WO2014024882A1 - 熱可塑性樹脂微細発泡反射シート、光反射板、バックライトパネルおよび発泡反射シートの製造方法 - Google Patents
熱可塑性樹脂微細発泡反射シート、光反射板、バックライトパネルおよび発泡反射シートの製造方法 Download PDFInfo
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Definitions
- the present invention relates to an amorphous resin thermoplastic resin foam sheet, a light reflector, a backlight panel, and a foam reflector sheet having fine bubbles and having one or more functions.
- the high functionality is calculated
- High functionality is various properties required for plastic products such as antifouling property, surface hardness, weather resistance, etc., but these can generally obtain sufficient functionality by applying to the surface layer part of the molded product There are many.
- a foamed product having high functionality is realized by adding a functional additive to the surface layer portion of the plastic foam sheet for the purpose of imparting such functionality.
- a functional additive greatly affects the foamability of the resin and causes the bubble structure to become coarse.
- a method for imparting high functionality without greatly affecting the foaming property a method using coating, laminating or the like is widely used (for example, see Reference 2).
- such a method has a problem of high cost because the number of steps increases.
- the foamed sheet tends to generate not only fine bubbles but also coarse bubbles of 0.5 mm or more (or a size of 1/2 or more of the sheet thickness) during foaming. In particular, this tendency becomes remarkable when the thermoplastic resin is an amorphous resin. Therefore, there was a problem that it was difficult to use as various molded articles including a light reflecting material.
- thermoplastic resin microfoaming reflection sheet having a fine and uniform cell structure with an average cell diameter of 10 ⁇ m or less and having high light reflection efficiency and functionality, a light reflection plate, a backlight panel, and a method for producing a foam reflection sheet.
- thermoplastic resin microfoam reflective sheet having a foam layer and a non-foam layer having a thickness of 150 ⁇ m or less and 30 ⁇ m or more above and below the foam layer, the foam layer being integrally molded, Thermoplastic resin fine foam having a uniform cell structure with an average cell diameter of 10 ⁇ m or less and 0.5 ⁇ m or more and a cell number density of 1 ⁇ 10 6 / mm 3 or more and 1.0 ⁇ 10 12 / mm 3 or less
- thermoplastic resin finely foamed reflective sheet comprising a function-imparting layer in at least one of the non-foamed layers.
- thermoplastic resin microfoaming reflection sheet according to (1) wherein the function-imparting layer is an antistatic layer or an ultraviolet absorbing layer containing an antistatic agent, an ultraviolet absorber or an antioxidant. .
- the antistatic agent, ultraviolet absorber or antioxidant contained only in the function-imparting layer, or contained in at least one layer of the function-imparting layer.
- the thermoplastic resin finely foamed reflective sheet according to (2) wherein the content of is greater than the content contained in the remaining layers.
- thermoplastic resin fine foam reflective sheet The thermoplastic resin finely foamed reflective sheet according to any one of (1) to (5), wherein the thermoplastic resin is polycarbonate.
- thermoplastic resin finely foamed reflective sheet according to any one of (1) to (8), wherein the surface specific resistance value is 1 ⁇ 10 12 ⁇ or less.
- a method for producing a foamed reflective sheet wherein the foamed reflective sheet is the thermoplastic resin microfoamed reflective sheet according to any one of (1) to (9), and the following steps (a) to ( A method for producing a foamed reflective sheet, comprising: c).
- a resin sheet having at least a three-layer structure comprising a thermoplastic resin layer for forming a foam layer and a thermoplastic resin layer for forming a non-foam layer, wherein at least one of the non-foam layers is
- a step (b) a step of impregnating the resin sheet with an inert high-pressure gas, and a step (c) of heating the resin sheet.
- Step of foaming a thermoplastic resin layer for forming a foamed layer (11)
- a foaming nucleating agent is used in an amount of 0.1 to 10 with respect to 100 parts by mass of the thermoplastic resin of the thermoplastic resin layer for forming the foamed layer.
- (12) A light reflecting plate comprising the thermoplastic resin microfoam reflecting sheet according to any one of (1) to (9).
- a backlight panel comprising the light reflecting plate according to (12).
- thermoplastic resin is used as a concept including a resin composed of one kind of thermoplastic resin and a blend resin composed of two or more kinds of thermoplastic resins. Therefore, the term “thermoplastic resin composition” means that when the thermoplastic resin is composed of one kind of thermoplastic resin, it means the kind of the thermoplastic resin, and the thermoplastic resin is two or more kinds of thermoplastic resins. If it is a blend resin comprising, it means the composition of the blend resin.
- a certain raw material, member, or structure is “consisting of a thermoplastic resin” or “formed from a thermoplastic resin” means that the raw material, member, or structure is composed only of a thermoplastic resin.
- it is used as a concept including an embodiment constituted by a composition in which various additives are blended in a thermoplastic resin.
- a form in which 80 to 100% by mass is made of a thermoplastic resin is a form “made of a thermoplastic resin” or “formed from a thermoplastic resin”.
- “consisting of a thermoplastic resin” or “formed from a thermoplastic resin” is preferably 90 to 100% by mass. More preferably 95 to 100% by mass is composed of a thermoplastic resin. This is the same when the thermoplastic resin is specified by a more specific resin name.
- thermoplastic resin finely foamed reflective sheet having a fine and uniform cell structure with an average cell diameter of 10 ⁇ m or less, high light reflection efficiency and functionality, a light reflector, a backlight panel, and the above-mentioned performance.
- an inexpensive and simple method for producing a foam reflection sheet can be provided.
- thermoplastic resin fine foam reflection sheet of this invention It is a schematic diagram which shows the longitudinal cross-section of one form of the thermoplastic resin fine foam reflection sheet of this invention.
- thermoplastic resin fine foamed reflective sheet according to the present invention will be described in detail with reference to the drawings, but the present invention is not limited to this embodiment.
- thermoplastic resin finely foamed reflective sheet of the present invention has a structure comprising a foamed layer (11) and a non-foamed layer (12) on both sides of the foamed layer.
- one or both of the non-foamed layers (12) on both sides of the foamed layer (11) include a function-imparting layer.
