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  • 专利说明
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    • 专利摘要:
    Disinfectant tablet for surfaces with dirt repellent and procedure for obtaining it. The invention consists of a bilayer tablet for the treatment and disinfection of surfaces, composed of a halogenated derivative of isocyanuric acid, together with a detergent and an additive, chemically incompatible with the former, encapsulated in a porous material. The tablet has chemical stability, and remains effective in its three functions, disinfection, detergency and repel dirt. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2672113A1
    申请号:ES201830195
    申请日:2018-03-01
    公开日:2018-06-12
    发明作者:Rebeca MONTEAGUDO OLIVAN；Joaquin Coronas Ceresuela；Laura GRACIA ZAMORA；Sergio MAYENCO UBIETO
    申请人:Orache Desinfection Sl；
    IPC主号:
    专利说明:

    OBJECT OF THE INVENTION
    The present invention relates to a bilayer tablet for the treatment and disinfection of surfaces with dirt repellent, composed of a halogenated derivative of isocyanuric acid, together with a detergent and an additive, chemically incompatible with the first, encapsulated in a porous material.
    The tablet has chemical stability, and remains effective in its three functions, disinfection, detergency and repel dirt.
    The invention also relates to the process of obtaining the tablet.
    The present invention concerns a tablet with disinfectant, detergent and dirt repellent functions, all in the same product, thereby reducing the use of other products, and therefore the packaging is smaller. Consequently, this invention substantially reduces the impact of this range of products on the environment.
    In addition, the present invention represents greater ease and security of application of the product by end users. Spills and subsequent possible contamination of the environment are avoided, as well as possible poisoning due to fluid intake or skin contact damage in the case of using the typical alternative liquid disinfectants. PRACTICAL FIELD OF APPLICATION
    The tablet of the invention is of special application in the treatment of soils of all types, including metal or wood, surfaces in the food industry, surfaces in farms


    and stables, walls, laboratories, outpatients, operating rooms, sports areas, etc.
    However, the tablet of the invention could also be used for water treatment. BACKGROUND OF THE INVENTION
    Halogenated derivatives tablets such as chloroisocyanuric acids and their salts have been widely used for a long time.
    Fundamentally they have been used as disinfectants in swimming pools, which is its main consumer market, but not so much as a surface disinfectant, which has always been a market led by sodium hypochlorite.
    15 For a few years, and due to the promotion of standards for environmental protection, it has acted by restricting the use of mercury cathode technology in the manufacture of chlorine. Thus, all chlorine is currently obtained in Europe by electrolysis from chlorides in membrane cells. This has meant an increase in
    20 the cost of sodium hypochlorite, and a reduction in its supply, accommodating substitutes.
    One of these is disinfectant tablets based on chloroisocyanuric acids, which can be used for surface disinfection. These pill products are easy and safe to use, as well as saving on transportation, since a kilogram of
    25 such tablets have the same disinfectant power as 37 liters of 3% sodium hypochlorite in water.
    All this has meant that the growth in sales of disinfectant tablets based on chloroisocyanuric acids has been substantial in recent years. Another added advantage of
    30 these tablets are their stability over time, thanks to the solid state formulation, which prevents the release of chlorine and therefore makes it a product with an expiration date much greater than its liquid counterparts.


    Disinfectant products are normally liquid, but when presented in a pill form they are easier to dose and store. This is because, on the one hand, there are no spills and therefore there are no losses or environmental pollution is encouraged. On the other hand, its transport and storage is simple, making this type of product very profitable logistically speaking.
    During the last years, there have been a great number of developments in tablet based on chloroisocyanuric acids, some of them bi-layer.
    In this regard, ES2574332 describes tablets comprising a compound selected from trichloroisocyanuric acid or dichloroisocyanuric acid and a salt of either, and a volatile additive encapsulated in a micro or mesoporous material with a pore size of between 0, 3 and 50 nm, a pore volume between 0.05 and 2 cm3 / g and a specific surface area between 100 and 5000 m2 / g.
    The tablets comprise, together with the chloroisocyanuric acid agent, an insect repellent additive or a fragrance, which is a reducing and volatile agent. The described tablets have at least two layers, the first formed by the insect repellent or the fragrance and the second layer containing the halogenated acid derived from isocyanuric acid. The product is a tablet whose purpose is the disinfection and treatment of water, mainly of swimming pools, with an additive encapsulated as a mosquito repellent.
    Patent No. ES 2388268 prior to that mentioned above discloses a tablet for the treatment and disinfection of water containing a halogenated derivative of the isocyanuric acid selected from trichloroisocyanuric acid, dichloroisocyanuric acid or a salt thereof and mica as a lubricating agent. The inclusion of any volatile additive in the composition is not mentioned in this document.
    GB1281796 discloses chloroisocyanuric acid compositions with coloring agents that are sensitive to the action of halogenated derivatives of isocyanuric acid by coating said colorants with a water-soluble and hydrate-forming inorganic salt before mixing with the rest of the components. .


