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    • 专利摘要:
    The present invention relates to a coating composition comprising: - from 4 to 17% by weight of hollow microspheres having a lower thermal conductivity (denoted lambda) at 0.1 Wm-1.K-1, - of 0.05 at 1% by weight of at least one linear alcohol whose hydrocarbon chain contains at least 8 carbon atoms; 5 to 25% by weight of at least one adhesion promoter chosen from dispersible or soluble polymers; water, comprising a glass transition temperature (Tg) of less than or equal to 65 ° C; 25 to 50% by weight of a non-hydraulic binder selected from the following mineral and metallic fillers: carbonate of an alkaline metal earth, alumina, silica, silicate of a metal selected from aluminum, alkali metals and alkaline earth metals, and mixtures thereof, said fillers having an average particle size of from 5 to 100 μm, 1% by weight of at least one thickening agent, - water, the percentages by weight being expressed in% by weight of dry matter relative to the total weight of the coating composition. The present invention also relates to its implementation method and its applications as a smoothing coating and / or thermal insulation for walls and ceilings.
    公开号:FR3015474A1
    申请号:FR1362984
    申请日:2013-12-19
    公开日:2015-06-26
    发明作者:Jessie Casimiro；Eric Verscheure
    申请人:Bostik SA；
    IPC主号:
    专利说明:

    [0001] Wall and ceiling coating composition with thermal insulation properties In the field of construction and building, thermal insulation refers to all the techniques used to limit heat transfer between the indoor environment and the building. external environment at a different temperature. It may be to limit heat losses from the inside to the outside or in the opposite direction limit the diffusion of heat from the outside to the inside. In the field of housing, these heat transfers can be done through different walls separating the living space from its external environment: attics and roof, walls, ceilings, windows and windows, floors. To overcome these heat leaks, there are solutions adapted to each of the aforementioned situations. The walls and ceilings represent important surfaces through which will exchange heat flow. By thermally insulating these parts of the building, it is thus possible to significantly improve the thermal performance of the building and reduce the energy costs of overheating or over-heating associated with poor insulation. There are three major known families of thermal insulation processes for walls and / or ceilings: - thermal insulation in the thickness of the wall, by incorporating insulating elements inside the wall (panels or insulating blocks, blocks shuttering, insulating foam) generally at the time of construction; - the thermal insulation from the inside, that is to say the insulation of the inner surface of the wall, and - the thermal insulation from the outside, that is to say the insulation of the exterior facade of the wall, which is exposed directly to climatic conditions (sun, wind, bad weather); the latter two techniques can be performed on an existing wall, unlike the first mentioned technique. Each of its processes correspond heat insulation means rarely adapted interchangeable. In particular, when it is desired to thermally isolate an existing wall, the insulating devices suitable for the interior insulation are generally not suitable for the external insulation, which must withstand external atmospheric agents. Similarly, insulating devices suitable for external insulation will not generally be suitable for interior insulation, because they are bulky or thick (5 to 8 centimeters) and have a rough appearance requiring a step of replanning. As part of this application, we have been interested in the thermal insulation of walls and ceilings, inside a building or residential space. The thermal insulation from the inside has the advantage of not modifying the external appearance of the space to be insulated, unlike the thermal insulation from the outside. The work can be undertaken without special administrative authorization. Most of the existing solutions for insulating a wall or ceiling from the inside is to assemble insulation panels, lining walls or false ceilings (made from expanded polystyrene, wool of glass, rockwool, etc.) or attach a counter-partition against the surface to be insulated by providing an air space or an interstitial surface filled with another insulator. However, these insulating systems are relatively thick and significantly reduce the volume and surface of the living space. In addition, the implementation of these partitions is complex and users are often reluctant to undertake such heavy work themselves, which involve the cutting of custom-made insulation materials, the preparation of walls that must also be free of moisture, and the laying of joints between insulating materials. When these partitions are poorly laid, assembled, fixed or dimensioned, interstices between the partitions can appear and generate more or less significant energy leakage or even water infiltration due to the condensation of the air humidity behind the walls. insulating partitions. This can eventually promote the appearance of fungi and mold in some cases. Furthermore, when it is desired to replace or improve the thermal insulation of a wall lined with an insulating partition without loss of substantial space, it is necessary to tear the existing lining, repair if necessary the support wall, and install a new insulation system that will be more efficient, for an equivalent thickness. As a result, all these insulation and renovation / restoration work is complex and not within the reach of any user. On the contrary, it is recommended to call on professionals in the field concerned to avoid the creation of thermal bridges, that is to say point or linear zones where the insulating barrier is interrupted. In the patent application EP 0 281 476, it is known to use liquid or pasty coating compositions of the two-component type (also called smoothing compound), obtained by mixing at the time of use of a component solid and a liquid component in a liquid to solid weight ratio ranging from 0.8 to 1, to thermally and acoustically isolate a wall from the inside or the outside. The solid component comprises from 20 to 60% of a hydraulic binder selected from the group consisting of plaster, cement and swelling calcium bentonite, from 10 to 40% by weight of a product selected from the group consisting of sawdust milled wood and slag, and from 2 to 10% by weight of micronized natural mica. The liquid component comprises dispersed in water a resin of an acrylic copolymer at basic pH in an amount representing from 30 to 50% by weight of the component, and a plasticizer. After mixing the solid component and the liquid component in a particular weight ratio, the composition resulting from said mixture is projected onto the surface to be isolated using a spraying machine. Although the implementation of these compositions seems simpler to achieve compared to that of the conventional solid thermal insulation systems described above, it still has many disadvantages. Indeed, these compositions can not be stored in the form of ready-to-use compositions because they build up and harden quickly after mixing the liquid and solid components (in less than about 3 hours). The implementation of this type of coating therefore requires at least two steps: one consisting in preparing the composition and the other consisting in applying the coating. In addition, the use of these compositions has the disadvantage of having to have a spraying machine and special tools to weigh, mix the solid and liquid components, and apply the composition obtained. This can be particularly difficult when large volumes of products are involved. In addition, the user is not immune to errors in weighing or mixing during the preparation of the composition, which can lead to heterogeneous mixture or a premature setting of the mixture, and therefore a non-homogeneous application of the composition on the support generating thermal bridges. The coating obtained after hardening of the coating layer on the support is also relatively thick (about 5 cm) and has a rough appearance of plaster, both unsightly and inappropriate for the superficial application of a decorative wall covering of finish, especially a thin and / or fragile decorative wall covering such as wallpaper. The latter risk indeed not to adhere or little to the raw surface of the hardened coating and peel quickly or tear in contact with the pins and asperities of the surface of the coating. The insulating coating thus obtained is therefore impractical for use as a finishing undercoat.
