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    • 专利摘要:
    The use has been described of a particulate material in a polymer article, or a polymer composition containing the particulate material, particularly a masterbatch, as well as a polymer film composition for reducing the transmission of near infrared radiation and allowing it to penetrate. transmission of visible light through the object, where i. the finely divided material is based on crystalline titanium dioxide, ii. the particles of the finely divided material are coated with an organic and / or an inorganic coating layer, iii. at least 20% weight of the particles of the particulate material have a particle size of at least 400 nm and at most 1000 nm, and iv. at least 1.5% weight and at most 40% weight of the particles in the particulate material have a particle size of at most 400 nm and at least 280 nm.
    公开号:BE1022168B1
    申请号:E2014/0763
    申请日:2014-10-10
    公开日:2016-02-23
    发明作者:Ann Swinnen；Dominique Theunynck；Ann Delmotte；Tony Daponte
    申请人:A. Schulman Plastics；
    IPC主号:
    专利说明:

    Specific use of a special fiberglass material
    TECHNICAL FIELD
    The present invention relates to the field of polyolefins film production. More specifically, the invention relates to the production of a film with a low transmission of infrared radiation, but through which a large part of the visible light passes through in a diffuse manner.
    BACKGROUND ART
    Exposure to sunlight over an extended period of time often has devastating consequences for most physical entities. That is why the colors of objects fade quickly and many materials can warp and show distortion under the large temperature fluctuations. The prolonged exposure causes deterioration of many materials and their aesthetic aspects, which is usually referred to as "aging," and typically leads to a considerably shorter service life and a need for replacement. Plants, animals and people are also often negatively influenced by prolonged exposure to sunlight. Sun protection has therefore become an important feature in many circumstances.
    Sunlight radiation occurs as visible light for approximately 45% of its energy, in the relatively narrow visible wavelength range of approximately 380 to approximately 700 nanometers (nm), but also for approximately 5% as ultraviolet radiation (UV) in the range of the shorter wavelengths of 280-380 nm and approximately 50% as infrared radiation (IR) in the even greater range of the longer wavelengths from 700 nm to approximately 1 mm.
    To make transparent surfaces, such as glass, more energy-resistant, special plastic films have been developed that as selectively as possible absorb the radiation from the range that is not visible to the eye, but either the previously harmful UV range or the heat-generating IR range. The range of the infrared radiation is usually divided into the near-infrared radiation range, N-IR or NIR or IR A & B, with a largest wavelength of up to about 2500 nm, and the long-wavelength or far IR range, with a range up to 50,000 nm or 50 μιη, and according to some authors even up to 1 mm. Because a large proportion of solar radiation has radiant energy with wavelengths in the near IR range, technological improvements have focused primarily on this. That is why films have been developed that have a better infrared absorption function, which results in a more even heat distribution and a more pleasant inside temperature with high light incidence. A disadvantage of these films is that the absorbed radiation is converted to heat in the film. Consequently, this absorption can cause local temperature rises, which are passed on to the substrate on which the film is applied. With many substrates such as glass, such local temperature rises lead to high mechanical loads and may even lead to glass breakage. A second drawback is that the absorbed heat, although transmitted to the inside in a more uniform manner, can also cause a significant temperature rise locally, which may still be undesirable.
    A high absorption of the incident solar energy does not necessarily lead to uncomplicated solutions. In order to limit or prevent these disadvantages as much as possible, films were developed with IR-reflecting properties, mainly focused on reflection in the NIR radiation range. These films offer a reduction in the heat absorption of a vehicle or building equipped with this during the summer, so that cooling energy can be saved. US 6797396 describes a birefringent dielectric multilayer film that is transparent to visible light, but in which at least 50% of the light is reflected in the wavelength region of 700-2000 nm, and which is made of different polymer layers and which does not contain any metals.
    To make an object more resistant to sunlight, sun-reflecting finely divided materials can be added to the construction material of the object, especially if it is a polymer, or to the paint or coating with which the object is subsequently coated. Conventional titanium dioxide particles are known to provide high solar reflection. These finely divided materials have a strong white color and given the required quantities, they cannot be used if a dark-colored object is desired. Also, these finely divided materials are not suitable for objects that must be transparent to visible light, such as transparent polymer foils or clear tops. WO 2009/136141 A1 describes a titanium dioxide (TiO 2) finely divided material with a large crystal size. It is indicated that the finely divided material strongly absorbs in the UV range of the spectrum (300-400 nm), efficiently scatters in the NIR region (700-2500 nm) and shows low scattering and low absorption in the visible range of the spectrum. spectrum (400-700 nm). The finely divided material thus shows high reflection of NIR radiation and at the same time little reflection of visible light in comparison with conventional finely divided materials. The special finely divided material is combined with a non-white dye in a vehicle and provides a single layer of coating that has sun reflection and a non-white color. It is therefore suitable to provide a high reflection of NIR radiation at relatively low concentrations and a reduced reflection of visible light in comparison with conventional finely divided materials. The finely divided material can be further coated with a metal oxide material to reduce its photocatalytic activity. The finely divided materials are recommended for use in various applications including a plastic object. The finely divided materials described were described with an average mass or an average mass of crystal root of 0.79, an average crystal size of 0.97 microns and an average particle size of 0.85 microns, or an average particle size of 0.69 microns. An uncoated finely divided material sample was added to an alkyd resin paint to measure reflection of black over the wavelength range of 400-2500 nm. An uncoated finely divided material was used in acrylic paint systems with different non-white colors, the reflection spectra of which were determined. A coated finely divided material was incorporated into an alkyd melamine formaldehyde-based paint and its durability was measured. Uncoated particulate material was used in plasticizer polyvinyl chloride slices stained with Pigment Green 17 and carbon black, and whose reflection spectra were measured over the wavelength range of 400-2600 nm and integrated to obtain a result for Total Solar Reflection. WO 2009/136141 A1 is concerned with and only measures the reflection of solar radiation, also referred to as "scattering", in particular the radiation in the NIR region of the solar spectrum, and at a secondary level also in the UV region. Neither any passage data nor any absorption data is collected for any of its products.
