JP5834415B2 - LAMINATED FILM MANUFACTURING METHOD AND MOLDED BODY MANUFACTURING METHOD - Google Patents

Description

  The present invention relates to a moldable metallic glossy film, and relates to a film and a molded body that can be suitably used for decorative exteriors such as household electric appliances and mobile phones.

Conventionally, as a resin film having a metal-like appearance (hereinafter referred to as a metal-like film), for example, a resin film having a thin metal layer formed by deposition or sputtering on one surface is known. It is mainly used for decorative purposes. However, this metallic film has a problem that problems such as peeling and cracking of the metal layer easily occur during molding. As a countermeasure against this problem, there is known a proposal (for example, see Patent Document 1) in which an adhesive layer is interposed between the resin film and the metal layer to improve adhesion, but the molding conditions are severe. Has not yet reached a satisfactory improvement.

  In addition, the ink component mixed with glittering powder (aluminum powder, etc.) and thermoplastic resin is solid-printed or coated on one side of the thermoplastic resin film, giving a metallic color and suitable for vacuum forming ( For example, Patent Document 2) has been proposed. In this case as well, a metal-like appearance cannot be obtained unless the metal powder is added at a high concentration, and also a resin film containing a metal at a high concentration. For this reason, there is a problem that recycling is difficult.

  On the other hand, various laminated films that exhibit a metallic tone without using a metal have been proposed. For example, a film that selectively reflects a specific wavelength (for example, by laminating resin layers having different refractive indexes alternately in multiple layers) Patent Documents 3 to 6) are known. Among these, a film that selectively reflects a specific wavelength acts as a filter that transmits or reflects specific light, and is used for a metallic reflector for a backlight such as a liquid crystal display and a reflective polarizer. .

  However, a laminated film using interference reflection often uses an amorphous resin for the resin of one layer if an attempt is made to make a difference in refractive index in order to enhance the metallic luster. In this case, the amorphous resin may be whitened and contracted by hot water depending on use conditions. In recent years, the use of decorative decorative films has been expanding, and boiling tests and high-temperature moisture resistance tests are also being imposed on reliability tests so that they can be used in various applications. What is superior to

  On the other hand, in film applications for laminated steel sheets using laminated films, the layer is actively used as a method to suppress whitening (hereinafter also referred to as hot water whitening) that occurs when it is in contact with hot water or kept under high temperature and high humidity. It is known to crystallize, and it is not hydrothermally whitened by adding a crystal component to an amorphous resin, increasing the crystallization speed, or providing a process for crystallization in a laminating process or the like (hereinafter referred to as this process). A method is also disclosed (for example, Patent Documents 8 to 15). However, when this method is applied, the difference in in-plane refractive index between the A layer and the B layer is difficult to be achieved and the glossiness is inferior, and it is difficult to achieve both glossiness and heat-resistant water whitening property.

  Further, as another method for suppressing hot water whitening of a laminated film, it has been proposed to inhibit water absorption into the layer. For example, it is known to reduce the progress of whitening by laminating a resin having a low water vapor transmission rate, such as a resin having a low water vapor transmission rate or a resin having a large amount of particles added to both surface layers.

JP-A-8-216334 (2nd page) JP-A-8-183057 (2nd page) Japanese Patent Laid-Open No. 3-41401 (2nd page) JP-A-4-295804 (page 2) Japanese translation of PCT publication No. 9-506837 (2nd page) JP 2007-203688 A (2nd page) Japanese Patent Laying-Open No. 2005-254629 (page 4) JP-A-6-126916 (2nd page) JP-A-9-012743 (2nd page) JP 2004-217683 A (2nd page) JP 2004-074450 A (page 2) JP 2004-114476 A (second page) JP 2004-175820 A (second page) JP 2005-153320 A (2nd page) JP 2007-277365 A (second page)

  The objective of this invention is providing the film which is excellent in a metallic glossiness, and has heat-resistant water whitening property.

In order to solve the above problems, the present invention has the following configuration. That is, a layer (A layer) made of crystalline polyester resin A and a layer (B layer) having an average layer thickness of 30 to 180 nm in which a crystalline resin is dispersed in amorphous polyester resin B are alternately arranged. A biaxially oriented film laminated with 200 or more layers, wherein the lamination ratio of the A layer and the B layer is in the range of 3.0 to 0.8, and the crystalline resin dispersed in the B layer is When the vertical cross section is observed with a transmission microscope (TEM), the area fraction of the crystalline resin portion dispersed in a diameter of 1 to 20 nm and occupying the area of the cross section of the B layer is 0.1 to 0.3. In addition, the A layer and the B layer laminated on the 200 layers or more are sandwiched between crystalline polyester resin layers having a thickness of 1 to 7 μm, and the B layer is a crystal having a composition different from that of the polyester resin B. Mix at least two kinds of functional polyester It is comprised by the obtained resin composition, As said at least 2 or more types of crystalline polyester, the crystalline polyester whose crystal melting temperature is 235 degreeC or more and 270 degrees C or less, and a crystal melting temperature are 180 degreeC or more and less than 235 degreeC The crystalline polyester is used, and is heated and aged at a temperature of (crystallization temperature −20) ° C. or more and (melting point −60) ° C. or less of any crystalline polyester contained in the B layer. It is the manufacturing method of the biaxially oriented laminated film characterized.

  The film of the present invention has excellent heat-resistant water whitening property, hardly causes whitening even when in contact with hot water, and is excellent in metallic luster, so that it is a glossy decoration material for automobile exterior members, mobile phones and household electric appliances. It can use suitably for.

  The present inventors have studied the solution of the problems of the prior art described above, and have found that the configuration can be dramatically improved by adopting the configuration described in the section for solving the problems.

  The phenomenon of whitening in a laminated film using an amorphous resin described in the above-mentioned section of the prior art investigated by the present inventors is used as an optical film by laminating two different kinds of resins in multiple layers. Its optical thickness is designed to be about 1/4 of the wavelength of the target light (half the wavelength of the target light as a pair of layers), and moisture may enter between layers in a high humidity atmosphere. In addition, when an amorphous resin is used, moisture easily enters the film through the amorphous part, which causes bubbles and causes whitening. A) The amorphous resin has a high amorphous property, b When the resin is soft) and the water absorption is high, bubbles tend to be generated more easily. Such bubble formation impairs the optical properties of the film.

