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    • 专利摘要:
    In a master batch containing a heat ray shielding component used to prepare a heat ray shielding transparent resin molded body, the master batch includes thermoplastic resin and hexaboride represented by XB 6 as main components (where X is La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca). The hexaboride, which is a heat ray shielding component, is contained in an amount of 0.01 to 20 parts by weight or less based on 100 parts by weight of the thermoplastic resin. The use of such a master batch enables simple manufacture of a heat ray shielding transparent resin molded article having a high visible ray transmitting ability and a high heat ray shielding function without depending on an expensive physical film forming method or the like.
    公开号:KR20040012567A
    申请号:KR1020030053025
    申请日:2003-07-31
    公开日:2004-02-11
    发明作者:후지타겐이치；아다치겐지
    申请人:스미토모 긴조쿠 고잔 가부시키가이샤；
    IPC主号:
    专利说明:

    MASTER BATCH CONTAINING HEAT RADIATION SHIELDING COMPONENT, AND HEAT RADIATION SHIELDING TRANSPARENT RESIN FORM AND HEAT RADIATION SHIELDING TRANSPARENT LAMINATE FOR WHICH THE MASTER BATCH HAS BEEN USED}
    [1] The present invention relates to a master batch used for the manufacture of heat shields (extrusion or molding) widely used in window materials, arcades, perforated domes, carports, etc. used in roofing and wall materials of buildings, automobiles, trams, aircraft, etc. will be. In particular, the present invention relates to a master batch containing a heat ray shielding component, which is used in the production of a transparent resin molded article having good visible light transmittance and an excellent heat ray shielding function, and further comprising a heat ray shielding transparent resin molded body and a heat ray to which the master batch is applied. It relates to a shielding transparent laminate.
    [2] In addition to visible light, there are ultraviolet rays and infrared rays in the sun rays coming through openings such as windows and doors of various buildings and vehicles. In the infrared rays contained in such solar rays, near-infrared rays having a wavelength of 800 to 2500 nm are called hot rays, and are introduced from the openings to cause an increase in the room temperature. In order to avoid such a temperature rise, in recent years, in the field of various buildings and window materials for automobiles, there is a rapid demand for a heat ray shielding molded article capable of blocking the heat rays while sufficiently absorbing visible light and suppressing the temperature rise in the room while maintaining the brightness. Is increasing. Many patents concerning such a heat shielding molded object have been proposed.
    [3] For example, a heat ray shielding sheet is proposed in which a heat ray reflecting film comprising a transparent resin film in which a metal or a metal oxide is attached to a vacuum is bonded to a transparent molded body such as a glass sheet, an acrylic sheet or a polycarbonate sheet (Japanese Patent Laid-Open). 61-277437, Japanese Patent Laid-Open No. 10-146919, Japanese Patent Laid-Open No. 2001-179887, etc.). However, such a heat-ray reflecting film itself is very expensive and requires a complicated process with an adhesion step or the like, which in turn is expensive. In addition, the heat ray shielding sheet has a drawback that the adhesiveness between the transparent molded body and the reflective film is not good and the film is peeled off due to change over time.
    [4] Many heat ray shielding sheets have also been proposed in which a metal or metal oxide is directly vacuum-deposited on the surface of a transparent molded body. However, these require a device that requires atmosphere control with high vacuum and high precision in manufacturing such a heat ray shielding sheet, which has a problem that the mass productivity is poor and the versatility becomes poor.
    [5] In addition, a heat ray shielding is also obtained by kneading an organic infrared absorber represented by, for example, a phthalocyanine compound or an anthraquinone compound into a thermoplastic transparent resin such as polyethylene terephthalate resin, polycarbonate resin, acrylic resin, polyethylene resin or polystyrene resin. Sheets and films for using them are also proposed. (See Japanese Patent Laid-Open No. 6-256541, Japanese Patent Laid-Open No. 6-264050, etc.). However, in order to sufficiently shield the hot wire, a large amount of infrared absorber must be blended. Mixing it in large amounts leaves a problem that can degrade the ability to transmit visible light. In addition, since organic compounds are used, their use in windows, such as buildings, vehicles, and the like, which are always directly exposed to direct sunlight, involves difficulties in weather resistance and cannot necessarily be said to be appropriate.
    [6] For example, a heat ray shielding sheet in which inorganic particles such as titanium oxide or mica coated with titanium oxide having heat ray reflecting ability are kneaded in a transparent resin such as an acrylic resin or a polycarbonate resin is further proposed. (See, for example, Japanese Patent Application Laid-Open No. 2-173060, Japanese Patent Laid-Open Publication No. 5-78544, etc.) However, this sheet requires the addition of a large amount of heat ray reflecting particles in order to improve the heat ray shielding ability, and thus heat ray reflection mixed. As the amount of particles increases, the visible light transmittance may be lowered. On the other hand, the addition of heat ray reflecting particles in a small amount can lead to an improvement in the visible light transmittance but the heat ray shielding ability can be lowered. Therefore, there is a problem that it is difficult to satisfy the heat ray shielding ability and the visible light transmitting ability at the same time. In addition, incorporating a large amount of hot-ray reflecting particles involves a problem that from the viewpoint of strength, the physical properties, in particular, impact resistance and toughness of the transparent resin molded body may be lowered.