    In spite of the teachings of the state of the art, there is still a need to have tablets that are stable and that maintain the effectiveness in the treatment and disinfection of surfaces, which would be expected to be obtained by simultaneously containing a halogenated acid derivative isocyanuric and an additive chemically incompatible with said derivative. DESCRIPTION OF THE INVENTION
    The disinfectant tablet that is recommended solves in a completely satisfactory way the problem previously exposed, in the different aspects mentioned, agglutinating in a same element and with a solid and homogeneous solution, in a layer, a disinfectant product based on a chloroisocyanuric acid, and in another layer, a detergent mixed homogeneously, with an organic additive such as glycerin to repel dust, encapsulated in a microporous or mesoporous material.
    The tablet of the invention, unlike others existing in the market, allows each layer of the tablet to have a specific and different hardness, thus guaranteeing that, despite being different materials, the dissolution rate is identical, so that one of the products is not released faster than another, which would cause the deposition of insoluble compounds or the permanence of one layer when the other had not yet dissolved.
    This specific combination is a great advance in the art, which does not fully present other combinations of commonly used chlorine-releasing reactive agents.
    Thus, the encapsulated additive and the active components of the tablet of the present invention do not chemically interact with each other, so that there is no deterioration thereof. Therefore, the halogenated compound remains stable. The processing of the tablet with the additives of interest is also improved. The encapsulation of the additive in the porous matrix allows its homogeneous mixing with the other components of the tablet. Likewise, the dissolution rate of the tablets is not altered by the presence of the encapsulated additive. In addition, the tablets of the invention do not leave residues in the phase


    aqueous to be treated, because they are all soluble or easily dispersible in water. Finally, the release of the additive in the water is carried out quickly and is prepared for application on the surface to be treated in just 2 minutes (the dissolution rate depends on the water temperature).
    More specifically, the tablet of the invention comprises:
    • A halogenated derivative of isocyanuric acid.
    • A detergent
    • An organic additive, chemically incompatible with the halogenated derivative of isocyanuric acid, encapsulated in a microporous or mesoporous material; where the microporous or mesoporous material has a pore size between 2 and 50 nm, and preferably about 14 nm on average; a pore volume between 0.05 and 2 cm3 / g and preferably about 0.6 cm3 / g, and a specific BET surface area between 100 and 5000 m2 / g, and preferably 168 m2 / g.
    In the context of the present invention, following the IUPAC nomenclature, the term mesoporous refers to those organic or inorganic materials that have pores with a size between 2-50 nm, while microporous refers to pores below 2 nm .
    Microporous and mesoporous materials suitable for the realization of the present invention are those that meet the properties of pore size, pore volume and specific surface area indicated above. Furthermore, said materials must be chemically compatible with the halogenated derivative of the isocyanuric acid used.
    Thus, the microporous or mesoporous materials suitable for the preparation of the tablets of the present invention are those that complying with the aforementioned properties are selected from metal and semi-metallic oxides such as silica (microporous, mesoporous, pyrogenic, crystalline, precipitated, gel) and aluminas; silicates and aluminosilicates (MCM-41, SBA-15 among others); aluminophosphates; clays such as kaolin, smectites, vermiculites, attapulgite, sepiolite; metal-organic structures (MOF);


    mesoporous organosylics; and zeolites such as clinoptilolite, mordenite, zeolite A, zeolite X, zeolite Y silicalite-1 and ZSM-5, among other possible.
    As for the amount of the halogenated derivative of the isocyanuric acid that participates in the tablet it will be comprised between 45% and 55% by weight of the total tablet.
    As for the additive used it can participate between 2.5% and 4% by weight. The amount of additive encapsulated in the microporous or mesoporous material is comprised between 1g additive / g material, and 3 g additive / g material, said additive being selected from one or more glycerins.
    On the other hand, the microporous material has pores smaller in diameter at 2 nm or, where appropriate, the mesoporous material has pore sizes between 2 and 50 nm and preferably about 14 nm on average; a pore volume between 0.05 and 2 cm3 / g and preferably about 0.6 cm3 / g, and a specific BET surface area between 100 and 5000 m2 / g, and preferably 168 m2 / g.
    Optionally the tablet could contain other additional components selected from the group consisting of detergents, softeners, rinsing facilitators, anti-scale and combinations thereof, said additional components being present in the tablet in an amount between 30 and 35% by weight. with respect to the total of the tablet.
    The tablet of the present invention has the ability to release chlorine in aqueous medium, so it is useful for disinfection and surface treatment, to be applied with a cloth, a cloth, with a pressure gun, etc. In the same way it can be used for water treatment and disinfection.
    As for the procedure for obtaining the tablet, it defines the following operational phases:
    a) encapsulation of the additive in the microporous or mesoporous material;


