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    • 专利摘要:
    The subject of the present invention is a whitening solid composition comprising at least one chlorine bleaching and detergency agent chosen from dichloroisocyanurates and at least one optical brightener, characterized in that the pH of said composition is between 5 and 9, and in that the dissolution time in aqueous solution of said composition is between 1 seconds and 30 minutes. . The present invention also relates to the use of such a composition for bleaching a textile, while ensuring the protection of textile fibers, their disinfection and washing.
    公开号:FR3045662A1
    申请号:FR1562896
    申请日:2015-12-21
    公开日:2017-06-23
    发明作者:Marion Omont-Manteghetti；Jacques Brosse；Maelle Reymond
    申请人:Eurotab SA；
    IPC主号:
    专利说明:

    FIBER PROTECTIVE WHITE CHLORINATED SOLID COMPOSITION
    The present invention relates to a solid whitening composition for washing, disinfecting and bleaching laundry while protecting the textile fibers.
    In the field of linen, chlorinated tablets are very often used for the purpose of disinfecting, however they are less often used for bleaching laundry unlike bleach. The disinfectant and whitening action of the chlorinated compositions used depends on the chemical elements present in solution. In particular, the disinfecting power and whitening power of a chlorinated product is related to the amount of hypochlorous acid and sodium hypochlorite present in solution. The amount of hypochlorous acid is all the more important that the pH of the solution is low and acid, and sodium hypochlorite is all the more present that the pH of the solution is high and basic. This is demonstrated by the E-pH diagram of chlorine provided in Figure 1.
    Sodium dichloroisocyanurate (DCCNA) products typically have a pH of around 6, dissolved in solution. Sodium dichloroisocyanurate then reacts with water to form hypochlorous acid. Such products therefore have a high disinfecting power.
    Bleach solutions have a pH between 9.5 and 12, and contain a large amount of sodium hypochlorite and a limited amount of hypochlorous acid, so they have a high whitening power.
    For the same amount of active chlorine, products based on sodium dichloroisocyanurate will have a better disinfecting power, and bleach better whitening power. As a result, chlorinated compositions comprising sodium dichloroisocyanurate are very little used in the field of laundry bleaching.
    Thus, in the field of chlorinated products for laundry bleaching, the products most commonly used in the prior art are liquid products based on sodium hypochlorite, that is to say bleach.
    However, the stability in storage and use of these products is still to be improved. Indeed, hypochlorite ions are degraded by solar UV rays and heat. In poor storage conditions, bleach can very quickly lose its effectiveness and stability. For this, the products of the prior art use specific containers, additional additives. We find, for example, the use of chlorine-stable opacifiers such as a latex to reduce the impact of UV (EP 1 865 051 and US 3,663,442), anti-free radicals (WO 99/15616), or a source of bromide (US 6,015,782).
    In addition, bleach is known to damage textile fibers in the wash and attack colors, such as the majority of known chlorine compositions. Without wishing to be bound by any theory, the damage to the textile fibers may be due to the source of chlorine itself which may be too aggressive, to a quantity of chlorine liberated locally and / or too much. This wear can also be related to the highly basic pH of the bleaching compositions.
    In US Pat. No. 4,741,858 there is disclosed a whitening granular composition based on lithium hypochlorite. In order to make this composition more stable with respect to certain components, and for the fabrics during washing, the solution proposed is to coat the lithium hypochlorite granules in order gradually to release the chlorine and thus to minimize the tissue damage.
    In the patent application CA 2,341,188, there is described a liquid whitening composition based on hypochlorite. In order to limit the damage to the tissues, it is added to the composition of the borate and / or boric acid (reprotoxic compound), combined with a surfactant.
    In order to improve the bleaching of the laundry, the products of the prior art sometimes use optically functional nanoparticles, such as optical brighteners or ultramarine-type dyes. However, the use of a dispersant is often recommended in such products, especially in liquid compositions, because dyes and brighteners would tend to precipitate. Without addition of dispersant, the concentration of optically functional nanoparticles would not be homogeneous when using the bleaching composition.
    Patent FR 1 453 213 describes in particular a chlorinated composition comprising an optical brightener and sodium tripolyphosphate for its stability; the pH of the solution must be between 9 and 11. The use of sodium tripolyphosphate for laundry is currently banned in Europe.
    In the patent application US 6,204,235, the optical brightener is microencapsulated to provide a certain stability over time in a chlorine solution.
    Very few chlorinated compositions of the prior art allow as much disinfection of laundry as bleaching. In addition, most of the compositions concerned are in the form of multilayer tablet for separating in different layers, the incompatible products between them. For example, these compositions comprise a layer comprising the chlorine source and another layer comprising functional ingredients that are not compatible with chlorine, such as enzymes or perfume (US Pat. No. 8,481,471, EP 0 481 547, WO 2013/084072 and EP 1). 352,949)
    The present invention relates to a bleaching solid chlorinated composition comprising at least one chlorine bleaching and detergency agent chosen from dichloroisocyanurates and at least one optical brightener, characterized in that the pH of said composition is between 5 and 9, and in that the dissolution time in aqueous solution of said composition is between 1 seconds and 30 minutes.
    The present invention makes it possible to obtain the bleaching properties of bleach while ensuring the protection of textile fibers. In particular, the invention makes it possible to better preserve the fibers and the colors of the fabrics during the process of bleaching the laundry, even after multiple washings, unlike bleach which, due to its too high pH and its liquid form (instantaneous dissolution ), strongly damages fabrics and colors.