    [7] Under such technical background, the inventors have already proposed a heat ray shielding coating liquid containing hexafluoride microparticles in various binders, and a heat ray shielding film obtained by applying the coating liquid to various types of molded bodies and subsequently drying (for example, For example, see Japanese Patent Application Laid-Open Nos. 11-181336, 2000-96034, and 2000-169765.
    [8] However, none of these proposals have been developed with respect to the master batches used to produce the heat shield shaped bodies.
    [9] Summary of the Invention
    [10] Therefore, the present inventors have studied variously by paying attention to the hexaboride having a large amount of free electrons. As a result, the inventors have succeeded in constructing a master batch containing a heat ray shielding component obtained by ultrafine atomizing a hexaboride by thermoplastic mixing means and dispersing the ultrafine particles in a thermoplastic resin.
    [11] They can also dilute and mix the master batch containing the heat shield component with the thermoplastic molding material and the resulting mixture can be prepared by any known method such as extrusion, injection molding or compression molding, such as sheet, film or spherical. It has been found that it can be molded into a desired shape, which makes it possible to produce hot-shielding transparent resin molded bodies and hot-shielding transparent laminates having a maximum transmittance in the visible light region and also showing strong absorption in the infrared region. It was.
    [12] More specifically, an object of the present invention is to provide a master batch containing a heat ray shielding component, and by using it (master batch), various types of heat ray shielding, having a high heat ray shielding function, while maintaining excellent visible light transmittance. The transparent resin molded article can be produced by a simple method without using an expensive physical film forming method.
    [13] Still another object of the present invention is to provide a heat shield transparent resin molded article and a heat shield transparent laminate, and for that, a master batch containing a heat shield component is used.
    [14] That is, the master batch containing the heat ray shielding component, which is used to prepare the heat ray shielding transparent resin molded body, contains a thermoplastic resin and a hexaboride represented by XB 6 as main components (where X is La, Ce, Pr, At least one selected from Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, and Ca). It is contained in an amount of at least 0.01 parts by weight or less than 20 parts by weight.
    [15] The heat ray shielding transparent resin molded body of the present invention is diluted with the master batch containing the heat ray shielding component with a thermoplastic resin molded material of the same kind as the thermoplastic resin of the master batch, or with a heterogeneous thermoplastic resin molded material having compatibility with the master batch. It is characterized by being obtained by mixing and molding (extrusion or molding) the resultant mixture into a predetermined form.
    [16] The heat ray shield transparent laminate of the present invention is also characterized by being obtained by laminating the above heat ray shield transparent resin molded body on another transparent molded body.
    [17] Description of Preferred Embodiments
    [18] The invention is described in detail below.
    [19] The master batch of the present invention is used for producing a heat ray shielding transparent resin molded article, and contains, as main components, a thermoplastic resin and a hexaboride which is a heat ray shielding component.
    [20] The master batch containing the heat ray shielding component according to the present invention is prepared by uniformly dispersing the hexaboride XB 6 fine particles in the thermoplastic resin serving as the heat ray shielding component. The hexaborate used in the present invention is typically lanthanum hexafluoride (LaB 6 ), cerium hexaborate (CeB 6 ), praseodymium hexafluoride (PrB 6 ), neodymium hexafluoride (NdB 6 ), hexaborate gadolinium (GdB 6), 6 boronated terbium (TbB 6), 6 boronated dysprosium (DyB 6), 6 boronated holmium (HoB 6), 6 boron white cerium (YB 6), 6 boronated samarium (SmB 6) , Europium hexafluoride (EuB 6 ), erbium hexafluoride (ErB 6 ), tulium borohydride (TmB 6 ), ytterbium hexaboride (YbB 6 ), lutetium hexafluoride (LuB 6 ), hexaborate Lanthanum-cerium [(La, Ce) B 6 ], strontium hexaboride (SrB 6 ) and calcium hexaborate (CaB 6 ).
    [21] As the hexafluoride fine particles used in the present invention, it is preferable that their surfaces do not oxidize. In many cases, however, they are usually slightly oxidized, and it is also somewhat unavoidable that surface oxidation occurs at the stage of dispersion of the fine particles. However, even in such a case, there is no change in the effectiveness of exhibiting the heat ray shielding effect. Thus, it is also possible to use surface oxidized hexaboride fine particles.