    b) mixing the halogenated derivative of isocyanuric acid with the additive encapsulated in the microporous or mesoporous material;
    c) mixing of additional components separately;
    d) compaction of the mixtures, each thanks to its corresponding distributor.
    The product that is added is chemically incompatible with the halogenated derivative of isocyanuric acid, so that in the present invention it will be encapsulated in the pores of a microporous or mesoporous material.
    There are various methodologies for encapsulating any of them being applicable for the present invention. One of these consists in dissolving, spraying or suspending the compound to be encapsulated in a suitable solvent until a homogeneous dispersion is obtained. Subsequently, a microporous or mesoporous material is immersed in this dispersion, for a certain period of time, depending on several factors, it may vary, until the additive is encapsulated in the pores of the material. Another alternative procedure is to make the encapsulating porous solid contact with the pure additive (eventually heated to a certain temperature to decrease its viscosity and thus favor contact with the porous solid) not dispersed, especially if it is a liquid additive such as glycerin . After this process the solvent is removed, either by evaporation, heating, or any other method. MOFs can also be used, these are metal-organic crystalline structures formed by metal ions or clusters coordinated with organic bi-or polydentate ligands and having porosity with their inorganic counterparts, the zeolites. Important examples of this type of materials are: MOF-5, HKUST-1, MIL-53 and MIL-101 with exceptional textural properties (specific BET areas of up to 7000 m2 / g). DESCRIPTION OF THE DRAWINGS
    To complement the description that will then be made and in order to help a better understanding of the features of the invention, according to an example


    Preferential to the practical realization thereof, an set of drawings is attached as an integral part of said description, where, as an illustration and not limitation, the following has been represented:
    Figure 1 shows the molecular structure related to the encapsulation of glycerin in a porous silica.
    Figure 2.- It consists of a bar chart in which it is shown how in terms of the pore diameter (related to the size of the possible molecule to be encapsulated) and the pore volume (related to the maximum adsorption capacity) the Zeolites and MOFs can be perfectly compared.
    Figure 3.- Shows a block diagram related to the process carried out for the study of the effect of glycerin addition.
    Figure 4.- Shows a comparative graph of the dust particle counts corresponding to respective surfaces treated with and without glycerin at different times.
    Figure 5.- Shows a schematic representation of the recording process of the equipment during the contact angle measurement.
    Figure 6.- Finally, it shows a bar chart corresponding to the contact angle values (in degrees) with error for glass surfaces treated with standard tablets and those modified with glycerin after treatment and after two days of exposure. EXAMPLES OF PRACTICAL APPLICATION
    Next, a series of examples will be documented for the study of the effect of the addition of glycerin in this type of tablets, according to the methodology represented in Figure 3, where initially a process of impregnation on silica is carried out and zeolite (1) in different proportions, after which (2) tablets are prepared with glycerin impregnated with silica and glycerin impregnated with glycerin, which dissolve (3) in water, treating different surfaces (4) and subject to exposures in different environments (5), for study (6) over the time of dust deposition,