    The present invention also makes it possible to obtain a chlorinated composition that allows both the disinfection of the laundry and its bleaching. The composition according to the invention has in particular a good washing efficiency on oxidizable stains.
    The present invention further allows the use of optical brightener without it being necessary to separate it from the chlorine agent and without it being degraded by the chlorine storage or during its use. Moreover, by the solid format of the composition, the amount of brightener is homogeneous for each wash without having to add dispersant or other additive to maintain a homogeneous dispersion in the product.
    The present invention thus makes it possible to prepare a chlorine bleaching composition which comprises at least one layer / mixture comprising both a chlorinated agent and an optical brightener without the need for separation of these compounds. The present invention will therefore have the advantage of allowing the preparation of a bleaching chlorine composition by means of a simple preparation process, with a reduced number of stages and a reduced number of components and not requiring separation of the various constituents. .
    The solid composition according to the present invention also allows a homogeneous and controlled release of chlorine in the washing solution, thereby avoiding the aggression of textile fibers by salting a large amount of chlorine in a localized manner.
    The composition according to the present invention thus makes it possible to propose a solution to the various disadvantages encountered in the prior art.
    The inventors have surprisingly discovered that the use of a chlorinated bleaching and detergency agent chosen from dichloroisocyanurates and at least one optical brightener in a solid chlorine bleaching composition having a pH of between 5 and 9 makes it possible to obtain bleaching properties of bleach while ensuring the protection of textile fibers and disinfection of laundry.
    The inventors have notably noted that when a composition comprising at least one chlorine bleaching and detergency agent chosen from among dichloroisocyanurates and at least one optical brightener is at a pH that is too acidic, that is to say less than 5, an interaction undesirable is created between the chlorine agent and the optical brightener within the composition, which induces a negative synergy and therefore decreases the effectiveness of chlorine on oxidizable stains and the effectiveness of the optical brightener on bleaching ; in addition, a pH that is too high, that is to say greater than 9, increases the wear of the fabrics during washing. The pH of the composition according to the invention makes it possible to balance the content of sodium hypochlorite and hypochlorous acid in the washing solution, while avoiding these inconveniences.
    The inventors have also discovered that when a certain amount of chlorine is rapidly released in a localized manner and / or in too large a quantity in the laundry, the wear of the fabrics increases considerably.
    Thus, the subject of the present invention is mainly a whitening solid composition comprising at least one chlorine bleaching and detergency agent chosen from dichloroisocyanurates and at least one optical brightener, characterized in that the pH of said composition is between 5 and 9, and in that the dissolution time in aqueous solution of said composition is between 1 seconds and 30 minutes.
    The pH of said composition is advantageously between 6 and 8.5, in particular between 6.5 and 8, more particularly 7.5.
    By abuse of language, we will speak here of pH of the solid composition instead of pH of the solution obtained by dissolving the solid composition at 10% by mass in an aqueous solution.
    The pH of the composition according to the invention can be measured using a pH meter after dissolution of the solid composition in a 10% by weight aqueous solution. It can also be measured by any other method known to those skilled in the art.
    The composition according to the invention is then formulated to reach, after dissolution at 10% by mass in an aqueous solution, a pH of between 5 and 9, advantageously between 6 and 8.5, in particular between 6.5 and 8, more especially 7.5.
    Preferably, the dissolution time of the whitening solid composition is between 30 seconds and 20 minutes, more particularly between 3 and 15 minutes, in particular between 5 and 15 minutes.
    The dissolution time is the time that the solid composition dissolves completely once introduced into the washing solution. The dissolution time is in particular measured in water at 30 ± 1 ° C and stirring at a speed between 150 and 250 rpm. This method is applicable to the measurement of the dissolution time of pellets or powders for the washing machine.
    The composition according to the invention is then also formulated to dissolve in a washing solution in a time of between 1 second and 30 minutes, in particular between 30 seconds and 20 minutes, more particularly between 3 and 15 minutes, in particular between 5 and 15 minutes. 15 minutes.
    Advantageously, the chlorine bleaching and detergency agent and the optical brightener are not separated in the composition according to the invention. The composition according to the invention thus comprises at least one homogeneous mixture comprising the chlorine bleaching and detergency agent and the optical brightener.
    The solid composition according to the invention can be considered as physically stable, that is to say that it undergoes no visual modification (pustules, lamination, change of color, caking, etc.) or of holding (softening, crumbling, disintegration in more than 30 minutes, etc.) when exposed to stressful conditions such as at a temperature of 38 ° C and a relative humidity of 70% for 4 weeks.
    The solid composition according to the invention can also be considered as chemically stable, that is to say that it does not undergo more than 15% by weight of active chlorine loss, relative to the total weight of initial active chlorine ( measured by iodometric assay with thiosulphate), that its constituents, in particular optical brightener, are not degraded or oxidized by the chlorine agent, and that no excessive drop in performance (such as bleaching, washing results, etc. .) is observed when the composition is exposed to stressful conditions such as at a temperature of 38 ° C and a relative humidity of 70% for 4 weeks.
    For the purposes of the present invention, the term "chlorine bleaching and detergency agent" is intended to mean a chlorine agent which makes it possible to release chlorine in a washing solution and which, when it is dissolved in the washing solution, has a washing action. and bleaching laundry. By washing or detergent action is meant the action of removing stains and / or bacteria present on the laundry. By whitening action, we mean the action to fight against the dulling of light colors, especially white, to give the linen its original color without damaging it.