    [0002] Also known from application US 2005/0126441 paint compositions having thermal insulation properties, used alone or in combination with a primer layer for the attachment of the paint composition on the surface to be coated. These paint compositions comprise infra-red reflective pigments and / or hollow glass microspheres. However, these compositions lead to coatings having an insufficient thickness (at most 300 i.tm) to allow good insulation of the walls. Indeed, these coatings are of little or no performance since they are applied as an inner coating or used as a sub-layer of a non-insulating material. In addition, when the wall or ceiling to be insulated is damaged, for example by the presence of holes or cracks up to 3 mm or even 1 cm deep, these compositions do not allow to cover continuously the damaged surface of the wall or ceiling, leaving these defects apparent. The result obtained is unsatisfactory aesthetically and does not ensure a continuous thermal insulation on the entire surface of the wall or ceiling. Moreover, these compositions may flake or crack, and thus create thermal bridges further impairing the thermal performance of the insulating coating. Blisters weakening the insulation can also appear over time on the surface of the coating, in the presence of moisture in the masonry, resulting in poor adhesion of the coating on the support surface.
    [0003] Thus, these existing thermal insulation systems are not entirely satisfactory and there is a need for a thermal insulation system to overcome all or part of the disadvantages of the prior art. In particular, there is a need to provide a thermal insulation system, easy and quick to implement on the inner surface of a wall or ceiling, and space-saving compared to existing systems. In particular, there is a need to formulate a thermal insulation system for interior wall and ceiling, which can be applied homogeneously to a surface to be insulated, and has an aesthetically acceptable and adapted to superimpose a wall cladding decorative finish, and in particular a thin and / or fragile decorative wall covering such as wallpaper. In particular, there is a need to find a thermal insulation system to effectively isolate both new surfaces that weakly or moderately damaged.
    [0004] In order to meet these needs, and in particular, in order to put within the reach of any user, even inexperienced, the installation and improvement of a thermal insulation system from the inside, without substantial loss of space , it has now been developed a wall thermal insulation system, fluid (liquid or pasty) as defined below.
    [0005] Thus, a first subject of the invention relates to a coating composition comprising: from 4 to 17% by weight of hollow microspheres (denoted a) having a lower thermal conductivity (denoted lambda) at 0.1 Wm-1.1 ( -1, - from 0.05 to 1% by weight of at least one linear alcohol (denoted b)) whose hydrocarbon chain contains at least 8 carbon atoms, - from 5 to 25% by weight of at least an adhesion promoter (denoted c)) chosen from dispersible or water-soluble polymers, having a glass transition temperature (Tg) of less than or equal to 65 ° C, of 25 to 50% by weight of a non-hydraulic binder (denoted d)) chosen from among the following mineral and metallic fillers: carbonate of an alkaline earth metal, alumina, silica, silicate of a metal chosen from aluminum, alkali metals and alkali metals; and mixtures thereof, said fillers having an average particle size of from 5 to 100 μm, of 0.1 to 1% by weight, ds of at least one thickening agent (denoted e), 20 - water (denoted f)), the percentages by weight being expressed in% by weight of dry matter relative to the total weight of the coating composition . In contrast, with existing thermal insulation systems, the coating composition according to the invention is easy and quick to implement, even for a less experienced user. In particular, the coating composition according to the invention can be applied homogeneously to the roll, without casting, and dries quickly. The coating composition according to the invention is a ready-to-use composition. It does not require any special preparation before use, and is sufficiently stable in storage, so as not to be formulated as a two-component or premix composition. Unlike two-component compositions which take up mass upon contact of the solid phase with the liquid phase, the coating composition according to the invention is a one-component composition which cures by evaporation of the water contained in the composition. Once hardened and dried, the composition according to the invention makes it possible to form a rigid material, and in particular a coating, having thermal insulation properties adapted to ensure good insulation of the walls and ceiling from the inside. The coating thus obtained has an acceptable thickness in view of the thermal insulation performance and minimum size desired. In particular, the coating advantageously has a thermal conductivity of less than 0.07 W.m1.K-1 (Watt per meter per kelvin), preferably less than 0.065 Wm-1.K-1 and a thickness of 0.5 at 5 millimeters, preferably ranging from 0.5 to 3 millimeters. Advantageously, the coating composition according to the invention can be applied with a thickness of up to three millimeters without problem of adhesion to the support or cracking, once dried. It has been found in particular that the use of 0.05 to 1% by weight of a fatty alcohol (whose hydrocarbon chain contains at least 8 carbon atoms) in the coating composition according to the invention, allowed to obtain a coating without cracks.