    In agriculture, the use of polymer films, in particular polyolefin films, has become widespread. One of the more important applications is the construction of inexpensive greenhouses, where a controlled atmosphere can be established for growing agricultural crops. Another application is the construction of cheap stables or shelters for animals, such as poultry. Such constructions can be set up very quickly, and may even be movable and / or transportable quickly.
    Especially in hot sunny climates, there is a preference to use films that reflect a large part of the infrared radiation of the sunlight, mainly in the so-called near-infrared (NIR) range from 700 nm to 2500 nm. When such near infrared radiation enters the greenhouse and touches a substrate, the substrate heats up. Subsequently, the emission of heat from this substrate by convection increases, as does the emission of long wavelength infrared radiation. Such long-wave infrared radiation is easily reflected by most materials, and its energy, once absorbed in the greenhouse, therefore tends to remain in the greenhouse. This phenomenon leads to additional warming of the atmosphere inside the greenhouse, including increased evaporation of water from the soil, animals and crops. This puts most crops and animals in a stress situation, which is usually not beneficial for their growth and economic returns. A low permeability, preferably by reflection, of the infrared radiation, in particular of the NIR radiation of the sunlight, is therefore important for maintaining the temperature in the greenhouse within the more desirable comfort zone for most agricultural crops. For animal shelters it is also important to keep the inside temperature low to reduce the stress levels of the animals.
    The use of NIR reflective films to prevent heat entry is by far the preferred option for reducing indoor temperatures in greenhouses, such as ventilation, evaporation, and whitening. In warm and sunny climates, the air is already quite warm, so that ventilation has only limited effectiveness. These climates are also usually quite dry, with a relative humidity of the ambient air falling below 10% around noon, and with water supplies that are scarce and salty. Evaporation of water usually involves a build-up of salts, which rapidly degrades the performance of most cooling systems. Whitening is cheap but is washed away by the rain and also reflects the useful part of the solar radiation spectrum.
    Therefore, there is a need for selective reduction of NIR transmittance, while transmitting as much of the visible light as possible.
    Indeed, for the photosynthesis reaction, and thus for plant growth, the plants need the radiation in the so-called "photosynthetic active radiation" or "photo-active radiation" (PAR) part of the sunlight, which is almost entirely within the range of the visible light, especially in the blue and red areas thereof.
    Greenhouse screens were developed for the purpose of sunlight reflection. These screens are usually placed against the ceilings of permanent greenhouses, usually made of glass, and can be opened and folded mechanically, usually through a complex system of pulleys and electric motors, usually in response to a change in weather conditions. The screens are usually woven and include strips made of metallized materials or of metal, usually aluminum, which provide for almost complete reflection. The screens generally further comprise strips of transparent polymer film, which allow part of the incident sunlight to pass through the photosynthesis reaction. A disadvantage of such screens is that part of the visible light, and therefore of the PAR radiation, is reflected.
    Moreover, greenhouses equipped with such screens represent a considerable investment for the grower. They are therefore especially affordable for the top range of crops. A much cheaper alternative can be offered by building the greenhouse with an agricultural polymer film. DE 2544245 describes a polymethyl methacrylate (PMMA) glazing material for buildings and vehicles with an interference pigment for shielding NIR radiation with a wavelength of 800-1500 nm. The pigment has a blue-red color and the light that passes through the glazing material has a yellow-green color. When applied to greenhouses, these panes would have the disadvantage that parts of the visible light that cannot be used by the plant are transmitted and converted to heat, while other parts, such as the red part that can be used by the plant, are reflected to become.
    A good agricultural film for greenhouses is characterized by a combination of a low transmittance, preferably a high reflection of the radiation in the near infrared wavelength range with a high transmittance of the radiation in the visible wavelength range, in particular of the PAR. US 2008/0292820 A1 describes in the paragraphs [0033-0034] IR radiation absorbing particles, comprising or made from lanthanum hexaboride, LaB6. Lanthan hexaboride is an effective NIR absorbent, with an absorption band centered at 900 nm. The IR radiation-absorbing nanoparticles can be dimensioned such that they do not have a major influence on the transmittance of visible light from the polymer binder layer. These nanoparticles can, for example, have any useful format, such as 1 to 100, 30 to 75 or 30 to 75 nm.
