of the bleaching peroxides, so that one takes advantage of their bleaching power in a more effective manner.
- zeolites as a carrier for catalysts laundering the type of free metal cation salts is described in European Patent Applications No. 224 952 and 224 953, which describes compositions which contain manganese (+2) absorbed on zeolites, so that oxidation of manganese to manganese oxide is avoided, which can cause stains on fabrics, by further improving the storage stability of the bleaching compositions which contain said system.
- compositions described in the present invention said drawbacks are not encountered, since the metal catalysts used do not undergo transformation by oxidation into species capable of causing stains on the washed fabrics.
- compositions in question can contain any type of cationic, amphoteric, zwitterionic, nonionic and anionic surfactants.
- anionic surfactants have a negative effect on catalysis, as indicated above.
- strong sequestering agents can only be included in detergent compositions which contain bleaching catalysts in very small quantities, less than 0.2% by weight of the composition, since they enter in competition with the ligands which form the catalytic complex, inhibiting the activity of the latter.
- compositions according to the invention may contain, in addition, constituents such as surfactants from other categories, foaming regulators, bleaching activators of the peroxide precursor type, polymers which inhibit encrustation and redeposition, structuring and / or alkaline salts, optical brighteners, photoactivators, tinting agents, colorants, perfumes and, in general, any type of additive that is commonly used in detergency.
- constituents such as surfactants from other categories, foaming regulators, bleaching activators of the peroxide precursor type, polymers which inhibit encrustation and redeposition, structuring and / or alkaline salts, optical brighteners, photoactivators, tinting agents, colorants, perfumes and, in general, any type of additive that is commonly used in detergency.
- the bleaching catalysts suitable for practicing the present invention are those formed from the salts of divalent metal cations having an atomic number between 25 and 29 with sequestering agents which form with said cations complexes which, at the usual alkaline pH in the washing, have a positive residual charge and have free coordination positions, or can undergo transformations, in the washing bath, in cash which have said free coordination positions.
- Said catalysts can be incorporated into the formulations which are the subject of the present invention, either in the form of the preformed complexes, or in the form of the precursors of the said complexes, in which case the latter are formed when the compositions are placed in aqueous solution.
- precursors of catalytic complexes should be understood to mean the salts of divalent cations with atomic number between 25 and 29 and the sequestering agents which form, with said salts, the complexes described in the above paragraph.
- these complexes are those formed by the salts of divalent metals with atomic number between 25 and 29 with diamines in which the nitrogen atoms are separated by a chain of at most five atoms, these diamines may or may not be substituted substituted, the substituents possibly comprising functional groups by means of which the diamines may or may not establish additional attachment points with the divalent metal with which they form the complexes.
- these complexes are those formed by divalent copper or divalent manganese with polyamines such as ethylenediamine, diethylenetriamine, 1,3-propylenediamine, 1,2-propylenediamine and 1,2-cyclohexylenediamine.
- Additional examples are the complexes formed by macrocyclic compounds such as 1,4,8,11-tetraaza-2,3,9,10-tetramethylcyclotetradeca-1,3,8,10-tetraene and the salts of divalent copper and divalent manganese.
- the peroxidized bleaching agents suitable for practicing the present invention are mineral persalts, both those which are real persalts and those which are compounds of addition of mineral salts and of hydrogen peroxide.
- Examples of this type of bleach are alkaline perborates, such as perbo sodium spleen, mono- or tetrahydrate, and alkaline percarbonates.
- the mineral phosphates mentioned in the description include orthophosphates, pyrophosphates and polyphosphates of alkali metals, and in particular sodium and potassium tripolyphosphates in their different degrees of hydration.
- alkaline aluminosilicates ion exchangers or zeolites it is possible to use both the crystallines that the amorphs or that amorphous / crystalline mixtures, both of natural origin and of synthetic origin.
- zeolites of formula (Na2O) P x , (Al2O3) y , (SiO2) z , wH2O, in which x is equal to 1, y has a value of 0.6 to 1, 3 and is preferably approximately 1, za a value of 1 to 4 and preferably of 2 to 3 or approximately 2, and wa a value of 0 to 9 and preferably of 2.5 to 6.
- the aluminosilicates of this type are commercially available products and are usually called zeolites A and X or their mixtures.
- the surfactant system includes different types of compounds.
- synthetic anionic surfactants those which are suitable for use in the present invention including the soluble salts of alkylbenzenesulfonates, alkylsulfates, alkyl (polyether) sulfates, ⁇ -olefinesulfonates, paraffinsulfonates, alkylglyceryl ether sulfonates, ⁇ -sulfocarboxylates and their esters, sulfates and sulfonates of fatty acid monoglycerides, alkylphenol (polyether) sulfates and the like.
- alkali metal alkylbenzenesulfonates are preferred, the alkyl chain of which is essentially linear and contains a number of carbon atoms between 10 and 14.
- surfactants used are nonionic surfactants, among which can be used those of the polyoxyalkylenated fatty alcohol type with a number of moles of alkylene oxide per mole of fatty alcohol between 2 and 20, and preferably between 3 and 15, and said fatty alcohols having straight or partially branched chains comprising a number of carbon atoms between 8 and 22.
- nonionic surfactants are the products of the oxyethylenation of lauryl alcohol and the products of the oxyethylenation of synthetic alcohols which are found on the market under brands such as Dobanol R , Synperonic R , Lutensol R , Lial R , etc.
- nonionic surfactants are the reaction products of alkylene oxides with alkylphenols in which the alkyl radical contains a number of carbon atoms between 7 and 11, so that the number of moles of oxide d alkylene per mole of alkylphenol is between 3 and 20, and preferably between 5 and 12.
- soaps of fatty acids saturated or unsaturated, comprising a number of carbon atoms between 8 and 24.
- alkaline salts of fatty acids mainly saturated, which preferably contain between 10 and 20 carbon atoms
- alkali salts of mixtures of fatty acids derived from tallow and coconut and palm oils being particularly preferred.
- Aminopolycarboxylic acids or their salts such as ethylenediaminetetraacetic or nitrilotriacetic acid, and the like, are suitable for use as potent sequestering agents.
- Organic phosphonic acids or their salts and hydroxycarboxylates or their salts are also suitable.
- proteolytic or amylolytic enzymes like those found on the market under the Maxatase R and Alcalase R brands.
- Cationic surfactants of the quaternary ammonium salt type in which at least one or two of the alkyl radicals are linear or partially branched C8-C18 carbon chains, can also be incorporated.
- amphoteric type surfactants which can also be used, are the water-soluble derivatives of secondary and tertiary aliphatic amines in which the aliphatic radical may comprise a straight or branched chain, and, among the water-soluble derivatives, one of the substituents contains from 8 to 18 carbon atoms and another consists of an anionic group such as, for example, a carboxy, sulfonate, phosphate or phosphonate group.
- surfactants known as surfactants with hybrid or zwitterionic ions such as the water-soluble derivatives of cationic aliphatic compounds with the quaternary ammonium, phosphoric and sulphonic groups, in which the radicals can comprise a linear or branched chain and in which one aliphatic substituents contains 8 to 18 carbon atoms and another contains an anionic group which is soluble in water.
- Substances that help prevent redeposition of soiling on fabrics during the washing process can also be added.
- examples are cellulose derivatives such as its carboxyalkylated or hydroxyalkylated compounds.
- compositions of the present invention is the structuring salts, among which there are a large number of mineral salts which are neutral to hydrolysis and which have a high solubility in water.
- structuring salts among which there are a large number of mineral salts which are neutral to hydrolysis and which have a high solubility in water.
- Alkalizing agents suitable for these compositions are the alkali metal salts derived from carbonic, orthosilicic, metasilicic acids and the like.
- Anionic fluorescent brighteners also known as optical brighteners, can also be used.
- these type of products those which are most suitable are the water-soluble sulphonated derivatives of stilbenes and the water-soluble sulphonated derivatives of distyrylbiphenyl.