  The present invention has a layer (B layer) in which a crystalline resin is dispersed in an amorphous polyester resin B, and the crystalline resin observes a vertical section of the film with a transmission electron microscope (TEM). In this case, it is dispersed in the amorphous polyester resin with a diameter of 1 to 20 nm. By doing so, the amorphous polyester is restrained and hot water whitening can be suppressed. Here, in the crystalline resin, “crystallinity” means that, in DSC, the heat of crystal fusion when the rate of temperature rise is 20 ° C./min is 10 to 100 mJ / mg. The crystalline resin may be a mixture of two or more kinds of resins. If the size of the crystalline resin is less than 1 nm, the effect of heat-resistant water whitening is low, and if it is greater than 20 nm, the film is undesirably whitened by light scattering. A more preferable diameter of the crystalline resin is 2 to 15 nm. The diameter of the crystalline resin is adjusted by the compatibility of the resin, the temperature during melt kneading, the number of rotations of the screw, and the melting time. Each resin has an optimum molten state capable of realizing good dispersion, and the heating temperature by the kneading apparatus is adjusted so as to be in this state. Also by these means, when the diameter of the crystalline resin is larger than the target range, a method of adding a compatibilizing agent is preferable. Preferably, the amorphous polyester resin and the crystalline resin are compounded in advance using a biaxial kneader, and the desired fine dispersion diameter can be obtained by using the chip.

  In the present invention, at least one of the crystalline resins dispersed in the polyester resin B is preferably a resin that is relatively compatible with the amorphous polyester resin, and is preferably a polyester resin. Further, at least one of the crystalline resins preferably has a crystal melting temperature of 225 ° C. or higher and 270 ° C. or lower. If the crystal melting temperature is lower than 225 ° C., the crystal is completely melted by the heat treatment in the tenter. As a result, the heat-resistant water whitening property is hardly exhibited. On the other hand, if the crystal melting temperature is higher than 270 ° C., unmelted material is mixed into the film during extrusion, which is not preferable. A particularly preferable crystal melting temperature is 240 ° C. or higher and 260 ° C. or lower. An example of a particularly preferable crystalline resin is a resin having the same composition as the polyester resin A described later. By dispersing in the polyester resin B, the adhesion with the A layer is improved, and a flow mark or the like at the time of melt extrusion. It is also difficult to cause stacking disorder.

  Further, in the biaxially oriented laminated film of the present invention, the crystalline resin dispersed in the B layer is a crystalline resin that occupies per unit area of the B layer cross section in the cross-sectional image when the vertical cross section of the film is observed with a TEM. Generation | occurrence | production of a bubble is suppressed as an area fraction of 0.1-0.3, and hot water whitening can be suppressed. When the area fraction is less than 0.1, the heat-resistant water whitening property is not sufficiently exhibited. On the other hand, if the area fraction is larger than 0.3, although there is no problem with the heat-resistant water whitening property, haze due to scattering increases and the metallic luster is impaired. A more preferable range is 0.15 to 0.25.

  The biaxially oriented laminated film of the present invention has a structure in which 200 layers or more of layers (A layer) made of crystalline polyester resin A and the B layer are alternately laminated. The alternately stacked structure is defined as having a structure in which the A layer and the B layer appear alternately in the thickness direction. The A layer and the B layer must each include 200 layers or more, but more preferably, the total number of layers of the A layer and the B layer is 600 layers or more. Further, the total number of layers of the A layer and the B layer is preferably 800 layers or more. If a structure in which 200 layers or more of the A layer and the B layer are laminated is not included, sufficient reflectance cannot be obtained, and the metallic appearance with high luminance is not obtained. Moreover, since the penetration | invasion of the water | moisture content to B layer is inhibited, so that there are many layers, it is advantageous to heat-resistant water whitening property. Further, when 200 layers or more of A layers and B layers are alternately included, it is easy to set the reflectance in the wavelength band of 400 nm to 1000 nm to 30% or more when each layer is a film having an appropriate optical thickness. . Further, when the total number of layers of the A layer and the B layer is 600 layers or more, it becomes easy to set the reflectance in the wavelength band of 400 nm to 1000 nm to 60% or more, and it has a metallic appearance with extremely high luminance. Becomes easy. Further, the upper limit value of the number of layers is not particularly limited, but it is 3000 layers or less in consideration of a decrease in wavelength selectivity due to a decrease in stacking accuracy due to an increase in the size of the device or an increase in the number of layers. This is common in normal use.

  The biaxially oriented film refers to a film in which the refractive index in the film longitudinal direction and the width direction is higher than the refractive index in the thickness direction, and can be usually obtained by stretching in the longitudinal direction and the width direction of the film.

  Moreover, when the average layer thickness of the B layer of the present invention is in the range of 30 to 180 nm, whitening and hot water whitening due to thermal crystallization can be suppressed. Even if the average layer thickness of the B layer is less than 30 μm, the effect is obtained, but it is not preferable because a metallic appearance cannot be obtained. Further, when the lamination ratio of the A layer and the B layer is in the range of 3.0 to 0.8, a metallic appearance can be obtained. More preferably, it is the range of 1.5-1.0.

  The crystalline polyester resin A used in the present invention preferably has a structure obtained by polycondensation of a dicarboxylic acid component and a diol component because of its simple synthesis. Here, the polyester resin A being crystalline means that the heat of crystal melting is 4 mJ / mg or more and the melting point is 230 ° C. or more in differential calorimetry (DSC). Typical examples of the polyester resin A that can be used include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and polyethylene diphenylate. It is. In particular, polyethylene terephthalate is preferable because it is inexpensive and can be used in a wide variety of applications. In the laminated film of the present invention, the crystalline polyester resin A is preferably polyethylene terephthalate or polyethylene naphthalate. The crystalline polyester resin A constituting the A layer may be a mixture of two or more polyester resins as long as it is crystalline.

  The amorphous polyester resin B used in the present invention is desirable because it is easy to synthesize. Like the polyester resin A, the amorphous polyester resin B desirably has a structure obtained by polycondensation of a dicarboxylic acid component and a diol component. Here, that the polyester resin B is amorphous means that the heat of crystal melting is 5 mJ / mg in a differential calorimetry (DSC) after exposure to an atmosphere of 150 ° C. for 24 hours. It means the following. In order to enhance glossiness, it is preferable to use a material having a refractive index as low as possible. Preferable amorphous polyester has, for example, a structure obtained by polycondensation using at least three or more dicarboxylic acid components and diol components. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, Examples include 4'-diphenylsulfone dicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexanedicarboxylic acid and ester-forming derivatives thereof. Examples of the glycol component include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, and 2,2-bis (4 ′ -Β-hydroxyethoxyphenyl) propane, isosorbate, 1,4-cyclohexanedimethanol, spiroglycol, and ester-forming derivatives thereof. As a particularly preferred amorphous polyester resin B, the ratio of terephthalic acid residues to the total dicarboxylic acid residues is 10 to 90 mol%, the ratio of cyclohexanedicarboxylic acid residues is 10 to 90 mol%, and the total diol It is a copolyester composed of spiroglycol having a proportion of ethylene glycol residues in the residues of 70 to 90 mol% and a proportion of spiroglycol residues of 10 to 30 mol%. The amorphous polyester resin B used for the B layer may be a mixture of two or more polyester resins as long as it is amorphous.