    [22] These hexaboride fine particles also have a greater heat shielding effect as they have higher integrity as crystals. However, those having low crystallinity and forming broad diffraction peaks in X-ray diffraction can also be used in the present invention, as long as the basic bonds inside the fine particles constitute a bond between each metal and boron, as long as they have a heat ray shielding effect. Because it can represent.
    [23] These hexaboride particles are also in the form of a powder having a color such as gray black, brown black or green black. However, if they are made to have a particle size sufficiently smaller than the visible light wavelength, and they are in a dispersed state in the heat ray shielding transparent resin molded body, heat ray permeability comes out of them from the heat ray shielding transparent resin molded body. Nevertheless, infrared shielding ability can be sufficiently obtained. The reason for it has not been explained in detail. Since there is a large amount of free electrons in these particles, and the absorption energy of the indirect transition between the bands by the free electrons inside and on the surface of the particles is near near infrared from the visible, the heat ray of this wavelength region is thus selective. It is thought to be reflected and absorbed.
    [24] Experiments have shown that in a film in which these fine particles are dispersed very finely and uniformly, the transmittance has a maximum value between the wavelengths of 400 nm and 700 nm, and has a minimum value between 700 nm and 1800 nm, and the difference between the transmittances between these maximum values and the minimum value is 15 It was observed that more than a point. Considering that the visible light wavelength is 380 nm to 780 nm and the broad-spectrum form with the visibility at around 550 nm, this heat ray shielding transparent resin effectively reflects and absorbs other light rays.
    [25] Here, the hexaborate fine particles have a very high heat ray shielding ability per unit weight. They compare their tin-doped indium oxide (ITO: JP-A-7-69632) and antimony-doped tin oxide (ATO), which are used as infrared cut-off powders, when they are used in amounts of 1/30 or less. Effect. Therefore, the quantity of all the microparticles | fine-particles used can be reduced significantly. This solves the problem caused when the heat ray shielding particles are mixed in a large amount into the heat ray shield transparent resin molded body, that is, the transparent resin molded body may have low physical properties, particularly low impact resistance and low toughness in terms of strength. In addition, when used in large quantities, the hexaboride particles have absorption in the visible region, and thus can be freely controlled by controlling the amount of particles to which absorption is added in the visible region, and also to control the brightness or Makes it possible to apply.
    [26] As for the hexaborate fine particle diameter used in the present invention, it can be arbitrarily provided that it functions as a heat ray shielding component. The hexaboride fine particles preferably have an average particle diameter of 1,000 nm or less, more preferably 200 nm or less. This is because any fine particles having an average particle diameter larger than 1,000 nm or coarse fine particles formed by agglomeration of fine particles can act as a light scattering source of the produced heat ray shielding transparent resin molded article and the transparent resin molded article looks like a cloud. As a lower limit, there is no special limitation. It is desirable for the hexaboride particles to have as small a particle diameter as possible, as long as such particles can be produced (in fact, it is difficult to produce hexaboride particles having a diameter of 1 nm or less).
    [27] However, transparent roofing materials and the like may need to have opaque light transmission rather than being transparent. In such a case, the heat ray shield transparent resin molded body may be preferably configured such that particles having a larger particle size are used to promote light scattering. However, particles larger than 1,000 nm may cause attenuation of the heat ray shielding ability itself, and therefore they may preferably have an average particle diameter of 1,000 nm or less, and more preferably 500 nm to 600 nm.
    [28] As the hexaboride particles used in the present invention, those surface-treated with a silane compound, a titanium compound, or a zirconia compound may be used. Treatment of the surface of the microparticles with such compounds enables the improvement of the water resistance of the hexaboride.
    [29] The thermoplastic resin used in the present invention is not particularly limited as long as it is a transparent thermoplastic resin having high light transmittance in the visible light region. For example, when a heat shield transparent resin molded body is formed on a plate having a thickness of 3 mm, a thermoplastic resin having 50% or more of visible light transmittance as described in JIS R 3106 and 30% or less of haze as described in JIS K 7105. It may include. Specifically mentioned, it may include acrylic resins, polycarbonate resins, polyether-imide resins, polyester resins, polystyrene resins, polyether-sulfone resins, fluorine resins and polyolefin resins. In the case of using the heat-shielding transparent molded body for various buildings and windows, etc., acrylic resins, polycarbonate resins, polyether-imide resins and fluorine resins are preferable in consideration of transparency, impact resistance, weather resistance, and the like.
    [30] As polycarbonate resin, aromatic polycarbonate is preferable. Aromatic polycarbonates include one or more dihydric phenolic compounds and phos represented by 2,2-bis (4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane Polymers obtained by known methods such as interfacial polymerization, solution polymerization or solid phase polymerization from carbonate precursors represented by zen or diphenyl carbonate.