    [0006] Furthermore, the coating composition according to the invention can be used as a smoothing coating to ensure the flatness of a surface of a support having small defects (asperities and / or holes and cracks up to 1 cm). deep and preferably up to 3 mm deep). In particular, it makes it possible to smooth the walls and the ceilings and thus to restore them and / or to prepare them for the installation of a superficial decorative wall covering such as wallpaper, upholstery, paint, varnish. The coating thus obtained has a uniform and flat surface relative to the surface plane of said support and may be covered with a thin and / or fragile decorative wall covering such as wallpaper. In particular, the coating obtained reduces or eliminate the feeling of cold wall when touching the wall, which is generally associated with insufficient thermal insulation of the wall. In addition, the insulating coating according to the invention may be covered with a decorative surface wall coating without significant loss or decrease in its insulating properties. Other objects and features or advantages of the present invention will become more apparent upon reading the description and examples. In the present application, in the absence of any indication to the contrary: the amounts expressed in the form of a percentage correspond to weight / weight percentages. In particular, the quantities relative to the ingredients noted a), b), c) d) and e) as described above and the additives possibly present in the composition according to the invention are expressed as a percentage by weight of dry matter per relative to the total weight of the coating composition according to the invention; the thermal conductivity is measured at 20 ° C., at atmospheric pressure and at 50% relative humidity. Thermal conductivity can be measured using a conductivity meter. - The average particle size (hollow microsphere or charge) is measured for a particle size distribution volume and corresponding to 50% by volume of the sample of particles analyzed. When the particles are spherical, the average particle size corresponds to the median diameter (D50 or Dv50) which corresponds to the diameter such that 50% of the volume particles are smaller than said diameter. In the present application, this value is expressed in micrometers and determined according to the NF ISO 13320-1 (1999) standard by laser diffraction on a MALVERN type apparatus. - Spherical or spherical, it is intended to characterize the particles (hollow microsphere or filler) having a shape ratio close to 1, ranging from 0.5 to 1.5 for example, such as oblong, ovoid, ellipsoidal particles and preferably 1, ie having a spherical shape. Such a shape ratio is defined as the ratio between the maximum distance between two points of the particle's surface, along a principal direction, over the minimum distance between two points of the particle's surface, in a direction substantially perpendicular to the main direction. The coating composition according to the invention comprises from 4 to 17% by weight of hollow microspheres having a thermal conductivity of less than 0.1 Wm-1 .Ki, preferably from 0.01 to 0.065 Wm-1.K- 1. Below this concentration range, the resulting coating has insufficient thermal insulation properties (i.e., a lambda value greater than 0.1W / (m.K)). Above such a concentration range, the composition is difficult to mix and can not be applied to the roll. Preferably, the coating composition according to the invention comprises from 7% to 17% by weight of hollow microspheres. The hollow microspheres used according to the invention can be chosen from any hollow microspheres consisting of glass or polymer, and having a thermal conductivity of less than 0.1 Wm-1.K-1, preferably ranging from 0, 01 to 0.065 Wm-1.K-1.
    [0007] The thermal conductivity of the hollow microspheres used according to the invention can be measured in the usual way, at 21 ° C. under 1 bar, in particular according to the standard EN NF 12664. The hollow microspheres used according to the invention preferably have a true density ranging from 0.5 to 0.5 g / cm 3, preferably 0.1 to 0.3 g / cm 3. The actual density of the hollow microspheres can be measured conventionally, for example using an air pycnometer. In particular, the hollow microspheres used according to the invention are preferably dispersible in water.
    [0008] Advantageously, the hollow microspheres used according to the invention are non-porous. This results in the fact that they do not absorb liquids, such as the water present in the coating composition according to the invention. The hollow microspheres used according to the invention preferably comprise an inert gas or a mixture of an inert gas such as air, at a gas pressure ranging from 0.3 × 10 5 to 7 × 10 5 Pa at 23 ° C., the (s) said (s) gas with thermal conductivity less than or equal to that of air. This gas (s) which is (or is) generally trapped during the manufacturing process of hollow microspheres, is (or is) therefore at least as thermally insulating as air. Preferably, the hollow microspheres used according to the invention may comprise a mixture of sulfur dioxide and dioxygen in a 2: 1 molar ratio.
    [0009] According to a preferred embodiment according to the invention, the hollow microspheres used according to the invention preferably have a single internal cavity. In this case, we speak of single-cell hollow microspheres as opposed to polycellular hollow microspheres such as perlite. According to this preferred embodiment according to the invention, the hollow microspheres comprise in their internal cavity a gas or mixture of inert gas as mentioned above, in particular a mixture of sulfur dioxide and oxygen in a 2: 1 molar ratio. . According to this preferred embodiment according to the invention, the hollow microspheres used according to the invention preferably have an external wall delimiting the inside of the internal cavity and the outer surface of the microsphere, of substantially homogeneous thickness and sufficient to to withstand the shocks related to the handling of these compounds during the preparation of the composition according to the invention, and to seal the gas contained in the microsphere.
    [0010] Among the hollow microspheres that can be used according to the invention, those having an average particle size (D 50) ranging from 0.10 to 100 μm, and more preferably from 25 to 70 μm, are preferred. As an example of hollow microspheres of glass usable include: - those of sodium borosilicate and calcium, such microspheres may be float glass and may have undergone a surface treatment based on epoxysilane or chromium chloride methacrylate. Such compounds mainly comprise silica, boron oxide, sodium and calcium salts generally introduced in the manufacture in the form of CaO and Na2O; those made of aluminosilicate. Such compounds mainly comprise silica and aluminum oxide (A1203 alumina). It is preferred to use hollow microspheres of sodium borosilicate and calcium borosilicate. Such hollow glass microspheres are sold under the SCOTCHLITE®K and S series by Kremer or under the name Glass Bubble (S and K series or float glass series) by the company 3M. As examples of hollow polymer microspheres that can be used, mention may be made of those based on thermoplastic polymers, such as vinylidene chloride / acrylonitrile microspheres. These are sold for example under the name "Expancele" by Akzo Nobel.