    analyzed by scanning electron microscope (7) and by measuring the contact angle (8), finally presenting (9) the results obtained.
    EXAMPLE 1:
    Glycerin is a viscous liquid and therefore cannot be formulated homogeneously by adding it directly to the bleach tablet mixture. Hence, the first step is to transport glycerin by means of an adsorbent. As starting materials, precipitated silica and a zeolite (zeolite Y with the FAU type structure) were chosen. Silica
    10 is an inert material (even used as a food additive under the E-551 label) of amorphous structure, but with great adsorption capacity and relatively low cost. Zeolite Y is a crystalline aluminosilicate with lower adsorption capacity and a higher cost but which due to its microporous structure could have different uses than silica in terms of adsorption of molecules through greater chemical interaction.
    15 To obtain the combinations (1) glycerin impregnated in silica and glycerin impregnated in zeolite, different mass ratios have been chosen and the products have been mixed directly, without any treatment. Glycerin is almost instantly adsorbed by materials, especially for low ratios. On the other hand, the
    20 same mixtures, but increasing the temperature from the environment (about 20-25 ° C) to 50 ° C in a later step in order to achieve a higher degree of mixing. The materials after impregnation and dried at room temperature are presented in the form of white powders.
    25 The glycerin and silica / zeolite combinations prepared are as follows:
    Tablet Preparation Conditions
    Si1-50 Silica: glycerin = 1: 2; 50 ° C
    Si2-50 Silica: glycerin = 1: 3; 50 ° C
    Si1-TA Silica: glycerin = 1: 2; room temperature
    Si2-TA Silica: glycerin = 1: 3; room temperature
    Z1-50 Zeolite: glycerin = 1: 1; 50 ° C
    Z1-TA Zeolite: glycerin = 1: 1; room temperature


    EXAMPLE 2:
    Once the combinations of glycerin impregnated in silica and glycerin impregnated in zeolite are obtained, these are added to the formulation of the bleach tablets (2) with a 5% mass proportion. This step was performed so that the conditions of preparation of the tablets are the same as those of the commercial ones. In this way, standard bleach tablets (already marketed) will be compared with pills prepared with impregnated glycerin.
    EXAMPLE 3
    In the next step (3) the tablets with and without glycerin are dissolved separately in a given volume of water. In the present case, one tablet is dissolved for every 2 liters of running water. Once dissolved, the surfaces have been treated with each of the products. The reference surface that has been chosen is glass (glass plates) as a model of tiled surfaces (whose surface is normally vitrified). The plates treated (4) with the products are exposed (5) in different environments for several times.
    EXAMPLE 4
    To monitor the result of the treatment (6) and exposure of the plates to the environment, two techniques have been chosen, scanning electron microscopy (7) (SEM) and contact angle measurement (8).
    Through the SEM it is possible to observe a microporous and nanometric scale surface so that differences in the amount of dust deposited between one surface and another can be seen. Unlike what happens in optical microscopy, SEM is a technique that uses an electron beam to obtain an image instead of a light beam. For this, a potential difference is applied to accelerate electrons and generate the beam that affects the sample in a high vacuum environment. It is necessary to previously coat the sample of a layer about nanometers thick of a metal or an alloy since the sample has to be conductive, in our case a coating of


    platinum. The results will show images of the plates treated with the standard pills and the glycerin tablets.
    As a starting point of the study, the pills with a higher glycerin content were taken and those that were impregnated in silica (Si2-TA), since it has been proven that it is more adsorbent of glycerin and also the material is smaller price. Figure 4 shows the differences that cause treatment with a standard tablet and another containing glycerin in dust deposition. In these samples there is a clear difference between the surfaces treated with and without glycerin at zero time, that is, after cleaning, the surface treated with glycerin appears cleaner (with fewer dust particles). This may be because glycerin helps repel dust present on the surface. Atmospheric dirt often contains little polar particles (especially if they have an organic origin) that have a worse interaction with hydrophilic surfaces. If the plates are exposed to the environment one day, it is also observed that the surface treated with glycerin remains cleaner. The same happens after three and four days of exposure. However, after two days the difference is not so clear. This highlights the intrinsic randomness to the sampling that must be taken into account when interpreting the results since the fouling of a surface depends on very variable factors that cannot be controlled when exposed to the normal environment such as temperature, humidity, wind or drafts, rain or even the place of placement of the plate.
    As of the fifth day of exposure, large differences between surfaces with and without glycerin are no longer observed.
    EXAMPLE 5
    The contact angle is a measure of the angle between a drop of a liquid, which is dropped in a controlled manner, and a certain surface. In our case the liquid is distilled water and the surfaces to be measured correspond to that of the treated glass plates. The more hydrophilic the surface is, the smaller the contact angle will be and vice versa. For surfaces treated with glycerin tablets, it is expected (given how polar the molecule is due to its three hydroxyl groups,) that the contact angle is smaller as surface hydrophilicity increases.