    [31] Acrylic resins are acrylic esters, vinyl acetate using methyl methacrylate, ethyl methacrylate, propyl methacrylate or butyl methacrylate as the main raw materials and, if necessary, acrylic groups having from 1 to 8 carbon atoms as copolymer components. Polymers or copolymers obtained using styrene, acrylonitrile or methacrylonitrile. Acrylic resins obtained by further multistage polymerization may also be used.
    [32] Fluorine resins include polyfluoroethylene, polydifluoroethylene, polytetrafluoroethylene, ethylene-difluoroethylene copolymers, ethylene-tetrafluoroethylene copolymers and tetrafluoroethylene-perfuloalkoxyethylene copolymers. It may include.
    [33] Regarding the content of the hexaboride with respect to the thermoplastic resin, the hexaboride has a content of 0.01 part by weight or more and less than 20 parts by weight, preferably 0.1 part by weight or more and 10 parts by weight or less, based on 100 parts by weight of the thermoplastic resin. Can be. If the content of the hexaboride is larger than this range, the hexaboride fine particles are agglomerated with each other and insufficiently dispersed in the resin, and thus the produced heat ray shielding transparent resin molded article can have a high haze value. It is also possible to cause dilution non-uniformity when diluting and mixing a master batch containing a heat shield component (hereinafter often referred to as "HRS-component-containing master batch") with a thermoplastic molded body material. If, on the other hand, the content of the hexaboride is smaller than the above range, any sufficient heat shielding can be obtained, in particular, when the transparent resin molded article produced is a film having a thickness of 100 μm or less, depending on the thickness of the manufactured heat shielding transparent resin molded article. You may not be able to.
    [34] As a method of dispersing the hexaborate fine particles in the thermoplastic resin, any method can be selected as long as they are a method in which the fine particles can be uniformly dispersed in the resin. For example, in order to prepare a dispersion of the hexaboride particles, the hexaboride particles are dispersed in any desired solvent by bead mills, ball mills or sand mills or by ultrasonic dispersion, and optionally together with other additive (s), This dispersion and pellets of powder or thermoplastic resin can be used as a blender and Benbury mixer, kneader, roll mill, single screw extruder such as ribbon blender, tumbling mixer, Nauta mixer, Henschel mixer, super mixer or planetary peristaltic screw mixer while removing solvent. A method can be used in which the melt is mixed uniformly by a kneader such as a twin screw extruder, and thus a mixture in which the hexaboride particles are uniformly dispersed in the thermoplastic resin can be produced. The mixture in which the hexagonal fine particles are uniformly dispersed in the thermoplastic resin also removes the solvent in the dispersion of the hexagonal fine particles by a known method, and selectively removes the powder or pellets of the obtained powder and the thermoplastic resin from other additive (s). ) Can be produced by a method of uniformly melt mixing. In addition, a method may be used in which powders of fine particles of undispersed hexaboride are added directly to the thermoplastic resin and they are uniformly melt mixed. It is sufficient for the hexagonal fine particles to be uniformly dispersed in the thermoplastic resin, and the method is not limited to these.
    [35] The mixture thus obtained is kneaded by a vented single screw extruder or twin screw extruder and then processed into pellets to obtain the HRS-component containing master batch of the present invention.
    [36] Pellets can be obtained by the most commonly available method of cutting melt extruded strands. Thus, as their shapes, columnar shapes and columnar shapes are available. It is also possible to employ "hot cut pelletizing (granulation)", where the melt extruded product is cut directly. In such cases, it is common for the pellets to have a shape close to a sphere.
    [37] Thus, the HRS-component-containing master batch of the present invention may adopt any shape or any shape. It may preferably be of the same shape and shape as the thermoplastic resin molded material used to dilute the master batch when the heat shield transparent resin molded body is formed.
    [38] The heat shield transparent resin molded article according to the present invention is obtained and obtained by diluting and mixing the HRS-component containing master batch with a thermoplastic resin molded material having a compatibility with the thermoplastic resin molded material of the same kind as the thermoplastic resin of the master batch or The mixture is shaped into the desired form.
    [39] Regarding the shape of the heat ray shielding transparent resin molded article, the resin molded article can be molded into a desired shape and can be planar or curved. In addition, about the thickness of a heat ray shielding transparent resin molding, it can adjust to desired thickness from form of a plate to film form as needed. The resin sheet formed in the planar form can be molded by post-processing in any form such as spherical form.
    [40] As a method for molding the heat ray shield transparent resin molded body, any method such as injection molding, extrusion, compression molding, and rotational molding can be used. In particular, a method of obtaining a molded body by injection molding and a method of obtaining a molded body by extrusion may be preferably adopted. As a method of obtaining a sheet or plate-like or film-shaped molded article by extrusion, such a molded article is produced by a method of removing a molten thermoplastic resin extruded using an extruder such as a T-die while cooling with a cooling roll. Molded bodies obtained by injection molding are preferably used in the body of automobiles such as window glass and roof of automobiles. Sheet or plate shaped or film shaped articles obtained by extrusion are used for dry products such as arcades and carports.