- the non-foamed layer may be a function-imparting layer.
- thermoplastic resin microfoam reflective sheet of the present invention the foam layer and the non-foam layer are both formed of a thermoplastic resin, but the composition of the thermoplastic resin forming the foam layer and the function formed in the non-foam layer The compositions of the thermoplastic resins forming the application layer are different from each other.
- the foam layer of the thermoplastic resin microfoam reflective sheet of the present invention is made of a thermoplastic resin.
- a polyolefin resin, a polyester resin, and a polycarbonate resin are mentioned, In this invention, a polyester resin and a polycarbonate resin are preferable. Of these, a polycarbonate resin is preferable because it is excellent in properties such as lightness, shape stability, and economical efficiency, and further in light reflection properties.
- the thermoplastic resin is preferably amorphous from the viewpoint of forming a non-foamed layer.
- the thickness of the foamed layer is appropriately determined depending on the use and mode of the above-mentioned reflection sheet and cannot be uniquely determined, but is preferably 300 to 5000 ⁇ m, more preferably 500 to 1500 ⁇ m.
- the polycarbonate resin is not particularly limited in the production method, but can be obtained by reacting an aliphatic or aromatic di- or polyol compound with phosgene or a carbonic acid diester. It can also be obtained by reacting an aromatic di- or polyol compound or a small amount thereof with a phosgene or a carbonic acid diester.
- Aromatic di- or polyol compounds include 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, Bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, hydroquinone, Resorcinol and 4,4′-dihydroxydiphenyl
- a foaming layer consists of a thermoplastic resin to which the bubbling nucleating agent was added as an additive.
- the bubbling nucleating agent By adding the bubbling nucleating agent, more bubble nuclei can be generated in the thermoplastic resin. Thereby, since the produced
- a polyester-type elastomer and a polycarbonate-type elastomer can be used suitably.
- the aerated nucleating agent is preferably blended in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
- the foamed layer is composed of a crystallization nucleating agent, a crystallization accelerator, an antioxidant, an antistatic agent, an ultraviolet light inhibitor, a light stabilizer, a fluorescent image whitening agent, a pigment, and a dye
- various additives such as a compatibilizer, a lubricant, a reinforcing agent, a flame retardant, a crosslinking agent, a crosslinking aid, a plasticizer, a thickener, and a thickener may be contained.
- the foamed layer contains a compound as described above other than the compound necessary for generating bubbles, such as an aerated nucleating agent, the content should be less than the content in the function-imparting layer described later. Is preferred.
- the foam layer provided in the thermoplastic resin fine foam reflective sheet of the present invention has air bubbles.
- the bubbles are preferably closed cells. More specifically, it is preferable that 70% or more of the total number of bubbles of the thermoplastic resin finely foamed reflective sheet is closed cells, more preferably 80 to 100%, still more preferably 90 to 100%, and still more preferably 95. ⁇ 100% are closed cells.
- the average bubble diameter is 10 ⁇ m or less, from the viewpoint of achieving both thinning and high reflectivity, 7.0 ⁇ m or less is preferable, 5.0 ⁇ m or less is more preferable, 3.0 ⁇ m or less is further preferable, and 2.0 ⁇ m or less is preferable. Is particularly preferred.
- the average bubble diameter is usually 0.5 ⁇ m or more and may be 1.0 ⁇ m or more. The average bubble diameter can be measured by the following method.
- the cell number density of the foam layer is 1.0 ⁇ 10 6 / mm 3 or more, and from the viewpoint of achieving both a reduction in thickness and a high reflectance, 1.0 ⁇ 10 7 / mm 3 to 1.0. ⁇ 10 11 pieces / mm 3 is preferable, and 1.0 ⁇ 10 8 pieces / mm 3 to 1.0 ⁇ 10 11 pieces / mm 3 is more preferable.
- the upper limit of the cell number density of the foam layer is 1.0 ⁇ 10 12 pieces / mm 3 or less, preferably 1.0 ⁇ 10 11 pieces / mm 3 .
- the cell number density of the foam layer can be measured by the following method.
- the resin constituting the non-foamed layer preferably contains the same thermoplastic resin as the foamed layer.
- the thermoplastic resin same as the foamed layer is preferably 50% by mass or more in the resin constituting the non-foamed layer, and when it is 100% by mass, that is, the same thermoplastic resin as the foamed layer is preferable, and among them the polycarbonate resin is preferable.
- the thickness of the non-foamed layer formed on the foam is 30 ⁇ m or more, and more preferably 60 ⁇ m or more.
- the thickness of the function-imparting layer that is integrally molded is less than 30 ⁇ m, and more preferably 25 ⁇ m or less.
- a non-foamed layer does not exceed 150 micrometers from a viewpoint of optical characteristic maintenance.
- the thickness of the non-foamed layer is less than 30 ⁇ m, the concentration of the functional material added to the non-foamed layer resin increases and the light absorbency increases. For this reason, optical characteristics, such as a reflectance, fall. Therefore, it is not desirable to form a non-foamed layer having a thickness of less than 30 ⁇ m.
- the thickness of the non-foamed layer can be measured with a scanning electron microscope (SEM) photograph. Specifically, a scanning electron microscope (SEM) photograph is taken, a parallel line is drawn on the surface portion of the thermoplastic resin fine foamed reflective sheet and a line on the most surface layer side of the bubble layer, and the interval between the parallel lines is determined as an unfoamed layer. It can be measured as the thickness of the non-foamed layer.
- SEM scanning electron microscope
- the non-foamed layer is composed of the above-mentioned thermoplastic resin, crystallization nucleating agent, crystallization accelerator, antioxidant, antistatic agent, UV inhibitor, light stabilizer, fluorescent image whitening agent, pigment, dye, compatibilizing agent. Further, various additives such as a lubricant, a reinforcing agent, a flame retardant, a crosslinking agent, a crosslinking aid, a plasticizer, a thickener, and a thickener may be contained.