    [0011] Preferably, the hollow polymer microspheres are not expandable under the pressure and temperature conditions of their use, for example at 1 bar for temperatures ranging from -30 ° C to 50 ° C. Among all these hollow microspheres of glass or polymer that may be used, it is preferred to use: those made of sodium borosilicate and calcium borosilicate, those of aluminosilicate, those of vinylidene chloride / acrylonitrile. Among all these hollow microspheres of glass or polymer that can be used, it is preferable to use more particularly those of glass and especially of glass, which are single-celled, non-porous, chosen from: those of borosilicate soda-lime glass, of thermal conductivity equal to 0.076 W / (mK) , with a real density ranging from 0.19 to 0.25 g / cm3 and a median diameter D50 of 29 μm, as sold under the name "Scotchlitee S22" by the company 3M; those made of borosilicate soda-lime glass, with a thermal conductivity equal to 0.046 W / (mK), with a real density ranging from 0.1 to 0.14 g / cm 3 and a median diameter D 50 of 46 μm, as sold under the name " Scotchlite® K1 "by 3M; those made of vinylidene chloride / acrylonitrile, of thermal conductivity equal to 0.049 W / (m · K), of the "Expancele" series for example. The hollow microspheres used according to the invention can be prepared by well-known manufacturing processes. The hollow microspheres of glass may in particular be prepared by a process as described in the application WO 2011/084407, making it possible to control the size, shape, density and resistance of hollow microspheres of glass. In this manufacturing process, a glass composition is melted and ground to obtain a grinding of particles of suitable size to obtain hollow microspheres of desired size. The glass grist is then heated under vacuum in contact with a flame at a temperature above the softening point of the glass composition, generally above 1300 ° C, to form hollow glass microspheres. The hollow microspheres may be obtained by using a blowing agent such as sulfur or sulfur dioxide, introduced into the glass grist before contact thereof with the flame. They can also be obtained without a swelling agent by carrying out the process described above at a pressure preferably lower than 6.773 Pa. The amount of swelling agent used, the flame temperature and the heating time of the grind can be adjusted to obtain hollow microspheres of desired density glass.
    [0012] The hollow microspheres of polymer may especially be prepared by a process as described in US Pat. No. 3,615,972, in which the hollow microspheres are formed by catalytically polymerizing an aqueous polymer microdispersion having homogeneously sized polymer droplets comprising a blowing agent. . The size of the polymer droplets can be adjusted by varying the agitation speed of the mixture, and can be stabilized with surfactant (s) and / or thickener (s) preventing coalescence of the droplets. Once polymerized, the resulting microspheres are filtered and dried and can undergo an expansion step to increase the size of the microspheres and reduce their wall thickness. During this step, the microspheres are heated to a temperature above the softening point of the polymer in order to cause the expansion of the internal cavity of the microsphere to reach their final dimension by evaporation of the blowing agent. The blowing gas then diffuses through the polymeric shell and is replaced by air. The hollow microspheres may also be unexpanded when the polymer selected for their preparation is crosslinked or has a high molecular weight. The coating composition according to the invention comprises from 0.05 to 1% by weight, preferably from 0.1 to 1% by weight, of at least one alcohol whose hydrocarbon chain comprises at least 8 carbon atoms, and preferably from 8 to 30 carbon atoms.
    [0013] The alcohol or alcohols used in the composition according to the invention may be selected from mono or polyols, comprising a linear hydrocarbon chain. Preferably, the alcohol used according to the invention is chosen from: linear fatty alcohols corresponding to the formula ROH, where R is a linear hydrocarbon chain, saturated or unsaturated, having from 8 to 30 carbon atoms. These alcohols, taken in combination with the other ingredients of the composition of the invention, make it possible to obtain a coating which does not crack. Among the commercially available products that can be used, mention may be made, for example, of the product "Loxanole 842 DP / 3" sold by BASF and corresponding to an aqueous dispersion of linear fatty alcohol containing 30% by weight of dry matter; polymeric alcohols comprising a linear hydrocarbon chain, such as polyvinyl alcohols, having a Tg ranging from 75 to 95 ° C. These alcohols, taken in combination with the other ingredients of the composition of the invention, make it possible to give the coating a satisfactory hardness. Among the commercially available products that can be used, mention may be made, for example, of the product "Solvitose® 17S" sold by the company AVEBE, which corresponds to a partially hydrolysed polyvinyl alcohol having a Tg of approximately 85 ° C. in the form of a powder; - and their mixture. More preferably, a mixture of linear fatty alcohol (s) of formula ROH, where R is a linear hydrocarbon chain, saturated or unsaturated, having from 8 to 30 carbon atoms and polyvinyl alcohol (s) vinyl ( s), having a Tg ranging from 75 to 95 ° C. The coating composition according to the invention comprises from 5 to 25% by weight, and preferably from 10 to 20% by weight, of at least one adhesion promoter chosen from dispersible or water-soluble polymers, having a glass transition temperature of less than or equal to 65 ° C, and preferably ranging from 5 ° C to 65 ° C. When the glass transition temperature of the polymer ranges from 5 to 65 ° C., the coating obtained after drying of the composition has a satisfactory hardness. In particular, the coating does not deform after drying. For Tg values above 65 ° C, the coating no longer has sufficient adhesion to the support. Examples of suitable adhesion promoters include copolymers of styrene and (meth) acrylic acid, copolymers of styrene and (meth) acrylic acid ester, styrene copolymers and (meth) acrylamide, said copolymers being silanized, homopolymers and copolymers of butadiene such as polybutadiene and polybutadiene-styrene, vinyl polymers such as polyvinyl chloride and polyvinyl acetate, polyurethanes, and mixtures thereof. In particular, the monomers of (meth) acrylic acid or (meth) acrylic acid ester used to prepare these adhesion agents may be chosen from: acrylic acid, methacrylic acid, alkyl (meth) acrylate of which the linear or branched, cyclic or acyclic alkyl part has from 1 to 18 carbon atoms, allyl (meth) acrylate, alkyl ether (meth) acrylate (or alkyloxyalkyl), each of which alkyl portions may be identical or different, is linear or branched, and comprises from 1 to 18 carbon atoms, - alkyl (aryl) alkyl ether (or aryloxyalkyl) (meth) acrylate ), the linear or branched alkyl part of which comprises from 1 to 18 carbon atoms, and the aryl part is a phenyl group, - the hydroxyalkyl (meth) acrylate whose linear or branched alkyl part comprises 1 to 18 carbon atoms, and is optionally interrupted by ester functions -C (= O) -O-, - the (m th) polypropylene glycol or polyethylene glycol acrylate. More specifically, the monomers of (meth) acrylic acid or of (meth) acrylic acid ester may be chosen from methyl acrylate and methyl methacrylate. ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate and the like. hexyl, ethylhexyl acrylate, ethylhexyl methacrylate, n-heptyl acrylate, n-heptyl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl methacrylate, acrylate hydroxyethyl, hydroxyethyl methacrylate, allyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, isodecyl acrylate, methacrylate isodecyl, 2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2- (2-ethoxyethoxy) ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate, caprolactone methacrylate, polypropylene glycol acrylate, polypropylene glycol methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, benzyl acrylate, benzyl methacrylate. Preferably, the agent or adhesion agents that can be used are (or are) chosen from styrene and acrylic acid copolymers or copolymers of styrene and acrylic acid ester.