    Although the plants need the radiant energy in the so-called "Photoactive Radiation" (PAR) region, most crops still suffer when exposed directly to this part of the sunlight, and can even burn. Plants prefer to receive this radiation in a diffuse way. Therefore, there is a need for a film with a high reflection for NIR radiation in combination with a high permeability in a diffuse manner of the radiation in the visible region comprising the PAR radiation. WO 96/03029 discloses multi-layer films composed of alternating layers of polycarbonate (PC), with a refractive index nD = 1.587 and polymethyl methacrylate (PMMA) with a refractive index nD = 1.491, which is significantly different from that of PC. The films exhibit strong radiation reflection at a wavelength in a given wavelength band, which band can be shifted by the variation of the layer thickness, number of alternating layers and the choice of the polymer materials, as long as the difference in refractive index is greater than 0.03. Example 1 describes a film that is permeable below 700 nm and highly reflective in the 715-755 nm range. The film contains 100 micro layers with a thickness of 100 nm (for each PC layer) and 140 nm (each PMMA layer). In Example 3, the film selectively reflects green light around 540 nm, but is nevertheless permeable to other radiation, including in the NIR region. A disadvantage of the films proposed in WO 96/03029 is their complex production and selection of polymeric materials that are rather scarce. Another disadvantage of films whose radiation reflection is based on interference is that their performance depends on the angle of incidence of the radiation, in this case the position of the sun relative to the orientation of the film. These films therefore experience relatively limited acceptability in terms of domains where they can be used advantageously. WO 96/26070 describes a three-layer polymer film, wherein all three layers comprise an interference pigment with a transparent support material in the form of plates coated with one or more metal oxides or transparent plates with a refractive index of more than 1.7. Suitable carrier materials are layered silicates, natural or synthetic mica, glass plates and silicon dioxide plates, with natural mica being preferred. The metal oxides used include tin, titanium, chromium, zirconium, cerium, iron and tungsten oxide, preferably titanium dioxide. The interference color depends on the thickness of the metal oxide layer. A pigment with a green interference color is preferably used. If titanium oxide is used, a layer thickness of 120-160 nm will produce a green interference color. The coated mica particles that are used have a size of 5000-40,000 nm. A large part of the short wave infrared of the sunlight is reflected by the applied interference pigments. If a green interference pigment is used, the green part of the incident light that is not used by the plant is also reflected. US 2008/0292820 A1 also describes a multilayer polymer film that has a turbidity value of at least 10% and furthermore controls the sun-resistant properties by light diffusion. The reflective and transmissive properties of the multi-layer polymeric infrared reflective film are a function of the refractive indices of the respective layers which are referred to in the document as micro-layers. Metals can be incorporated into the film in various successive metallic layers, and can act as a Fabry-Perot interference filter to reflect the IR light and / or in particular the so-called near-infrared light. The film further comprises a scattering layer or surface. Explained is a multi-layer IR reflecting film with 224 alternating micro layers of PET and coPMMA, which was laminated to a Fasara San Marino or a Fasara Milano decorative film using an optically transparent adhesive. These films are even more complex compared to the films described above. They thus suffer the same disadvantage of limited acceptability in areas of application.
    The disadvantage of these interference-based technologies is that every application may need a movie specially developed for this purpose. A certain film can therefore only perform well in a very specific application. US 2008/0008832 A1 discloses deeply colored roofing granules that provide increased solar heat reflection. A highly reflective white pigmented inner layer is used as a substrate to reflect additional infrared radiation, while an outer colored coating with IR reflective interference plate pigments is used to provide desired colors. The light interference plate pigments are shown to exhibit a significantly higher solar heat reflection compared to the traditional inorganic color pigment, for example iron oxide red pigments. U.S. Pat. When incorporated into shingles, these grains have a higher Total Solar Reflection (TSR) compared to a standard product with the same visual appearance. JP2005330466A describes the use of 0.5 to 1.5 micrometer diameter IR reflecting particles, optionally TiO 2, coated with a resin film that is transparent to infrared radiation. The film coating can contain a substantially non-IR-absorbing pigment. Although these products have large particle diameters, they are not described as being made from large crystal size titanium dioxide as in the products of the present invention. As discussed in more detail below, the particle size and crystal size of a TiO2 particle are not necessarily the same.
    Therefore, there remains a need for a simple solution to provide polymer films with a high reflection coefficient for NIR radiation combined with a high transmittance of visible radiation, whereby the radiation in the visible region of the spectrum is transmitted in a diffuse manner. A simple solution is needed to be able to penetrate a number of very cost-sensitive applications such as greenhouses and animal enclosures.
    The present invention has for its object to remedy the problem described above or at least to mitigate it and / or to offer general improvements.
    DESCRIPTION OF THE INVENTION
    According to the invention, the use is provided as defined in one of the appended claims.
    The invention therefore provides the use of a finely divided material in a polymeric article for reducing the transmission of near infrared radiation and for allowing the transmission of visible light through the article, wherein the finely divided material is based on crystalline titanium dioxide, ie containing TiO2, in the anatase and / or the rutile crystal form, - the particles of the particulate material are coated with an organic and / or inorganic coating, - at least 20% by weight of the particles of the particulate material have a particle size of at least at least 400 nm and at most 1000 nm, as measured by X-Ray disk centrifuge, - at least 1.5% weight and at most 40% weight of the particles in the finely divided material have a particle size of less than 400 nm and at least 280 nm .
    In another embodiment, the invention provides for the use of a polymer composition comprising the particulate material as defined in the use of the particulate material of the present invention at a concentration of 500 ppm weight to 70% weight, with respect to total weight of the composition, in the production of a polymeric article for reducing the transmission of near infrared radiation and for allowing the transmission of visible light through the article.
    In yet another embodiment, the invention provides a polymer film composition that attains the finely divided material as defined in the use of the present invention in a concentration of 500 ppm by weight to 3.0% by weight, relative to the total weight of the composition. at least 1000 ppm, more preferably at least 1500 ppm, even more preferably at least 2000 ppm and even more preferably at least 2500 ppm by weight, and optionally at most 2.0% by weight, preferably at most 1.0% weight, more preferably at most 8000 ppm by weight, even more preferably at most 7000 ppm by weight, even more preferably at most 6000 ppm, preferably at most 5000 ppm, with respect to the total weight of the composition, in the production of a polymer film to reduce the transmission of near infrared radiation and to allow the transmission of visible light through the polymer film.
    We have found that the finely divided material according to the present invention is very suitable for the production of an agricultural film or fabric. The large amount of particles in the finely divided material with a particle size in the range of 400-1000 nm ensure a reduced transmittance of radiation in the NIR wavelength range of 700-2500 nm, preferably a high reflection of this NIR radiation as part of the sunlight, compared to the conventional TiO 2 based finely divided materials known in the art. The particle size of conventional rutile TiO 2 is from 250-400 nm, while conventional anatase TiO 2 has a particle size from 200 to 400 nm. This reduced permeability of NIR radiation entails a reduced influx of solar radiation energy in a construction made with a polymer film comprising the finely divided material, such as a greenhouse or an animal shed or shelter, so that the temperature of the atmosphere in the construction can be kept lower which leads to less water evaporation, to a lower stress level in plants, crops and / or animals that are kept under the polymer film or in the structure.