  Examples of another preferable amorphous polyester resin B include a copolymer polyester having a structure obtained by copolymerization using ethylene glycol, spiro glycol and butylene glycol, and the three kinds of diols. There is a polyester obtained by blending a polyester having a structure obtained by polymerization. In the polyester containing cyclohexanedicarboxylic acid and spiroglycol, the difference between the in-plane average refractive index of the A layer and the in-plane average refractive index of the B layer becomes large, and a film having a high reflectance can be obtained. Moreover, since the glass transition temperature difference with polyethylene terephthalate or polyethylene naphthalate is small, it is difficult to be overstretched at the time of molding, and it is preferable that delamination is difficult. However, on the other hand, the polyester containing cyclohexanedicarboxylic acid and spiroglycol may be reduced in heat-resistant water whitening property, so it is also preferable to use it by kneading with other amorphous polyester having a low refractive index. It is a mode.

In the biaxially oriented laminated film of the present invention, the B layer is composed of a resin composition obtained by mixing the polyester resin B and at least two kinds of crystalline polyesters having different compositions, and the at least as two or more crystalline polyester, a crystalline polyester crystalline melting temperature of 235 ° C. or higher 270 ° C. or less, Ru der those crystalline polyester crystalline melting temperature of 235 lower than ° C. 180 ° C. or higher was used. If a crystalline polyester having a crystal melting temperature of 235 ° C. or higher and 270 ° C. or lower is included, the oriented crystals remain unmelted even in the heat treatment of the tenter, so that the heat-resistant water whitening property is exhibited. An example of a particularly preferable crystalline polyester is polyester resin A. By being finely dispersed in polyester resin B, adhesion with A layer is improved, and stacking disorder such as a flow mark hardly occurs during melt extrusion.

  Further, it is preferable to use a crystalline polyester having a crystal melting temperature of 180 ° C. or higher and lower than 235 ° C., because the crystal is melted by the heat treatment of the tenter and the reflectance is improved. In particular, when the crystal melting temperature is 2 to 7 ° C. lower than the tenter heat treatment temperature, the orientation is relaxed, but a few fine crystals remain, so that high reflectivity can be achieved while maintaining the heat-resistant water whitening property. This is preferable because it is possible. Further, when the layer thickness of the B layer is in the range of 30 to 180 nm, the orientationally relaxed microcrystals are less likely to grow even when heated by a hydrothermal test, which is more effective. Moreover, it is preferable that these 2 types of resin is contained in the ratio of 0.5-2. In contrast to a crystalline polyester having a crystal melting temperature of 235 ° C. or higher and 270 ° C. or lower, if the crystalline polyester having a crystal melting temperature of 180 ° C. or higher and lower than 235 ° C. is lower than 0.5, the reflectance does not increase so much. On the other hand, when it is larger than 2, the number of constrained crystals is too small, and the heat-resistant water whitening property is low.

  As the crystalline polyester having a crystal melting temperature of 180 ° C. or higher and 235 ° C. or lower, polybutylene terephthalate, isophthalic acid copolymerized polyethylene terephthalate, 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate, or the like is preferable. On the other hand, since polybutylene terephthalate has a high crystallization speed and is easily whitened, isophthalic acid copolymerized polyethylene terephthalate and 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate are particularly preferable.

  In the A layer and B layer of the biaxially oriented laminated polyester film of the present invention, various additives such as an antioxidant, an antistatic agent, a crystal nucleating agent, inorganic particles, and organic particles are added to the extent that the characteristics of the invention are not impaired. Further, a thickener, a heat stabilizer, a lubricant, an infrared absorber, an ultraviolet absorber, a dopant for adjusting the refractive index, and the like may be added.

  In the biaxially oriented laminated polyester film of the present invention, the A layer and the B layer are not equal in in-plane average refractive index in order to produce a metallic luster. The in-plane average refractive index of the A layer is preferably relatively higher than the in-plane average refractive index of the B layer. The difference between the in-plane average refractive index of the A layer and the in-plane average refractive index of the B layer is preferably 0.03 or more. More preferably, it is 0.05 or more, More preferably, it is 0.1 or more. When the in-plane average refractive index difference is smaller than 0.03, sufficient reflectance may not be obtained. Further, when the difference between the in-plane average refractive index and the thickness direction refractive index of the A layer is 0.03 or more, and the difference between the in-plane average refractive index and the thickness direction refractive index of the B layer is 0.03 or less, the incident angle Even if becomes larger, the reflectance of the reflection peak does not decrease, which is more preferable.

  As a preferable combination of the crystalline polyester resin A and the amorphous polyester resin B, a combination in which the glass transition temperature difference between the polyester resin A and the polyester resin B is 20 ° C. or less is preferable. When the glass transition temperature difference is larger than 20 ° C., the thickness uniformity at the time of forming the laminated film becomes poor, and the appearance of metallic luster tends to be poor. Also, when a laminated film is formed, problems such as overstretching tend to occur.

In the biaxially oriented laminated film of the present invention, the A layer and the B layer laminated on the 200 layers or more are sandwiched between crystalline polyester resin layers (referred to as C layers for convenience) having a thickness of 1 to 7 μm. Here, there may be a layer made of another resin between the A layer and the B layer and the C layer which are the outermost layers of the A layer and the B layer laminated to 200 layers or more, but the layers are directly laminated. It is desirable. By providing such a C layer, it is difficult for water vapor to enter, and the heat-resistant water whitening property is excellent. Furthermore, by making the layer B less likely to be impregnated with water vapor due to the water vapor barrier effect due to the multi-interface, and by setting the layer thickness of the layer B in the range of 30 to 180 nm, the growth of the thermal crystals of the layer B and the bubbles during the hydrothermal treatment Growth is suppressed The biaxially oriented laminated film of the present invention preferably has an absolute reflectance of 20% or more in the wavelength band of 400 nm to 700 nm. Thereby, a glossy film can be obtained. For this purpose, the band to be reflected can be brought close to a desired value by gradually increasing or decreasing the layer thickness within a range of 20 nm to 500 nm. A more ideal range of the layer thickness is 30 nm or more and 370 nm or less. More preferably, the absolute reflectance in the wavelength band of 400 nm to 1000 nm on both surfaces of the film is 30% or more. In this case, the glossy feeling is maintained after molding, and the color hardly changes depending on the viewing angle. This is because the absolute reflectance is also 30% or higher on the higher wavelength side (700 nm or more) than visible light. Even if the film thickness is reduced by stretching or the reflection band is shifted to the lower wavelength side depending on the viewing angle. This is because the absolute reflectance in the visible light region can be maintained at 30% or more. More preferably, the absolute reflectance in the wavelength band of 400 nm to 1000 nm is 60% or more. The higher the absolute reflectance, the higher the glossiness and the metallic appearance. The reflection band is designed so that reflection occurs based on the thickness of each layer based on Equation 1 below. The reflectance is controlled by the difference in refractive index between the A layer and the B layer and the number of layers of the A layer and the B layer.
2 × (na · da + nb · db) = λ Equation 1
na: In-plane average refractive index of the A layer nb: In-plane average refractive index of the B layer da: Layer thickness (nm) of the A layer
db: Layer thickness of layer B (nm)
λ: main reflection wavelength (primary reflection wavelength)
By taking such a structure, the biaxially oriented laminated film of the present invention is excellent in the texture as a metallic tone, and a film excellent in heat-resistant water whitening property can be obtained. The heat-resistant water whitening as used herein means that the film appearance is hardly whitened when brought into contact with hot water or high-temperature steam at least 60 ° C. or more and 120 ° C. or less. The film preferably has a haze of less than 8% after hot water treatment at 95 ° C. for 1 hour. If it is less than 8%, the laminated film of the present invention can be suitably used as a decorative material. More preferably, it is less than 6%, More preferably, it is less than 4%.