    [41] The heat shield transparent resin molded article itself may be used alone for structural materials such as window glass and amide, and in addition, the transparent resin molded article may be laminated to other transparent molded articles such as inorganic glass sheets, resin glass sheets or resin films by any method. As an integrated heat ray shielding transparent laminate obtained by this, it can be used for structural materials. For example, the heat radiation shielding transparent resin molded body previously molded into a film shape can be integrally laminated on the inorganic glass sheet by thermal lamination to obtain a heat radiation shielding transparent laminate having a heat radiation shielding function and a dispersion prevention performance. Further, at the same time as the formation of the heat ray shielding transparent resin molded body by thermal lamination, coextrusion, press molding, injection molding or the like, it can be laminated and integrated into another transparent molded body to obtain a heat ray shielding transparent laminate. Such a heat shield transparent laminate can be used as a more useful structural material because it can effectively compensate for mutual defects while effectively showing the advantages of each of the two formed bodies.
    [42] The master batch containing the heat shield component according to the invention can be further mixed with any additives commonly available. For example, those which are available as additives are dyes generally used to dye thermoplastics, such as azo dyes, cyanine dyes, quinoline dyes, perylene dyes and carbon black to impart any color tone as needed Or in addition to pigments hindered-phenol type or phosphorus type stabilizers; Mold release agents, hydroxybenzophenone series, salicylic acid series, HALS series, triazole series or triazine series ultraviolet absorbers; Coupling agents; Surfactants; Antistatic agents and the like, and any of these may be mixed in an effective amount.
    [43] As described in detail above, the use of the HRS-component-containing master batch according to the present invention, in which the hexaboride is uniformly dispersed as a heat ray shielding component in the thermoplastic resin, does not use any expensive physical film formation method or complicated process, and the visible light region is used. It is possible to provide a heat radiation shielding transparent resin molded article and a heat radiation shielding transparent laminate having a high heat radiation shielding function and a high permeability.
    [44] The resulting heat shield transparent resin moldings and heat shield transparent laminates also shield the solar energy coming through them when used in window and carports, arcades, etc. in automobiles and building materials, reducing the load on air conditioning (cooling) and It has the effect of lowering the senses and at the same time has the effect of saving energy and having high utility from an environmental point of view.
    [45] The invention is described in more detail by the examples given below. The invention is in no way limited by the following examples.
    [46] In the following examples, only examples using lanthanum hexaboride are described. However, it was confirmed that the same effect can be obtained for other hexaborates, as in the embodiment described in Japanese Patent Application Laid-Open No. 2000-96034.
    [47] Example One
    [48] As a heat ray shielding component, 200 g of lanthanum hexafluoride (LaB 6 ) particles having an average particle diameter of 67 nm, 700 g of toluene, and an appropriate amount of water and a dispersant were mixed, and the resulting mixture was used with a zirconia ball having a diameter of 4 mm for 100 hours. Further mixing by ball mill produced a 1 kg dispersion of lanthanum hexaboride fine particles. (Hereinafter, simply "A liquid")
    [49] Further, toluene in the liquid A was removed using a spray dryer to obtain a dispersed powder of lanthanum hexaboride particles (hereinafter simply “powder A”).
    [50] Next, to the pellets of the thermoplastic polycarbonate resin, Powder A thus obtained is added so as to have a LaB 6 concentration of 2.0% by weight (corresponding to 2.0 parts by weight based on 100 parts by weight of resin), and they are uniformly mixed by a blender. And melt-kneaded using a twin screw extruder. The extruded strand was cut into pellets to obtain a master batch containing the heat shield component (hereinafter simply referred to as "master batch A").
    [51] Next, the master batch A and the polycarbonate resin pellets are uniformly mixed by the blender to dilute the master batch A with the polycarbonate resin pellets to obtain a LaB 6 concentration of 0.01% by weight, followed by a 1.0 mm thickness using a T-die. Was extruded into a sheet of to obtain a heat ray shielding transparent resin molded article in which lanthanum hexaboride fine particles were uniformly dispersed in the whole resin.
    [52] The optical properties of the heat radiation shielding transparent resin molded product (polycarbonate sheet) thus produced were measured by Spectrophotometer U-4000 manufactured by Hitachi Co., Ltd., and solar radiation transmittance and visible light transmittance were calculated according to JIS R 3106.
    [53] The obtained results are shown in Table 1.
    [54] Example 2
    [55] A master batch containing a heat ray shielding component was obtained in the same manner as in Example 1 except that pellets were prepared using an acrylic resin as the thermoplastic resin. More specifically, Powder A and acrylic resin pellets were mixed to obtain numerical values as indicated in the "Master Batch Composition" column of Table 1, and melt kneaded using a twin screw extruder. The extruded strand was cut into pellets to obtain a master batch containing the heat ray shielding component according to the present example (hereinafter simply referred to as "master batch B").
