JP5169317B2 - Compact - Google Patents

Description

  The present invention relates to a molded body, and more particularly to a decorative molded body.

  In products (parts) such as automobile-related decorative parts as well as various home appliances and building materials, various decorations such as woodgrain, cloth-like, metal-like, etc. are used to enhance the design. Recently, a high-brightness metallic appearance has been demanded.

  The most commonly used technique for imparting a metallic tone to various molded parts is painting. Although painting can give various designs and functions to products, it often uses organic solvents and has a great impact on the environment. In addition, recycling may not be easy due to the influence of the coating film, and the existence of a coating process is regarded as a problem in the recent increase in environmental problems.

  Other methods for imparting a metallic tone include plating and vapor deposition. In the case of plating or vapor deposition, there is a problem that recycling is difficult due to the metal layer. However, in the case of plating in particular, since the influence of heavy metals on the environment is great, an alternative is strongly demanded. Furthermore, in the case of plating or vapor deposition, because of its electromagnetic shielding properties due to its metal layer, it is becoming a problem when used as a decorative material for automobiles and mobile phones, which may cause radio interference. . Moreover, the resin molded body containing a metal component has a problem that it is difficult to recycle. Furthermore, there has been a problem that the luminance is lowered due to deterioration of the metal film due to heat during insert molding or the like.

A technology that uses a film that selectively reflects light of a specific wavelength by alternately laminating multiple layers of resin layers with different refractive indexes as materials that have a gloss like metal that does not use metal (for example, patents) There are references 1-2). However, when these films are formed on the base material by insert molding or the like, it is partially discolored in the vicinity of the gate portion or corners where the base resin flows in due to the influence of heat and pressure during insert molding. There were problems such as. In addition, a gate is an inflow port through which molten resin injected from a nozzle passes through a sprue and a runner and flows into a mold cavity serving as a molded body.
Japanese Patent Laid-Open No. 3-41401 JP-A-4-295804

  The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a molded article that has radio wave permeability, is excellent in recyclability, and does not cause partial discoloration during molding. It is another object of the present invention to provide a molded article having a high brightness which has not been conventionally obtained.

In order to solve the above problems, the molded article of the present invention is a molded article obtained by covering a substrate with a laminated film having a laminate number of 30 or more and comprising at least a layer made of resin A and a layer made of resin B. Thus, the ratio (Hg / Ha) of the number of layers Hg of the laminated film coated on the portion close to the gate portion to the number of layers Ha of the laminated film coated on the portion separated from the gate portion is 0.7 to 1. 05 Ri der hereinafter heat of the exothermic peak observed in the range of 100 ° C. to 200 DEG ° C. in the DSC measurement of the laminated film covering the said shaped body, 0 J / g or more 5 J / g or less der Rukoto It is characterized by.

  The molded article of the present invention has radio wave permeability, excellent recyclability, and does not cause partial discoloration during molding.

  Moreover, a high-luminance molded body can be obtained.

  In order to achieve the above object, the molded article of the present invention is a molded article in which a substrate is coated with a laminated film having a laminate number of 30 or more, comprising at least a layer made of resin A and a layer made of resin B. Thus, the ratio (Hg / Ha) of the number of layers Hg of the laminated film coated on the portion close to the gate portion to the number of layers Ha of the laminated film coated on the portion separated from the gate portion is 0.7 to 1. Must be less than 05. Such a molded body has radio wave permeability, excellent recyclability, and does not cause partial discoloration during molding.

  The resin in the present invention may be either a thermoplastic resin or a curable resin. Further, it may be a homo resin, a copolymer resin or a blend of two or more kinds of resins. More preferably, it is a thermoplastic resin because of good moldability. In each resin, various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, thermal stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant for adjusting the refractive index may be added.

  Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyethylene terephthalate, polybutylene terephthalate, and polypropylene terephthalate.・ Polybutyl succinate ・ Polyester resin such as polyethylene-2,6-naphthalate, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin -Fluoropolymers such as ethylene tetrafluoride-6 propylene copolymer, vinylidene fluoride resin, acrylic resin such as PMMA, methacrylic resin, poly Tar resins, polyglycolic acid resins, polylactic acid resins, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-ethylene - propylene rubber-styrene copolymer or the like can be used. Among these, polyester is particularly preferable from the viewpoint of strength, heat resistance, and transparency.

  The polyester referred to in the present invention refers to a homopolyester or a copolyester that is a polycondensate of a dicarboxylic acid component skeleton and a diol component skeleton. Here, typical examples of the homopolyester include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and polyethylene diphenylate. In particular, polyethylene terephthalate is preferable because it is inexpensive and can be used in a wide variety of applications.

  The copolyester in the present invention is defined as a polycondensate comprising at least three or more components selected from the following components having a dicarboxylic acid skeleton and components having a diol skeleton. Components having a dicarboxylic acid skeleton include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-diphenyldicarboxylic acid. 4,4′-diphenylsulfone dicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexanedicarboxylic acid and ester derivatives thereof. Examples of the component having a glycol skeleton 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 the like can be mentioned.

In the present invention, the in-plane average refractive index of the layer made of the resin A is relatively higher or lower than the in-plane average refractive index of the layer made of the resin B. 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 0.1-0.15. When the refractive index difference is smaller than 0.03, a sufficient reflectance cannot be obtained, which is not preferable. 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 resin A and the resin B in the present invention, it is first preferable that the absolute value of the difference in SP value between the resin A and the resin B is 1.0 or less. When the absolute value of the difference in SP value is 1.0 or less, delamination hardly occurs. More preferably, it has a layer made of the resin A and a layer made of the resin B containing the same basic skeleton as the resin A. Here, the basic skeleton is a repeating unit constituting the resin. For example, when one resin is polyethylene terephthalate, ethylene terephthalate is the basic skeleton. As another example, when one resin is polyethylene, ethylene is a basic skeleton. When the resin A and the resin B are resins containing the same basic skeleton, peeling between layers is less likely to occur.

Moreover, as a preferable combination of the resin A and the resin B, the glass transition temperature difference between the resin A and the resin B is preferably 20 ° C. or less. 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 becomes poor. Also, when a laminated film is formed, problems such as overstretching tend to occur.
In the laminated film of the present invention, it is preferable that the resin A is a polyester containing polyethylene terephthalate or polyethylene naphthalate and the resin B is a polyester containing spiroglycol. The polyester comprising spiroglycol refers to a copolyester copolymerized with spiroglycol, a homopolyester, or a polyester blended with them. Polyesters containing spiroglycol are preferred because they have a small glass transition temperature difference from polyethylene terephthalate or polyethylene naphthalate, so that they are not easily stretched at the time of molding and are also difficult to delaminate. More preferably, it is preferable that the resin A comprises polyethylene terephthalate or polyethylene naphthalate, and the resin B is a polyester comprising spiroglycol and cyclohexanedicarboxylic acid. If the resin B is a polyester comprising spiroglycol and cyclohexanedicarboxylic acid, the difference in the in-plane refractive index from polyethylene terephthalate or polyethylene naphthalate is increased, so that high reflectance is easily obtained. Moreover, since the glass transition temperature difference with polyethylene terephthalate or polyethylene naphthalate is small and the adhesiveness is excellent, it is difficult to be over-stretched at the time of molding and is also difficult to delaminate.

  As the laminated film in the present invention, the number of laminated layers including at least a layer made of the resin A and a layer made of the resin B must be 30 or more. Here, the number of stacked layers is more preferably 100 or more, and further preferably 600 or more. A film with a larger number of layers has a higher reflectance and a film having a wider reflection band can be easily obtained. When the number of layers is 600 or more, it becomes easy to achieve a glossiness of 650 or more.