Further, the biaxially oriented laminated film of the present invention, any of the crystalline polyester constituting the layer B (the crystallization temperature -20) ° C. or higher, Ru Ejingusu heated at a temperature of (melting point -60) ° C. or less. By performing heat aging, a large number of microcrystal nuclei in the B layer are generated, and the heat-resistant water whitening property is improved. In particular, when the average layer thickness of the B layer is in the range of 30 to 180 nm, crystal growth is suppressed and crystal nuclei are generated. Therefore, whitening due to thermal crystallization can be suppressed relatively while suppressing hot water whitening. Therefore, it is preferable. The aging time varies depending on the temperature, but if it is in the temperature range of (crystallization temperature-20 to crystallization temperature-10) ° C., it is 1 hour to less than 12 hours, and if it is higher than (crystallization temperature−10) ° C., it is 5 It is preferable that it is less than 1 minute.

  When the biaxially oriented laminated film of the present invention is used for a molded body, the molded body is made of a resin base material, the biaxially oriented laminated film of the present invention integrally laminated on the surface of the base material, and if necessary. It is preferable to have a colored layer. The material of the substrate is not particularly limited as long as it can be molded by various molding methods. For example, acrylic resin, polycarbonate resin, polybutylene terephthalate resin, acrylonitrile-butadiene styrene copolymer (ABS resin), acrylonitrile-styrene copolymer Examples include polymers (AS resins), FPR resins, polystyrene resins, polyether methylene resins, and polypropylene foam resins. The color tone and shape can be variously selected according to the purpose. A preferable resin is preferable because the surface hardness is improved by using a resin substrate having a high hardness such as an acrylic resin. As a method of integral molding of resin molding and laminated film, a sheet or film for decorative molding on which a pattern or the like is printed is used, and the sheet is integrated with the surface of the base material of the molded body by in-mold decorative molding. Although the method is widely performed, it is not particularly limited, and other methods such as injection molding, press molding, in-mold transfer molding method, thermoject method, CFI method and the like may be used.

  On the surface of the biaxially oriented laminated film of the present invention, a hard coat layer, a colored layer, a slippery layer, an antistatic layer, an anti-abrasion layer, an antireflection layer, an ultraviolet absorption layer, a printing layer, a transparent conductive layer, a gas barrier layer Functional layers such as a hologram layer, a release layer, an adhesive layer, an emboss layer, and an adhesive layer may be formed.

  Since the biaxially oriented laminated film of the present invention is composed of a polymer and basically does not contain metal or heavy metal, it has a low environmental load, is excellent in recyclability, and does not cause electromagnetic interference. In addition, since various molding methods such as vacuum molding, vacuum pressure molding, plug-assist vacuum pressure molding, in-mold molding, insert molding, cold molding, and press molding can be applied, three-dimensional shapes shall be formed at low cost. Is possible. The molding method is not particularly limited, and generally known molding methods such as vacuum molding method, vacuum / pressure forming method, blow molding method, press molding method, insert injection molding method, in-mold (gold) It can be molded by a molding method, an extrusion molding method, or the like. The vacuum forming method and the vacuum / pressure forming method are as follows. First, a pressure-sensitive adhesive sheet for molding processing is attached to the entire surface or a part of a thermoplastic resin substrate, and this laminate is placed at a predetermined position of a molding machine and heated. Soften, feed wooden mold or mold from below, draw in vacuum and adhere to the mold (vacuum forming method), or draw in vacuum and press with compressed air from the opposite side to adhere to the mold (vacuum and pressure forming method) This is a molding method in which the molded body is removed from the mold after cooling and a molded body is obtained.

  In the molded body thus molded, the biaxially oriented laminated film of the present invention preferably has a structure in which the end is bent inward or is covered with a molding resin and the end face is not exposed. . By adopting such a structure, it is possible to prevent moisture from entering from the end face, so that hot water whitening can be suppressed.

  Next, the manufacturing method of the biaxially oriented laminated film of the present invention will be described below with specific examples.

  The crystalline polyester resin A can be obtained by using a commercially available polyester resin or by polycondensation by a known method. For example, in the case of a polyethylene terephthalate (hereinafter referred to as PET) resin, it is obtained as follows. be able to.

  Magnesium acetate and antimony trioxide are added to a mixture of dimethyl terephthalate and ethylene glycol, the temperature is gradually raised, and finally the ester exchange reaction is performed while distilling methanol at 220 ° C. Next, an 85% aqueous solution of phosphoric acid is added to the transesterification reaction product, and then transferred to a polycondensation reaction kettle. The reaction system is gradually depressurized while being heated in the polymerization kettle, and a polycondensation reaction is performed at 290 ° C. under a reduced pressure of 1 hPa to obtain a polyethylene terephthalate resin having a desired intrinsic viscosity. In the case of adding particles, it is preferable to carry out polymerization by adding a slurry in which particles are dispersed in ethylene glycol to a polymerization reaction kettle so as to have a predetermined particle concentration.

  As the amorphous polyester resin B, a commercially available polyester resin can be used or obtained by polycondensation by a known method. For example, in the case of a PET resin copolymerized with cyclohexanedicarboxylic acid and spiroglycol, It can be obtained as follows.

  While adding manganese acetate and potassium hydroxide to a mixture of dimethyl terephthalate, dimethyl cyclohexanedicarboxylate, spiroglycol and ethylene glycol, dissolve the mixture, gradually raise the temperature, and finally distill methanol at 235 ° C. A transesterification reaction is performed. Next, after adding a trimethyl phosphoric acid / ethylene glycol solution and a phosphorus-based antioxidant to the transesterification product, the product is transferred to a polycondensation reaction kettle. The reaction system is gradually depressurized while heating in the polymerization kettle, and a polycondensation reaction is performed at 285 ° C. under a reduced pressure of 1 hPa to obtain a copolymer PET resin having a desired intrinsic viscosity. In the case of adding particles, it is preferable to carry out polymerization by adding a slurry in which particles are dispersed in ethylene glycol to a polymerization reaction kettle so as to have a predetermined particle concentration.