    [56] Next, a heat shielding transparent resin molded article was obtained in the same manner as in Example 1 except that the master batch was diluted with acrylic resin pellets. More specifically, the master batch B and the acrylic resin pellets are uniformly mixed by a blender to dilute the master batch B with the acrylic resin pellets to obtain the numerical values as shown in the "Composition of the heat shield transparent resin molded body" column of Table 1, Subsequently, extrusion was carried out to a sheet having a thickness of 1.0 mm using a T-die to obtain a heat ray shielding transparent resin molded article in which lanthanum hexaboride fine particles were uniformly dispersed in the entire resin. The optical characteristic of such a heat ray shielding transparent resin molded object is also shown in Table 1.
    [57] Example 3
    [58] A master batch containing the heat ray shielding component was obtained in the same manner as in Example 1 except that the pellets were prepared using the polyether-imide resin as the thermoplastic resin. More specifically, Powder A and the polyether-imide resin pellets were mixed to obtain the numerical values as shown in the “Master Batch Composition” column of Table 1, and melt kneaded using a twin screw extruder. The strand extruded therefrom was cut into pellets to obtain a master batch containing the heat ray shielding component according to the present example (hereinafter simply referred to as "master batch C").
    [59] Next, a heat shielding transparent resin molded article was obtained in the same manner as in Example 1 except that the master batch was diluted with polyether-imide pellets. More specifically, the master batch C and the polyether-imide resin pellets are uniformly mixed by a blender, the master batch C is diluted in the polyether-imide resin pellets, and the "composition of the heat shield transparent resin molded body" of Table 1 is used. The numerical values as shown in the column were obtained, and then extruded into a sheet having a thickness of 1.0 mm using a T-die to obtain a heat ray shielding transparent resin molded article in which lanthanum hexaboride fine particles were uniformly dispersed in all the resins. Table 1 also shows the optical characteristics of this heat ray shielding transparent resin molded body.
    [60] Example 4
    [61] A master batch containing the heat ray shielding component was obtained in the same manner as in Example 1 except that pellets were prepared using polyethylene terephthalate resin as the thermoplastic resin. More specifically, the powder A and the polyethylene terephthalate resin pellets are mixed to obtain the numerical values as shown in the "Master Batch Composition" column in Table 1, and the following procedure of Example 1 is repeated to heat shield components according to the present example. A master batch containing was obtained (hereinafter simply "master batch D").
    [62] Next, the master batch D and the polyethylene terephthalate resin pellets are uniformly mixed by a blender, and the master batch D is diluted with the polyethylene terephthalate resin pellets, as shown in the "Composition of the heat shield transparent resin molded body" column of Table 1. Numerical values were obtained and then extruded into a 0.1 mm thick film using a T-die to obtain a heat ray shield transparent resin molded article in which lanthanum hexaboride particles were uniformly dispersed in the entire resin. Table 1 also shows the optical characteristics of this heat ray shielding transparent resin molded body.
    [63] Example 5
    [64] A master batch containing a heat shield component was obtained in the same manner as in Example 1 except that pellets were prepared using ETFE (ethylene-tetrafluoroethylene copolymer) resin as the thermoplastic resin. More specifically, the powder A and the ETFE resin pellets were mixed to obtain the numerical values as shown in the "Master Batch Composition" column in Table 1, followed by repeating the procedure in Example 1 to obtain the heat ray shielding component according to this Example. A master batch containing was obtained (hereinafter simply "master batch E").
    [65] Next, a heat shielding transparent resin molded article was obtained in the same manner as in Example 4 except that the master batch was diluted with EFTE pellets. More specifically, the master batch E and the ETFE resin pellets were mixed to dilute the master batch E with the ETFE resin pellets to obtain the numerical values as shown in the "Composition of the heat shield transparent resin molded body" column of Table 1, followed by Example 4 The process was repeated to obtain a heat ray shielding transparent resin molded article in which lanthanum hexaboride fine particles were uniformly dispersed in the whole resin. Table 1 also shows optical characteristics of the heat ray shielding transparent resin molded body.
    [66] Example 6
    [67] 50 g of methyltrimethoxysilane was added to 950 g of A liquid, and these were stirred with a mechanical stirrer. Thereafter, toluene in the liquid A was removed with a spray dryer to obtain a dispersed powder of lanthanum hexaboride fine particles surface-treated with a silane compound (hereinafter simply "powder B").
    [68] Next, in the same manner as in Example 1, Powder B and the polycarbonate resin pellets were mixed to obtain the numerical values indicated by the "master batch composition" in Table 1, and the subsequent procedure of Example 1 was repeated to heat wire according to the present Example. A master batch containing the shielding component was obtained (hereafter simply "master batch F").