    We have further found that the particulate material can also be used in a silage film, namely a film used for outdoor storage of natural products such as hay and cuttings from other plants for animal green fodder, usually towards an upcoming winter period, which natural products are preferably undergo an anaerobic fermentation in order to increase the lactic acid content, thereby increasing the nutritional value of the natural products. We have found that the use of the finely divided material of the present invention also reduces the temperature of the silage film as well as that of the enclosure defined by the silage film. We have found that this reduction in temperature provides better oxygen barrier properties of the film and thus a more effective anaerobic environment in the enclosure thereby promoting the desired fermentation.
    We have further found that the relatively small amount of particles in the finely divided material with a particle size in the range of 280-400 nm cause increased transmittance of radiation in the visible light wavelength range of 400-700 nm, in particular in the PAR part of that area, such as the blue and red light areas of the visible part of the spectrum. This has the advantage that, in comparison with the conventional TiO2 finely divided materials known in the art, more of the part of the sunlight required for the photosynthesis reaction is transmitted through the film and reaches the crops growing in the greenhouse, whereby the growth of the crops as well as their usable yield can be improved. The increased transmittance of visible light is also beneficial to any animal life below the film that comprises the finely divided material. Animals in a shelter or shed with a film cover containing the finely divided material will feel more comfortable under increased exposure to daylight and thus experience a lower voltage level, compared to films with the usual TiO2 particulate materials known in the art. Also the bees in the greenhouse, which guarantee the pollination of the flowers of the crops that need to develop into useful products, can better perform their pollination task under increased exposure to daylight through a film lid containing the finely divided material, compared to the conventional Ti02 finely divided materials which are known in the art.
    We have further found that the minimum amount of particles in the particulate material with a particle size in the 280-400 nm range also provides a high degree of diffusion of the transmitted visible light from the solar light spectrum. Particularly useful in hot sunny climates, but also somewhat playing a role in more temperate climates, this has the advantage that the crops and / or animals under the film comprising the finely divided material are also less directly exposed to the visible part of the sunlight, such that they run a lower risk of overheating and even burning, so that the voltage level is again reduced.
    We have further found that the particulate material in the use according to the present invention also exhibits a reduced transmittance of radiation in the UV part of the solar spectrum, which ranges from about 200 to about 380 nm. When used in the film at a relatively high dosage of the particulate material, such as silage film, this can further improve the oxygen barrier properties of the film, and also discourage insects and flies from getting under the silage film. When used in the film with relatively low dosage of the finely divided material, such as with agricultural film for greenhouse construction, it still transmits UV light with a wavelength of about 340 nm, a wavelength that is not noticed by the human eye, but which is captured by the bees. This is conducive to the comfort level of the bees under the film with the finely divided material, such that these insects feel better and are more active in carrying out their pollination task.
    We have also found that the coating layer on the particles of the particulate material can provide reduced photocatalytic activity of the particulate material to the polymeric matrix in which it is embedded. Titanium dioxide is a strong UV adsorbent and after such exposure the absorbed energy is released by the release of radicals. These radicals can degrade most polymer matrices. Providing a physical coating, a kind of physical shell around the titanium dioxide, slows the migration of the radicals into the matrix, for example by increasing the path length before they can reach the matrix, where the time to reach the matrix can be considerable compared to the half-life of the radical itself, such that most radicals may have disappeared before they are able to reach the polymer matrix.
    We have further found that the coating layer can further provide improved dispersibility of the particles of the particulate material and less yellowing and / or better opacity of the article with the particulate material.
    DETAILED DESCRIPTION
    The present invention is described below with respect to certain embodiments and with reference to certain drawings, but the invention is not limited thereto but only by the claims. The drawings described are only schematic and are not limitative. In the drawings, the size of certain elements may be exaggerated and not drawn to scale for illustrative purposes. The dimensions and the relative dimensions do not necessarily correspond to actual reductions in the practice of the invention.
    In addition, the terms first, second, third and the like are used in the description and in the claims to distinguish between similar elements and not necessarily for describing a sequential or chronological order. The terms are interchangeable under appropriate conditions and the embodiments of the invention may function in sequences other than described or illustrated herein.
    In addition, the terms top, bottom, top, bottom and the like in the description and claims are used for descriptive purposes and not necessarily for describing relative positions. The terms used as such are interchangeable under appropriate conditions and the embodiments of the invention described herein may function in orientations other than those described or illustrated herein.
    The term "comprising" used in the claims is not to be construed as being limited to the means listed thereafter; it does not exclude other elements or steps. It is to be interpreted as indicating the presence of the aforementioned characteristics, integers, steps or components as intended, but does not exclude the presence or addition of one or more other characteristics, integers, steps or components, or groups thereof. Thus, the scope of the expression "a device comprising means A and B" should not be limited to devices consisting only of components A and B. It means that with regard to the present invention, the only relevant parts of the device A and B to be. Accordingly, the terms "comprising" and "including" include the more restrictive terms "essentially consisting of" and "consisting of".
    In the context of the present invention, the particle size is defined as the diameter of the smallest sphere that completely encompasses the particle.
    In the context of the present invention, light, and in particular visible light, is defined as a form of radiant energy at one or more wavelengths that can be absorbed, reflected and / or transmitted upon hitting an object. In general, a combination of these three phenomena takes place.
    In the context of the present invention, indicated concentrations are expressed in units of weight unless otherwise specified. The term "average" refers to the statistical average unless otherwise specified. Average size refers to the "geometric volume average size" unless otherwise stated.
    Although the average particle size is averaged on a weight basis, the average crystal size is given on a number basis, because the analytical techniques used provide their results on this basis unless otherwise stated.