    The greater the interaction between the surface (the glass plates), the smaller the angle, since the greater the hydrophilicity, the smaller the angle and vice versa, the greater the angle, the more hydrophobic the surface will be.
    5 Well, according to figure 5, with respect to the contact angle results, it is verified that after cleaning with glycerin tablets (day 0) the contact angle is smaller than in the standard tablets.
    Therefore, the latter surface is less hydrophilic and tends to attract more dust
    10 considering that it is on average and taking into account its complex composition is not very polar or hydrophobic, as mentioned above. After two days of exposure it is seen that the contact angle value tends to equalize. This is partly due to the presence of dust particles that influence the measurements, although in this case it is not possible to establish a direct relationship between the number of dust particles and
    15 the results obtained.

    权利要求:
    Claims (1)
    [1]
    1st.- Disinfectant tablet for surfaces with dirt repellent, characterized in that it is composed of:
    • A halogenated derivative of isocyanuric acid.
    • A detergent
    • An organic additive, chemically incompatible with the halogenated derivative of isocyanuric acid, encapsulated in a microporous or mesoporous material; where the microporous or mesoporous material has a pore size between 2 and 50 nm, and preferably about 14 nm on average; a pore volume between 0.05 and 2 cm3 / g and preferably about 0.6 cm3 / g, and a specific BET surface area between 100 and 5000 m2 / g, and preferably 168 m2 / g.
    2nd.- Disinfectant tablet for surfaces with dirt repellent, according to claim 1, characterized in that the amount of the halogenated derivative of isocyanuric acid is between 45% and 55% by weight of the total tablet.
    3rd.- Disinfectant tablet for surfaces with dirt repellent, according to claims 1 and 2, characterized in that the microporous or mesoporous material is selected from a clay, a metal-organic structure (MOF), a mesoporous silica and a zeolite, or between any porous solid capable of housing the organic additive.
    4th.- Disinfectant tablet for surfaces with dirt repellent, according to claims 1 to 2, characterized in that the microporous or mesoporous material is selected from a microporous silica, a pyrogenic silica, a crystalline silica, a precipitated silica, silica gel and a zeolite .
    5th.- Disinfectant tablet for surfaces with dirt repellent, according to claims 1 to 4, characterized in that the tablet comprises an amount of additive between 2.5% and 4% by weight.

    6th.-Disinfectant tablet for surfaces with dirt repellent, according to claims 1 to 5, characterized in that the amount of additive encapsulated in the microporous or mesoporous material is comprised between 1g additive / g material, and 3 g additive / g material.
    7th Disinfectant tablet for surfaces with dirt repellent, according to claims 1 to 6 where the additive is selected from one or more glycerins.
    8th.-Disinfectant pill for surfaces with dirt repellent, according to claims 1 to 7, characterized in that the microporous material has pores smaller in diameter at 2 nm or in its case the mesoporous material has pore sizes between 2 and 50 nm and preferably about 14 nm on average; a pore volume between 0.05 and 2 cm3 / g and preferably about 0.6 cm3 / g, and a specific BET surface area between 100 and 5000 m2 / g, and preferably 168 m2 / g.
    9th.-Disinfectant tablet for surfaces with dirt repellent, according to claims 1 to 8, characterized in that it comprises other additional components selected from the group consisting of detergents, softeners, rinsing facilitators, anti-scale and combinations thereof.
    10th.- Disinfectant tablet for surfaces with dirt repellent, according to claim 9, characterized in that the additional components are present in the tablet in an amount between 30 and 35% by weight with respect to the total of the tablet.
    11th.-Procedure for obtaining the disinfectant tablet of claims 1 to 10, characterized in that the following operational phases are established therein:
    a) encapsulation of the additive in the microporous or mesoporous material;
    b) mixing the halogenated derivative of isocyanuric acid with the additive encapsulated in the microporous or mesoporous material;
    c) mixing of additional components separately;

    d) compaction of the mixtures, each thanks to its corresponding distributor.


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    同族专利:
    公开号 | 公开日
    ES2672113B2|2019-05-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2007291207A|2006-04-24|2007-11-08|Yamazaki Corp|Dust-attaching agent|
    US20090023620A1|2007-06-20|2009-01-22|Maria Ochomogo|Natural Cleaning Compositions|
    ES2574332A1|2014-12-16|2016-06-16|Ercros, S.A.|Tablets for water treatment and disinfection |
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201830195A|ES2672113B2|2018-03-01|2018-03-01|DISINFECTANT TABLE FOR SURFACES, WITH REPELLENT OF DIRT AND PROCESS OF OBTAINING THE SAME.|ES201830195A| ES2672113B2|2018-03-01|2018-03-01|DISINFECTANT TABLE FOR SURFACES, WITH REPELLENT OF DIRT AND PROCESS OF OBTAINING THE SAME.|
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