- these products sold by Ciba-Geigy, among which we can mention those of the brands Tinopal R 5BMS, Tinopal R DMS, Tinopal R LMS-X and Tinopal R CBS-X.
- Said polymers are the water-soluble salts of polycarboxylic homo- or copolymers having a configuration such that the carboxylic radicals are separated from one another by one or two carbon atoms.
- Products of this type are homo- or copolymers of monomer units such as, for example, maleic anhydride, maleic acid, methylvinyl ether, acrylic acid, methacrylic acid, and the like. These products are found on the market under names such as Sokalan R , Gantrez R , Primal R and the like.
- foam regulators other than soaps or nonionic surfactants having a high degree of oxyethylenation, such as, for example, waxes, saturated hydrocarbons, esters of phosphoric acid and silicones.
- silicones such as combinations of dialkylpolysiloxanes with finely divided silica and silanated silicas or, alternatively, copolymers of dialkylpolysiloxanes with glycol or ethylene oxide radicals.
- Said special silicones are sold by the company Dow Corning under the references Q2-3092, DB-100, DC-190, DC-193, DC-198. Said silicones can be used as presented by the supplier, or else protected by granulation and coating with inert materials to avoid their interaction with the constituents of the detergent composition.
- compositions according to the invention are indicated and the reflectance results of EMPA-114 fabrics of 10 ⁇ 10 cm washed with said detergent compositions whitening.
- EMPA-114 corresponds to standard cotton fabrics stained with red wine according to the standards of the Eidgenössiche Materialierithese of Switzerland.
- Detergent compositions are prepared according to the following formulations:
- Examples 1 to 7 correspond to compositions according to what is described in the present invention and, for this reason, all these compositions provide a high bleaching efficiency in washing EMPA-114 stains, which leads to reflectance values. high.
- Example 8 corresponds to a detergent composition which does not fulfill the conditions of the present invention.
- Example 9 corresponds to reference compositions and contains only perborate and a catalyst in the absence of any other constituent, and offers the same concentration of perborate in the washing bath as the compositions of Examples 1 to 8 .
- compositions of Examples 1 to 9 are studied by washing standard stains with them by means of the washing process described below.
- a dose of 210 grams of the detergent composition to be studied is introduced into the detergent compartment of a Zanussi 630 stainless steel washing machine and a washing cycle is programmed at a temperature of 30 ° C for 70 minutes, after which rinse cycles, which last a total of 40 minutes.
- the fabrics are removed from the washing machine and dried at room temperature.
- the reflectance measurements are made in an Ultrascan device from the company Hunterlab, with a lamp with JCR type halogen of 9.5 V and 55 W, with a D65 / 10 ° type light, inclusion of gloss and an ultraviolet filter.
- Examples 1 to 7 which correspond to detergent bleaching compositions which fulfill the conditions described in the present invention, provide reflectances of the washed fabrics higher than those which is obtained by washing with a composition which contains only perborate and a catalyst (Example 9).
- Example 9 the composition of Example 8 which does not meet the conditions of the present invention, provides even more reflectance. weak than that obtained with the reference composition of Example 9.
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Abstract
Description
La présente invention concerne des compositions détergentes ayant un effet de blanchiment sur les textiles, adaptées pour contenir un système de blanchiment à base de composés peroxydés et de complexes de métaux divalents de numéro atomique compris entre 25 et 29 (ou de leurs précurseurs), qui ont, dans les conditions du lavage, une charge nette positive et jouent le rôle de catalyseurs de la décomposition des peroxydes, augmentant l'efficacité de blanchiment des compositions détergentes aux basses températures.The present invention relates to detergent compositions having a bleaching effect on textiles, suitable for containing a bleaching system based on peroxide compounds and divalent metal complexes with atomic number between 25 and 29 (or their precursors), which have, under the washing conditions, a positive net charge and act as catalysts for the decomposition of peroxides, increasing the bleaching efficiency of detergent compositions at low temperatures.
On connaît depuis longtemps l'utilisation de composés peroxydés dans des compositions pour le lavage du linge et d'autres compositions destinées à une utilisation domestique ou industrielle, ces composés étant particulièrement utiles pour éliminer les taches ayant une teneur significative en matières colorées, comme les taches de café, de thé, de fruits, de vin et de cosmétiques.The use of peroxidized compounds in compositions for washing clothes and other compositions intended for domestic or industrial use has been known for a long time, these compounds being particularly useful for removing stains having a significant content of colored materials, such as stains from coffee, tea, fruit, wine and cosmetics.
Dans ce but, on utilise une grande variété de peroxydes, comme le peroxyde d'hydrogène, les persels minéraux comme les perborates, les percarbonates, les persulfates, les perphosphates et analogues, et les acides percarboxyliques organiques.For this purpose, a wide variety of peroxides are used, such as hydrogen peroxide, mineral persalts such as perborates, percarbonates, persulfates, perphosphates and the like, and organic percarboxylic acids.
Parmi ces composés, ceux qui produisent du peroxyde d'hydrogène en solution sont très efficaces aux températures élevées, mais leur efficacité diminue très notablement lorsque la température baisse, ce qui les rend mal adaptés à la pratique actuelle du lavage domestique, qui met en jeu des températures relativement basses. En outre, la nécessité de travailler à des températures élevées dans les opérations de lavage industriel qui emploient ce type d'agents de blanchiment implique une forte dépense énergétique, qui a des répercussions sur le coût des opérations.Among these compounds, those which produce hydrogen peroxide in solution are very effective at high temperatures, but their efficiency decreases very markedly when the temperature drops, which makes them ill-suited to the current practice of household washing, which involves relatively low temperatures. In addition, the need to work at high temperatures in industrial washing operations which employ this type of bleaching agent involves a high energy expenditure, which has repercussions on the cost of operations.
Pour résoudre ce problème, on a proposé d'ajouter des composés organiques contenant, par exemple, des groupes ester, nitrile et/ou amide, aux compositions détergentes renfermant des agents de blanchiment à base de peroxydes, ces composés permettant d'améliorer l'efficacité du blanchiment aux basses températures, en produisant des peracides. Cependant, ces composés, que l'on connaît dans la technique sous le nom d'activateurs de blanchiment, doivent être ajoutés en proportions relativement élevées pour être efficaces. Par conséquent, le coût du produit s'accroît, avec, en outre, la possibilité pour l'activateur de blanchiment d'entraver l'action des autres constituants des formulations finies.To solve this problem, it has been proposed to add organic compounds containing, for example, ester, nitrile and / or amide groups, to the detergent compositions containing bleaches based on peroxides, these compounds making it possible to improve the effectiveness of bleaching at low temperatures, producing peracids. However, these compounds, which are known in the art as bleach activators, must be added in relatively high proportions to be effective. Consequently, the cost of the product increases, with, in addition, the possibility for the bleach activator to hinder the action of the other constituents of the finished formulations.
Une autre solution décrite pour améliorer le comportement des détergents avec les agents de blanchiment peroxydés consiste à incorporer dans la formulation de petites quantités de cations métalliques sous forme de complexes de coordination, pour que la capacité intrinsèque des cations métalliques à décomposer les peroxydes demeure controlée, ce qui permet d'obtenir un effet bénéfique sur l'efficacité du blanchiment des peroxydes, comme le décrit, par exemple, le brevet britannique no 984 459 et le brevet US no 3 156 654.Another solution described to improve the behavior of detergents with peroxidized bleaching agents consists in incorporating into the formulation of small quantities of metal cations in the form of coordination complexes, so that the intrinsic capacity of metal cations to decompose peroxides remains controlled, which allows to obtain a beneficial effect on the effectiveness of the peroxide bleaching as described in, e.g., British patent No. 984,459 and US patent No. 3,156,654.
Dans notre demande de brevet espagnol numéro 8803242, on propose d'utiliser certains complexes de métaux lourds divalents qui, dans les conditions de pH alcalin habituelles des opérations de blanchiment, ont une charge nette positive et sont très efficaces pour réaliser le blanchiment avec des peroxydes aux basses températures.In our Spanish patent application number 8803242, it is proposed to use certain divalent heavy metal complexes which, under the usual alkaline pH conditions of bleaching operations, have a positive net charge and are very effective in carrying out bleaching with peroxides at low temperatures.