    In one embodiment of the present invention, the use further consists of diffusing at least a part of the photoactive radiation of the visible light, and preferably the majority of the visible light, preferably for increasing the percentage of turbidity through the article, more preferably wherein the turbidity is measured according to ASTM D1003. This has the advantage that everything that is protected from the sun by the polymer article according to the application of the present invention is less exposed to the direct influence of the visible part of the sunlight, so that local overheating is reduced. This has the advantage for plants and crops for a reduced risk of local burning, to animals for a reduced risk of local overheating, and increases comfort and thereby reduces the stress level of living things under such shield.
    In an embodiment of the present invention, at least a portion of the UV light spectrum, preferably UV light, is observed by bees, transmitted through the polymer article, preferably in a diffuse manner. It has been found that the bees need a specific spectrum of the UV light, estimated at approximately 340 nm, to improve the pollination of the plants in the greenhouses.
    In an embodiment of the present invention, the particle size distribution of the particles of the particulate material shows a significant peak in the range of 400-1000 nm, preferably at most 900 nm, more preferably at most 800 nm, even more preferably at most at 700 nm, preferably at most 650 nm, more preferably at most 600 nm, also preferably at least 450 nm, more preferably at least 500 nm and also preferably the particle size distribution of the particles of the particulate material is unimodal and its single peak in the specified range. This has the advantage of further reducing the transmittance of the radiation in the NIR region of the solar spectrum and / or further enhancing the effectiveness of the finely divided material in achieving the technical effects that are the object of the use according to the present invention .
    In an embodiment of the present invention, the particles of the particulate material have an average particle size of at least 400 nm and at most 1200 nm, preferably more than 400 nm, more preferably at least 450 nm, even more preferably at least 500 nm, preferably at least 600 nm, more preferably at least 700 nm, even more preferably at least 800 nm, and optionally at most 1100 nm, preferably at most 1000 nm, more preferably at most 900 nm, with more preferably at most 800 nm, even more preferably at most 700 nm, preferably at most 650 nm, more preferably at most 600 nm and even more preferably at most 550 nm. This has the advantage of further reducing the transmittance of the radiation in the NIR region of the solar spectrum and / or further enhancing the effectiveness of the finely divided material in achieving the technical effects that are the object of the use according to the present invention .
    In an embodiment of the present invention, at least 30% weight of the particles of the particulate material have a particle size of at least 400 nm and at most 1000 nm, preferably at least 40%, more preferably at least 50%, with more preferably at least 60%, even more preferably at least 70%, preferably at least 80%, more preferably at least 90% weight of the particles of the finely divided material with a particle size in the specified range, and preferably this particle size range being at most 900 nm, more preferably at most 800 nm. This has the advantage of further reducing the permeability of the radiation in the NIR region of the solar spectrum and / or further promoting the effectiveness of the particulate material in achieving the technical effects that are the object of the use according to the present invention invention.
    In an embodiment of the present invention, at least 60% weight of the particles of the finely divided material have a particle size of at most 1000 nm, preferably at least 70% weight, more preferably at least 80%, even more preferably at least 90% and even more preferably at least 95% weight of the particles of the finely divided material with a particle size of at most 1000 nm. This has the advantage of further reducing the permeability of the radiation in the NIR region of the solar spectrum and / or further promoting the effectiveness of the particulate material in achieving the technical effects that are the object of the use according to the present invention invention.
    In an embodiment of the present invention, at least 2.0% weight of the particles have a particle size of less than 400 nm and at least 280 nm, preferably at least 3.0% weight, more preferably at least 4.0% weight , even more preferably at least 5.0% weight, preferably at least 7.0% weight, more preferably at least 10% weight, even more preferably at least 15% weight of the particles with a particle size in the specified range, and optionally at most 35% by weight, preferably at most 30% by weight, more preferably at most 25% by weight, preferably at most 20% by weight, more preferably at most 15% by weight and even more preferably at most at most 10% weight of the particles with a particle size in the specified 280-400 nm. This has the advantage that the diffusion of the visible light from the solar radiation spectrum is increased, while maintaining a high transmittance of the visible light, in particular the PAR part thereof, which is necessary for photosynthesis reaction in plants.
    In an embodiment of the present invention, the particles of the particulate material were treated prior to use to selectively remove certain size fractions, preferably to remove particles with a particle size of at least 5000 nm, preferably at least 3000 nm, preferably the particles are removed by a centrifuge treatment. This has the advantage that less effective particles in the finely divided material are reduced and / or avoided, so that the effectiveness of the finely divided material in achieving its desired technical effect is enhanced.
    In an embodiment of the present invention, the titanium dioxide has a TiO 2 content of at least 80% by weight, preferably at least 85% by weight, more preferably at least 90% by weight, preferably at least 92% by weight, more preferably at least least 93% weight. This has the advantage that the finely divided material is more efficient in achieving the desired effects.
    In an embodiment of the present invention, the polymer article contains at most 100 ppm by weight of Fe 2 O 3, preferably at most 80 ppm, more preferably at most 60 ppm, even more preferably 40 ppm, even more preferably at most 20 ppm, at preferably at most 10 ppm, more preferably at most 5 ppm, even more preferably at most 1 ppm to prevent premature degradation of the polymer film.
    In an embodiment of the present invention, at least 50% by weight of the TiO2 crystals are in the rutile crystal form, preferably at least 60%, more preferably at least 70%, even more preferably at least 80%, preferably at least at least 90%, more preferably at least 95%, even more preferably at least 99%, even more preferably at least 99.5% by weight. This has the advantage that the rutile shape offers a higher refractive index, which results in more effective particles of the finely divided material in realizing the desired effects. An additional advantage is that less finely divided material is required to achieve a desired level of impediment to the permeability of the NIR radiation, in combination with a desired permeability of visible light. With optimization, this has the advantage that the effects achieved are stronger.