- a function-imparting layer is provided as at least one constituent layer in at least one of the non-foamed layers. It is more preferable to provide a function-imparting layer in the non-foamed layers on both sides of the foamed layer. In that case, the position of the non-foamed layer is not particularly limited as long as the function-imparting layer is included in the non-foamed layer. Although the outermost layer, the innermost layer, or the intermediate layer may be used, the outermost layer or the innermost layer is actually preferable.
- the function in the function-imparting layer is a function other than the direct reflection prevention itself such as antistatic, ultraviolet absorption, and deterioration prevention.
- antistatic and ultraviolet absorption can be particularly suitably imparted.
- the thickness of the function-imparting layer to be integrally formed to be less than 30 ⁇ m (more preferably 25 ⁇ m or less), generation of coarse bubbles (so-called “fluff”) can be prevented.
- Such functions are preferably expressed by adding an additive, and as such an additive, an antistatic agent, an ultraviolet absorber, and an antioxidant are preferable, and these may be used alone or in combination. It doesn't matter. In the present invention, it is preferable to use these in combination, and it is particularly preferable to use an antistatic agent and an ultraviolet absorber in combination.
- the antistatic agent may be an organic antistatic agent or an inorganic antistatic agent.
- an organic antistatic agent is preferable, and an anionic, cationic or nonionic surfactant is preferable. Of these, anionic surfactants are preferred.
- anionic surfactants are preferred.
- As such a surfactant for example, Denon V-57S and Denon 2723 manufactured by Maruzen Oil Chemical Co., Ltd. are preferably used.
- the content of the antistatic agent is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and further preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the resin of the function-imparting layer. preferable.
- UV absorbers include hindered amines, salicylic acids, benzophenones, benzotriazoles, benzoxazinones, cyanoacrylates, triazines, benzoates, anilate oxalates, organic nickels, and other organic materials. And inorganic compounds obtained by a sol-gel method or the like. Of these, colorless ones are preferred.
- hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6- Tetramethylpiperidine polycondensate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4 -Piberidylbenzoate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl Malonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetra Methyl pipera Dinone) and the like.
- salicylic acid compounds include
- benzophenone compounds include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-ethoxy-benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4 -Methoxy-5-sulfobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane and the like.
- benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy -3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-octylphenol) benzotriazole, 2- (2'-hydroxy-3) ', 5'-di-t-amylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 (2H-benzotriazol-2-yl) phenol], 2 (2′
- cyanoacrylate compounds examples include 2-ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and 1,3-bis- [2′-cyano-3. , 3′-diphenylacryloyloxy] -2,2-bis-[(2-cyano-3 ′, 3′-diphenylacryloyl) oxy] methylpropane and the like.
- Triazines include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxy-phenol, 2- (4,6-bis-2,4-dimethyl And phenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxy-phenol.
- benzoate compounds include 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, resorcinol monobenzoate, and methyl orthobenzoylbenzoate.
- the organic compound include 2-ethoxy-2′-ethyl oxazac acid bisanilide
- examples of the organic nickel compound include nickel bis (octylphenyl) sulfide and [2,2′-thiobis (4-tert-octylphenol). Lat)]-n-butylamine nickel, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl-phosphate monoethylate, nickel dibutyldithiocarbamate and the like.
- Examples of the benzoxazinone compound include 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazin-4-one].
- Examples of the malonic ester compounds include propanedioic acid [(4-methoxyphenyl) -methylene] -dimethyl ester.
- the content of the ultraviolet absorber is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin of the function-imparting layer. Part by mass is more preferable.
- antioxidants examples include phenolic antioxidants, hindered phenolic antioxidants, aniline antioxidants, trivalent phosphorus compounds, ascorbic acid, hydroxylamines, and various other reducing agents.
- the antioxidant acts to stabilize the ultraviolet absorber, and the content of the antioxidant is preferably 0.05 to 10 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin of the function-imparting layer. More preferred is 5 parts by mass, and even more preferred is 1 to 2 parts by mass.
- thermoplastic resin microfoaming reflection sheet of the present invention is formed by integrally molding a resin sheet having at least a three-layer structure comprising a thermoplastic resin layer for forming a foamed layer and a thermoplastic resin layer for forming a non-foamed layer. It is prepared and manufactured using this resin sheet.
- at least one of the non-foamed layers includes a function-imparting layer and contains an additive that imparts a function.
- the non-foamed layer may be a function-imparting layer. More specifically, it is preferably produced through the following steps (a) to (c).
- A a step of preparing a resin sheet having at least a three-layer structure comprising a thermoplastic resin layer for forming a foam layer and a thermoplastic resin layer for forming a non-foam layer by integral molding by coextrusion;
- B impregnating the resin sheet with an inert high-pressure gas, and
- c heating the resin sheet to foam a thermoplastic resin layer for forming a foamed layer.
- the resin sheet having at least a three-layer structure produced in the step (a) includes a thermoplastic resin layer for forming a foamed layer, and a thermoplastic resin layer for forming a non-foamed layer provided on both sides thereof.
- the structure has a three-layer structure, the structure of four or more layers can be appropriately selected according to the shape of the target foam sheet.
- the thermoplastic resin layer for forming the foam layer is made of the thermoplastic resin constituting the above-mentioned foam layer
- the thermoplastic resin layer for forming the non-foam layer is the thermoplastic constituting the above-mentioned non-foam layer.
- the non-foamed layers on both sides of the foamed layer include a function-imparting layer and include an additive that imparts a function.
- the resin sheet obtained in the step (a) is impregnated with an inert gas.
- a roll is formed by overlapping and winding the resin sheet obtained in the step (a) and a separator, and the roll is held in a pressurized inert gas atmosphere to impregnate the resin sheet with the inert gas.
- the separator may be any separator as long as it has a void through which an inert gas or an organic solvent used as needed can freely enter and exit, and the permeation of the inert gas into itself can be ignored. If a suitable example of a separator is shown, a resinous nonwoven fabric and metal net
- the resin sheet obtained in the step (a) is preferably impregnated with an inert gas in an unstretched state. If the film is stretched, the gas may not sufficiently penetrate into the sheet.
- the resin sheet Before impregnating the resin sheet on which the roll is formed with an inert gas, the resin sheet may contain an organic solvent.