Lesdits complexes n'agissent pas en réglant la quantité de métal libre pour que cette dernière soit celle qui catalyse efficacement la décomposition; au lieu de cela, ce sont les complexes eux-mêmes, ou les espèces complexes qu'ils produisent en solution, qui catalysent cette décomposition sur les substrats à blanchir, ce qui fait que l'on peut obtenir une efficacité de blanchiment aux basses températures supérieure à celle que l'on obtient avec une catalyse par le métal libre.Said complexes do not act by regulating the amount of free metal so that the latter is that which effectively catalyzes the decomposition; instead, it is the complexes themselves, or the complex species they produce in solution, that catalyze this decomposition on the substrates to be bleached, so that bleaching efficiency can be obtained at low temperatures higher than that obtained with catalysis by free metal.
Cependant, on a observé que l'efficacité des compositions de blanchiment décrites dans la demande espagnole no 8803242 présente une forte dépendance vis-à-vis de la dureté de l'eau, ainsi que des constituants supplémentaires qui constituent la composition détergente.However, it was observed that the effectiveness of the bleaching compositions described in the Spanish application No. 8803242 shows a strong dependence with respect to the water hardness, as well as additional components constituting the detergent composition.
Cette dépendance se manifeste par une efficacité plus faible des compositions qui contiennent les peroxydes et les catalyseurs décrits dans la demande no 8803242 lorsqu'on travaille dans l'eau dure, par rapport à celle que l'on obtient dans l'eau déminéralisée. En outre, l'incorporation du système de blanchiment décrit dans les compositions détergentes habituelles provoque aussi une diminution de l'efficacité dudit système.This dependence is manifested by a lower efficiency of compositions containing peroxides and catalysts described in patent application No. 8803242 when working in hard water compared to that obtained in deionized water. In addition, the incorporation of the bleaching system described in the usual detergent compositions also causes a reduction in the effectiveness of said system.
Ce comportement n'est pas inattendu, car l'inclusion, dans les compositions finies, d'additifs ayant une forte réactivité, comme les catalyseurs de blanchiment utilisés dans les compositions décrites dans la présente invention, crée généralement des difficultés considérables, car la stabilité, tant des additifs que des constituants restants de la formulation, doit être assurée.This behavior is not unexpected, since the inclusion, in finished compositions, of additives having a high reactivity, such as the bleaching catalysts used in the compositions described in the present invention, generally creates considerable difficulties, because the stability , both additives and remaining constituents of the formulation, must be ensured.
En outre, le problème de rendre compatibles des additifs réactifs dans des formulations finies ne se limite pas à assurer la stabilité des formulations; il s'agit aussi d'obtenir la stabilité des différents constituants dans le bain de lavage, où ils sont en contact beaucoup plus intime du fait qu'ils y sont dissous.In addition, the problem of making reactive additives compatible in finished formulations is not limited to ensuring the stability of the formulations; it is also a question of obtaining the stability of the various constituents in the washing bath, where they are in much more intimate contact because they are dissolved there.
L'objet de la présente invention est ainsi de produire une composition détergente et de blanchiment stable qui renferme un système de blanchiment constitué par un composé peroxydé et un sel soluble d'un cation de métal lourd divalent de numéro atomique compris entre 25 et 29 et un agent séquestrant capable de former, avec le sel métallique, dans le bain de lavage, un complexe catalytique comportant une charge résiduelle positive, et qui est ca pable de fournir l'efficacité de blanchiment maximale dans les eaux dures et aux basses températures. Le sel de cation métallique et l'agent séquestrant peuvent être incorporés dans les compositions détergentes et de blanchiment tels quels ou sous forme du complexe préformé.The object of the present invention is thus to produce a stable detergent and bleaching composition which contains a bleaching system consisting of a peroxidized compound and a soluble salt of a divalent heavy metal cation with atomic number between 25 and 29 and a sequestering agent capable of forming, with the metal salt, in the washing bath, a catalytic complex comprising a positive residual charge, and which is ca able to provide maximum bleaching efficiency in hard water and at low temperatures. The metal cation salt and the sequestering agent can be incorporated into the detergent and bleaching compositions as such or in the form of the preformed complex.
Selon la présente invention, il est décrit des compositions détergentes qui contiennent un système de blanchiment à base d'un composé peroxydé et d'un complexe de métal catalytique ou de ses précurseurs, selon ce qui a été décrit dans le paragraphe ci-dessus, et qui conviennent pour renforcer l'efficacité du système de blanchiment dans l'opération de lavage.According to the present invention, detergent compositions are described which contain a bleaching system based on a peroxide compound and on a catalytic metal complex or its precursors, according to what has been described in the above paragraph, and which are suitable for enhancing the efficiency of the bleaching system in the washing operation.
Le principal problème que pose l'incorporation des systèmes de blanchiment précités dans les compositions détergentes en usage actuellement est le fait que les phosphates minéraux inactivent les catalyseurs de blanchiment décrits ci-dessus, ce qui diminue sensiblement leur puissance de blanchiment.The main problem posed by the incorporation of the above-mentioned bleaching systems in the detergent compositions currently in use is the fact that the mineral phosphates inactivate the bleaching catalysts described above, which significantly reduces their bleaching power.
Cela représente un inconvénient sérieux, car on utilise les phosphates minéraux de manière généralisée comme adjuvants de détergence dans les compositions détergentes habituelles.This represents a serious drawback, since mineral phosphates are used in a generalized manner as detergency builders in the usual detergent compositions.
En outre, on a observé que les tensioactifs anioniques, qui constituent un autre des ingrédients clés de la majorité des formulations de détergents, peuvent également entraver l'activité catalytique des catalyseurs de blanchiment décrits ci-dessus.In addition, it has been observed that anionic surfactants, which are another of the key ingredients in the majority of detergent formulations, can also impede the catalytic activity of the bleaching catalysts described above.
De plus, la teneur en cations alcalino-terreux dans le bain de lavage, que l'on désigne habituellement par le terme "dureté", a également une influence négative sur l'activité de blanchiment catalytique. Ce fait empire à cause de l'impossibilité d'ajouter des quantités importantes d'agents séquestrants puissants aux compositions détergentes en question, car lesdits agents séquestrants détruisent les complexes catalytiques en faisant concurrence aux ligands dont ils sont constitués.In addition, the content of alkaline earth cations in the washing bath, which is usually designated by the term "hardness", also has a negative influence on the catalytic bleaching activity. This fact worsens because of the impossibility of adding large quantities of powerful sequestering agents to the detergent compositions in question, since said sequestering agents destroy the catalytic complexes by competing with the ligands of which they are made up.
On a maintenant découvert des compositions détergentes, qui sont efficaces dans les eaux dures, dans lesquelles il est possible d'incorporer les catalyseurs décrits ci-dessus, non seulement sans perte d'activité catalytique de ces derniers, mais aussi, de façon surprenante, avec une amélioration de l'efficacité des catalyseurs par rapport à celle présentée dans l'eau dure.We have now discovered detergent compositions, which are effective in hard water, in which it is possible to incorporate the catalysts described above, not only without loss of catalytic activity of the latter, but also, surprisingly, with an improvement in the efficiency of the catalysts compared to that presented in hard water.