    For the purposes of the present invention, "linen" is intended to mean all articles of cloth for domestic use or clothing. For example, "laundry" means clothing, curtains, sheets, tablecloths, bed linen, towels, sleeping bags, tents, tapestries, carpets, etc. The chlorine bleaching and detergency agent is more particularly chosen from sodium dichloroisocyanurate, potassium dichloroisocyanurate, or their mixture, preferably sodium dichloroisocyanurate.
    Dichloroisocyanurates of sodium and potassium may be anhydrous or dihydrated.
    The dichloroisocyanurates of sodium and potassium may be in amorphous or crystalline form.
    In aqueous solution, the dichloroisocyanurates hydrolyze to form isocyanuric acid, hypochlorous acid (HCIO) and the corresponding salts, such as sodium hypochlorite (NaClO). The degree of hydrolysis and the hypochlorite ion content depend on the pH.
    Preferably, in the composition according to the invention, the chlorine bleaching and detergency agent is the sole source of chlorine.
    In a particular embodiment of the invention, the chlorine bleaching and detergency agent is not separated from the other compounds of the composition according to the invention. A particular advantage of the present invention is therefore to be able to obtain an effective, physically and chemically stable bleaching composition without the need for separation of the chlorine agent from the other compounds.
    Advantageously, the solid composition according to the invention comprises at least 5% by weight of chlorine bleaching and detergency agent, in particular between 5% and 99.9%, relative to the total weight of the composition.
    The chlorine bleaching and detergency content will be adapted according to the amount of chlorine to be released in a wash bath. It is known to those skilled in the art that the amount of chlorine to be released must be controlled according to the volume of the wash bath. Thus, for a given washing bath volume, the chlorinated agent content will be adapted as a function of the mass of the solid composition according to the invention. The amount of chlorine to be released into the wash bath is generally from 0.02% to 5% by weight, based on 1 liter of wash bath. Thus, by way of example and in a nonlimiting manner, for a volume of washing bath of 15 L and a solid composition according to the invention having a mass of between 2 g and 30 g, the content of chlorine bleaching agent and detergency is between 50% and 99.9% by weight, relative to the total weight of the composition. Likewise, for a volume of washing bath of 15 L and a solid composition according to the invention having a mass of between 31 g and 50 g, the bleaching and detergency chlorine content is between 25% and 50% by weight. weight, relative to the total weight of the composition. More particularly, still by way of example, for a volume of washing bath of 15 L and a solid composition according to the invention of 2 g, the content of chlorine bleaching and detergency agent is between 80% and 99.9 % by weight, relative to the total weight of the composition. Similarly, for a volume of washing bath of 15 L and a solid composition according to the invention of 5 g, the content of chlorine bleaching and detergency agent is between 60% and 99.9% by weight, relative to total weight of the composition.
    For the purposes of the present invention, the term "optical brightener" means a compound which absorbs ultraviolet electromagnetic radiation between 300 nm and 400 nm wavelength and then re-emits this energy by fluorescence in the visible range between 400 nm and 500 nm, the wavelengths between blue-violet and blue-green with a maximum in blue. The optical brightener, when applied to a material, thus makes it possible to complete the range of visible light and thus to give the material a whitening effect.
    In the context of the present invention, the optical brightener is dispersed homogeneously in the composition according to the invention. In addition, the optical brightener is not degraded by chlorine during storage or use of the composition according to the invention. The optical brightener may in particular be chosen from derivatives of disulphonic acid, derivatives of Bis (triazinylamino) stilbene, derivatives of flavonic acid, derivatives of naphthalimide, derivatives of pyrene derivatives of diaminostilbene (DAS), mono- or polysulfonated 4-4 'distyrylbiphenyl (DSBP), 4,4'-bis- (4-chloro-2-sulphostyryl) diphenyl, 4,4'-bis (2-sulphostyryl) biphenyl methyl umbelliferone, coumarin, dihydroquinolinone, 1,3-diaryl-pyrazoline, benzoxazole, benzimidazole, benzisoxazole.
    Advantageously, the solid composition according to the invention comprises from 0.01% to 10% by weight of one or more optical brighteners, relative to the total weight of the composition.
    As for the chlorine bleaching and detergency agent, the optical brightener content will be adjusted according to the amount to be released in the wash bath. The amount of optical brightener to be released in the wash bath is generally between 0.0005% and 0.1% by weight relative to 1 liter of washing bath. Thus, by way of example and without limitation, for a volume of washing bath of 15 L and a solid composition according to the invention having a mass of between 2 g and 30 g, the optical brightener content will be between 0.01% and 10% by weight, relative to the total weight of the composition. Similarly, for a volume of wash bath of 15 L and a solid composition according to the invention having a mass of between 31 g and 50 g the content of optical brightener will be between 0.05% and 5% by weight, by relative to the total weight of the composition.
    Preferably, the composition according to the invention comprises at least one agent for acting on the dissolution of the composition, such as an effervescent agent, a disintegrating agent, a bursting agent or their mixture.