- an organic solvent is contained in the resin sheet, the crystallinity of the thermoplastic resin sheet can be improved, the rigidity of the sheet is improved, and the trace of the separator hardly remains on the sheet surface.
- an effect of shortening the permeation time of the inert gas can be expected.
- organic solvent examples include benzene, toluene, methyl ethyl ketone, ethyl formate, acetone, acetic acid, dioxane, m-cresol, aniline, acrylonitrile, dimethyl phthalate, nitroethane, nitromethane, and benzyl alcohol.
- acetone is preferably used.
- the above inert gas includes helium, nitrogen, carbon dioxide, argon and the like. Among these, carbon dioxide is preferable because it can be contained in a large amount in the thermoplastic resin.
- the osmotic pressure of the inert gas is room temperature (for example, 17 ° C.), preferably 0.2 to 15 MPa, more preferably 0.25 to 10 MPa.
- the permeation time of the inert gas is usually 1 hour or longer (preferably 1 to 30 hours), and it is preferable that the inert gas permeates until a saturated state is reached.
- the resin sheet impregnated with the inert gas obtained in the step (b) is foamed.
- the thermoplastic resin layer for forming the foamed layer is foamed, and the thermoplastic resin layer for forming the non-foamed layer is not foamed.
- the foamed layer can be formed by removing the separator from the roll and heating the resin sheet to a temperature equal to or higher than the softening point of the thermoplastic resin for forming the foamed layer. This heating is preferably performed at a temperature lower than the melting point of the foam layer.
- the heating temperature for foaming is preferably 120 to 240 ° C, more preferably 130 to 200 ° C.
- the heating time is preferably 30 seconds to 10 minutes, more preferably 10 seconds to 5 minutes.
- thermoplastic resin layer for forming the foamed layer foaming the thermoplastic resin layer for forming the foamed layer and not foaming the thermoplastic resin layer for forming the non-foamed layer.
- an aerated nucleating agent is added to a thermoplastic resin layer for forming a foamed layer
- a crystallization nucleating agent or a crystallization accelerator is added to a thermoplastic resin layer for forming a non-foamed layer.
- the foamability of each resin layer can be controlled to some extent.
- the foamability can be controlled more strictly. Suitable examples of such a thermoplastic resin are as described above.
- the thickness of the thermoplastic resin finely foamed reflective sheet of the present invention is preferably 0.2 to 2.0 mm, more preferably 0.5 to 1.5 mm, still more preferably 0.8 to 1. 2 mm, particularly preferably 0.9 to 1.1 mm, and most preferably 1.0 ⁇ 0.05 mm.
- the specific gravity of the foamed sheet of the present invention is preferably 0.2 to 0.7, more preferably 0.3 to 0.7, and further preferably 0.4 to 0.65. .
- the specific gravity may be 0.5 or less.
- the thermoplastic resin microfoaming reflection sheet of the present invention preferably has a reflectance (based on a standard white plate made of aluminum oxide) of 98% or more at a wavelength of 550 nm. Moreover, it is preferable that the reflectance (standard aluminum white board made from aluminum oxide) at a wavelength of 350 nm is 30% or less.
- the reflectance at a wavelength of 550 nm and the reflectance at a wavelength of 350 nm of the thermoplastic resin finely foamed reflective sheet can be measured as follows.
- a spectrophotometer for example, U-4100 manufactured by Hitachi High-Tech Co., Ltd. is used, and an aluminum oxide white plate (210-0740: manufactured by Hitachi High-Tech Fielding Co., Ltd.) is used as a reference.
- a spectral slit for example, under the condition of a spectral slit of 4 nm, 550 nm or 350 nm Measure the reflectance at a wavelength of.
- the specific resistance value on the surface of the thermoplastic resin microfoamed reflective sheet is preferably 1 ⁇ 10 12 ⁇ or less.
- the upper limit of the surface resistivity of the thermoplastic resin microfoaming reflection sheet is 1 ⁇ 10 14 ⁇ or less, and practical antistatic properties cannot be obtained with a surface resistivity exceeding this value.
- thermoplastic resin finely foamed reflective sheet The density of the entire thermoplastic resin finely foamed reflective sheet was measured by an underwater substitution method.
- thermoplastic resin fine foamed reflective sheet of the present invention is not particularly limited, and can be used as, for example, a light reflecting plate or a diaphragm for a speaker, and can be suitably used as a light reflecting plate. . More specifically, it is suitable as a light reflecting plate used in a backlight panel such as a liquid crystal display device.
- thermoplastic resin finely foamed reflective sheet of the present invention may be coated with a paint containing the various additives described above, and such a thermoplastic resin finely foamed reflective sheet is also coated with the thermoplastic resin finely foamed sheet of the present invention. Included in the foam reflective sheet.
- Example 1 A system in which 0.5% by mass of NJ Star NU100 manufactured by Nippon Kayaku is added to polycarbonate resin SI8000L manufactured by Sumika Stylon Polycarbonate Co., Ltd. is used as a foam layer, and a functional layer having a thickness of 18 ⁇ m is laminated on both sides of the foam layer.
- a polycarbonate sheet having a thickness of 600 ⁇ m was obtained.
- the functionalized layer is SI8000L manufactured by Sumika Stylon Polycarbonate, Inc., 0.5% by mass of surfactant antistatic agent Denon V-57S (manufactured by Maruzen Oil Chemical Co., Ltd.), and 0.25% by mass of benzophenone UV absorber.
- the added compound was used.
- the obtained sheet was treated in carbon dioxide at 17 ° C. and 5.5 MPa for 24 hours, and then heated in an atmosphere at 145 ° C. for 1 minute to produce a foamed sheet.
- the thickness of the foam sheet was 1000 ⁇ m. The following measurement and evaluation were performed on this foam sheet
- Thickness of the unfoamed layer Take a scanning electron microscope (SEM) photograph, draw a parallel line between the surface of the foam sheet and the line on the most surface layer side of the foam layer, and the interval between the parallel lines as the unfoamed layer thickness It was measured.
- SEM scanning electron microscope
- L, u, and v represent the differences in coordinate values in the color space.