  Moreover, it is preferable that the laminated film in the present invention includes a structure in which layers made of the resin A and layers made of the resin B are alternately laminated. That is, it is defined that there is a portion having a structure in which layers made of the resin A and layers made of the resin B layer are alternately stacked in the thickness direction.

  Moreover, since the laminated | multilayer film in this invention are comprised from a polymer, they become a high reflectance film and a metal tone film which permeate | transmit electromagnetic waves. Here, the electromagnetic wave means a part of infrared rays and a frequency of 3 Hz to 3 THz.

  In the laminated film of the present invention, it is preferable that the resin A is a polyester comprising polyethylene terephthalate or polyethylene naphthalate, and the resin B is a polyester comprising cyclohexanedimethanol. The polyester comprising cyclohexanedimethanol refers to a copolyester obtained by copolymerizing cyclohexanedimethanol, a homopolyester, or a polyester obtained by blending them. Polyesters containing cyclohexanedimethanol are preferred because they have a small glass transition temperature difference from polyethylene terephthalate or polyethylene naphthalate, so that they are unlikely to be overstretched during molding and are also difficult to delaminate. More preferably, the resin B is an ethylene terephthalate polycondensate having a copolymerization amount of cyclohexanedimethanol of 15 mol% to 60 mol%. In this way, while having high reflection performance, the change in optical characteristics due to heating and aging is particularly small, and peeling between layers is less likely to occur. An ethylene terephthalate polycondensate having a copolymerization amount of cyclohexanedimethanol of 15 mol% or more and 60 mol% or less adheres very strongly to polyethylene terephthalate. In addition, the cyclohexanedimethanol group has a cis or trans isomer as a geometric isomer, and a chair type or a boat type as a conformational isomer. In addition, the change in optical characteristics due to thermal history is even less, and blurring during film formation hardly occurs.

  In addition, the laminated film in the present invention has an easy-adhesion layer, an easy-slip layer, a hard coat layer, an antistatic layer, an abrasion-resistant layer, an antireflection layer, a color correction layer, an ultraviolet absorption layer, a printing layer, a metal on the surface. Functional layers such as a layer, a transparent conductive layer, a gas barrier layer, a hologram layer, a release layer, an adhesive layer, an emboss layer, and an adhesive layer may be formed.

  In the molded article of the present invention, a base material must be coated with a laminated film having at least 30 layers including a layer made of resin A and a layer made of resin B. Here, the substrate is preferably a resin. More preferably, it is a thermoplastic resin. Moreover, as a coating location, what is necessary is just to coat | cover a part of base material, and any of a part of single side | surface, the whole single side | surface, each part of both surfaces, and the whole both surfaces may be sufficient.

  In the molded body of the present invention, the ratio (Hg / Ha) of the number of layers Hg of the laminated film covered at a site close to the gate part and the number of layers Ha of the laminated film covered at a site away from the gate part is 0. Must be between 7 and 1.05. More preferably, it is 0.8 or more and 1.0 or less. The ratio (Hg / Ha) of the number of layers Hg of the laminated film coated on the portion close to the gate portion to the number of layers Ha of the laminated film coated on the portion separated from the gate portion is 0.7 or more and 1.05 or less. If it is, discoloration hardly occurs.

  The part close to the gate part means a part of the molded body existing in a space in a sphere having a radius of 1 cm with the gate part as the center. Moreover, the site | part away from the gate part means the site | part of the molded object with a radius of 1 cm or more centering on the gate part. When there is no laminated film covering the space in a sphere having a radius of 1 cm with the gate portion as the center, the portion closest to the gate portion is set as the portion close to the gate portion, and 1 cm from the portion close to the gate portion. The part away from the gate part is the part away from the gate part.

The laminated film covering the molded body of the present invention has an exothermic peak calorie (cold crystallization calorie) observed in the range of 100 ° C. to 200 ° C. in DSC measurement of 0 J / g or more and 5 J / g or less. It is necessary . In such a case, discoloration can be suppressed even in molding at a higher temperature, and discoloration does not occur even if the molded product is stored at a high temperature.