    [0014] More preferably, using an aqueous emulsion of one of these copolymers, optionally silanized. Such products are sold, for example, under the name "Acronale S813" (styrene / acrylic acid ester copolymer, having a Tg of 28 ° C., available in the form of an aqueous dispersion of 49 to 51% by weight of dry extract) or "Acronale S533" (copolymer of styrene and acrylic acid, having a Tg of 5 ° C., available in the form of an aqueous dispersion of 51 to 53% by weight of solids) by BASF. The use of copolymers of styrene and silanized acrylic acid or copolymers of styrene and silanized acrylic acid ester makes it possible to obtain a coating having particularly satisfactory mechanical properties (water resistance for example). The coating composition according to the invention comprises from 25 to 50% by weight of a non-hydraulic binder selected from the following mineral and metal fillers: carbonate of an alkaline earth metal, alumina, silica, silicate of a metal selected from aluminum, alkali metals and alkaline earth metals, and mixtures thereof, said fillers having an average particle size ranging from 5 to 100 iam. Preferably, the mineral or metal filler or fillers are chosen from among the following fillers: calcium carbonate, magnesium carbonate, alumina, silica, aluminum silicate, magnesium silicate, sodium silicate, potassium silicate, mica, and their mixed.
    [0015] The filler (s) used in the composition of the invention may be in hydrated or anhydrous form. These particles are different from hollow microspheres of glass or polymer of thermal conductivity less than 0.1 W.m-1.K-1. In particular, these charges are not hollow. These fillers may be of various shapes, for example spherical. Among the fillers that can be used according to the invention, use is preferably made of mineral fillers, and more preferentially mineral fillers chosen from calcium carbonate and silica.
    [0016] According to one particular embodiment, mineral fillers having a real density ranging from 2.5 to 3 g / cm 3 are preferably used. These charges are commercially available. By way of example, mention may be made of calcium carbonate of average particle size D50 equal to approximately 22 μm, and of actual charge density of 2.7 g / cm 3, sold under the name BEATITE® 30 by the company Onyx and Marble Granules (OMG), the silica of average size approximately i.tm, and actual charge density of 2.65 g / cm3, sold under the name Millicil C6 by the company Sifraco. The coating composition according to the invention comprises from 0.1 to 1% by weight of at least one thickening agent.
    [0017] Any thickener usually used in conventional smoothing compositions can be used. The nature and the content of thickener (s) usable (s) according to the invention are suitably chosen in order to obtain the expected rheological properties. Advantageously, the thickening agent (s) may be selected from clay, polysaccharide thickeners such as starch and modified starch thickeners, cellulosic thickeners, and their mixtures, possibly in the presence of sodium hydroxide. Preferably, a sufficient quantity of sodium hydroxide is added to the composition according to the invention to obtain a basic pH. This makes it possible to improve the rheological properties of the thickening agent and therefore those of the coating composition.
    [0018] Among the cellulosic thickeners that may be used, mention may be made of cellulose and its alkyl and / or hydroxyalkyl derivatives, the identical or different alkyl part of which has from 1 to 4 carbon atoms, and preferably from 1 to 3 carbon atoms. By way of example, mention may be made of methyl cellulose, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose. These thickeners are well known to those skilled in the art and all commercially available.
    [0019] Among all these thickeners, it is preferred to use a mixture of thickeners comprising at least one thickening agent having further water retention properties. By way of example, mention may be made of a mixture of "Bentonee EW" corresponding to clay in powder form sold by the company ELEMENTIS Specialties, and "Addilosee 200 R" corresponding to a thickening agent and retention agent of water based on modified starch, in powder form. The coating composition according to the invention comprises water. The water content is adjusted according to the other ingredients present in the composition. Preferably, this content ranges from 20 to 34% by weight of the total weight of the composition. The coating composition according to the invention may further comprise at least one additive chosen from the dispersants of fillers, plasticizers, biocides and anti-foams. The coating composition according to the invention may comprise at least one homopolymer of acrylic acid acting as a charge dispersant. When one or more additives is or are present in the composition, the total content of additives preferably does not exceed 2% and more preferably does not exceed 1% by weight relative to the total weight of the composition. Preferably, the coating composition according to the invention comprises from 0.5% to 2% by weight of additives. According to a preferred embodiment, the coating composition according to the invention does not comprise a hydraulic binder such as plaster, cement or calcium bentonite. The presence of a significant amount of hydraulic binder in the composition according to the invention risks leading to rapid setting thereof in contact with the water of the composition. The coating composition according to the invention is prepared by simple mixing of the various ingredients constituting it. It can then be stored dry, protected from the air, in an airtight packaging to prevent the water contained in the coating composition from evaporating. The composition can thus be stored for up to 18 months. Another subject of the present application relates to a process for implementing a coating composition according to the invention comprising the following steps: (i) application in one or more successive layers of said composition on the surface of a support to isolate using a roller and / or a trowel, then (ii) drying said layer, and (iii) optionally applying to said layer of hardened plaster, a layer of a material not insulation, such as a decorative wall covering layer. Steps (i) and (ii) can be repeated one or more times before the implementation of step (iii) where appropriate. The coating composition according to the invention can be applied to the roller on the surface of a support to be isolated. The use of a roll makes it possible to spread the coating composition easily and homogeneously over the entire surface to be insulated. Once spread, the surface of the composition can then be smoothed using a trowel. The time elapsed between each application of composition is preferably less than 30 minutes. Step (i) may be followed by a smoothing step using a smoother when the surface of the composition applied at the end of step (i) is not or not sufficiently smooth. The smoothing step can be carried out either by applying a new layer of coating composition using a trowel, the smoothing being then simultaneously with the application of the composition, or by smoothing the surface of the composition applied from step (i) without superposition of a new layer of coating composition, according to the skill level of the user in the field of wall coating