- the obtained sheet was a uniform foam having a bubble diameter of about 1 ⁇ m, a density of 330 kg / m 3 , and an unfoamed layer of about 50 ⁇ m in the surface layer portion.
- the reflectance at a wavelength of 550 nm of the foamed sheet was 100% (Al 2 O 3 standard), and the reflectance at a wavelength of 350 nm was 28% (Al 2 O 3 standard).
- the surface resistivity was 1.83 ⁇ 10 11 ⁇ , and the color difference ⁇ E after the ultraviolet irradiation test was 13. The obtained results are summarized in Table 1 below.
- Example 2 A foam sheet was produced in the same manner as in Example 1 except that the thickness of the function-imparting layers on both the front and back surfaces was changed to 30 ⁇ m. Evaluation similar to Example 1 was performed.
- the obtained sheet was a uniform foam having a bubble diameter of about 1 ⁇ m, a density of 330 kg / m 3 , and an unfoamed layer of about 50 ⁇ m in the surface layer portion.
- the reflectance at a wavelength of 550 nm of the foamed sheet was 98% (Al 2 O 3 standard), and the reflectance at a wavelength of 350 nm was 13% (Al 2 O 3 standard).
- the surface resistivity was 8.62 ⁇ 10 10 ⁇ , and the color difference ⁇ E after the ultraviolet irradiation test was 8.
- Comparative Example 1 Using the same compound as in Example 1, a 600 ⁇ m-thick polycarbonate sheet obtained by laminating a 60 ⁇ m function-imparting layer on the front and back surfaces was obtained by the method described in Example 1. A large amount of balloon-shaped blisters were generated on the surface of the obtained sheet, and it was not possible to obtain a sample that could be evaluated for optical properties, surface resistivity, ultraviolet irradiation test, and the like.
- Comparative Example 2 0.5% by mass of a surfactant-based antistatic agent Denon V-57S (manufactured by Maruzen Oil Chemical Co., Ltd.) and 0.25% by mass of a benzophenone-based UV absorber are added to the same compound as the foamed layer of Example 1.
- a polycarbonate sheet having a single-layer structure having a thickness of 600 ⁇ m was obtained from the obtained compound.
- the obtained sheet was foamed by the method described in Example 1 to obtain a sheet.
- the average sheet diameter of the obtained sheet was a coarse cell structure of about 20 ⁇ m, and the density was 330 kg / m 3 .
- the reflectance of the foamed sheet at a wavelength of 550 nm was 96% (Al 2 O 3 standard), and the reflectance at a wavelength of 350 nm was 11% (Al 2 O 3 standard).
- the color difference ⁇ E after the ultraviolet irradiation test was 5.57 ⁇ 10 10 ⁇ .
- Both Examples 1 and 2 of the present invention have a fine and uniform cell structure with an average cell diameter of 1 ⁇ m and a high reflectance. From this, it turns out that it is useful as a light reflection board and a backlight panel by using the thermoplastic resin fine foam reflection sheet of this invention.
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Abstract
Description
そこで、光反射性に優れる微細な気泡を有し、高い成形加工性を有する樹脂シートが照明や液晶バックライトの反射板等として利用されている(例えば特許文献1参照)。
ところで、照明器具等のような外気に暴露される用途に供される光反射板には高い機能性が求められる。高い機能性とは防汚性、表面硬度、耐候性等のプラスチック製品に求められる種々の特性であるが、これらは一般的に成型体の表層部への付与により十分な機能性を得られるものが多い。