    In an embodiment of the present invention, titanium dioxide has an average crystal size of at least 400 nm and at most 1200 nm, preferably more than 400 nm, more preferably at least 450 nm, even more preferably at least 500 nm, preferably at least at least 600 nm, more preferably at least 700 nm, even more preferably at least 800 nm, and optionally at most 1100 nm, preferably at most 1000 nm, more preferably at most 900 nm, even more preferably at most 800 nm nm, even more preferably at most 700 nm, preferably at most 650 nm, more preferably at most 600 nm, even more preferably at most 550 nm. The applicants have found that this feature has the advantage that it further reduces the transmittance of the radiation in the NIR region of the solar spectrum and increases the diffusion of the visible light that is transmitted and / or further enhances the effectiveness of the particulate material in achieving the technical effects that are the object of the use according to the present invention
    In an embodiment of the present invention, the titanium dioxide is substantially white, the finely divided material preferably having a brightness value L * in the CIE L * a * b * color space of more than 80, preferably at least 85, more preferably at least at least 90, even more preferably at least 95, with an absolute value of a * of less than 5 and an absolute value of b * of less than 5. The applicants have found that in combination with the amount of particles with a particle size smaller than 400 nm, that this function brings the effect of increased diffusion of the visible light transmitted through the object over the full range of the visible light, so that the risk of local overheating on everything protected by the object of incident sunlight is more effectively reduced. The CIE L * a * b * color space describes all colors visible to the human eye and should be used as a device-independent model as a reference. The three coordinates of CIELAB represent the brightness of the color (L * = 0 yields black and L * = 100 gives diffuse white, high gloss white can be even higher), which is expressed in the position between red / magenta and green (a *, negative values indicate green while a positive value indicates magenta) and its position between yellow and blue (b *, negative values indicate blue and positive values indicate yellow). An L * value of 80 indicates a light whitish color, while a value of 95 indicates a very light color. A lighter color shows a lower heat absorption compared to a more dark color. The film will therefore, thanks to this function, absorb less heat and can therefore have a longer lifespan because the aging process is delayed.
    In one embodiment of the present invention, the coating layer represents 0.50 to 20% by weight with respect to the total weight of the particles of the particulate material, preferably at most 15% by weight, more preferably at most 10% by weight, more preferably at most 5% weight, even more preferably at most 3% weight with respect to the total weight of the particles of the particulate material. We have found that these levels are effective in achieving the desired effect of reduced photocatalytic activity, as well as the other benefits of the coating. The effectiveness of the coating can depend on the choice of material. A coating layer comprising SiO 2 can therefore be more efficient compared to a layer comprising a similar concentration of Al 2 O 3, and can therefore be used thinner and represent a lower weight compared to the total weight of particles of the particulate material.
    In an embodiment of the present invention, the coating layer comprises one or more oxide materials. We have found that these materials are particularly effective in reducing the photocatalytic activity of the particles of the particulate material.
    In an embodiment of the present invention, the oxide material is an oxide and / or hydrated oxide, for example a hydroxide, of one or more elements that are, with reference to the IUPAC Periodic Table of June 22, 2007: - Group 4 and 12 transition metals selected from Ti, Zr and Zn and / or group 13 to 15 p-block elements selected from Si, Al, P and Sn and / or lanthanides, the material preferably being selected from Al 2 O 3, SiO 2, ZrO 2, CeO 2, P 2 O 5 , and combinations thereof, more preferably the oxide comprising P 2 O 5, more preferably in combination with Al 2 O 3 and / or SiO 2. We have found that these compounds are particularly effective in reducing the photocatalytic activity of the particles of the particulate material.
    In an embodiment of the present invention, the particles of the particulate material were subjected to an organic surface treatment, preferably with a compound selected from a polyol, an amine, an alkanolamine, a silane and a silane derivative, such as, for example, triethoxyoctylsilane, a silicone derivative, trimethylolpropane , pentaerythritol, triethanolamine, alkyl phosphonic acid, n-octyl phosphonic acid, trimethylolethane and mixtures thereof. We have found that such a treatment improves the dispersibility of the particles of the finely divided material in the surrounding matrix.
    In an embodiment of the present invention, the article is a polymer film, preferably a polyolefin, preferably a film based on a polymer with ethylene as at least one monomer, preferably a film based on a material selected from the list consisting of polyethylene, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), metallocene linear low density polyethylene (mLLDPE), ethylene vinyl acetate copolymer, ethylene butenyl copolymer, ethylene vinyl alcohol copolymer (EVOH), polyethylene terephthalate copolymer (PET) polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP) and mixtures thereof. We have found that these polymers are particularly suitable as a basis for agricultural film or leaves.
    In an embodiment of the present invention, the polymer of the article further comprises at least one of the additives known in the art, such as at least one additive selected from the list consisting of a UV absorber, a near-IR absorber, a far-IR absorber, a near-IR reflector, a far-IR reflector, a stabilizer, an antioxidant, a processing aid, an antistatic agent, a coloring agent, an inorganic salt, a pearl-gloss pigment, an NIR-reflecting agent, a anti-fogging agent, a filler, an anti-blocking agent, a light stabilizer, a lubricant, a UV-blocker, a diffusing agent and combinations thereof. It has been found that such additives provide additional properties to the article and / or enhance the effects offered by the present invention.
    In an embodiment of the use of the polymer composition of the present invention, the polymer composition comprises the finely divided material in a concentration of 500 ppm weight to 70% weight, relative to the total weight of the composition. We have found that these levels are effective in achieving the desired effects. Depending on the concentration, the degree of completion of the various effects can be further influenced. A higher concentration thus leads to a more effective impediment to the transmission of the NIR radiation, as well as a higher turbidity and a higher degree of diffusion of the transmitted visible light, while on the other hand a lower concentration can increase the transmission of the visible light in in particular the PAR part thereof. In warm and sunny climates it will therefore be useful to work with a higher concentration of the particulate material according to the present invention, while in a more temperate climate a lower concentration of particulate material may be more easily acceptable and even desirable due to the higher PAR transmission and the associated benefits for plant growth.