The molded article of the present invention preferably has a portion having a glossiness of 500 or more. When the glossiness is 500 or more, the brightness is high and the metallic tone is high-quality. More preferably, the glossiness is 650 or more.

In the molded body of the present invention, the ratio (Tf / Tc) between the thickness Tc of the laminated film coated near the corner of the molded body and the thickness Tf of the laminated film coated on the flat portion of the molded body is 0. It is preferably 8 or more and 3 or less. If it is 0.8 or more and 3 or less, there is little abrupt change in the optical characteristics, so that the color change due to the site is not noticeable and the appearance becomes uniform. Here, the corner portion refers to a corner having a corner R of 5 mm or less, and the flat portion refers to a portion separated from the corner portion by 10 mm or more.

  In the molded article of the present invention, the heat of fusion of the laminated film is preferably 18 J / g or more and 40 J / g or less. When the heat of fusion satisfies the above conditions, the heat resistance is excellent, and discoloration during molding can be further suppressed. The heat of fusion is the heat amount of the endothermic peak due to crystal melting observed when the laminated film is subjected to DSC measurement, and the DSC measurement conditions are described in the physical property value evaluation method. When two or more endothermic peaks are observed, the total amount of heat of each endothermic peak is defined as the heat of fusion.

  In addition to the laminated film, the molded article of the present invention may include any of a hard coat layer, an embossed layer, a weather resistant layer (UV cut layer), a colored layer / printed layer, an adhesive layer, a binder layer, and the like. preferable. Such a molded body can be composed of an all-polymer and does not contain metal or heavy metal, and therefore has a low environmental load, excellent recyclability, and excellent radio wave permeability. The molded product of the present invention preferably has a colored layer. In addition, various molding methods such as vacuum forming, vacuum pressure forming, plug-assist vacuum pressure forming, in-mold forming, insert forming, cold forming, press forming, drawing forming, and pressure forming can be applied. It is possible to obtain. Such a molded body can be preferably used for a mobile phone, a telephone, a personal computer, an audio device, a home appliance, a wireless communication device, a radome, an automobile interior / exterior component, a building material, a game machine, an amusement device, a packaging container, and the like. In particular, the molded article of the present invention is a device having a function of performing information communication wirelessly, such as a mobile phone, a telephone, a personal computer, an audio device, a home appliance, a wireless communication device, an in-vehicle component such as a radome, or a game machine. It is preferably used as a decorative part of a device. Since the molded article of the present invention has a metallic appearance and is excellent in radio wave transmission, it does not cause electromagnetic interference unlike conventional metallic decoration materials. For this reason, when the molded article of the present invention is used as a decorative part of an information communication device, the device can be reduced in size and thickness, and the degree of freedom in circuit design inside the information communication device is increased.

  Next, the preferable manufacturing method of the molded object of this invention is demonstrated below. First, the manufacturing method of the laminated film which coat | covers a molded object is demonstrated.

Two types of resins A and B are prepared in the form of pellets. Here, the resin A and / or the resin B is preferably a crystalline resin. When it is a crystalline resin, it becomes easy to achieve Hg / Ha from 0.7 to 1.05. More preferably, one resin is a crystalline resin and the other resin is an amorphous resin. In this case, it becomes easier to achieve Hg / Ha from 0.7 to 1.05, and the calorific value of the exothermic peak observed in the range of 100 ° C. to 200 ° C. in the DSC measurement of the laminated film is from 0 J / g to 5 J. / G or less.
The pellets are dried in hot air or under vacuum as necessary, and then supplied to a separate extruder. In the extruder, the resin melted by heating to a temperature equal to or higher than the melting point is made uniform in the amount of resin extruded by a gear pump or the like, and foreign matter or denatured resin is removed through a filter or the like.