  The method for producing the film of the present invention using the polyester resin obtained as described above will be described with specific examples. First, when mixing the polyester resin to be used, it measures and mixes so that it may become a specific ratio. Next, drying is performed, for example, at 150 ° C. for 5 hours in a nitrogen atmosphere or a vacuum atmosphere, and the moisture content in the polyester resin is preferably 50 ppm or less. Thereafter, it is supplied to an extruder and melt extruded. In addition, when performing melt extrusion using a vent type twin screw extruder, the resin drying step may be omitted. Next, foreign matter is removed and the amount of extrusion is leveled through a filter and a gear pump, and the sheet is discharged from the T die onto the cooling drum in a sheet form. In that case, for example, a method of applying static electricity using a wire-like electrode or a tape-like electrode, a casting method in which a water film is provided between the casting drum and the extruded polymer sheet, and the glass transition of the polyester resin of the A layer by changing the casting drum temperature. The sheet polymer is brought into close contact with the casting drum by a method of sticking the extruded polymer at a point temperature to (glass transition temperature −20) (° C.), or a method combining a plurality of these methods, and solidified by cooling. An unstretched film is obtained. Among these casting methods, when using polyester, a method of applying an electrostatic force is preferably used from the viewpoint of productivity and flatness.

  Subsequently, the unstretched film is stretched in the longitudinal direction and then stretched in the width direction, or the stretched film is stretched in the width direction and then stretched in the longitudinal direction, or the longitudinal direction and the width direction of the film. The film is stretched by a simultaneous biaxial stretching method or the like that stretches substantially simultaneously to form a biaxially oriented film.

  The stretching ratio in such stretching operation is preferably 2.5 to 3.5 times, more preferably 2.8 to 3.5 times, and particularly preferably 3 to 3 times in each of the longitudinal direction and the width direction. .4 times is adopted. The stretching speed is desirably 1,000 to 200,000% / min. Further, the stretching temperature is a glass transition temperature of the polyester resin of the layer A to (glass transition temperature +50) (° C.), more preferably 90 to 130 ° C., particularly preferably the stretching temperature in the longitudinal direction. The stretching temperature in the width direction is preferably 90 to 110 ° C. Further, the stretching may be performed a plurality of times in each direction.

  Furthermore, the film is heat-treated after biaxial stretching. The heat treatment can be performed by any conventionally known method such as in an oven or on a heated roll. This heat treatment is carried out at a temperature of 120 ° C. or higher and below the melting point of the polyester of the A layer, and is preferably a heat treatment temperature of 200 to 240 ° C. From the viewpoint of transparency and dimensional stability of the film, it is more preferably 210 to 235 ° C. The heat treatment time can be arbitrarily set within a range not deteriorating the characteristics, and is preferably 1 to 60 seconds, more preferably 1 to 30 seconds. Further, the heat treatment may be performed by relaxing the film in the longitudinal direction and / or the width direction. Further, before the transverse stretching step, at least one surface can be subjected to corona treatment or a coating layer can be provided in order to improve the adhesive force with the ink printing layer, the adhesive, and the vapor deposition layer. The coating liquid at this time is applied to the transparent substrate using a known coating means such as a roll coater, a gravure coater, a micro gravure coater, a bar coater, a die coater, or a dip coater.

  Next, the case of simultaneous biaxial stretching will be described. In the case of simultaneous biaxial stretching, the resulting cast film is subjected to surface treatment such as corona treatment, flame treatment, and plasma treatment as necessary, and then, such as slipperiness, easy adhesion, antistatic properties, etc. The function may be imparted by in-line coating.

  Next, the cast film is guided to a simultaneous biaxial tenter, and conveyed while holding both ends of the film with clips, and stretched in the longitudinal direction and the width direction simultaneously and / or stepwise. As simultaneous biaxial stretching machines, there are pantograph method, screw method, drive motor method, linear motor method, but it is possible to change the stretching ratio arbitrarily and drive motor method that can perform relaxation treatment at any place or A linear motor system is preferred. Although the stretching magnification varies depending on the type of resin, it is usually preferably 6 to 50 times as the area magnification. When polyethylene terephthalate is used as one of the resins constituting the laminated film, the area magnification is 8 to 30 times. Is particularly preferably used. In particular, in the case of simultaneous biaxial stretching, it is preferable to make the stretching ratios in the longitudinal direction and the width direction the same and to make the stretching speeds substantially equal in order to suppress the in-plane orientation difference. Moreover, as extending | stretching temperature, the glass transition temperature-glass transition temperature +120 degreeC of resin which comprises a laminated | multilayer film are preferable.

  In order to impart flatness and dimensional stability, the biaxially stretched film is preferably subsequently subjected to a heat treatment not less than the stretching temperature and not more than the melting point in the tenter. In order to suppress the distribution of the main alignment axis in the width direction during this heat treatment, it is preferable to perform a relaxation treatment in the longitudinal direction immediately before and / or immediately after entering the heat treatment zone. After being heat-treated in this way, it is gradually cooled down uniformly, then cooled to room temperature and wound up. Moreover, you may perform a relaxation | loosening process in a longitudinal direction and / or the width direction at the time of annealing from heat processing as needed. Immediately before and / or immediately after entering the heat treatment zone, a relaxation treatment is performed in the longitudinal direction.

  Next, the manufacturing method of the polyester film by a multilayer lamination extrusion method is demonstrated. A crystalline polyester resin A and an amorphous polyester resin B in which a crystalline resin is dispersed are prepared in the form of pellets or the like. When the C layer is formed of a resin different from the A layer, a resin used for the C layer is prepared. The pellets are dried in hot air or under vacuum as necessary, and then supplied to a separate extruder. In the extruder, the resin that has been heated and melted to the melting point or higher is made uniform in the extrusion amount of the resin by a gear pump or the like, and foreign matter or denatured resin is removed through a filter or the like.

  Next, the crystalline polyester resin A and the amorphous polyester resin B in which the crystalline resin is dispersed, which are fed out from different flow paths using these two or more extruders, are fed into the multilayer laminating apparatus. As the multilayer stacking apparatus, a multi-manifold die or a field block can be used. Moreover, you may combine these arbitrarily. The structure of the feed block has at least one member in a comb-shaped slit plate having a large number of fine slits, and the crystalline polyester resin A and the crystalline resin extruded from two extruders are dispersed. Amorphous polyester resin B is introduced into the slit plate via each manifold. Here, if the amorphous polyester resin B in which the crystalline polyester resin A and the crystalline resin are dispersed selectively flows into the slits through the introduction plate, finally, A / A multilayer film such as B / A / B / A (A represents an A layer and B represents a B layer; the same applies hereinafter) can be formed. In addition, the number of layers can be increased by further overlapping the slit plates. Further, when the resin C is provided on both surface layers, the resin C is introduced from the third extruder to the surface layer side of the three-layer composite device (feed block), and the multilayer film is introduced to the center layer, thereby providing C A multilayer film such as / A / B / A... A / B / A / C can be formed.

  Thus, the multilayer laminated | multilayered melt can be performed similarly to the manufacturing method of the above-mentioned polyester film, and a biaxially oriented laminated film can be obtained.