    For the purposes of the present invention, the term "effervescent agent" means a compound capable of releasing gas when it is brought into contact with water or another liquid. The effervescent agent allows more particularly the composition to fragment and / or dissolve rapidly in water or other liquid, especially in a washing solution. The effervescent agent may in particular be chosen from organic acids, their anhydrides or their salts (such as adipic acid, citric acid, malic acid, tartaric acid, malonic acid, fumaric, maleic acid, succinic acid and mixtures thereof), carbonates or bicarbonates (such as sodium carbonate or bicarbonate, potassium carbonate or bicarbonate, carbonate or calcium bicarbonate, magnesium carbonate or bicarbonate and their mixture ), and a mixture of these. Advantageously, the effervescent agent is a bicarbonate, in particular sodium bicarbonate. More preferably, the effervescent agent is a mixture of sodium bicarbonate and an organic acid, especially adipic acid or citric acid. Preferably, the effervescent agent is a sodium bicarbonate / adipic acid pair.
    For the purposes of the present invention, the term "disintegrating agent" is understood to mean a solid compound which is soluble in an aqueous solution and dissolves rapidly in aqueous solution, which makes it possible to improve the permeability of a solid composition when it is applied. contact with an aqueous solution. The disintegrating agent may in particular be chosen from alginic acid, carboxymethylcellulose calcium, sodium carboxymethylcellulose, colloidal silicon dioxide, croscarmellose sodium, crospovidone, guar gum, magnesium aluminum silicate, methylcellulose, microcrystalline cellulose, polyacrilin potassium, cellulose powder, pregelatinized starch, sodium alginate, starch, carboxymethyl starch, corn starch, potato starch, starch glycolate Calcium carbonate, cross-linked carboxymethylcellulose, low-substituted hydroxypropylcellulose, carmellose, carmellose sodium, carmellose calcium, agar, carob, karaya, pectin, gum tragacanth, bentonite, cation exchange resin , polyvinylpyrrolidone, crosslinked polyvinylpyrrolidone, alginates, potassium polacrillin, citrus pulp, sodium lauryl sulfate, and the like rs mixtures.
    For the purposes of the present invention, the term "bursting agent" is intended to mean a compound making it possible to increase the rate of disintegration and / or dissolution of a solid composition by swelling, plastic deformation, wicking effect, when comes in contact with water or other liquid. The bursting agent may in particular be chosen from starches, modified or otherwise, starch derivatives, celluloses, modified or otherwise, cellulose derivatives, crosslinked polyacrylates, crosslinked polyvinylpyrrolidones, polysaccharides, alginates such as alginic acid and sodium alginate, aluminum silicate derivatives, silica and / or gums and derivatives, and mixtures thereof.
    Advantageously, the composition according to the invention comprises between 0% and 70% by weight, preferably between 0.01% and 70% of at least one agent for acting on the dissolution of the composition, such as an agent. effervescent, a disintegrating agent, a bursting agent or mixtures thereof, relative to the total weight of the composition.
    It is known to those skilled in the art that the amount of agent (s) for acting on the dissolution of the composition is adapted as a function of the dissolution time to be obtained, the total volume of the washing bath and the quantity of chlorinated agent and optical brightener present in the composition. Thus, by way of example and in a nonlimiting manner, for a volume of washing bath of 15 L and a solid composition according to the invention having a mass of between 2 g and 30 g, the content of agent (s) allowing to act on the dissolution of the composition will be between 0% to 40% by weight, preferably 0.01% to 40% relative to the total weight of the composition. Similarly, for a volume of washing bath of 15 L and a solid composition according to the invention having a mass of between 31 g and 50 g, the agent content (s) to act on the dissolution of the composition will be between 40% and 70% by weight, relative to the total weight of the composition.
    Preferably, the agent for acting on the dissolution is at least one effervescent agent and at least one disintegrating agent, in particular a pair of effervescent agents and a disintegrating agent. In this context, the disintegration agent may be more particularly croscarmellose sodium and the effervescent agent will be chosen in particular from carbonates and bicarbonates, including sodium bicarbonate, citric acid and adipic acid, and their mixtures or a couple sodium bicarbonate / adipic acid and sodium bicarbonate / citric acid. More preferably, the agent for acting on the dissolution is a mixture of sodium bicarbonate and an organic acid, especially adipic acid or citric acid. Preferably, the agent for acting on the dissolution is a sodium bicarbonate / adipic acid or sodium bicarbonate / citric acid pair.
    In the context of the present invention, the nature and the content of the effervescent agent or the pair of effervescent agents also make it possible to achieve, after dissolution at 10% by mass in an aqueous solution, a pH of between 5 and 9, advantageously between 6 and 8.5, in particular between 6.5 and 8, more particularly 7.5. Thus, when the effervescent agent pair is a sodium bicarbonate / adipic acid or sodium bicarbonate / citric acid pair, the sodium bicarbonate / acid ratio is adapted to obtain the target pH. This ratio will be more particularly between 95: 5 and 40:60, in particular between 95: 5 and 50:50, more particularly between 95: 5 and 70:30, advantageously between 95: 5 and 80:20, more advantageously between 95: 5 and 90:10.
    The solid composition according to the invention may also comprise at least one additional additive, such as an inert filler, a surfactant, a pH regulator, an enzyme, an antifoaming agent, a binding agent, a perfume or a dye. These additional additives are, for example, as defined in patent application EP 1 352 949.
    When a surfactant is added to the solid composition, it will advantageously be anionic.