Les compositions détergentes qui conviennent pour renfermer les catalyseurs décrits ci-dessus, et qui améliorent le comportement de ces derniers dans les eaux dures, ont une combinaison de caractéristiques qui les rendent adaptées pour assurer l'efficacité des catalyseurs qu'elles contiennent. Lesdites caractéristiques sont décrites ci-dessous :The detergent compositions which are suitable for containing the catalysts described above, and which improve the behavior of the latter in hard water, have a combination of characteristics which make them suitable for ensuring the effectiveness of the catalysts which they contain. These characteristics are described below:
Elles contiennent une quantité réduite de phosphates minéraux, spécifiquement moins de 1% en poids de la composition. Ces quantités de phosphates minéraux assurent que, dans les concentrations de détergent que l'on emploie habituellement dans le lavage, la concentration en phosphate du bain ne dépasse pas 10⁻⁴ molaire. Des concentrations en phosphates supérieures dans le bain de lavage inhibent en partie l'effet de renforcement du blanchiment qu'ont les catalyseurs.They contain a reduced amount of mineral phosphates, specifically less than 1% by weight of the composition. These amounts of mineral phosphates ensure that, in the concentrations of detergent that are usually used in washing, the phosphate concentration of the bath does not exceed 10⁻⁴ molar. Higher phosphate concentrations in the wash bath partially inhibit the whitening enhancement effect of the catalysts.
Elles contiennent des zéolithes, en remplacement des phosphates minéraux, comme adjuvants de détergence. Les zéolithes présentent un bon pouvoir d'adjuvant de détergence sans posséder un pouvoir séquestrant qui leur permettrait de concurrencer les ligands du complexe catalytique, inactivant ce dernier.They contain zeolites, replacing mineral phosphates, as detergency builders. Zeolites have a good detergency builder power without having a sequestering power which would allow them to compete with the ligands of the catalytic complex, inactivating the latter.
En outre, les zéolithes ont l'effet bénéfique supplémentaire, lorsqu'on les utilise pour absorber le catalyseur de blanchiment sur elles-mêmes, en l'incorporant ainsi dans les compositions détergentes. Ledit effet bénéfique supplémentaire consiste en une baisse de la vitesse de décomposition des peroxydes de blanchiment, ce qui fait que l'on bénéficie de leur pouvoir de blanchiment d'une manière plus efficace.In addition, zeolites have the additional beneficial effect, when used to absorb the bleach catalyst on themselves, thereby incorporating it into detergent compositions. Said additional beneficial effect consists in a reduction in the rate of decomposition of the bleaching peroxides, so that one takes advantage of their bleaching power in a more effective manner.
L'utilisation de zéolithes comme support pour catalyseurs de blanchiment du type des sels de cations métalliques libres est décrite dans les demandes de brevets européens no 224 952 et 224 953, où sont décrites des compositions qui contiennent du manganèse (+2) absorbé sur des zéolithes, de sorte que l'on évite l'oxydation du manganèse en oxyde de manganèse, qui peut causer des taches sur les tissus, en améliorant en plus la stabilité au stockage des compositions de blanchiment qui contiennent ledit système.The use of zeolites as a carrier for catalysts laundering the type of free metal cation salts is described in European Patent Applications No. 224 952 and 224 953, which describes compositions which contain manganese (+2) absorbed on zeolites, so that oxidation of manganese to manganese oxide is avoided, which can cause stains on fabrics, by further improving the storage stability of the bleaching compositions which contain said system.
Dans les compositions décrites dans la présente invention, lesdits inconvénients ne se rencontrent pas, car les catalyseurs métalliques utilisés ne subissent pas de transformation par oxydation en espèces capables de causer des taches sur les tissus lavés.In the compositions described in the present invention, said drawbacks are not encountered, since the metal catalysts used do not undergo transformation by oxidation into species capable of causing stains on the washed fabrics.
Les compositions en question peuvent contenir n'importe quel type de tensioactifs cationiques, amphotères, zwittérioniques, non ioniques et anioniques. Toutefois, les tensioactifs anioniques présentent un effet négatif sur la catalyse, comme on l'a indiqué ci-dessus.The compositions in question can contain any type of cationic, amphoteric, zwitterionic, nonionic and anionic surfactants. However, anionic surfactants have a negative effect on catalysis, as indicated above.
Néanmoins, on a découvert que, si la formulation contient simultanément des tensioactifs anioniques et non ioniques, tels que le rapport de la quantité des premiers à la quantité des derniers soit inférieure ou égale à 2,0, on arrive à éliminer l'effet négatif des tensioactifs anioniques sur les catalyseurs.Nevertheless, it has been discovered that, if the formulation simultaneously contains anionic and nonionic surfactants, such that the ratio of the quantity of the former to the quantity of the latter is less than or equal to 2.0, the negative effect can be eliminated. anionic surfactants on the catalysts.
Enfin, comme on l'a déjà indiqué, on ne peut inclure des agents séquestrants puissants dans les compositions détergentes qui renferment des catalyseurs de blanchiment qu'en très faibles quantités, inférieures à 0,2% en poids de la composition, car ils entrent en compétition avec les ligands qui forment le complexe catalytique, inhibant l'activité de ce dernier.Finally, as already indicated, strong sequestering agents can only be included in detergent compositions which contain bleaching catalysts in very small quantities, less than 0.2% by weight of the composition, since they enter in competition with the ligands which form the catalytic complex, inhibiting the activity of the latter.
Selon la présente invention, il est proposé des détergents de blanchiment ayant la composition suivante, exprimée en pourcentage pondéral :
- A. De 0,001% à 1,5%, exprimé en poids du cation métallique, d'un complexe catalytique formé de sels de métaux divalents de numéro atomique compris entre 25 et 29 et d'agents séquestrants qui forment des complexes catalytiques chargés positivement avec lesdits cations métalliques dans le bain de lavage, ledit catalyseur étant présent sous forme du complexe ou de ses précurseurs. B. De 1 à 30% d'agents de blanchiment peroxydés. C. De 0% à 1% d'adjuvants de détergence du type phosphate ou polyphosphate minéral.
- D. De 5% à 40% d'aluminosilicates alcalins, également connus sous le nom de zéolithes.
- E. De 3% à 25% de tensioactifs non ioniques et/ou anioniques, de façon que le rapport en poids des tensioactifs anioniques aux tensioactifs non ioniques soit inférieur à 2,0.
- F. De 0% à 0,2% d'agents séquestrants puissants.
- A. From 0.001% to 1.5%, expressed by weight of the metal cation, of a catalytic complex formed from divalent metal salts with atomic number between 25 and 29 and sequestering agents which form positively charged catalytic complexes with said metal cations in the washing bath, said catalyst being present in the form of the complex or of its precursors. B. From 1 to 30% of peroxide bleaches. C. From 0% to 1% of detergency builders of the phosphate or mineral polyphosphate type.
- D. From 5% to 40% of alkaline aluminosilicates, also known as zeolites.
- E. From 3% to 25% of nonionic and / or anionic surfactants, so that the weight ratio of anionic surfactants to nonionic surfactants is less than 2.0.
- F. From 0% to 0.2% of strong sequestering agents.
Les compositions selon l'invention peuvent contenir, en outre, des constituants comme des tensioactifs d'autres catégories, des régulateurs de moussage, des activateurs de blanchiment du type des précurseurs de peroxydes, des polymères qui inhibent l'incrustation et la redéposition, des sels structurants et/ou alcalins, des azurants optiques, des photoactivateurs, des agents teintants, des colorants, des parfums et, en général, tout type d'additif que l'on emploie couramment en détergence.The compositions according to the invention may contain, in addition, constituents such as surfactants from other categories, foaming regulators, bleaching activators of the peroxide precursor type, polymers which inhibit encrustation and redeposition, structuring and / or alkaline salts, optical brighteners, photoactivators, tinting agents, colorants, perfumes and, in general, any type of additive that is commonly used in detergency.
Les différents constituants que l'on peut incorporer dans les détergents décrits dans la présente invention sont détaillés ci-dessous.The various constituents which can be incorporated into the detergents described in the present invention are detailed below.
Les catalyseurs de blanchiment convenables pour mettre en oeuvre la présente invention sont ceux formés des sels de cations de métaux divalents ayant un numéro atomique compris entre 25 et 29 avec des agents séquestrants qui forment avec lesdits cations des complexes qui, aux pH alcalins habituels dans le lavage, ont une charge résiduelle positive et possèdent des positions de coordination libres, ou peuvent subir des transformations, dans le bain de lavage, en espèces qui possèdent lesdites positions de coordination libres.The bleaching catalysts suitable for practicing the present invention are those formed from the salts of divalent metal cations having an atomic number between 25 and 29 with sequestering agents which form with said cations complexes which, at the usual alkaline pH in the washing, have a positive residual charge and have free coordination positions, or can undergo transformations, in the washing bath, in cash which have said free coordination positions.