発泡性に大きな影響を与えず、高い機能性を付与する方法としては塗布、ラミネート等による方法が広く用いられている(例えば参考文献2参照)。しかしながら、このような方法は工程数が増えるため高コスト化の問題を抱えている。
しかし、発泡シートは発泡の際に微細な気泡だけでなく0.5mm以上(もしくはシート厚の1/2以上大きさ)の粗大な気泡が生じやすい。特に熱可塑性樹脂が非晶性樹脂である場合、この傾向が顕著となる。そのため、光反射材をはじめとする各種成形品として使用することが困難であるという問題があった。
(2)前記機能付与層が、帯電防止剤、紫外線吸収剤または酸化防止剤を含有する帯電防止層もしくは紫外線吸収層であることを特徴とする(1)に記載の熱可塑性樹脂微細発泡反射シート。
(3)前記帯電防止剤、紫外線吸収剤または酸化防止剤が、前記機能付与層のみに含有するか、または前記機能付与層の少なくとも1層に含有する帯電防止剤、紫外線吸収剤または酸化防止剤の含有量が、残りの層に含有する含有量より多いことを特徴とする(2)に記載の熱可塑性樹脂微細発泡反射シート。
(4)前記非発泡層がいずれも前記機能付与層を含むことを特徴とする(1)~(3)のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
(5)前記機能付与層中の樹脂の50質量%以上が前記発泡層と同じ熱可塑性樹脂によって構成されていることを特徴とする(1)~(4)のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
(6)前記熱可塑性樹脂が、ポリカーボネートであることを特徴とする(1)~(5)のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
(7)550nmの波長での反射率(酸化アルミニウム製標準白色板基準)が98%以上であることを特徴とする(1)~(6)のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
(8)350nmの波長での反射率(酸化アルミニウム製標準白色板基準)が30%以下であることを特徴とする(1)~(7)のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
(9)表面固有抵抗値が1×1012Ω以下であることを特徴とする(1)~(8)のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
(10)発泡反射シートの製造方法であって、発泡反射シートが(1)~(9)のいずれか1項に記載の熱可塑性樹脂微細発泡反射シートであり、かつ下記工程(a)~(c)を含むことを特徴とする発泡反射シートの製造方法。
(a)発泡層を形成するための熱可塑性樹脂層と、非発泡層を形成するための熱可塑性樹脂層とからなる少なくとも3層構造の樹脂シートであって、該非発泡性層の少なくとも一方が機能付与層を含み、該3層構造の樹脂シートを、共押出による一体成型により調製する工程
(b)該樹脂シートに不活性高圧ガスを含浸させる工程
(c)該樹脂シートを加熱して、発泡層を形成するための熱可塑性樹脂層を発泡させる工程
(11)発泡層を形成するための熱可塑性樹脂層の熱可塑性樹脂100質量部に対して気泡化核剤が、0.1~10質量部配合されている(10)に記載の発泡反射シートの製造方法。
(12)(1)~(9)のいずれか1項に記載の熱可塑性樹脂微細発泡反射シートからなる光反射板。
(13)(12)に記載の光反射板を有することを特徴とするバックライトパネル。
具体的には、80~100質量%が熱可塑性樹脂で構成されている形態は「熱可塑性樹脂からなる」または「熱可塑性樹脂から形成される」形態である。また、「熱可塑性樹脂からなる」または「熱可塑性樹脂から形成される」とは、好ましくは90~100質量%。より好ましくは95~100質量%が熱可塑性樹脂で構成される形態である。このことは、熱可塑性樹脂がより具体的な樹脂名で特定されている場合も同様である。
本発明の熱可塑性樹脂微細発泡反射シートにおいて、発泡層と非発泡層はいずれも熱可塑性樹脂で形成されるが、発泡層を形成する熱可塑性樹脂の組成と、非発泡層に形成された機能付与層を形成する熱可塑性樹脂の組成は、互いに異なっている。
本発明の熱可塑性樹脂微細発泡反射シートの発泡層は、熱可塑性樹脂からなる。当該熱可塑性樹脂に特に制限はないが、ポリオレフィン樹脂、ポリエステル樹脂、ポリカーボネート樹脂が挙げられ、本発明においては、ポリエステル樹脂、ポリカーボネート樹脂が好ましい。なかでもポリカーボネート樹脂は、軽量性、形状安定性、経済性などの特性に優れ、さらに光反射特性に優れるため好ましい。
なお、熱可塑性樹脂は非発泡層形成の観点から非晶性のものが好ましい。
発泡層の厚さは、上記の反射シートの用途、様態等により適宜に定まり、一義的に定めることはできないが、好ましくは300~5000μm、より好ましくは500~1500μmである。
気泡化核剤は、熱可塑性樹脂100質量部に対して0.1~10質量部配合されていることが好ましい。
なお、発泡層が気泡化核剤のように気泡を発生させるのに必要な化合物以外で、上記のような化合物を含有する場合、その含有量は、後述する機能付与層における含有量より少ないことが好ましい。
平均気泡径は10μm以下であるが、薄肉化と高反射率化の両立の観点から、7.0μm以下が好ましく、5.0μm以下がより好ましく、3.0μm以下がさらに好ましく、2.0μm以下が特に好ましい。
また、平均気泡径は、通常には0.5μm以上であり、1.0μm以上であってもよい。
なお、平均気泡径は以下の方法で測定できる。
ASTM D3576-77に準拠して求めた。発泡シートの断面の走査電子顕微鏡(SEM)写真を撮影し、撮影したSEM写真上に水平方向と垂直方向に直線を引き、直線が横切る気泡の弦の個々の長さを測定し、この平均値tを求めた。写真の倍率をMとして、下記式に代入して平均気泡径dを求める。
なお、発泡層の気泡数密度は以下の方法で測定できる。
発泡シートの縦断面についてSEM写真を撮影し、このSEM写真上において発泡層中の任意の100×100μmの領域を無作為に選び、その中に存在する気泡数nを計数し、1mm2当たりに存在する気泡数を算出する。得られた数値を3/2乗することで1mm3当たりの気泡数に換算し気泡数密度とした。
発泡体に形成される非発泡層の肉厚は30μm以上であり、60μm以上あることがより好ましい。また、一体成形する機能付与層の肉厚は30μm未満であり、より好ましくは25μm以下である。また、光学特性維持の観点から非発泡層は150μmを超えないことが好ましい。
非発泡層の厚みが30μm未満とすると非発泡層樹脂への機能性材料の添加濃度が増大し吸光性が増大する。このため、反射率等の光学特性が低下する。そのため、厚みが30μm未満の非発泡層を形成することは望ましくない。
具体的には、走査電子顕微鏡(SEM)写真を撮影し、熱可塑性樹脂微細発泡反射シートの表面部と気泡層の最も表層側のラインに平行線を引き、この平行線の間隔を未発泡層としての非発泡層の厚みとして測定できる。
本発明では、上記非発泡層の少なくとも一方において、その少なくともひとつの構成層として、機能付与層を設ける。発泡層の両面の非発泡層内に機能付与層を設けるのがより好ましい。その場合、機能付与層は、非発泡層内に含まれていればその非発泡層の位置は特に限定されない。最外層でも、最内層でも、中間層であってもよいが、実際上、最外層もしくは最内層がよい。