    The composition according to the invention comprises less than 15% by weight, preferably less than 10% by weight, of an additional additive, relative to the total weight of the composition. Thus, the composition according to the invention has the advantage of being particularly simple, that is to say that it advantageously comprises less than seven constituents, preferably less than six constituents, in particular less than five constituents.
    Preferably, the whitening solid composition as described above comprises, by weight relative to the total weight of the composition: between 5% and 99.9% of a chlorine bleaching and detergency agent chosen from dichloroisocyanurates, 0.01% to 10% of at least one optical brightener, between 0% and 70%, of at least one agent for acting on the dissolution of the composition, such as an effervescent agent, a disintegrating agent , a bursting agent or mixtures thereof, between 0% and 0.30% perfume; and - less than 15% of another additional additive.
    In particular, when the washing bath has a volume of 15 L and the whitening solid composition as described above has a weight of between 2 g and 30 g, it comprises, by weight relative to the total weight of the composition: between 50% and 99.9% of a chlorinated bleaching and detergency agent chosen from among dichloroisocyanurates, between 0.1% and 10% of at least one optical brightener, and between 0% and 40% of at least one agent allowing acting on the dissolution of the composition, such as an effervescent agent, a disintegrating agent, a bursting agent or mixtures thereof, between 0% and 0.30% of perfume; and - less than 10% of another additional additive.
    In particular, when the washing bath has a volume of 15 L and the whitening solid composition as described above has a weight of between 31 g and 50 g, it comprises, by weight relative to the total weight of the composition: between 25% and 50% of a chlorinated bleaching and detergency agent chosen from among dichloroisocyanurates, between 0.05% and 5% of at least one optical brightener, and between 40% and 70% of at least one agent for acting on the dissolution of the composition, such as an effervescent agent, a disintegrating agent, a burner or mixtures thereof, - between 0% and 0.30% perfume; and - less than 10% of another additional additive.
    In the context of the present invention, the whitening solid composition may be in the form of granules, powder or a solid tablet.
    When the composition according to the invention is in the form of powder or granules, its dissolution can in particular be delayed by incorporating the composition into a water-soluble sachet (pouch) or by incorporating into the composition. For the purpose of the present invention, the term "water-soluble pouch" or "pouch" is intended to mean a bag adapted to comprise powder and to dissolve in a controlled manner in an aqueous solution.
    Preferably, the whitening solid composition is in the form of a solid tablet.
    For the purposes of the present invention, the term "solid tablet" is intended to mean a compacted composition consisting of a set of particles compactly grouped in such a way that they can be handled without disintegrating.
    When the composition according to the invention is in the form of a solid tablet, it is possible to modify the dissolution time by modifying the effervescent content, in particular by modifying the ratio of the effervescent couple, by modifying the level of disintegration agent. and / or bursting, applying a higher or lower compression force during the implementation, adding a surfactant to slow the dissolution, changing the shape or weight of the tablet, etc.
    The tablet of a chlorinated composition according to the invention may consist of a layer or a stack of several layers which are superimposed on each other, thus forming a uniform and compact block. The layers may be of similar or different compositions, or even similar or different colors.
    In the context of the present invention, the tablet according to the invention preferably comprises at least one layer comprising both the chlorinated agent and the optical brightener. When an agent for acting on the dissolution of the composition is present in the composition, the tablet according to the invention preferably comprises at least one layer comprising both the chlorine agent, the optical brightener, and the agent for acting on the dissolution of the composition. Preferably, the tablet according to the invention consists of a single layer.
    The tablet may have a cylindrical shape with a section having any shape such as a circular, oval, octagonal or parallelepiped shape. When the section of the compacted composition is parallelepipedic, typically square or rectangular, the corners of the compacted composition can be curved so that they are less brittle. Each layer has the same section so that the stack they form together is uniform. The compacted composition may also have any other geometrical shape (star, diamond, etc.).
    The tablet has a mass of between 1 g and 250 g, advantageously between 1 g and 100 g, more advantageously between 2 g and 50 g and in particular between 2 g and 20 g.
    The tablet has a mechanical strength of between 10 N and 5000 N, advantageously between 30 N and 3000 N, more preferably between 50 N and 1500 N.
    The chlorinated composition according to the invention, compacted in tablet form, can in particular be manufactured according to the following preparation method: a) mixing the various components homogeneously, including at least one chlorine bleaching and detergency agent, at least one optical brightener, to form a composition; b) Pre-compact the composition, in particular by direct compression, for example on rotary presses; c) optionally, introducing on the first layer obtained in step b) a composition as obtained in step a) to form a second layer and then pre-compact the new composition as performed in step b); d) possibly repeat step c) as many times as necessary layers; and e) compacting the layer obtained in step b) or all the layers obtained in step c) or d), in particular by direct compression, for example on rotary presses, to obtain a compacted composition.
    The pre-compaction forces used are in particular between 5 kN and 200 kN, advantageously between 5 kN and 100 kN and more advantageously between 10 kN and 80 kN. The compaction force used is in particular between 20 kN and 1000 kN, advantageously between 40 kN and 600 kN and more advantageously between 60 kN and 250 kN.
    The compacted composition thus obtained is resistant to shocks.
    The present invention also relates to the use of a whitening solid composition as described above for the bleaching of a textile.
    In particular, the present invention relates to the use of a whitening solid composition as described above for the bleaching of a textile while ensuring the protection of textile fibers.