An evaluation method of physical property values used in the present invention will be described.
(Method for evaluating physical properties)
(1) Intrinsic viscosity The intrinsic viscosity of the polyester resin and the film was measured at 25 ° C. using an Ostwald viscometer after dissolving the polyester or film in orthochlorophenol.
(2) Composition of polyester Polyester resin or film is dissolved in hexafluoroisopropanol (HFIP) or a mixed solvent of HFIP and chloroform, and each monomer residue and by-product diethylene glycol is contained using ¹ H-NMR and ¹³ C-NMR. The amount was quantified.
(3) Lamination thickness and number of laminations The layer structure of the film was determined by electron microscope observation of a sample obtained by cutting a vertical cross section with respect to the film surface using a microtome. That is, using a transmission electron microscope H-7100FA type (manufactured by Hitachi, Ltd.), the cross section of the film was magnified 4000 times at an acceleration voltage of 75 kV, a cross-sectional photograph was taken, and the layer configuration and each layer thickness were measured. In some cases, in order to obtain high contrast, a staining technique using a known RuO ₄ or OsO ₄ may be used.
(4) Crystal melting calorie, crystal melting temperature Using a differential calorimeter (DSC) “DSC-RDC220” (manufactured by Seiko Denshi Kogyo), measurement and calculation were performed according to JIS-K-7122 (1987). After being melted and discharged, the sample immediately cooled with cold water of 10 ° C. or lower was heated from 25 ° C. to 290 ° C. at 20 ° C./min. At this time, the peak top at the time of crystal melting was taken as the crystal melting temperature, and the integrated value from the baseline was taken as the heat of crystal melting (1st). This was cooled to 10 ° C., and again heated to 290 ° C. at 20 ° C./min, so that the crystal melting temperature and the heat of crystal melting were 2nd. Moreover, when there were two peak tops, the integrated value from the baseline of each peak top was calculated, and the sum was used as the amount of heat of crystal melting.
(5) Haze It measured based on JIS-K7136 using the haze meter (HGM-2DP by Suga Test Instruments Co., Ltd.). In addition, the measurement was performed twice and the average value was calculated | required.
(6) Size of crystalline resin in B layer and area fraction of crystalline resin Size of crystalline resin in amorphous polyester resin B and area of crystalline resin per unit area in vertical section of layer B The rate was calculated | required by the transmission electron microscope (TEM) observation about the sample which cut out the cross section using the microtome. That is, using a transmission electron microscope H-7100FA type (manufactured by Hitachi, Ltd.), the cross section of the film was magnified 10000 to 40000 times under the condition of an acceleration voltage of 75 kV, and a cross-sectional photograph was taken. In some cases, in order to obtain high contrast, a staining technique using a known RuO ₄ or OsO ₄ was used.
(7) Heat-resistant water whitening The film was immersed in hot water at 95 ° C. for 60 minutes and air-dried for 24 hours, and then haze was measured. The difference between the haze before and after the treatment was defined as Δhaze. Moreover, in the case of the molded object, after performing the hot water treatment, the film was peeled off from the molding resin and measured in the same manner.
(8) Reflectivity / reflectance band A spectrophotometer UV-3150 manufactured by Shimadzu Corporation is attached with an absolute reflectance measuring device ASR-3105 having an incident angle of 5 °, and according to the attached instruction manual, 400 to 400 Absolute reflectance up to 1500 nm was measured.
Scan speed: High-speed sampling pitch: 1 nm
Measurement mode: Single slit width: 30 nm
Light source switching wavelength: 360 nm
Detector switching wavelength: 805 nm
S / R switching: Standard detector lock: Automatic slit program: Standard.

In addition, the reflection band in this invention is defined as a wavelength range which shows the absolute reflectance of 30% or more continuously within the wavelength range of 300-1500 nm.
(9) Reflectance after heating The framed film was heat-treated in an oven at 150 ° C. for 1 minute and cooled to room temperature, and then the absolute reflectance was measured by the method (8).

Hereinafter, Examples 1-9 are read as Comparative Examples 10-18, and Examples 11-20 are read as Comparative Examples 19-28.
Example 1
As polyester resin A, polyethylene terephthalate (hereinafter also referred to as PET) [Toray F20S] having an intrinsic viscosity of 0.65, a crystal melting temperature of 255 ° C., a crystal melting heat of 41 mJ / mg, and a crystallization temperature of 155 ° C. is used. GN001 [manufactured by Eastman Chemical] (hereinafter also referred to as PETG), and polyester resin B mixed with PET [Toray F20S] as a crystalline resin in a weight ratio of 82/18, and vented coaxial biaxial extrusion A chip that was melt-kneaded in a machine and solidified the discharged material with cold water was used. The polyester resin A and the polyester resin B in which the crystalline resin was dispersed were dried and then supplied to separate extruders.

  The polyester resin A and the polyester resin B in which the crystalline resin is dispersed are each melted at 270 ° C. by an extruder, passed through five FSS type leaf disk filters, and then discharged by a gear pump. While weighing A / polyester resin B = 1.2 / 1, the polyester resin A and the slit plate 1 having 267 slits, the slit plate 2 having 269 slits, and the slit plate 3 having 267 slits are used. The polyester resin B in which the crystalline resin is dispersed is alternately laminated, and merged with a feed block to obtain a laminate having 801 layers. The polyester resin A and the polyester resin B in which the crystalline resin is dispersed are changed so that the thickness of each layer gradually increases from the surface side to the opposite surface side in the feed block. The polyester resin B in which the layers and the crystalline resin are dispersed is alternately laminated in the thickness direction including 400 layers. In addition, the slit shape was designed so that the layer thicknesses of the adjacent A layer and B layer were substantially the same. Further, the flow path was branched before joining the feed block, and the PET was laminated as a C layer on the outer side of the outermost layer of the A layer and the B layer laminated by a gear pump so as to have a thickness of 1 μm. In this design, a reflection band exists between 350 nm and 1200 nm. After the laminate composed of 801 layers thus obtained was supplied to the multi-manifold die, and further, the layer made of the polyester resin A supplied from another extruder was formed on the surface layer, and then formed into a sheet shape. It was rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. by electrostatic application. The flow path shape and the total discharge amount were set so that the time from when the polyester resin A and the polyester resin B in which the crystalline resin was dispersed merged to the rapid cooling and solidification on the casting drum was about 8 minutes. .

  The obtained cast film was heated with a roll group set at 75 ° C., stretched 3.3 times in the longitudinal direction while rapidly heated by a radiation heater, and then cooled once. Next, this uniaxially stretched film was guided to a tenter, preheated with hot air of 100 ° C., and then stretched 3.5 times in the transverse direction at a temperature of 110 ° C. The stretched film was directly heat-treated with hot air at 230 ° C. in a tenter, subsequently subjected to a relaxation treatment of 5% in the width direction at the same temperature, and then gradually cooled to room temperature and wound up.