    In an embodiment of the present invention, the polymer composition is a masterbatch composition, the masterbatch composition preferably being based on a polyolefin, more preferably on a polymer with ethylene as at least one monomer, more preferably on a polymer selected from the list consisting of polyethylene, high density polyethylene, low density polyethylene, linear low density polyethylene, metallocene linear low density polyethylene (mLLDPE), ethylene vinyl acetate copolymer, ethylene butenyl copolymer, ethylene vinyl alcohol copolymer, copolymer polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA) , polypropylene (PP), and mixtures thereof.
    In an embodiment of the present invention, the masterbatch composition comprises from 2.0% weight to 70% weight of the particulate material, preferably at most 60% by weight, more preferably at most 50% by weight, even more preferably at most 40% weight, even more preferably at most 30% weight, preferably at most 25% weight, more preferably at most 20% weight, even more preferably at most 15% weighted and even more preferably at most 10% weight at preferably at most 5.0% by weight, more preferably at most 3.0% by weight of the finely divided material. We have found that these concentrations provide a masterbatch that is very suitable for further downstream use, such as in the production of an agricultural polymer film.
    In an embodiment of using the polymer film composition of the present invention, the polymer film composition comprises the finely divided material in a concentration of 500 ppm by weight to 3.0% by weight, with respect to the total weight of the composition, preferably at least 1000 ppm, more preferably at least 1500 ppm, even more preferably at least 2000 ppm and even more preferably at least 2500 ppm by weight, and optionally at most 2.0% by weight, preferably at most 1.0% by weight, more preferably at most 8000 ppm by weight, even more preferably at most 7000 ppm, even more preferably at most 6000 ppm, preferably at most 5000 ppm by weight, with respect to the total weight of the composition, in the production of a polymer film for reducing the transmission of near infrared radiation and for increasing the transmission of visible light through the polymer film, preferably also for the far increased diffusion of visible light through the polymer film. We have found that these levels are effective in achieving the desired effects. Depending on the concentration level, the degree of completion of the different effects can be further influenced. A higher concentration thus leads to a more effective obstruction of the permeability of the NIR radiation, as well as to a higher turbidity and a higher degree of diffusion of the visible light emitted, while on the other hand a lower concentration level can increase the permeability of the visible light in in particular the PAR part thereof. In warm and sunny climates, it will therefore be useful to work according to the present invention with a higher concentration of the particulate material, while in the more temperate climate a lower concentration of particulate material can be easily acceptable and even desirable because of the higher PAR permeability and the accompanying benefits for plant growth and animal comfort.
    In an embodiment of the present invention, the polymer film composition is based on a polyolefin, more preferably on an ethylene polymer and at least one monomer, more preferably a polymer selected from the list consisting of polyethylene, high density polyethylene, low density polyethylene, linear low density polyethylene, metallocene linear low density polyethylene (mLLDPE), ethylene vinyl acetate copolymer, ethylene butenyl acetate copolymer, ethylene vinyl alcohol copolymer, polyethylene terephthalate copolymer, polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), and mixtures thereof.
    In an embodiment of the present invention, the polymer film has at least one layer made of the polymer film composition.
    In one embodiment, the polymer film comprising at least one layer made of the polymer film composition of the present invention further comprises at least one of the additives known in the art, such as at least one additive selected from the list consisting of a UV absorber, a near-IR absorber, a far-IR absorber, a near-IR reflector, a far-IR reflector, a stabilizer, an antioxidant, a processing aid, an antistatic agent, a colorant, an inorganic salt, a pearl-gloss pigment, an NIR-reflecting substance, a veil, an filler, an anti-contacting agent, a light stabilizer, a lubricant, a UV-blocker, a diffusing agent and combinations thereof.
    In an embodiment of the present invention, the at least one layer in the polymer film is a top layer of a multi-layer film, which further comprises at least one additional film layer, optionally at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or even 15 extra film layers. With correct installation, namely in the right direction with respect to the incident energy radiation, the top layer is therefore not only shielding for the underlying objects and / or animals, but also for the underlying layers of the entire film, which is a great advantage compared to of the expected lifetime of the film, usually regardless of the application.
    In an embodiment of the present invention, the polymer film has a transmittance in the visible light region, defined as the 380-700 nm wavelength region of at least 30%, preferably at least 40%, more preferably at least 50%, preferably at least 55%, more preferably at least 60%, even more preferably at least 65%.
    In an embodiment of the present invention, the polymer film has a transmittance in the photoactive region, defined as the wavelength region of 400-700 nm of at least 30%, preferably at least 40%, more preferably at least 50%, at preferably at least 55%, more preferably at least 60%, even more preferably at least 65%.
    In an embodiment of the present invention, the polymer film has a transmittance of the near infrared radiation in the wavelength range from above 700 to 2500 nm of at most 90%, preferably at most 85%, more preferably at most 80%, with still more more preferably at most 75%, preferably at most 70%, more preferably at most 60%, even more preferably at most 50%, even more preferably at most 40%. Applicants have found that the film of the present invention is therefore more efficient in keeping out the desired effects of the NIR radiation.
    In an embodiment of the present invention, the polymer film has a turbidity of at least 20%, preferably at least 25%, more preferably at least 30%, even more preferably at least 35%, preferably at least 40%, more preferably at least 50%, even more preferably at least 60%, even more preferably at least 70%, preferably at least 80%, more preferably at least 90%, wherein the turbidity is preferably measured according to ASTM D1003.
    Methods suitable for preparing the titanium dioxide-based particulate material of the present invention include, but are not limited to, the sulfate process, the chloride process, the fluoride process, the hydrothermal process, the aerosol process, and the leaching process. Additional information for engaging the present invention can be found in US2013 / 0048925, and the documents referred to.