Lesdits catalyseurs peuvent être incorporés dans les formulations qui font l'objet de la présente invention, soit sous forme des complexes préformés, soit sous forme des précurseurs desdits complexes, auquel cas ces derniers se forment lorsque les compositions sont mises en solution aqueuse. Par précurseurs des complexes catalytiques, on doit entendre les sels de cations divalents de numéro atomique compris entre 25 et 29 et les agents séquestrants qui forment avec lesdits sels les complexes décrits dans la paragraphe ci-dessus.Said catalysts can be incorporated into the formulations which are the subject of the present invention, either in the form of the preformed complexes, or in the form of the precursors of the said complexes, in which case the latter are formed when the compositions are placed in aqueous solution. The term “precursors of catalytic complexes” should be understood to mean the salts of divalent cations with atomic number between 25 and 29 and the sequestering agents which form, with said salts, the complexes described in the above paragraph.
Des exemples de ces complexes sont ceux formés par les sels de métaux divalents de numéro atomique compris entre 25 et 29 avec les diamines dont les atomes d'azote sont séparés par une chaîne d'au plus cinq atomes, ces diamines pouvant être substituées ou non substituées, les substituants pouvant comporter des groupes fonctionnels au moyen desquels les diamines peuvent ou non établir des points de fixation supplémentaires avec le métal divalent avec lequel elles forment les complexes.Examples of these complexes are those formed by the salts of divalent metals with atomic number between 25 and 29 with diamines in which the nitrogen atoms are separated by a chain of at most five atoms, these diamines may or may not be substituted substituted, the substituents possibly comprising functional groups by means of which the diamines may or may not establish additional attachment points with the divalent metal with which they form the complexes.
Des exemples de ces complexes sont ceux formés par le cuivre divalent ou le manganèse divalent avec les polyamines comme l'éthylènediamine, la diéthylènetriamine, la 1,3-propylènediamine, la 1,2-propylènediamine et la 1,2-cyclohexylènediamine.Examples of these complexes are those formed by divalent copper or divalent manganese with polyamines such as ethylenediamine, diethylenetriamine, 1,3-propylenediamine, 1,2-propylenediamine and 1,2-cyclohexylenediamine.
Des exemples supplémentaires sont les complexes formés par les composés macrocycliques comme le 1,4,8,11-tétraaza-2,3,9,10-tétraméthylcyclotétradéca-1,3,8,10-tétraène et les sels de cuivre divalent et de manganèse divalent.Additional examples are the complexes formed by macrocyclic compounds such as 1,4,8,11-tetraaza-2,3,9,10-tetramethylcyclotetradeca-1,3,8,10-tetraene and the salts of divalent copper and divalent manganese.
Les agents de blanchiment peroxydés convenables pour mettre en oeuvre la présente invention sont les persels minéraux, à la fois ceux qui sont de vrais persels et ceux qui sont des composés d'addition de sels minéraux et de peroxyde d'hydrogène. Des exemples de ce type d'agent de blanchiment sont les perborates alcalins, comme le perbo rate de sodium, mono- ou tétrahydraté, et les percarbonates alcalins.The peroxidized bleaching agents suitable for practicing the present invention are mineral persalts, both those which are real persalts and those which are compounds of addition of mineral salts and of hydrogen peroxide. Examples of this type of bleach are alkaline perborates, such as perbo sodium spleen, mono- or tetrahydrate, and alkaline percarbonates.
Les phosphates minéraux cités dans la description englobent les orthophosphates, les pyrophosphates et les polyphosphates de métaux alcalins, et en particulier les tripolyphosphates de sodium et de potassium dans leurs différents degrés d'hydratation.The mineral phosphates mentioned in the description include orthophosphates, pyrophosphates and polyphosphates of alkali metals, and in particular sodium and potassium tripolyphosphates in their different degrees of hydration.
En ce qui concerne les aluminosilicates alcalins échangeurs d'ions ou zéolithes, on peut utiliser aussi bien les cristallines que les amorphes ou que des mélanges amorphes/cristallines, tant d'origine naturelle que d'origine synthétique.As regards the alkaline aluminosilicates ion exchangers or zeolites, it is possible to use both the crystallines that the amorphs or that amorphous / crystalline mixtures, both of natural origin and of synthetic origin.
Celles qui conviennent particulièrement bien sont les zéolithes synthétiques finement divisées de formule (Na₂O)Px,(Al₂O₃)y,(SiO₂)z,wH₂O, dans laquelle x est égal à 1, y a une valeur de 0,6 à 1,3 et est de préférence d'environ 1, z a une valeur de 1 à 4 et de préférence de 2 à 3 ou d'environ 2, et w a une valeur de 0 à 9 et de préférence de 2,5 à 6. Les aluminosilicates de ce type sont des produits disponibles dans le commerce et sont habituellement nommés zéolithes A et X ou leurs mélanges.Those which are particularly suitable are the finely divided synthetic zeolites of formula (Na₂O) P x , (Al₂O₃) y , (SiO₂) z , wH₂O, in which x is equal to 1, y has a value of 0.6 to 1, 3 and is preferably approximately 1, za a value of 1 to 4 and preferably of 2 to 3 or approximately 2, and wa a value of 0 to 9 and preferably of 2.5 to 6. The aluminosilicates of this type are commercially available products and are usually called zeolites A and X or their mixtures.
Le système de tensioactifs comprend différents types de composés. En premier lieu, les tensioactifs anioniques synthétiques, ceux qui conviennent pour être utilisés dans la présente invention englobant les sels solubles d'alkylbenzènesulfonates, alkylsulfates, alkyl(polyéther)sulfates, α-oléfinesulfonates, paraffinesulfonates, alkylglycéryléthersulfonates, α-sulfocarboxylates et leurs esters, sulfates et sulfonates de monoglycérides d'acides gras, alkylphénol(polyéther)sulfates et analogues. Parmi eux, on préfère les alkylbenzènesulfonates de métal alcalin dont la chaîne alkyle est essentiellement linéaire et contient un nombre d'atomes de carbone compris entre 10 et 14.The surfactant system includes different types of compounds. First, synthetic anionic surfactants, those which are suitable for use in the present invention including the soluble salts of alkylbenzenesulfonates, alkylsulfates, alkyl (polyether) sulfates, α-olefinesulfonates, paraffinsulfonates, alkylglyceryl ether sulfonates, α-sulfocarboxylates and their esters, sulfates and sulfonates of fatty acid monoglycerides, alkylphenol (polyether) sulfates and the like. Among them, alkali metal alkylbenzenesulfonates are preferred, the alkyl chain of which is essentially linear and contains a number of carbon atoms between 10 and 14.
Une autre catégorie de tensioactifs employés sont les tensioactifs non ioniques, parmi lesquels on peut utiliser ceux du type alcool gras polyoxyalkyléné avec un nombre de moles d'oxyde d'alkylène par mole d'alcool gras compris entre 2 et 20, et de préférence entre 3 et 15, et lesdits alcools gras ayant des chaînes linéaires ou partiellement ramifiées comportant un nombre d'atomes de carbone compris entre 8 et 22. Des exemples desdits tensioactifs sont les produits de l'oxyéthylénation de l'alcool laurylique et les produits de l'oxyéthylénation d'alcools synthétiques que l'on trouve sur le marché sous les marques telles que DobanolR, SynperonicR, LutensolR, LialR, etc.Another category of surfactants used are nonionic surfactants, among which can be used those of the polyoxyalkylenated fatty alcohol type with a number of moles of alkylene oxide per mole of fatty alcohol between 2 and 20, and preferably between 3 and 15, and said fatty alcohols having straight or partially branched chains comprising a number of carbon atoms between 8 and 22. Examples of said surfactants are the products of the oxyethylenation of lauryl alcohol and the products of the oxyethylenation of synthetic alcohols which are found on the market under brands such as Dobanol R , Synperonic R , Lutensol R , Lial R , etc.