    The present invention also relates to the use of a solid whitening composition as described above for the bleaching of a textile while ensuring disinfection and washing, including the washing of oxidizable stains.
    Description of the Figures
    Figure 1 shows the E-pH diagram of chlorine.
    FIG. 2 represents the release profile of the chlorine in a washing solution comprising bleach (♦), the composition 3 (), the composition 4 (A), the composition 1 (x) and the composition 5 ... ( 5K)
    Figure 3 shows the influence of pH on washing efficiency (♦), bleaching () and chemical wear (a) of tissue for liquid bleach solution and sodium dichloroisocyanurate solution ( DCCNa).
    Figure 4 shows the influence of the tested compositions on the protection of the fiber of a fabric.
    The following examples are intended to illustrate the present invention.
    Examples
    Example 1 Preparation of solid compositions according to the invention
    The following compositions are prepared by mixing the various ingredients listed in Table 1 below:
    Table 1: Composition of the mixtures prepared according to the invention
    The percentages are expressed in mass relative to the total mass of the composition
    When the solid composition is in tablet form, the mixtures obtained are then compressed using a 20 mm diameter cylindrical tooling on an OOMPa hydraulic press.
    The pH of the solid compositions is measured according to the following method:
    Preparation: The solid composition is dissolved in tap water at 20 ° C, 10% by weight.
    Equipment: • S 1 pH meter IMMO LABO 008 • S Standard solutions (buffer solution) at pH = 7 and 4 and / or 10. • S Magnetic bar, magnetic stirrer Operating mode: • S Calibrate the pH meter with the standard solutions pH = 7; pH = 4; then pH = 10 • S Measure the desired solution. Read the pH value read on the screen after stabilization.
    The pH values obtained as a result of these measurements are as follows:
    Example 2 Efficacy Tests of the Compositions According to the Invention
    In order to measure the effectiveness of the compositions according to the invention, the following tests are carried out: Bleaching test; - Chemical wear test of the fabric; - Washing efficiency test; - color preservation test; and dissolution test.
    These tests are carried out on the compositions mentioned in Example 1. The results are then compared with the results obtained for the control compositions described in Table 2 below:
    Table 2: Control compositions
    The percentages are expressed by weight relative to the total mass of the composition.> Conditions of bleaching and fabric wear tests: • Washing machine: Miele Softtronic W5794 front loading drum machine with a maximum capacity of 7kg. • Cycle used: 30 ° C. • Number of washes: 25 washes with cumulative effect. • Hardness of water: 25 ± 2 degrees French. • Laundry load: 4.5 kg of cotton towels. • Method of introduction: The products are introduced into the doser of the machine from the beginning of the washing. • Test fabrics: Two samples (40cm x 30cm) over-threaded cotton meeting the specifications developed in the ISO 2267 standards are introduced into the machine: nature: pure cotton, minimum commercial length: 27 mm weave: canvas number of warp threads: 25 ± 2 threads per centimeter number of threads in weft: 25 ± 2 threads per centimeter - simple thread count: 30 ± 2 tex (tex = weight in g of 1 km of thread) - twist: 700 ± 25 turns / m square meter: 170 ± 10 g> Method of measurement: chemical wear-degree of polymerization The chemical wear is due to the degrading action of certain products on the macromolecules of celluloses of fibers and fabric during washing.
    The determination of the average degree of polymerization of the cellulose is carried out by measuring the viscosity at 25 ° C. of a solution of a cotton sample subjected to the test in a suitable solvent with respect to the viscosity of the solvent itself. .
    Two measurements are taken per strip, ie 4 measurements per product.
    The higher the value obtained, the lower the wear of the fabric. The lower the value obtained, the greater the wear of the fabric.
    A difference of 100 points is considered significant. > Measuring method: Degree of whiteness according to Ganz's formula (with UVt
    The degree of white (W) and the deviation of hue (TV) are calculated according to the equations:
    W = DxY + Pxx + Qxy + C with: D, P, Q and C: constants of spectrophotometer Y, x, y: colorimetric values TV = mxx + nxy + k with: m, n and k: constants of spectrophotometer x and y: color values If TV is between: - 0.5 and 0.5: TD = N ® no hue deviation - 0.5 and - 1.5: TD = RI ® slight hue deviation in the red - 1.5 and - 2.5: TD = R2 ® hue deviation visible in the red - 2.5 and - 3.5: TD = R3 ® significant hue deviation in the red 0.5 and 1.5: TD = G1 ® slight hue deviation in green 1.5 and 2.5: TD = G2 ® hue deviation visible in green 2.5 and 3.5: TD = G3 ® significant hue deviation in green
    A difference of 10 points is considered significant. > Test conditions for washing on oxidizable stains: • Washing machine: Miele Novotronic W980 front-loading drum machine with a maximum capacity of 5kg. • Cycle used: Washing: Temperature rise: 5 minutes Tier at 30 ° C: 30 minutes
    Volume of water: 15 liters Rinses: Three: 11, 11, 11 minutes Volume of water: 14 liters Spinages: Three: 2, 4, 7 minutes Total cycle time: 81 minutes • Number of washes: Removal of dirt and spots: 3, with no cumulative effect. • Degree of white: 3, with cumulative effect. • Hardness of water: 25 ± 2 degrees French. • Load of laundry: 3 kg of cotton towels.