機能付与層における機能は、帯電防止、紫外線吸収、劣化防止等の直接反射防止そのもの以外の機能である。この機能のうち、本発明では、帯電防止や紫外線吸収が特に好適に付与できる。一体成形する機能付与層の肉厚を30μm未満(より好ましくは25μm以下)とすることで、粗大な気泡(いわゆる「フクレ」)の発生を防ぐことができる。
本発明においては有機の帯電防止剤が好ましく、アニオン系、カチオン系もしくはノニオン系の界面活性剤が好ましい。なかでもアニオン系の界面活性剤が好ましい。
このような界面活性剤は、例えば、丸善油化工業(株)のデノンV-57S、デノン2723が好ましく使用される。
帯電防止剤の含有量は、機能付与層の樹脂100質量部に対して、0.05~5質量部が好ましく、0.1~5質量部がより好ましく、0.1~2質量部がさらに好ましい。
サリチル酸系化合物としては、p-t-ブチルフェニルサリシレート、p-オクチルフェニルサリシレート等が挙げられる。
マロン酸エステル系化合物としては、プロパンジオイック酸[(4-メトキシフェニル)-メチレン]-ジメチルエステル等が挙げられる。
紫外線吸収剤(含光安定剤)の含有量は、機能付与層の樹脂100質量部に対して、0.05~10質量部が好ましく、0.1~5質量部がより好ましく、1~2質量部がさらに好ましい。
酸化防止剤は、紫外線吸収剤の安定化にも作用し、酸化防止剤の含有量は、機能付与層の樹脂100質量部に対して、0.05~10質量部が好ましく、0.1~5質量部がより好ましく、1~2質量部がさらに好ましい。
本発明の熱可塑性樹脂微細発泡反射シートの製造方法について以下に説明する。
本発明の熱可塑性樹脂微細発泡反射シートは、発泡層を形成するための熱可塑性樹脂層と、非発泡層を形成するための熱可塑性樹脂層からなる少なくとも3層構造の樹脂シートを一体成型により調製し、この樹脂シートを用いて製造される。
このうち、非発泡層の少なくとも一方に機能付与層を含み、機能を付与する添加剤を含有する。なお、非発泡層が機能付与層であっても構わない。
より具体的には、下記工程(a)~(c)を経て製造されることが好ましい。
(b)該樹脂シートに不活性高圧ガスを含浸させる工程、及び
(c)該樹脂シートを加熱して、発泡層を形成するための熱可塑性樹脂層を発泡させる工程。
本発明においては、発泡層の両面の非発泡層に機能付与層を含み、機能を付与する添加剤を含むことが好ましい。
また、上記工程(a)で得られた樹脂シートは無延伸の状態で不活性ガスを含浸させることが好ましい。延伸させてしまうと、ガスがシート内に十分に浸透しなくなるおそれがある。
有機溶剤としては、例えば、ベンゼン、トルエン、メチルエチルケトン、ギ酸エチル、アセトン、酢酸、ジオキサン、m-クレゾール、アニリン、アクリロニトリル、フタル酸ジメチル、ニトロエタン、ニトロメタン、ベンジルアルコールが挙げられる。なかでもアセトンが好適に用いられる。
また、加熱時間は30秒~10分が好ましく、10秒~5分がより好ましい。
熱可塑性樹脂微細発泡反射シートの550nmの波長での反射率と350nmの波長での反射率の測定は下記のようにして測定することができる。
分光光度計(例えば、日立ハイテク社製U-4100を使用し、リファレンスに酸化アルミニウム白色板(210-0740:日立ハイテクフィールディング社製)を使用し、例えば、分光スリット4nmの条件で、550nmもしくは350nmの波長での反射率を測定する。
熱可塑性樹脂微細発泡反射シートの表面固有抵抗値をこのように調整することで、熱可塑性樹脂微細発泡反射シートに帯電防止性を付与することができ、長期的な高反射性を維持することが可能となる。
高抵抗測定装置(例えば、アドバンテスト製R8340A)を用い50mmφプローブにて、印加電圧500Vの条件の下、表面固有抵抗値の測定を行う。
熱可塑性樹脂微細発泡反射シート全体の密度は、水中置換法で測定した。
住化スタイロンポリカーボネート社製のポリカーボネート樹脂SI8000Lに新日本理化製エヌジェスターNU100を0.5質量%添加した系を発泡層とし、この発泡層の表裏の両面に18μmの厚みの機能付与層を積層した厚みが600μmのポリカーボネートシートを得た。機能付与層は住化スタイロンポリカーボネート社製SI8000Lに界面活性剤系帯電防止剤のデノンV-57S(丸善油化工業社製)を0.5質量%、ベンゾフェノン系紫外線吸収剤を0.25質量%添加したコンパウンドとした。得られたシートを17℃、5.5MPaの二酸化炭素中で24時間処理した後、145℃の雰囲気中で1分間加熱し、発泡シートを作製した。発泡シートの厚みは1000μmであった。
この発泡シートに対して、以下の測定と評価を行った。
走査電子顕微鏡(SEM)写真を撮影し、発泡シートの表面部と気泡層の最も表層側のラインに平行線を引き、この平行線の間隔を未発泡層厚として測定した。
ASTM D3576-77に準拠して求めた。発泡シートの断面の走査電子顕微鏡(SEM)写真を撮影し、撮影したSEM写真上に水平方向と垂直方向に直線を引き、直線が横切る気泡の弦の個々の長さを測定し、この平均値tを求めた。写真の倍率をMとして、下記式に代入して平均気泡径dを求めた。
発泡シートの縦断面についてSEM写真を撮影し、このSEM写真上において発泡層中の任意の100×100μmの領域を無作為に選び、その中に存在する気泡数nを計数し、1mm2当たりに存在する気泡数を算出した。得られた数値を3/2乗することで1mm3当たりの気泡数に換算し、気泡数密度とした。
水中置換法にて発泡シートの比重を測定し、これを発泡体の密度とした。
・全光線反射率
(株)日立ハイテクノロジーズ製の分光光度計 U-4100を用いて、分光スリット4nmの条件にて350nm、550nmの波長におけ反射率を測定した。表1には、酸化アルミニウムの微粉末を固めた白板の反射率を100%としたときの各発泡シートの反射率を相対値で示している。
JIS K 6911に準拠して求めた。ADVANTEST製のR8340Aを使用し、高抵抗測定用チャンバーR12702Aにて表面固有抵抗値の測定を行った。
コニカミノルタ社製のCM-300を使用し、Luv表示系における色調の測定を行った後、スガ試験器社製の愛スーパーUVテスターにて300μW/m2、照射距離100mmの条件で16時間の照射を行った。照射後のサンプルを再度、上記CM-300を使用して測定を行い、下記式から、色差ΔEを求め、耐紫外線変色性の評価を行った。
得られた結果を下記表1にまとめた。
表裏の両面の機能付与層の厚みを30μmに変更した以外は、実施例1と同様にして発泡シートを作製した。
実施例1と同様の評価を行った。
得られたシートは気泡径1μm程度の均一な発泡体であり、密度は330kg/m3であり、表層部に50μm程度の未発泡層を有していた。発泡シートの550nmの波長での反射率は98%(Al2O3基準)、350nmの波長での反射率は13%(Al2O3基準)であった。また、表面固有抵抗値は8.62×1010Ω、紫外線照射試験後の色差のΔEは8であった。
実施例1と同様のコンパウンドを用い、表裏面に60μmの機能付与層を積層した600μm厚のポリカーボネートシートを実施例1に記載の方法にて発泡したシートを得た。得られたシート表面には多量の風船状のフクレが発生し、光学特性、表面固有抵抗値、紫外線照射試験等の評価が実施可能なサンプルを得ることができなかった。