    [69] Thereafter, in the same manner as in Example 1, the master batch F and the polycarbonate resin pellets were mixed, and the master batch F was diluted with the polycarbonate resin pellets to give the numerical values as shown in the "Composition of the heat shield transparent resin molded body" column in Table 1. Then, the subsequent process of Example 1 was repeated and the heat-ray shielding transparent resin molding which lanthanum hexaboride microparticles | fine-particles were disperse | distributed uniformly to all resin was obtained. The optical characteristic of this heat ray shielding transparent resin molding (polycarbonate sheet) is also shown in Table 1.
    [70] Comparative example
    [71] To the pellets of the thermoplastic polycarbonate resin, powder A was added so that the concentration of LaB 6 was 16.7% by weight (corresponding to 20.0 parts by weight based on 100 parts by weight of resin), and these were mixed uniformly by a blender, followed by biaxial The melt kneading was carried out using an extruder. The extruded strand from it was cut into pellets to obtain a master batch containing the heat shield component (hereafter simply "master batch G").
    [72] Next, the master batch G and the polycarbonate resin pellets are uniformly mixed by the blender, and the master batch G is diluted with the polycarbonate resin pellets to obtain a concentration of LaB 6 of 0.01% by weight, followed by 1.0 mm using a T-die. It extruded into the sheet of thickness, and obtained the heat ray shielding transparent resin molding which concerns on the comparative example in which the lanthanum hexaboride microparticles | fine-particles were disperse | distributed uniformly to all resin. Table 1 shows the optical characteristics of this heat ray shielding transparent resin molded body.
    [73]
    [74] -Rating-
    [75] 1.Appearance evaluation of HRS-component-containing master batch and heat shield transparent resin molded articles according to Examples and Comparative Examples:
    [76] In the HRS-component containing master batch according to the comparative example, its LaB 6 content was 20.0 parts by weight based on 100 parts by weight of the polycarbonate resin, thus making it possible to uniformly disperse LaB 6 particles when preparing the master batch. There was no. As a result, coarse particles were seen in the heat shield transparent resin molded article produced using the HRS-component containing master batch according to the comparative example, and the molded article had a rough surface.
    [77] In the step of diluting the HRS-component containing master batch according to the comparative example with polycarbonate resin pellets, the master batch was added to the polycarbonate resin pellets in a very small amount (the LaB 6 content was 20.0% by weight based on 100 parts by weight of the polycarbonate resin). Part by volume, it follows that the blending portion of the HRS-component containing master batch for dilution polycarbonate resin pellets is smaller). Therefore, LaB 6 fine particles were not uniformly dispersed in the resin molded body, and color shading was observed. Moreover, because of such nonuniform distribution, the solar radiation transmittance of the heat ray shielding transparent resin molded body which concerns on a comparative example showed the numerical value of 63.0%, and it was confirmed that it is worse than the heat ray shielding transparent resin molded body which concerns on an Example.
    [78] On the other hand, for the HRS-component-containing master batch according to the example, wherein the LaB 6 content is set to 0.01 to 20 parts by weight or less, the same drawbacks as in the comparative example are not seen, and the HRS- according to the examples is not found. It was confirmed that an excellent heat ray shielding transparent resin molded body can be manufactured using a component containing master batch.
    [79] 2. Evaluation of the water resistance test of the heat shield transparent resin molded article according to Examples 1 to 6:
    [80] In order to evaluate the water resistance of the heat radiation shielding transparent resin molded article according to Examples 1 to 6, the following heat radiation shielding transparent laminate produced by using the heat radiation shielding coating liquid prepared by containing the water resistance thereof in the inorganic binder Compared with that of.
    [81] (Production of Heat Shield Transparent Laminate)
    [82] Ethyl silicate solution prepared using 10 g of ethyl silicate 40, 27 g of ethanol, 8 g of 5% aqueous hydrochloric acid solution and 5 g of water, the average degree of polymerization of which is tetra- to pentamers, was obtained from Tama Chemical Industries, Ltd. Thoroughly mixing and stirring to prepare 50 g of liquid ethyl silicate mixture (hereafter simply "B liquid").
    [83] Next, the liquid A in Example 1 was mixed with this liquid B, and the resulting mixture was further diluted with diacetone alcohol to have a LaB 6 concentration of 0.2 wt% and a SiO 2 concentration of 2.5 wt%, and applied with a heat shield. A liquid was prepared.
    [84] Thereafter, 15 g of this heat ray shielding coating liquid was applied onto a polycarbonate sheet having a thickness of 2.0 mm by a spin coater, and the coated sheet was put into a 100 ° C electric furnace and then heated for 30 minutes to form a heat ray shielding film formed on the polycarbonate sheet. A heat ray shielding transparent laminate having a thickness was prepared. The optical properties of this heat shield transparent laminate were measured to find that its visible light transmittance and solar radiation transmittance were 78% and 57.9%, respectively.