    Note: Pre-washed charges at 60 ° C are used with non-azure ECE detergent. • Method of introduction: The products are introduced into the doser of the machine from the beginning of the washing. • Tissues tests: By washing, we introduce, by pinning them on cloths, 2 series of fabrics (cotton) following:
    - EQUEST tea
    EQUEST tomato sauce
    - Red wine EQUEST - Blueberry CFT CS 15 - Grass CFT CS08
    Additional soiling: 4 samples WFK-SBL 2004 by washing. > Measurement method: Removal of dirt and stains
    Spectrophotometric measurements (measurements of the amount of light reflected by the tissue) make it possible to calculate the percentages of removal of the soil. The removal of dirt is expressed by the formula:
    A = reflectance of blank sample B = reflectance of control sample C = reflectance of sample soiled after wash
    Reflectances are determined using the green trichromatic component, without the action of optical brighteners.
    Number of measurements taken per sample = 2 Number of samples per wash = 2 Number of washes = 3
    That is 2x2x3 = 12 measurements by soiling and by product.
    In the classifications below, it will be admitted that two products are significantly different if the difference between them is greater than or equal to 2 points. > Conditions of color preservation tests: • Washing machine: Miele Novotronic W838 front loading drum machine with a maximum capacity of 7kg. • Cycle used: 30 ° C. • Number of washes: 6 washes with cumulative effect. • Hardness of water: 25 ± 2 degrees French. • Laundry load: 4.5 kg of cotton towels. • Method of introduction: The products are introduced into the doser of the machine from the beginning of the washing.
    Test fabrics: Two samples (40cm x 30cm) over-threaded cotton are introduced into the machine:
    > Measurement method: color preservation
    Spectrophotometric measurements (measurements of the amount of light reflected by the tissue) make it possible to calculate the percentages of removal of the soil. The removal of dirt is expressed by the formula:
    A = reflectance of blank sample B = reflectance of control sample C = reflectance of sample soiled after wash
    Reflectances are determined using the green trichromatic component, with the action of optical brighteners.
    Number of measurements made per sample = 4 Number of samples per wash = 2 Let 2x4 = 8 measurements per colored tissue.
    In the classifications below, it will be admitted that two products are significantly different if the difference between them is greater than or equal to 2 points. > Procedure for the measurement of the dissolution time:
    This method is applicable to the measurement of the dissolution time of pellets or powders for the washing machine.
    Principle: The method implemented makes it possible to simulate the dissolution of a pellet or a powder in a washing machine drum, and to follow in parallel the evolution of the active chlorine content released into the water.
    Operating mode:
    - Fill a beaker with 1.8L of tap water at 30 ± 1 ° C - Put the beaker on a magnetic stirrer, and place a medium sized magnetic bar in the bottom of the beaker - Place a cage in the top of the beaker so that the cage is immersed while being as high as possible only for a tablet - Set the stirring speed between 150 and 250 rpm. - Place the electrode following the release of the active chlorine in the water so that it soaks sufficiently for the measurement. - Place the tablet in the cage above the beaker, or powder directly into the water, while triggering the stopwatch
    Observe the melting of the pellet in the cage and / or the disappearance of the residues in the bottom of the beaker - In parallel with the dissolution, the measurement of the active chlorine is done by an iodometric determination with thiosulphate, to follow its evolution in time on the computer connected to the electrode. - Record the time when no residue remains in the cage and the beaker Stop the measurement and stopwatch when the amount of active chlorine in the water stabilizes (which means that the dissolution is complete), or reached a maximum and decreases. > Results:
    The results of the tests cited above are grouped in the following Table 3:
    Table 3: Results
    For the first three tests, fiber protection, bleaching, and washing efficiency on oxidizable stains, the higher the results, the better. Respectively, the higher the product whitens, eliminates oxidizable stains, and respects the fabrics. For the last test, color preservation, the higher the results, the more the color is worn, and the lower the results, the more colors are preserved.
    Figure 2 illustrates the release profile of chlorine in the wash solution. Figures 3 and 4 respectively illustrate the influence of pH on the washing and bleaching efficiency and on the chemical wear of the fabric, and the influence of the compositions studied on the protection of the fiber. From these graphs it can be seen that bleach instantly releases the amount of active chlorine in the wash. The composition according to the invention in powder form releases the active chlorine very quickly but by its composition (pH and nature of the chlorine), the tissues are better preserved than washing with bleach. The compositions according to the invention in the form of a solid tablet allow a more progressive release of the active chlorine and thus preserves the tissues all the better. All this for the same result in terms of money laundering.
    Example 3 Examples of Solid Compositions According to the Invention
    The solid compositions according to the invention may especially correspond to the following compositions:
    * Percentages are expressed in mass relative to the total mass of the composition
    权利要求:
    Claims (13)
    [1" id="c-fr-0001]
    1. Use of a solid whitening composition for bleaching a textile while ensuring the protection of the fiber, characterized in that said composition comprises at least one chlorine bleaching and detergency agent chosen from dichloroisocyanurates and at least one brightener optical, and characterized in that the pH of said composition is between 5 and 9, and in that the dissolution time in aqueous solution of said composition is between 1 second and 30 minutes.
    [2" id="c-fr-0002]
    2. Use according to claim 1, characterized in that the pH of said composition is between 6 and 8.5, in particular the pH is 6.5 and 8.
    [3" id="c-fr-0003]
    3. Use according to any one of claims 1 and 2, characterized in that the dissolution time in aqueous solution of said composition is between 30 seconds and 20 minutes, more particularly between 3 minutes and 15 minutes.