  The thickness of the obtained biaxially oriented laminated film was 100 μm. The average thickness of the A layer was 136 μm, the average thickness of the B layer was 113 μm, and the thickness of the outermost layer was 1 μm. The obtained results are shown in Table 1.

(Example 2)
Polyester terephthalate copolymer having intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% cyclohexanedicarboxylic acid component and 20 mol% spiroglycol component) was used as polyester resin B, and PET [made by Toray] was used as polyester resin B with crystalline resin. F20S] and antioxidant “ADK STAB” AS36 (manufactured by ADEKA) at a weight ratio of 75/25 / 0.05, melted and kneaded in a twin screw extruder with a vent, The chip solidified with was used. Other conditions and devices were the same as in Example 1. However, the feed block uses a material having a small number of slits, has a structure of 401 layers of polyester resin A and 201 layers of polyester resin A and 200 layers of polyester resin B in which a crystalline resin is dispersed, and the thickness of the obtained film Was 50 μm. The obtained results are shown in Table 1.

(Example 3)
Polyester terephthalate copolymer having intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% cyclohexanedicarboxylic acid component and 20 mol% spiroglycol component) was used as polyester resin B, and PET [made by Toray] was used as polyester resin B with crystalline resin. F20S] and antioxidant “ADK STAB” AS36 (manufactured by ADEKA) at a weight ratio of 75/25 / 0.05, melted and kneaded in a twin screw extruder with a vent, The chip solidified with was used. Other conditions and devices were the same as in Example 1. The thickness of the obtained film was 100 μm. The obtained results are shown in Table 1.

Example 4
Polyester terephthalate copolymer having intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% cyclohexanedicarboxylic acid component and 20 mol% spiroglycol component) was used as polyester resin B, and PET [made by Toray] was used as polyester resin B with crystalline resin. F20S] and antioxidant “ADK STAB” AS36 [manufactured by ADEKA] at a weight ratio of 70/30 / 0.05, melted and kneaded with a vented twin-screw extruder, and the discharged product was cooled with cold water. The chip solidified with was used. Other conditions and devices were the same as in Example 1. The thickness of the obtained film was 100 μm. The obtained results are shown in Table 1.

(Example 5)
As polyester resin B, a polyethylene terephthalate copolymer having an intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% of cyclohexanedicarboxylic acid component and 20 mol% of spiroglycol component) was used. 12. “Trecon” (registered trademark) [1200T] manufactured by Toray, which is a polybutylene terephthalate (hereinafter also referred to as PBT) having a crystal melting temperature of 223 ° C., a crystal melting heat of 55 mJ / mg, and a crystallization temperature of 120 ° C. F20S] and antioxidant “ADK STAB” AS36 [made by ADEKA] are mixed at a weight ratio of 70/20/10 / 0.05, melted and kneaded by a twin screw extruder with a vent, and discharged. A chip obtained by solidifying the product with cold water was used. Other conditions and devices were the same as in Example 1. The thickness of the obtained film was 100 μm. Further, this laminated film was kept in an atmosphere of 40 ° C. for one day. The obtained results are shown in Table 1.

(Example 6)
Same as Example 5. However, the heat treatment temperature of the tenter was 235 ° C., and no heat aging was performed. The obtained results are shown in Table 1.

(Example 7)
Polyester terephthalate copolymer having intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% cyclohexanedicarboxylic acid component and 20 mol% spiroglycol component) is used as polyester resin B, and PBT “Trecon” is used as polyester resin B as crystalline resin. (Registered trademark) [Toray 1200S], PET [Toray F20S], and antioxidant “Adeka Stub” AS36 [ADEKA] are mixed at a weight ratio of 70/10/20 / 0.05, A chip was prepared by melting and kneading in a twin screw extruder with a vent and solidifying the discharge with cold water. Other conditions and devices were the same as in Example 1. The thickness of the obtained film was 100 μm. Further, this laminated film was kept in an atmosphere of 40 ° C. for one day. The obtained results are shown in Table 1.

(Example 8)
A laminated film was obtained in the same manner as in Example 7. However, the gear pump is adjusted so that the discharge ratio is polyester resin A / polyester resin B = 0.8 / 1. The obtained results are shown in Table 1.

Example 9
A laminated film was obtained in the same manner as in Example 7. However, the gear pump is adjusted so that the discharge ratio is polyester resin A / polyester resin B = 3/1. The obtained results are shown in Table 1.

(Example 10)
The laminated film obtained in the same manner as in Example 7 was kept in an atmosphere at 100 ° C. for 10 minutes. The obtained results are shown in Table 1. The obtained results are shown in Table 1.

(Example 11)
As polyester resin B, a copolymer of polyethylene terephthalate having an intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% of cyclohexanedicarboxylic acid component and 20 mol% of spiroglycol component) was used. Polyethylene terephthalate copolymerized with 12 mol% of isophthalic acid having a heat of crystal melting of 17 mJ / mg and a crystallization temperature of 159 ° C. (hereinafter also referred to as PETI) [manufactured by Toray], PET [Toray F20S], and an antioxidant “Adeka Stub” AS36 (manufactured by ADEKA) was mixed at a weight ratio of 70/10/20 / 0.05, melted and kneaded in a twin screw extruder with a vent, and the discharged material was solidified with cold water. Was used. Other conditions and devices were the same as in Example 1. The thickness of the obtained film was 100 μm. The obtained results are shown in Table 1.

(Example 12)
The laminated film obtained in the same manner as in Example 11 was kept in an atmosphere at 40 ° C. for one day. The obtained results are shown in Table 1.

(Example 13)
The laminated film obtained in the same manner as in Example 11 was held in an atmosphere at 120 ° C. for 10 minutes. The obtained results are shown in Table 1.

(Example 14)
As polyester resin B, a copolymer of polyethylene terephthalate having an intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% cyclohexanedicarboxylic acid component and 20 mol% spiroglycol component) was used. GN001 [manufactured by Eastman Chemical] and polyester resin B In addition, PET [Toray F20S] as a crystalline resin and antioxidant “Adeka Stub” AS36 [ADEKA] are mixed at a weight ratio of 50/30/20 / 0.05, and a twin screw extrusion with a vent is made. A chip that was melt-kneaded in a machine and solidified the discharged material with cold water was used. Other conditions and devices were the same as in Example 1. The thickness of the obtained film was 100 μm. The obtained results are shown in Table 1.

(Example 15)
As polyester resin B, a polyethylene terephthalate copolymer having an intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% cyclohexanedicarboxylic acid component and 20 mol% spiroglycol component) was used, and GN001 (hereinafter also referred to as PETG) [Eastman Chemical] Made of polyester resin B with PET [Toray F20S] and antioxidant “ADK STAB” AS36 [made by ADEKA] in a weight ratio of 70/10/20 / 0.05. Then, a chip was used in which the discharged material was solidified with cold water by melting and kneading with a vented twin screw extruder. Other conditions and devices were the same as in Example 1. The thickness of the obtained film was 100 μm. The obtained results are shown in Table 1.