application. Thus, according to a first variant of the invention, the process for implementing a coating composition according to the invention comprises at least the following steps: (i ') applying a first layer of said composition to a surface of a support with a roller, for spreading a homogeneous amount of the composition, and then (ii ') applying a second layer of said composition to said first deposited layer using a smoothing, to smooth the surface of the deposited composition, the time elapsed between the first and second application of composition being less than 30 minutes, then (iii ') drying the coating composition, then (iv') possible application on said hardened coating layer, a layer of a non-insulating material, such as a decorative wall covering layer. According to this first variant, the steps (i '), (ii') and then (iii ') can be repeated one or more times before the implementation of step (iv') where appropriate. Alternatively, the steps (ii ') and then (iii') can be repeated one or more times before the implementation of step (iv ') where appropriate. According to a second variant of the invention, the process for implementing a coating composition according to the invention comprises at least the following steps: (i ") applying a first layer of said composition to a surface a support with a roller, to spread a homogeneous amount of the composition, then (ii ") smoothing the surface with a smoothing without adding additional material, then (iii") drying the coating composition, then (iv ") optionally applying to said hardened coating layer, a layer of a non-insulating material, such as a decorative wall covering layer. According to this second variant, the steps (i ") and then (ii") can be repeated one or more times before the implementation of step (iv ") if appropriate.This variant is particularly preferred because it can be set implemented by any user, even little experienced in the field of application of wall coatings.In fact, these process steps are particularly easy to implement and allow, even for an inexperienced user, successful smoothing of The use of a roller makes it possible to spread the composition rapidly and in a homogeneous manner, in order to correct the defects of the surface of the support, and the coating composition has a hardening and drying time. 30 minutes, which gives the user time to correct any defects and irregularities left on the surface of the first coating layer. invention, the method of implementation of a coating composition according to the invention, comprises at least the following steps: (i "') application of a layer of said composition on a surface of a support, preferably in a single pass, using a smoothing, then (ii '") drying of the coating composition, then (iii'") possible application on said hardened coating layer, a layer of A non-insulating material, such as a decorative wall covering layer According to this third variant, the steps (i '") and then (ii"') can be repeated one or more times, before the implementation of the step (iii "') where appropriate.
    [0020] This method allows the rapid and precise application of the composition according to the invention and represents a considerable time saving compared with the use of a composition of two-component type. For each of the aforementioned processes, the entire composition applied over the entire surface of the support represents a grammage ranging from 200 to 1000 g / m2. Such a basis weight makes it possible to obtain a coating of the desired thickness as described below. Among the rollers that can be used according to the invention, it is preferred to use rolls of textured honeycombed foams, for example made of polyamide or polyester. These rollers make it easier to spread the coating composition according to the invention.
    [0021] The coating composition according to the invention cures during the step of drying by evaporation of the water contained in the composition. In general, the drying is done in the open air at 20 ° C. After 24 hours, the coating is completely dry and hard. Once dried, the coating formed by the cured coating composition preferably has a thickness of from 0.5 to 5 millimeters, preferably from 0.5 to 3 mm, and more preferably from 1 to 2 mm. The implementation of the methods described above thus makes it possible advantageously to obtain a support coated with a hardened coating layer with a thickness ranging from 0.5 to 5 millimeters, preferably from 0.5 to 3 mm, and better still from 1 to 2 mm. The support intended to be covered with the coating composition according to the invention may consist of any building material, new or to be restored, with defects up to 1 cm deep. It may be plaster, gypsum wallboard, mortar, concrete, wood, bricks, tiles, leached and / or printed paints. The non-insulating material capable of covering the coating layer may be of the same nature as the support or of a different nature. It may be a decorative wall covering, including a thin and / or fragile decorative wall covering. The decorative wall covering may be wallpaper, upholstery, paint, varnish. By "non-insulating" is meant that the material does not have a thermal conductivity of less than 0.1W.m-1.K-1. Another subject of the present invention relates to an insulating material and in particular a support coated with a cured coating layer having a thickness ranging from 0.5 to 5 millimeters, preferably from 0.5 to 3 mm, and better still from 1 to 2 mm, obtainable by the method as defined in one of the preceding paragraphs. The present application also relates to the use of a coating composition according to the invention as a smoothing coating and thermal insulation for walls and ceilings.
    [0022] These combined properties make it easy to isolate and restore old walls and ceilings at the same time. In particular, the coating composition according to the invention is useful for forming a thermal insulating interior wall coating, having a thermal conductivity of less than 0.07 Wm-1.1 (-1, and more preferably less than 0.065 Wm-1.1 (- The following examples are given purely by way of illustration of the invention and can not be interpreted in order to limit the scope thereof.Examples of the invention: The coating compositions 1 to 5 according to the invention are produced by mixing the various ingredients. indicated in Table 1. Unless otherwise indicated, the contents indicated in this table are expressed in% by weight of dry ingredients relative to the total weight of the composition.
    [0023] Table 1 Compositions 1 2 3 4 5 a) Glass hollow microspheres 14.3 - - - - (Scotchlite0 S22, 0.076 Wm-1.K-1) Microspheres - 15 7.5 10.0 12.0 hollow glass ( Scotchlite® KI, 0.047 Wm-1.K-1) b) Linear Fatty Alcohol 0.1 0.1 0.1 0.1 0.1 C8-C30 (Loxanol®842 DP / 3) Polyvinyl Alcohol (Solvitose017S) 0.4 0.4 0.4 0.4 0.4 c) Copolymer of 14.7 12.7 12.7 12.7 12.3 (styrene-butyl acrylate), Tg = 10 ° C d) Carbonate 34.7 36.4 43.9 41.4 29.1 Calcium (Beatite 030) e) Clay Thickener (Bentone OEW) 0.2 0.3 0.3 0.3 0.3 Polysaccharide Thickener (Addilose 200R® ) 0.3 0.3 0.3 0.3 0.3 Soda liquor qsp qsp qsp qsp pH> 7 pH> 7 pH> 7 pH> 7 pH> 7 Additives 0.9 * 0.9 * 0, 9 * 0.9 * 0.9 * f) Water qs 100 qs 100 qs 100 qs qs 100 qs qs means "enough to reach" *: quantity expressed in% by wet weight relative to the total weight of the composition can be stored for up to 18 months in a dry airtight case with air and moisture.