実施例1の発泡層と同様のコンパウンドに対し界面活性剤系帯電防止剤デノンV-57S(丸善油化工業社製)を0.5質量%、ベンゾフェノン系紫外線吸収剤を0.25質量%添加したコンパウンドにて厚さ600μmの単一層構造のポリカーボネートシートを得た。得られたシートを実施例1に記載の方法にて発泡したシートを得た。得られたシートの平均気泡径は20μm程度の粗大な気泡構造であり、密度は330kg/m3であった。発泡シートの550nmの波長での反射率は96%(Al2O3基準)、350nmの波長での反射率は11%(Al2O3基準)であった。また、5.57×1010Ω、紫外線照射試験後の色差のΔEは9であった。
11 発泡層
12 非発泡層又は機能付与層を含む非発泡層
13 気泡
Claims (13)
- 発泡層と、該発泡層を挟んで上下に、150μm以下で30μm以上の厚みの非発泡層を有する熱可塑性樹脂微細発泡反射シートであって、一体成形されてなり、該発泡層が、平均気泡径10μm以下0.5μm以上で、かつ気泡数密度が1×106個/mm3以上1.0×1012個/mm3以下の均一な気泡構造を有する熱可塑性樹脂微細発泡体であり、該非発泡層の少なくとも一方に機能付与層を含むことを特徴とする熱可塑性樹脂微細発泡反射シート。
- 前記機能付与層が、帯電防止剤、紫外線吸収剤または酸化防止剤を含有する帯電防止層もしくは紫外線吸収層であることを特徴とする請求項1に記載の熱可塑性樹脂微細発泡反射シート。
- 前記帯電防止剤、紫外線吸収剤または酸化防止剤が、前記機能付与層のみに含有するか、または前記機能付与層の少なくとも1層に含有する帯電防止剤、紫外線吸収剤または酸化防止剤の含有量が、残りの層に含有する含有量より多いことを特徴とする請求項2に記載の熱可塑性樹脂微細発泡反射シート。
- 前記非発泡層がいずれも前記機能付与層を含むことを特徴とする請求項1~3のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
- 前記機能付与層中の樹脂の50質量%以上が前記発泡層と同じ熱可塑性樹脂によって構成されていることを特徴とする請求項1~4のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
- 前記熱可塑性樹脂が、ポリカーボネートであることを特徴とする請求項1~5のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
- 550nmの波長での反射率(酸化アルミニウム製標準白色板基準)が98%以上であることを特徴とする請求項1~6のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
- 350nmの波長での反射率(酸化アルミニウム製標準白色板基準)が30%以下であることを特徴とする請求項1~7のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
- 表面固有抵抗値が1×1012Ω以下であることを特徴とする請求項1~8のいずれか1項に記載の熱可塑性樹脂微細発泡反射シート。
- 発泡反射シートの製造方法であって、発泡反射シートが請求項1~9のいずれか1項に記載の熱可塑性樹脂微細発泡反射シートであり、かつ下記工程(a)~(c)を含むことを特徴とする発泡反射シートの製造方法。
(a)発泡層を形成するための熱可塑性樹脂層と、非発泡層を形成するための熱可塑性樹脂層とからなる少なくとも3層構造の樹脂シートであって、該非発泡性層の少なくとも一方が機能付与層を含み、該3層構造の樹脂シートを、共押出による一体成型により調製する工程
(b)該樹脂シートに不活性高圧ガスを含浸させる工程
(c)該樹脂シートを加熱して、発泡層を形成するための熱可塑性樹脂層を発泡させる工程 - 発泡層を形成するための熱可塑性樹脂層の熱可塑性樹脂100質量部に対して気泡化核剤が、0.1~10質量部配合されている請求項10に記載の発泡反射シートの製造方法。
- 請求項1~9のいずれか1項に記載の熱可塑性樹脂微細発泡反射シートからなる光反射板。
- 請求項12に記載の光反射板を有することを特徴とするバックライトパネル。
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KR20147007630A KR20140107176A (ko) | 2012-08-09 | 2013-08-06 | 열가소성 수지 미세 발포 반사시트, 광 반사판, 백라이트 패널 및 발포 반사시트의 제조방법 |
EP13828107.6A EP2884313A4 (en) | 2012-08-09 | 2013-08-06 | THERMOPLASTIC RESIN MICRO-FOAM REFLECTIVE SHEET, OPTICAL REFLECTION PLATE, BACKLIGHT PANEL, AND PROCESS FOR PRODUCING FOAM REFLECTIVE SHEET |
CN201380003151.6A CN103827702B (zh) | 2012-08-09 | 2013-08-06 | 热塑性树脂微细发泡反射片、光反射板、背光面板及发泡反射片的制造方法 |
US14/330,325 US9908300B2 (en) | 2012-08-09 | 2014-07-14 | Thermoplastic resin finely-foamed reflective sheet, light-reflecting plate, backlight panel, and method of producing the foamed reflective sheet |
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JP2018082352A (ja) * | 2016-11-17 | 2018-05-24 | 古河電気工業株式会社 | 光反射板、照明装置、照明装置からの音の取り出し方法 |
JP2019050577A (ja) * | 2018-10-10 | 2019-03-28 | 古河電気工業株式会社 | 音響振動板を兼ねる光反射板を具備するled照明装置、及び、音響振動板を兼ねる光反射板を具備するled照明装置からの音の取り出し方法 |
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EP2884313A4 (en) | 2016-01-20 |
US9908300B2 (en) | 2018-03-06 |
US20140322505A1 (en) | 2014-10-30 |
TW201408475A (zh) | 2014-03-01 |
EP2884313A1 (en) | 2015-06-17 |
JP6026434B2 (ja) | 2016-11-16 |
TWI554386B (zh) | 2016-10-21 |
KR20140107176A (ko) | 2014-09-04 |
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JPWO2014024882A1 (ja) | 2016-07-25 |
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