    The titanium dioxide itself can comprise one or more dopants which can be incorporated during preparation by known methods. The dopants may include, but are not limited to, calcium, magnesium, sodium, nickel, aluminum, antimony, phosphorus, and / or cesium. The titanium dioxide particles can be treated as known in the art with a coating agent to form coated titanium dioxide or coated doped titanium dioxide. For example, the first finely divided material can be dispersed in water together with the coating agent. The coating agent can be an inorganic oxide or aqueous oxide such as Al 2 O 3, SiO 2, ZrO 2, P 2 O 5, sodium silicate, aluminum chloride, etc. After coating, the first finely divided material can be washed and dried before being ground, for example in an air jet mill or micronizer, to to separate particles that are stuck together by the coating. In this milling phase, an organic surface treatment with polyols, amines, alkyl phosphonic acids and silicone derivatives can also be used if desired. Further details can be found in US 2013/0209717, and the documents referred to.
    ANALYTICAL METHODS
    CRYSTAL SIZE
    The average crystal size can preferably be determined by transmission electron microscopy (TEM) on a rubbed sample with image analysis of the resulting photo (for example, using a Quantimet 570 Image Analyzer). This can be confirmed with reference to the NANOSPHERE ™ latex size standard 3200 from NIST with a certified size of 199 +/- 6 nm.
    PARTICLE SIZE
    The average particle size can preferably be determined by x-ray sedimentation. To measure particle size in this regard, the product is subjected to high shear mixing, in the presence of a suitable dispersant, to disperse the particles without pulverization. The particle size distribution is measured with a Brookhaven XDC X-ray disk centrifuge. Average particle size and particle size distribution, by weight, can be included.
    ASTM 1003D
    The absorption and scattering behavior of a transparent specimen determines how much light will be transmitted and how objects will be displayed through the transparent product. The objective measurement of transparency can be made using a turbidity meter (for example using a BYK Gardner Haze-gard dual) according to the following principle: a light beam hits the sample and enters an integrating sphere. The inner surface of the sphere is uniformly covered with a matte white material to allow diffusion. A detector in the sphere measures total permeability and turbidity of permeability.
    A ring sensor then detects the narrow angle scattering light (brightness).
    PERMISSIBILITY AND REFLECTION
    To measure transmittance and / or reflection, the amount of transmitted light in the UV, visible and near-infrared region is preferably measured with a UV-VIS-NIR spectrophotometer, and we prefer a Perkin Elmer Lambda 950 equipped with a large integrated sphere PELA 1000 of 150 mm. This makes it possible to measure reflective, diffuse and reflective materials, as well as the total permeability of transparent and semi-opaque material. The amount of light emitted through a sample can be detected with this device in a wavelength range from 190 nm to 3300 nm.
    Turbidity
    Turbidity is preferably measured according to ASTM D1003, and is defined therein as the percentage of light transmitted through an object that is scattered more than 2.5 ° away from the direction of the incident beam. Materials with turbidity values greater than 30% are considered diffusive. Testing is preferably performed with a spectrophotometer, according to procedure B.
    Having now fully described the invention, it will be apparent to those skilled in the art that the invention can be implemented within a wide range of parameters within what is claimed without departing from the scope of the invention as defined by the claims.
    权利要求:
    Claims (15)
    [1]
    CONCLUSIONS
    Use of a finely divided material in a polymeric article for reducing transmittance of near infrared radiation and for allowing visible light to pass through the article, the finely divided material being based on crystalline titanium dioxide, ie containing TiO 2 , in the anatase and / or rutile crystal form, the particles of the particulate material are coated with an organic and / or inorganic coating layer, at least 20% by weight of the particles of the particulate material have a particle size of at least 400 nm and at least 1000 nm maximum, at least 1.5% weight and at most 40% weight of the particles in the particulate material have a particle size of less than 400 nm and at least 280 nm.
    [2]
    The use according to claim 1 for diffusing at least a portion of the photoactive radiation from the visible light.
    [3]
    The use according to claim 1 or 2 for transmitting at least a portion of the UV light spectrum.
    [4]
    The use according to any one of the preceding claims, wherein the particle size distribution of the particles of the particulate material exhibits an important peak in the range of 400-1000 nm, and preferably the particle size distribution of the particles of the particulate material is unimodal and the only peak is in the specified range.
    [5]
    The use according to any one of the preceding claims, wherein the particles of the finely divided material have an average particle size of at least 400 nm and at most 1200 nm.
    [6]
    The use according to any one of the preceding claims wherein at least 30% weight of the particles of the finely divided material have a particle size of at least 400 nm and at most 1000 nm.
    [7]
    The use according to any one of the preceding claims wherein at least 60% weight of the particles of the finely divided material have a particle size of at most 1000 nm.
    [8]
    The use according to any one of the preceding claims wherein at least 2.0% weight of the particles have a particle size that is smaller than 400 nm and at least 280 nm.
    [9]
    The use according to any one of the preceding claims, wherein the titanium dioxide has an average crystal size of at least 400 nm and at most 1200 nm.
    [10]
    The use according to any one of the preceding claims, wherein the coating layer comprises one or more oxide materials.
    [11]
    The use according to any one of the preceding claims, wherein the particles of the finely divided material have undergone an organic surface treatment.
    [12]
    The use of a polymer composition containing the finely divided material as defined in the use according to any one of the preceding claims in a concentration of 500 ppm by weight to at most 70% weight, with respect to the total weight of the composition, in the production of a polymeric article for reducing transmission of near infrared radiation and for increasing transmission of visible light through the article.
    [13]
    The use according to the preceding claim, wherein the polymer composition is a masterbatch composition.
    [14]
    The use of a polymer film composition containing the finely divided material as defined in the use according to any one of the preceding claims in a concentration of 500 ppm by weight to at most 3.0% by weight, with respect to the total weight of the composition, in the production of a polymer film for reducing the transmission of near infrared radiation and for increasing the transmission of visible light through the polymer film.
    [15]
    The use of claim 14 wherein the polymer film has at least one layer made from the polymer film composition.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    EP13188310|2013-10-11|
    EP131883100|2013-10-11|
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