    [0024] These compositions were applied easily and homogeneously on various supports (wall, ceiling) roller and then smooth, in a layer of thickness ranging from 0.5 to 3 mm. Once cured, the coating layer has a smooth, flawless surface. Measurement of Thermal Conductivity For each of Examples 1 to 5, the thermal conductivity of the composition, when dried for a given thickness, is measured at 23 ° C. at a relative humidity of 50%. The measurement is made using a measuring probe connected to a NEOTIM FP2C thermal conductivity meter. For this purpose, in two parallelepiped Teflon-shaped molds of given length, width and thickness, the composition to be tested is applied so as to form it in the form of a test piece 50 mm long, 70 mm wide and of given thickness. indicated in Table 2. After complete drying of the test specimen, and demolding, the measurement probe is then placed between the two test pieces of the composition. Then, the two plates of the composition are pressed slightly against each other so that the measurement probe is sandwiched between these two plates.
    [0025] The results of the thermal conductivity measurements are expressed in watts per meter per Kelvin and are shown in Table 2. Table 2 Characterization 1 2 3 4 5 Thickness (mm) 0.9 2.1 1.3 1.9 1.9 Thermal Conductivity 0.066 0.050 0.068 0.058 0.049 (W / (mK)) All samples tested according to the invention have a thermal conductivity of less than 0.07W.m-1K-120
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. Coating composition comprising: - from 4 to 17% by weight of hollow microspheres having a lower thermal conductivity (denoted lambda) at 0.1 Wm-1.1 (-1, - from 0.05 to 1% by weight of Au less a linear alcohol whose hydrocarbon chain comprises at least 8 carbon atoms, 5 to 25% by weight of at least one adhesion promoter chosen from dispersible or water-soluble polymers having a transition temperature vitreous (Tg) less than or equal to 65 ° C, - 25 to 50% by weight of a non-hydraulic binder selected from the following mineral and metal fillers: carbonate of an alkaline earth metal, alumina, silica, silicate d a metal selected from aluminum, alkali metals and alkaline earth metals, and mixtures thereof, said fillers having an average particle size of from 5 to 100 μm, - from 0.1 to 1% by weight of at least one thickening agent, - water, the percentages by weight being expressed in% in ids of dry matter relative to the total weight of the coating composition.
    [0002]
    2. Coating composition according to claim 1, characterized in that the hollow microspheres have a real density ranging from 0.05 to 0.5 g / cm3.
    [0003]
    3. Coating composition according to one of claims 1 to 2, characterized in that the hollow microspheres are hollow microspheres having an average particle size (D50) ranging from 0.10 to 100 μm.
    [0004]
    4. coating composition according to one of claims 1 to 3, characterized in that the hollow microspheres are hollow microspheres of glass or polymer selected from those of sodium borosilicate and calcium, those of aluminosilicate, and those of vinylidene chloride / acrylonitrile.
    [0005]
    5. Coating composition according to one of claims 1 to 4, characterized in that the alcohol is a mixture of linear fatty alcohol (s) of formula ROH, where R is a linear hydrocarbon chain, saturated or unsaturated, having 8 to 30 carbon atoms and polyvinyl alcohol (s), having a Tg ranging from 75 to 95 ° C.
    [0006]
    6. Coating composition according to one of claims 1 to 5, characterized in that the dispersible or water-soluble polymer is selected from copolymers of styrene and (meth) acrylic acid, styrene copolymers and (meth) acrylic acid ester, copolymers of styrene and (meth) acrylamide, said copolymers being silanized, homopolymers and copolymers of butadiene such as polybutadiene and polybutadienestyrene, vinyl polymers such as polyvinyl chloride and polyvinylacetate, polyurethanes, and mixtures thereof.
    [0007]
    7. coating composition according to one of claims 1 to 6, characterized in that the inorganic filler is selected from calcium carbonate and silica.
    [0008]
    8. Coating composition according to one of claims 1 to 7, characterized in that the thickening agent is selected from clay, polysaccharide thickeners and mixtures thereof, optionally in the presence of sodium hydroxide.
    [0009]
    9. A method of carrying out a composition as defined in any one of claims 1 to 8, comprising at least the following steps: (i) application in one or more successive layers of said composition on a surface of a support using a roller and / or a trowel, then (ii) drying said layer, and (iii) optionally applying to said layer of hardened plaster, a layer of a material not insulating.
    [0010]
    10. Method according to claim 9, characterized in that it comprises at least the following steps: (i ') application of a first layer of a composition as defined in any one of claims 1 to 8 on a surface of a support with a roll, and then (ii ') applying a second layer of a composition as defined in any one of claims 1 to 8 to said first layer deposited at the using a smoothing machine, the time elapsed between the first and the second application of composition being less than 30 minutes, or (ii ") smoothing the surface with a smoothing machine without adding additional material, and then (iii ') drying the coating composition, and then (iv') optionally applying to said hardened coating layer, a layer of a non-insulating material.
    [0011]
    11. A method according to claim 9, characterized in that it comprises at least the following steps: (i "') application of a layer of a composition as defined in any one of claims 1 to 8 on a surface of a support, using a trowel, then (ii ") drying the coating composition, then (iii" ') possible application on said hardened coating layer, a layer of a non-insulating material.
    [0012]
    12. The method of claim 9 or 10, characterized in that the roller used in step (i) or (i ') is selected from the textured foam rolls honeycomb.