Comme tensioactifs non ioniques, conviennent également les produits de réaction d'oxydes d'alkylène avec les alkylphénols dans lesquels le radical alkyle contient un nombre d'atomes de carbone compris entre 7 et 11, de façon que le nombre de moles d'oxyde d'alkylène par mole d'alkylphénol soit compris entre 3 et 20, et de préférence entre 5 et 12.Also suitable as nonionic surfactants are the reaction products of alkylene oxides with alkylphenols in which the alkyl radical contains a number of carbon atoms between 7 and 11, so that the number of moles of oxide d alkylene per mole of alkylphenol is between 3 and 20, and preferably between 5 and 12.
On peut aussi utiliser comme tensioactifs les savons d'acides gras, saturés ou insaturés, comportant un nombre d'atomes de carbone compris entre 8 et 24. Comme exemples desdits savons, on peut citer les sels alcalins d'acides gras, principalement saturés, qui contiennent de préférence entre 10 et 20 atomes de carbone, les sels alcalins de mélanges d'acides gras dérivés du suif et des huiles de coprah et de palme étant particulièrement préférés.It is also possible to use as surfactants soaps of fatty acids, saturated or unsaturated, comprising a number of carbon atoms between 8 and 24. As examples of said soaps, there may be mentioned the alkaline salts of fatty acids, mainly saturated, which preferably contain between 10 and 20 carbon atoms, the alkali salts of mixtures of fatty acids derived from tallow and coconut and palm oils being particularly preferred.
Les acides aminopolycarboxyliques ou leurs sels, comme l'acide éthylènediaminetétraacétique ou nitrilotriacétique, et analogues, conviennent pour être utilisés comme agents séquestrants puissants. Les acides phosphoniques organiques ou leurs sels et les hydroxycarboxylates ou leurs sels conviennent également.Aminopolycarboxylic acids or their salts, such as ethylenediaminetetraacetic or nitrilotriacetic acid, and the like, are suitable for use as potent sequestering agents. Organic phosphonic acids or their salts and hydroxycarboxylates or their salts are also suitable.
En plus des constituants essentiels déjà mentionnés, il peut s'avérer avantageux de compléter les compositions détergentes de l'invention par un autre type de constituants facultatifs.In addition to the essential constituents already mentioned, it may prove advantageous to supplement the detergent compositions of the invention with another type of optional constituents.
Parmi ce type de constituants facultatifs, on peut mentionner les enzymes protéolytiques ou amylolytiques comme celles que l'on trouve sur le marché sous les marques MaxataseR et AlcalaseR.Among this type of optional constituents, mention may be made of proteolytic or amylolytic enzymes like those found on the market under the Maxatase R and Alcalase R brands.
Les tensioactifs cationiques du type des sels d'ammonium quaternaire, dans lesquels au moins un ou deux des radicaux alkyle sont des chaînes carbonées en C₈-C₁₈ linéaires ou partiellement ramifiées, peuvent également être incorporés.Cationic surfactants of the quaternary ammonium salt type, in which at least one or two of the alkyl radicals are linear or partially branched C₈-C₁₈ carbon chains, can also be incorporated.
Parmi les tensioactifs du type amphotère, que l'on peut aussi utiliser, figurent les dérivés hydrosolubles d'amines aliphatiques secondaires et tertiaires dans lesquelles le radical aliphatique peut comporter une chaîne linéaire ou ramifiée, et, parmi les dérivés hydrosolubles, un des substituants contient de 8 à 18 atomes de carbone et un autre est constitué d'un groupe anionique comme, par exemple, un groupe carboxy, sulfonate, phosphate ou phosphonate.Among the amphoteric type surfactants, which can also be used, are the water-soluble derivatives of secondary and tertiary aliphatic amines in which the aliphatic radical may comprise a straight or branched chain, and, among the water-soluble derivatives, one of the substituents contains from 8 to 18 carbon atoms and another consists of an anionic group such as, for example, a carboxy, sulfonate, phosphate or phosphonate group.
On peut aussi utiliser les tensioactifs connus comme tensioactifs à ions hybrides ou zwittérioniques, comme les dérivés hydrosolubles de composés aliphatiques cationiques avec les groupes ammonium quaternaire, phosphoriques et sulfoniques, dans lesquels les radicaux peuvent comporter une chaîne linéaire ou ramifiée et dans lesquels l'un des substituants aliphatiques contient de 8 à 18 atomes de carbone et un autre contient un groupe anionique qui est soluble dans l'eau.It is also possible to use the surfactants known as surfactants with hybrid or zwitterionic ions, such as the water-soluble derivatives of cationic aliphatic compounds with the quaternary ammonium, phosphoric and sulphonic groups, in which the radicals can comprise a linear or branched chain and in which one aliphatic substituents contains 8 to 18 carbon atoms and another contains an anionic group which is soluble in water.
Les substances qui aident à éviter la redéposition des salissures sur les tissus pendant l'opération de lavage peuvent également être ajoutées. Des exemples sont les dérivés de la cellulose comme ses composés carboxyalkylés ou hydroxyalkylés.Substances that help prevent redeposition of soiling on fabrics during the washing process can also be added. Examples are cellulose derivatives such as its carboxyalkylated or hydroxyalkylated compounds.
Un autre constituant facultatif dans les compositions de la présente invention est les sels structurants, parmi lesquels on trouve un grand nombre de sels minéraux qui sont neutres à l'hydrolyse et qui ont une solubilité dans l'eau élevée. Parmi les sels préférés, on peut citer le sulfate de sodium.Another optional constituent in the compositions of the present invention is the structuring salts, among which there are a large number of mineral salts which are neutral to hydrolysis and which have a high solubility in water. Among the preferred salts, mention may be made of sodium sulfate.
Les agents alcalinisants convenables pour ces compositions sont les sels de métaux alcalins dérivés des acides carbonique, orthosilicique, métasilicique et analogues.Alkalizing agents suitable for these compositions are the alkali metal salts derived from carbonic, orthosilicic, metasilicic acids and the like.
Les agents d'avivage fluorescents anioniques, également connus sous le nom d'azurants optiques, peuvent aussi être employés. Parmi ce type de produits, ceux qui conviennent le mieux sont les dérivés sulfonés hydrosolubles de stilbènes et les dérivés sulfonés hydrosolubles de distyrylbiphényle. Il existe une grande variété de ces produits commercialisés par Ciba-Geigy, parmi lesquels on peut citer ceux des marques TinopalR 5BMS, TinopalR DMS, TinopalR LMS-X et TinopalR CBS-X.Anionic fluorescent brighteners, also known as optical brighteners, can also be used. Among this type of products, those which are most suitable are the water-soluble sulphonated derivatives of stilbenes and the water-soluble sulphonated derivatives of distyrylbiphenyl. There is a wide variety of these products sold by Ciba-Geigy, among which we can mention those of the brands Tinopal R 5BMS, Tinopal R DMS, Tinopal R LMS-X and Tinopal R CBS-X.
D'autres constituants avantageux sont les polymères qui produisent un meilleur aspect du linge lavé, car ils manifestent une action inhibitrice sur l'incrustation, c est-à-dire qu'ils empêchent les sels minéraux insolubles qui se forment dans le bain de lavage de se déposer sur les tissus, produisant un phénomène de grisaillement et de durcissement cumulatif. Lesdits polymères sont les sels hydrosolubles d'homo- ou de copolymères polycarboxyliques ayant une configuration telle que les radicaux carboxyliques sont séparés les uns des autres par un ou deux atomes de carbone. Les produits de ce type sont des homo- ou des copolymères de motifs monomères tels que, par exemple, l'anhydride maléique, l'acide maléique, le méthylvinyléther, l'acide acrylique, l'acide méthacrylique, et analogues. Ces produits se trouvent sur le marché sous des noms tels que SokalanR, GantrezR, PrimalR et analogues.Other advantageous constituents are the polymers which produce a better appearance of the washed linen, because they manifest an inhibiting action on the incrustation, that is to say that they prevent the insoluble mineral salts which form in the washing bath. to settle on the tissues, producing a phenomenon of graying and cumulative hardening. Said polymers are the water-soluble salts of polycarboxylic homo- or copolymers having a configuration such that the carboxylic radicals are separated from one another by one or two carbon atoms. Products of this type are homo- or copolymers of monomer units such as, for example, maleic anhydride, maleic acid, methylvinyl ether, acrylic acid, methacrylic acid, and the like. These products are found on the market under names such as Sokalan R , Gantrez R , Primal R and the like.