    [4" id="c-fr-0004]
    4. A whitening solid composition characterized in that it comprises at least one chlorine bleaching and detergency agent chosen from dichloroisocyanurates and at least one optical brightener, and characterized in that the pH of said composition is between 5 and 9, and the dissolution time in aqueous solution of said composition is between 1 second and 30 minutes.
    [5" id="c-fr-0005]
    5. Composition according to claim 4, characterized in that the pH is between 6 and 8.5, in particular the pH is 6.5 and 8.
    [6" id="c-fr-0006]
    6. Composition according to claim 4 or 5, characterized in that the chlorine bleaching agent and detergent is sodium dichloroisocyanurate, potassium dichloroisocyanurate, or a mixture thereof.
    [7" id="c-fr-0007]
    7. Composition according to any one of claims 4 to 6, characterized in that the dissolution time in aqueous solution of said composition is between 30 seconds and 20 minutes, more particularly between 3 minutes and 15 minutes.
    [8" id="c-fr-0008]
    8. Composition according to any one of claims 4 to 7, characterized in that said solid composition is in the form of a solid tablet, granules or powder such as a free powder or an incoiporated powder in a water-soluble bag.
    [9" id="c-fr-0009]
    9. Composition according to any one of claims 4 to 8, characterized in that said solid composition is in the form of a solid tablet.
    [10" id="c-fr-0010]
    10. Composition according to any one of claims 4 to 9, characterized in that the optical brightener is selected from derivatives of disulfonic acid, Bis (triazinylamino) -stilbene derivatives, the derivatives of the acid flavonic, naphthalimide derivatives, pyrene derivatives diaminostilbene derivatives (DAS), mono- or polysulfonated 4-4 'distyryl-biphenyl (DSBP), 4,4'-bis- (4-chloro-2-sulphostyryl) diphenyl, sodium 4,4'-bis (2-sulfostyryl) biphenyl methyl umbelliferone, coumarin, dihydroquinolinone, 1,3-diaryl-pyrazoline, benzoxazole, benzimidazole, benzisoxazole.
    [11" id="c-fr-0011]
    11. Composition according to any of claims 4 to 10, characterized in that said composition further comprises at least one additional additive, such as an effervescent agent, a disintegrating agent, a burner, and mixtures thereof.
    [12" id="c-fr-0012]
    12. Composition according to any one of claims 4 to 11, characterized in that said composition comprises, by weight relative to the total weight of the composition: - between 5% and 99.9% of a selected chlorine bleaching and detergency agent among the dichloroisocyanurates, from 0.01% to 10% of at least one optical brightener, and between 0% and 70% of at least one agent for acting on the dissolution of the composition, such as an effervescent agent a disintegrating agent, a blowing agent or mixtures thereof, between 0% and 0.30% perfume; and - less than 15% of another additional additive.
    [13" id="c-fr-0013]
    13. Use according to any one of claims 1 to 3, characterized in that the composition is as defined in claims 6 and 8 to 12.
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    同族专利:
    公开号 | 公开日
    US10894933B2|2021-01-19|
    EP3394235A1|2018-10-31|
    WO2017109399A1|2017-06-29|
    US20190024023A1|2019-01-24|
    FR3045662B1|2020-10-02|
    引用文献:
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    FR2838131B1|2002-04-08|2004-07-23|Eurotab|DETERGENT SHELF COMPRISING TWO REACTIVE DISSOLVING LAYERS SEPARATED BY A BARRIER LAYER|
    US6486111B1|2002-04-18|2002-11-26|Colgate-Palmolive Company|Antibacterial cleaning compositions in the form of a tablet|
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    WO2013084072A2|2011-12-07|2013-06-13|Eurotab|Compacted product for the bleaching of fabrics|WO2019115830A1|2017-12-15|2019-06-20|Eurotab|Chlorine tablet packaging|
    FR3075183B1|2017-12-15|2020-12-18|Eurotab|CHLORINE TABLET PACKAGING|
    CN109957468A|2017-12-25|2019-07-02|浙江神英科技有限公司|A kind of plant laundry effervescent tablet in olive oil source and preparation method thereof|
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    法律状态:
    2017-01-02| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-23| PLSC| Publication of the preliminary search report|Effective date: 20170623 |
    2017-12-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-12-12| PLFP| Fee payment|Year of fee payment: 5 |
    2020-12-14| PLFP| Fee payment|Year of fee payment: 6 |
    2021-07-02| TP| Transmission of property|Owner name: EUROTAB OPERATIONS, FR Effective date: 20210527 |
    2021-11-10| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1562896A|FR3045662B1|2015-12-21|2015-12-21|WHITENING CHLORINATED SOLID COMPOSITION PROTECTING THE FIBER|FR1562896A| FR3045662B1|2015-12-21|2015-12-21|WHITENING CHLORINATED SOLID COMPOSITION PROTECTING THE FIBER|
    PCT/FR2016/053593| WO2017109399A1|2015-12-21|2016-12-21|Chlorinated solid bleaching composition which protects the fibre|
    US16/064,683| US10894933B2|2015-12-21|2016-12-21|Chlorinated solid bleaching composition which protects the fibre|
    EP16826130.3A| EP3394235A1|2015-12-21|2016-12-21|Chlorinated solid bleaching composition which protects the fibre|
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