    [85] Next, the heat-shielding transparent laminate thus obtained was stored in a constant temperature-humidity device composed of a temperature of 80 ° C. and a humidity condition of 95% RH for 100 days, and then re-measured its optical properties to determine visible light transmittance and The solar transmittances were found to be 81% and 62.4%, respectively, indicating that the visible and solar transmittances increased by 3% and 4.5%, respectively.
    [86] On the other hand, the heat shield polycarbonate sheet obtained in Example 1 was stored in a constant temperature-humidity apparatus consisting of a temperature of 80 ° C. and a humidity condition of 95% RH for 100 days, and then re-measured its optical properties to produce visible It was found that the light and solar transmittances were 78.5% and 59.2%, respectively, indicating that the visible and solar transmittances increased slightly by 0.3% and 0.3%, respectively.
    [87] The heat shield polycarbonate sheet obtained in Example 6 was also stored in a constant temperature-humidity device consisting of a temperature of 80 ° C. and a humidity condition of 95% RH for 100 days, and then re-measured its optical properties to show visible light. The transmittance and solar transmittance were found to be 77.7% and 59.0%, respectively, indicating no change in optical properties.
    [88] From these results, in the heat shield transparent laminate obtained using the heat shield coating liquid, due to its very thin heat shield film, a large number of lanthanum hexafluoride hexavalent particles contacted with the water content to decompose lanthanum hexafluoride microparticles. It is confirmed that this causes the heat ray shielding performance of the laminate to be lowered.
    [89] On the other hand, in the heat radiation shielding polycarbonate sheet obtained in Example 1, the lanthanum hexaboride fine particles are uniformly dispersed in the polycarbonate resin, and the lanthanum hexaboride fine particles are less in contact with the water content to improve water resistance. It is confirmed that it causes.
    [90] In the heat radiation shielding polycarbonate sheet obtained in Example 6, since the lanthanum hexaboride fine particles surface-treated with the silane coupling agent are used, its water resistance is further improved than the heat radiation shielding polycarbonate sheet obtained in Example 1 It is also confirmed.
    权利要求:
    Claims (6)
    [1" claim-type="Currently amended] A master batch containing a heat ray shielding component used to prepare a heat ray shield transparent resin molded article, wherein the master batch is
    Its main component contains a thermoplastic resin and a hexaboride represented by XB 6
    (Where X is at least one selected from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca),
    The hexaboride, which is a heat ray shielding component, is contained in an amount of 0.01 to 20 parts by weight or less based on 100 parts by weight of the thermoplastic resin.
    [2" claim-type="Currently amended] The method of claim 1, wherein the thermoplastic resin is at least one selected from acrylic resin, polycarbonate resin, polyether-imide resin, polystyrene resin, polyether-sulfone resin, fluorine resin, polyolefin resin and polyester resin. Master batch.
    [3" claim-type="Currently amended] The master batch of claim 1 or 2, wherein the hexaborate comprises fine particles having an average particle diameter of 1,000 nm or less.
    [4" claim-type="Currently amended] The master batch according to claim 1 or 2, wherein the hexaboride is surface treated with at least one selected from a silane compound, a titanium compound, and a zirconia compound.
    [5" claim-type="Currently amended] The master batch according to claim 1 is diluted and mixed with a thermoplastic molded body material homogeneous with the thermoplastic resin of the master batch, or with a heterogeneous thermoplastic molded body material compatible with the master batch, and the resulting mixture is in a predetermined form. It is obtained by shape | molding, The heat ray shielding transparent resin molded object characterized by the above-mentioned.
    [6" claim-type="Currently amended] A heat radiation shielding transparent resin molded article obtained by laminating the heat radiation shielding transparent resin molded article according to claim 5 to another transparent molding.
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    同族专利:
    公开号 | 公开日
    US20040028920A1|2004-02-12|
    JP4349779B2|2009-10-21|
    KR101003728B1|2010-12-23|
    US7666930B2|2010-02-23|
    US20060009559A1|2006-01-12|
    CN1329444C|2007-08-01|
    CN1477150A|2004-02-25|
    JP2004059875A|2004-02-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-07-31|Priority to JPJP-P-2002-00223896
    2002-07-31|Priority to JP2002223896A
    2003-07-31|Application filed by 스미토모 긴조쿠 고잔 가부시키가이샤
    2004-02-11|Publication of KR20040012567A
    2010-12-23|Application granted
    2010-12-23|Publication of KR101003728B1
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2002-00223896|2002-07-31|
    JP2002223896A|JP4349779B2|2002-07-31|2002-07-31|Heat ray shielding transparent resin molding and heat ray shielding transparent laminate|
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