(Example 16)
The laminated film obtained in the same manner as in Example 15 was kept in an atmosphere at 120 ° C. for 10 minutes. The obtained results are shown in Table 1.

(Example 17)
As polyester resin B, polyethylene terephthalate (hereinafter also referred to as PETA) copolymerized with 25 mol% of adipic acid having an intrinsic viscosity of 0.72 and 10 mol% of isophthalic acid (hereinafter also referred to as PETA) and polyester resin B with a crystalline resin PET [ Toray] was mixed at a weight ratio of 85/15, melt-kneaded with a vented twin screw extruder, and the discharged material was solidified with cold water. Other conditions and devices were the same as in Example 1. The thickness of the obtained film was 100 μm. The obtained results are shown in Table 1.

(Example 18)
On the surface of the laminated film obtained in the same manner as in Example 3, a binder IMB-003 made by Teikoku Ink Manufacturing Co., Ltd. was formed with a thickness of 3 μm. Then, after pre-molding by press molding and trimming into a mobile phone shape, insert molding was performed under the following molding conditions. At this time, the film end face was joined to the step portion of the resin.

Mold temperature: 80 ° C Molding resin temperature: 260 ° C Molding resin: SD polycarbonate (IM6011)
Clamping pressure: 60 ton Molded casing: mobile phone The molded body thus obtained was held in an atmosphere of 100 ° C. for 1 day. The obtained results are shown in Table 1.

(Example 19)
On the surface of the laminated film obtained in the same manner as in Example 5, a binder IMB-003 made by Teikoku Ink Manufacturing Co., Ltd. was formed with a thickness of 3 μm. Then, after pre-molding by press molding and trimming into a mobile phone shape, insert molding was performed under the following molding conditions. At this time, the film end face was joined to the step portion of the resin. Mold temperature: 80 ° C. Molding resin temperature: 260 ° C. Molding resin: SD polycarbonate (IM6011)
Clamping pressure: 60 ton Molded casing: Mobile phone (Example 20)
Insert molding was performed in the same manner as in Example 19. However, the film end face is not bonded to the resin and is exposed as it is. The results are shown in Table 1.

(Comparative Example 1)
Same as Example 2. However, a feed block was not used in the laminating apparatus, and a three-layered structure was formed through pinole that was an A / B / A stack. As for the thickness of each layer, the average thickness of the A layer was 35 μm, and the average thickness of the B layer was 30 μm. The obtained results are shown in Table 1.

(Comparative Example 2)
Same as Example 2. However, the polyester resin A and the polyester resin B were alternately laminated by a slit plate having 51 slits and merged in a feed block to obtain a laminated body laminated in 51 layers. The obtained results are shown in Table 1.

(Comparative Example 3)
Same as Example 3. However, the polyester resin A and the polyester resin B are alternately laminated by the slit plate 1 having 68 slits, the slit plate 2 having 67 slits, and the slit plate 3 having 68 slits, and joined at a feed block, It was set as the laminated body laminated | stacked on 201 layers. The obtained results are shown in Table 1.

(Comparative Example 4)
In place of the polyester resin B, a copolymer of polyethylene terephthalate having an intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% cyclohexanedicarboxylic acid component and 20 mol% spiroglycol component), PBT [manufactured by Toray], and “Adeka Stub” AS36 [Adeka] was mixed at a weight ratio of 70/30 / 0.05, and a chip in which the discharged material was solidified with cold water by melt-kneading with a vented twin-screw extruder was used. Other conditions and devices were the same as in Example 1. The thickness of the obtained film was 100 μm. The obtained results are shown in Table 1.

(Comparative Example 5)
The laminated film obtained in the same manner as in Example 5 was kept in an atmosphere of 190 ° C. for 10 minutes. The obtained results are shown in Table 1. The obtained results are shown in Table 1.

(Comparative Example 6)
The same apparatus and conditions as in Example 1 were used except that a polyethylene terephthalate copolymer having an intrinsic viscosity of 0.72 (PET copolymerized with 30 mol% cyclohexanedicarboxylic acid component and 20 mol% spiroglycol component) was used as polyester resin B. To obtain a laminated film. The obtained results are shown in Table 1.

(Comparative Example 7)
The laminated film obtained in the same manner as in Comparative Example 6 was kept in an atmosphere at 40 ° C. for one day. The obtained results are shown in Table 1. The obtained results are shown in Table 1.

(Comparative Example 8)
A laminated film obtained in the same manner as in Comparative Example 6 was held in an atmosphere at 120 ° C. for 10 minutes. The obtained results are shown in Table 1. The obtained results are shown in Table 1.
(Comparative Example 9)
The same apparatus as in Example 1 except that as the polyester resin B, polyethylene terephthalate (hereinafter also referred to as PETA) copolymerized with 25 mol% adipic acid having an intrinsic viscosity of 0.72 and 10% isophthalic acid (hereinafter also referred to as PETA) was used. -A laminated film was obtained under the conditions. The obtained results are shown in Table 1.

Claims (3)

200 layers each consisting of crystalline polyester resin A (layer A) and layers having an average layer thickness of 30 to 180 nm in which crystalline resin is dispersed in amorphous polyester resin B (layer B) A biaxially oriented film laminated as described above, wherein the lamination ratio of the A layer and the B layer is in the range of 3.0 to 0.8, and the crystalline resin dispersed in the B layer is a vertical section of the film. Is observed with a transmission microscope (TEM), the area fraction of the crystalline resin portion dispersed in the diameter of 1 to 20 nm and occupying the area of the B layer cross section is 0.1 to 0.3, and The A layer and the B layer laminated on the 200 layers or more are sandwiched between layers of a crystalline polyester resin having a thickness of 1 to 7 μm, and the B layer is a crystalline polyester having a composition different from that of the polyester resin B. A tree obtained by mixing at least two types The at least two or more kinds of crystalline polyesters are composed of a fat composition, a crystalline polyester having a crystal melting temperature of 235 ° C. or higher and 270 ° C. or lower, and a crystal having a crystal melting temperature of 180 ° C. or higher and lower than 235 ° C. A crystalline polyester is used, which is heat-aged at a temperature of (crystallization temperature −20) ° C. or higher and (melting point −60) ° C. or lower of any crystalline polyester included in the B layer. A method for producing a biaxially oriented laminated film. In the polyester resin B, the proportion of terephthalic acid residues in all dicarboxylic acid residues is 10 to 90 mol%, the ratio of cyclohexanedicarboxylic acid residues is 10 to 90 mol%, and ethylene glycol in all diol residues The method for producing a laminated film according to claim 1, comprising a copolyester having a residue ratio of 70 to 90 mol% and a spiroglycol residue ratio of 10 to 30 mol%. The laminate film obtained by the method for producing a laminate film according to claim 1 or 2, wherein the laminate film is a molded body using the laminate film, and an end portion of the laminate film is coated with a molding resin. Manufacturing method of a molded object.