Il est aussi possible d'incorporer des régulateurs de moussage différents des savons ou des tensioactifs non ioniques ayant un degré élevé d'oxyéthylénation, comme, par exemple, les cires, les hydrocarbures saturés, les esters de l'acide phosphorique et les silicones. Dans ce contexte, on préfère les silicones comme les combinaisons de dialkylpolysiloxanes avec de la silice finement divisée et les silices silanées ou, en variante, les copolymères de dialkylpolysiloxanes avec des radicaux glycol ou oxyde d'éthylène. Lesdites silicones spéciales sont commercialisées par la firme Dow Corning sous les références Q2-3092, DB-100, DC-190, DC-193, DC-198. Lesdites silicones peuvent être utilisées telles que présentées par le fournisseur, ou bien protégées au moyen d'une granulation et d'un enrobage avec des matériaux inertes pour éviter leur interaction avec les constituants de la composition détergente.It is also possible to incorporate foam regulators other than soaps or nonionic surfactants having a high degree of oxyethylenation, such as, for example, waxes, saturated hydrocarbons, esters of phosphoric acid and silicones. In this context, we prefer silicones such as combinations of dialkylpolysiloxanes with finely divided silica and silanated silicas or, alternatively, copolymers of dialkylpolysiloxanes with glycol or ethylene oxide radicals. Said special silicones are sold by the company Dow Corning under the references Q2-3092, DB-100, DC-190, DC-193, DC-198. Said silicones can be used as presented by the supplier, or else protected by granulation and coating with inert materials to avoid their interaction with the constituents of the detergent composition.
Enfin, il est utile de noter que, à titre de constituants présents seulement en quantité très infime et dont le seul rôle est d'améliorer la présentation du produit, on ajoute à la composition des parfums, des colorants, des opacifiants et analogues.Finally, it is useful to note that, as constituents present only in very small quantities and whose only role is to improve the presentation of the product, perfumes, dyes, opacifiers and the like are added to the composition.
A titre d'exemples, et sans qu'il soit possible de les considérer comme limitant le cadre de la présente invention, on indique différentes compositions selon l'invention et les résultats de réflectance des tissus EMPA-114 de 10x10cm lavés avec lesdites compositions détergentes de blanchiment.By way of examples, and without it being possible to consider them as limiting the scope of the present invention, different compositions according to the invention are indicated and the reflectance results of EMPA-114 fabrics of 10 × 10 cm washed with said detergent compositions whitening.
Il convient d'expliquer que la désignation EMPA-114 correspond à des tissus en coton standards tachés de vin rouge selon les normes de la Eidgenössiche Materialprüfungsamt de Suisse.It should be explained that the designation EMPA-114 corresponds to standard cotton fabrics stained with red wine according to the standards of the Eidgenössiche Materialprüfungsamt of Switzerland.
De même, les abréviations suivantes seront utilisées pour désigner chacun des constituants présents dans les compositions détergentes utilisées dans ces exemples :
- C1 : Perborate de sodium monohydraté.
- C2 : Chlorure cuivrique dihydraté.
- C3 : Diéthylènetétramine.
- C4 : Ethylènediamine.
- C5 : Alkyl(linéaire en C₁₂)benzènesulfonate de sodium.
- C6 : Mélange de savon de suif et de savon de poisson avec 16% de C₂₀-C₂₂.
- C7 : Alcool de suif hydrogéné avec 11 moles d'oxyde d'éthylène.
- C8 : Tripolyphosphate pentasodique préhydraté.
- C9 : Zéolithe cristalline de type A WessalithR de Degussa.
- C10 : Polyacrylate SOKA-LANR CP-5 de faible masse moléculaire.
- C11 : Ethylènediaminetétraacétate de sodium (EDTA).
- C12 : Nitrilotriacétate de sodium TrilonR A sous forme pulvérisée de BASF.
- C13 : Sel hexasodique de l'acide éthylènediaminetétraméthylènephosphonique DequestR 2046 de Monsanto.
- C14 : Carbonate de sodium.
- C15 : Sulfate de sodium anhydre.
- C16 : Carboxyméthylcellulose sodique.
- C17 : Silicate de sodium avec un rapport Na₂O/SiO₂ = 1:2,3.
- C18 : H₂O.
- C1: Sodium perborate monohydrate.
- C2: Cupric chloride dihydrate.
- C3: Diethylenetetramine.
- C4: Ethylenediamine.
- C5: Alkyl (linear in C₁₂) sodium benzenesulfonate.
- C6: Mixture of tallow soap and fish soap with 16% C₂₀-C₂₂.
- C7: Hydrogenated tallow with 11 moles of ethylene oxide.
- C8: Prehydrated pentasodium tripolyphosphate.
- C9: Wessalith R type A crystalline zeolite from Degussa.
- C10: SOKA-LAN R CP-5 polyacrylate of low molecular weight.
- C11: Sodium ethylenediaminetetraacetate (EDTA).
- C12: Sodium nitrilotriacetate Trilon R A in spray form of BASF.
- C13: Hexasodium salt of ethylenediaminetetramethylenephosphonic acid Dequest R 2046 from Monsanto.
- C14: Sodium carbonate.
- C15: Anhydrous sodium sulfate.
- C16: Sodium carboxymethylcellulose.
- C17: Sodium silicate with a Na₂O / SiO₂ ratio = 1: 2.3.
- C18: H₂O.
On prépare des compositions détergentes selon les formulations suivantes :
Il convient d'expliquer que les constituants C2, C3 et C4, qui sont respectivement le chlorure cuivrique dihydraté, la diéthylènetriamine et l'éthylènediamine, sont combinés pour former le complexe de blanchiment catalytique dans le bain de lavage.It should be explained that the components C2, C3 and C4, which are cupric chloride dihydrate, diethylenetriamine and ethylenediamine, respectively, are combined to form the catalytic bleaching complex in the washing bath.
Pour rendre les exemples homogènes, afin que les mesures de réflectance des différentes compositions soient directement comparables, tous les exemples ont été réalisés au moyen de catalyseurs comportant le cuivre comme cation métallique. En outre, pour la même raison, on a pris l'éthylènediamine comme agent complexant dans tous les exemples, sauf le numéro 7, dans lequel on a utilisé la diéthylènetriamine avec une composition identique à celle de l'exemple 2, pour montrer l'influence du changement de ligand.To make the examples homogeneous, so that the reflectance measurements of the different compositions are directly comparable, all the examples were carried out using catalysts comprising copper as metal cation. Furthermore, for the same reason, ethylenediamine was used as complexing agent in all of the examples, except
Les exemples 1 à 7 correspondent à des compositions selon ce qui est décrit dans la présente invention et, pour cette raison, toutes ces compositions fournissent une grande efficacité de blanchiment dans le lavage des taches EMPA-114, ce qui conduit à des valeurs de réflectance élevées.Examples 1 to 7 correspond to compositions according to what is described in the present invention and, for this reason, all these compositions provide a high bleaching efficiency in washing EMPA-114 stains, which leads to reflectance values. high.
L'exemple 8 correspond à une composition détergente qui ne remplit pas les conditions de la présente invention.Example 8 corresponds to a detergent composition which does not fulfill the conditions of the present invention.