    [0013]
    13. Support coated with a layer of cured coating composition having a thickness ranging from 0.5 to 3 millimeters obtainable by the method as defined in any one of claims 9 to 11.
    [0014]
    14. Use of a composition as defined in any one of claims 1 to 8 as a smoothing coating and / or thermal insulation for walls and ceilings.
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    同族专利:
    公开号 | 公开日
    FR3015474B1|2016-01-01|
    EP2886523B1|2018-10-03|
    US20150176267A1|2015-06-25|
    RU2014151475A|2016-07-10|
    US9540803B2|2017-01-10|
    RU2014151475A3|2018-08-16|
    RU2706038C2|2019-11-13|
    EP2886523A1|2015-06-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2001077242A2|2000-04-12|2001-10-18|Bostik Findley Ltd.|Water-resistant grout and title adhesive composition|
    US20050271882A1|2004-06-05|2005-12-08|Walther Ingrid Frieda M|Coating composition for plastic substrates|
    DE102005040091A1|2005-08-24|2007-03-01|Alsecco Gmbh & Co. Kg|Light plaster in pasty form|
    EP2289862A1|2009-07-31|2011-03-02|Druckfarben Hellas S.A.|Thermal insulation system for buildings and for liquid storage and transportation systems|
    US3615972A|1967-04-28|1971-10-26|Dow Chemical Co|Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same|
    FR2611738B1|1987-03-03|1991-07-12|Kleinfelden Jean|PROTECTIVE COATING AGAINST EXTERNAL AGENTS|
    DE19717936A1|1997-04-29|1998-11-05|Henkel Kgaa|Use of alcohols as additives for plasters and / or mortars|
    US8287998B2|2003-12-01|2012-10-16|Anthony David Skelhorn|Composition of a thermaly insulating coating system|
    RU2318782C1|2006-06-02|2008-03-10|Евгений Борисович Брянцев|Heat-insulating coat|
    RU2400508C1|2009-01-30|2010-09-27|Борис Григорьевич Печеный|Water-dispersed composition and method of its production|
    US8261577B2|2009-12-21|2012-09-11|3M Innovative Properties Company|Method for making hollow microspheres|
    PL2386610T3|2010-04-27|2013-10-31|Akzo Nobel Coatings Int Bv|Improved low titanium dioxide coatings|EP2930284A1|2014-04-09|2015-10-14|Sika Technology AG|Process for preparing a surface for decoration|
    EP3156382A1|2015-10-12|2017-04-19|Daw Se|Coating compositions, coatings from the coating compositions, components containing the coatings, method for the preparation of coatings and the use of the coating compositions|
    US20170268229A1|2016-03-16|2017-09-21|USG Interiors, LLC.|Construction products with an acoustically transparent coating|
    WO2018007248A1|2016-07-08|2018-01-11|Akzo Nobel Coatings International B.V.|Heat insulating coating composition, method for applying such coating composition and kit of parts comprising such coating composition|
    IT201600128724A1|2016-12-20|2018-06-20|Vincenzo Falcone|COMPOSITION FOR A THERMAL LOW-THERMAL COATING AND HIGH ENERGY EFFICIENCY AND PROCEDURE FOR ITS PREPARATION, ITS FINISHING, AND USES OF THE SAME|
    CN110066644B|2018-01-22|2021-09-14|中国石油化工股份有限公司|Extracting and cutting agent for qi stagnation and preparation method|
    CN110066647B|2018-01-22|2021-08-31|中国石油化工股份有限公司|High-temperature-resistant air-stagnation plug for well drilling and preparation method thereof|
    US20210071010A1|2018-03-21|2021-03-11|Nouryon Chemicals International B.V.|Coatings with solar reflective properties|
    CN108947569B|2018-08-30|2021-10-01|盛世瑶兰（深圳）科技有限公司|High-strength hollow heat-insulation building material and application thereof|
    WO2020094207A1|2018-11-06|2020-05-14|Knauf Gips Kg|Composition for a low shrinkage pasty fill and finishing material, pasty fill and finishing material, and method for producing a pasty fil and finishing material|
    CN111662600A|2019-05-17|2020-09-15|亚科维亚科技有限公司|Anti-highlight orthographic projection coating and orthographic projection screen|
    WO2021001689A1|2019-07-01|2021-01-07|GIUSEPPE DI MARIA S.p.A.|Thermally insulating coating composition|
    CN110467878B|2019-08-28|2021-08-06|沈华初|Long-acting heat-insulating and cooling coating for energy-saving building and preparation method thereof|
    US20210276917A1|2020-03-06|2021-09-09|United States Gypsum Company|Low shrinkage, fast drying spackling or joint compound|
    FR3108351A1|2020-03-17|2021-09-24|Produits De Revetement Du Batiment|Process for laying ceramic coating and composition for laying said coating on a support|
    CN111517829A|2020-05-27|2020-08-11|广西欧神诺陶瓷有限公司|Anti-skid antibacterial ceramic tile and preparation method thereof|
    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 3 |
    2016-11-11| PLFP| Fee payment|Year of fee payment: 4 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 5 |
    2018-11-20| PLFP| Fee payment|Year of fee payment: 6 |
    2020-10-16| ST| Notification of lapse|Effective date: 20200910 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362984A|FR3015474B1|2013-12-19|2013-12-19|WALL AND CEILING COATING COMPOSITION HAVING THERMAL INSULATION PROPERTIES|FR1362984A| FR3015474B1|2013-12-19|2013-12-19|WALL AND CEILING COATING COMPOSITION HAVING THERMAL INSULATION PROPERTIES|
    EP14196748.9A| EP2886523B1|2013-12-19|2014-12-08|Wall and ceiling coating composition having heat insulation properties|
    US14/572,387| US9540803B2|2013-12-19|2014-12-16|Wall and ceiling coating composition having heat insulation properties|
    RU2014151475A| RU2706038C2|2013-12-19|2014-12-18|Composition of wall and ceiling coating, having heat insulation properties|
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