Enfin, l'exemple 9 correspond à des compositions de référence et ne contient que du perborate et un catalyseur en l'absence de tout autre constituant, et offre la même concentration de perborate dans le bain de lavage que les compositions des exemples 1 à 8.Finally, Example 9 corresponds to reference compositions and contains only perborate and a catalyst in the absence of any other constituent, and offers the same concentration of perborate in the washing bath as the compositions of Examples 1 to 8 .
On étudie les compositions des exemples 1 à 9 en lavant avec elles des taches standards au moyen du procédé de lavage décrit ci-dessous.The compositions of Examples 1 to 9 are studied by washing standard stains with them by means of the washing process described below.
On introduit dans le compartiment pour détergent d'une machine à laver en acier inoxydable Zanussi 630 une dose de 210 grammes de la composition détergente à étudier et on programme un cycle de lavage à une température de 30°C durant 70 minutes, après quoi commencent les cycles de rinçage, qui durent au total 40 minutes.A dose of 210 grams of the detergent composition to be studied is introduced into the detergent compartment of a Zanussi 630 stainless steel washing machine and a washing cycle is programmed at a temperature of 30 ° C for 70 minutes, after which rinse cycles, which last a total of 40 minutes.
On retire les tissus de la machine à laver et on les sèche à la température ambiante.The fabrics are removed from the washing machine and dried at room temperature.
Les mesures de réflectance sont faites dans un appareil Ultrascan de la firme Hunterlab, avec une lampe à halogène de type JCR de 9,5 V et 55 W, avec une lumière de type D65/10°, inclusion de brillance et d'un filtre à ultraviolet.The reflectance measurements are made in an Ultrascan device from the company Hunterlab, with a lamp with JCR type halogen of 9.5 V and 55 W, with a D65 / 10 ° type light, inclusion of gloss and an ultraviolet filter.
Les réflectances des tissus lavés avec chacune des compositions du tableau 1 figurent au tableau 2 et sont représentées graphiquement sur le graphique 1.
Comme le montre le tableau 2, et comme le montre mieux visuellement le graphique 1, les exemples 1 à 7, qui correspondent à des compositions détergentes de blanchiment qui remplissent les conditions décrites dans la présente invention, fournissent des réflectances des tissus lavés supérieures à celles que l'on obtient par lavage avec une composition qui ne contient que du perborate et un catalyseur (exemple 9). Toutefois, la composition de l'exemple 8, qui ne remplit pas les conditions de la présente invention, fournit une réflectance encore plus faible que celle que l'on obtient avec la composition de référence de l'exemple 9.As shown in Table 2, and as shown more visually in
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES8902082A ES2016465A6 (en) | 1989-06-14 | 1989-06-14 | Textile bleaching compositions effective at low temperatures. |
ES8902082 | 1989-06-14 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0414581A1 true EP0414581A1 (en) | 1991-02-27 |
EP0414581B1 EP0414581B1 (en) | 1995-09-20 |
EP0414581B2 EP0414581B2 (en) | 2003-10-15 |
Family
ID=8262530
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90401635A Expired - Lifetime EP0414581B2 (en) | 1989-06-14 | 1990-06-13 | Textile bleaching compositions effective at low temperatures |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0414581B2 (en) |
AT (1) | ATE128178T1 (en) |
DE (1) | DE69022515T3 (en) |
ES (2) | ES2016465A6 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0549272A1 (en) * | 1991-12-20 | 1993-06-30 | Unilever Plc | Bleach activation |
EP0549271A1 (en) * | 1991-12-20 | 1993-06-30 | Unilever Plc | Bleach activation |
EP0832969A2 (en) * | 1996-09-26 | 1998-04-01 | Henkel Kommanditgesellschaft auf Aktien | Catalytic active agent for improved bleading |
US6069122A (en) * | 1997-06-16 | 2000-05-30 | The Procter & Gamble Company | Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution |
US6069123A (en) * | 1995-06-30 | 2000-05-30 | Procter & Gamble Company | Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety |
WO2002064721A1 (en) * | 2001-02-13 | 2002-08-22 | Unilever Plc | Composition and method for bleaching a substrate |
US6589926B1 (en) | 1998-06-02 | 2003-07-08 | Procter & Gamble Company | Dishwashing detergent compositions containing organic diamines |
US6727212B2 (en) | 1997-11-10 | 2004-04-27 | The Procter & Gamble Company | Method for softening soil on hard surfaces |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3002271A1 (en) * | 1980-01-23 | 1981-07-30 | VEB Waschmittelwerk Genthin, Stammbetrieb, DDR 3280 Genthin | Bleaching mixt. for detergent compsns. - contg. (in)organic peroxy cpd. opt. activator and water-soluble metal chelate complex |
EP0111963A2 (en) * | 1982-12-17 | 1984-06-27 | Unilever N.V. | Detergent compositions |
EP0141470A2 (en) * | 1983-11-08 | 1985-05-15 | Unilever N.V. | Manganese adjuncts, their preparation and use |
EP0224953A2 (en) * | 1985-12-06 | 1987-06-10 | Unilever N.V. | Phosphates in manganese catalyzed bleach compositions |
-
1989
- 1989-06-14 ES ES8902082A patent/ES2016465A6/en not_active Expired - Fee Related
-
1990
- 1990-06-13 AT AT90401635T patent/ATE128178T1/en active
- 1990-06-13 DE DE69022515T patent/DE69022515T3/en not_active Expired - Lifetime
- 1990-06-13 ES ES90401635T patent/ES2078955T5/en not_active Expired - Lifetime
- 1990-06-13 EP EP90401635A patent/EP0414581B2/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3002271A1 (en) * | 1980-01-23 | 1981-07-30 | VEB Waschmittelwerk Genthin, Stammbetrieb, DDR 3280 Genthin | Bleaching mixt. for detergent compsns. - contg. (in)organic peroxy cpd. opt. activator and water-soluble metal chelate complex |
EP0111963A2 (en) * | 1982-12-17 | 1984-06-27 | Unilever N.V. | Detergent compositions |
EP0141470A2 (en) * | 1983-11-08 | 1985-05-15 | Unilever N.V. | Manganese adjuncts, their preparation and use |
EP0224953A2 (en) * | 1985-12-06 | 1987-06-10 | Unilever N.V. | Phosphates in manganese catalyzed bleach compositions |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0549272A1 (en) * | 1991-12-20 | 1993-06-30 | Unilever Plc | Bleach activation |
EP0549271A1 (en) * | 1991-12-20 | 1993-06-30 | Unilever Plc | Bleach activation |
US5314635A (en) * | 1991-12-20 | 1994-05-24 | Lever Brothers Company, Division Of Conopco, Inc. | Bleach activation |
US6069123A (en) * | 1995-06-30 | 2000-05-30 | Procter & Gamble Company | Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety |
EP0832969A2 (en) * | 1996-09-26 | 1998-04-01 | Henkel Kommanditgesellschaft auf Aktien | Catalytic active agent for improved bleading |
EP0832969A3 (en) * | 1996-09-26 | 1998-09-02 | Henkel Kommanditgesellschaft auf Aktien | Catalytic active agent for improved bleading |
US6069122A (en) * | 1997-06-16 | 2000-05-30 | The Procter & Gamble Company | Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution |
US6727212B2 (en) | 1997-11-10 | 2004-04-27 | The Procter & Gamble Company | Method for softening soil on hard surfaces |
US6589926B1 (en) | 1998-06-02 | 2003-07-08 | Procter & Gamble Company | Dishwashing detergent compositions containing organic diamines |
WO2002064721A1 (en) * | 2001-02-13 | 2002-08-22 | Unilever Plc | Composition and method for bleaching a substrate |
Also Published As
Publication number | Publication date |
---|---|
ES2016465A6 (en) | 1990-11-01 |
DE69022515T3 (en) | 2004-06-03 |
ES2078955T3 (en) | 1996-01-01 |
EP0414581B2 (en) | 2003-10-15 |
ATE128178T1 (en) | 1995-10-15 |
DE69022515D1 (en) | 1995-10-26 |
EP0414581B1 (en) | 1995-09-20 |
DE69022515T2 (en) | 1996-05-15 |
ES2078955T5 (en) | 2004-05-16 |
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