  Resins A and B sent out from different flow paths using these two or more extruders are then fed into the multilayer laminating apparatus. As the multilayer laminating apparatus, a multi-manifold die, a feed block, a static mixer, or the like can be used. In particular, in order to efficiently obtain the configuration of the present invention, at least two members having a large number of fine slits are separately provided. It is preferable to use a feed block containing at least one.

  When such a feed block is used, since the apparatus does not become extremely large, there is little foreign matter due to thermal degradation, and high-precision lamination is possible even when the number of laminations is extremely large. Also, the stacking accuracy in the width direction is significantly improved as compared with the prior art. It is also possible to form an arbitrary layer thickness configuration. In this apparatus, since the thickness of each layer can be adjusted by the shape (length, width) of the slit, any layer thickness can be achieved. On the other hand, in the conventional apparatus, in order to achieve lamination of 300 layers or more, it is common to use a square mixer together. However, in such a method, the lamination flow is deformed and laminated in a similar shape. In addition, it has been difficult to achieve an arbitrary layer thickness. For this reason, the layer structure which is the feature of the present application can be easily achieved. Here, when the volume ratio determined from the layer thickness of the crystalline resin to the amorphous resin is 1.5 times or more and 3.5 times or less, Hg / Ha is more easily 0.8 times or more and 1 time or less. Can be achieved.

  The molten laminate formed in the desired layer configuration in this way is then formed into a desired shape by a die and then discharged. And the sheet | seat laminated | stacked in the multilayer discharged | emitted from die | dye is extruded on cooling bodies, such as a casting drum, and is cooled and solidified, and a casting film is obtained. At this time, it is preferable to use a wire-like, tape-like, needle-like, or knife-like electrode to be brought into close contact with a cooling body such as a casting drum by an electrostatic force and rapidly solidify. Also preferred is a method in which air is blown out from a slit-like, spot-like, or planar device to be brought into close contact with a cooling body such as a casting drum and rapidly cooled and solidified, or brought into close contact with a cooling body with a nip roll and rapidly solidified.

  The casting film thus obtained is preferably biaxially stretched as necessary. Biaxial stretching also makes it easy to achieve Hg / Ha of 0.7 or more and 1.05 or less. Here, biaxial stretching refers to stretching in the longitudinal direction and the width direction. Stretching may be performed sequentially in two directions or simultaneously in two directions. Further, re-stretching may be performed in the longitudinal direction and / or the width direction. In particular, in the present invention, it is preferable to use simultaneous biaxial stretching from the viewpoint of suppressing in-plane orientation difference and suppressing surface scratches.

  First, the case of sequential biaxial stretching will be described. Here, stretching in the longitudinal direction refers to stretching for imparting molecular orientation in the longitudinal direction to the film, and is usually performed by a difference in peripheral speed of the roll, and this stretching may be performed in one step. Alternatively, a plurality of roll pairs may be used in multiple stages. Although it changes with kinds of resin as a magnification of extending | stretching, 2 to 15 times is preferable normally, and when polyethylene terephthalate is used for either of the resin which comprises a laminated | multilayer film, 2 to 7 times are used especially preferably. Moreover, as extending | stretching temperature, the glass transition temperature-glass transition temperature +100 degreeC of resin which comprises a laminated | multilayer film are preferable.

  The uniaxially stretched film thus obtained is subjected to surface treatment such as corona treatment, flame treatment, and plasma treatment as necessary, and then functions such as slipperiness, easy adhesion, and antistatic properties are provided. It may be applied by in-line coating.

  The stretching in the width direction refers to stretching for giving the film an orientation in the width direction. Usually, the tenter is used to convey the film while holding both ends of the film with clips, and the film is stretched in the width direction. Although it changes with kinds of resin as a magnification of extending | stretching, 2 to 15 times is preferable normally, and when polyethylene terephthalate is used for either of the resin which comprises a laminated | multilayer film, 2 to 7 times are used especially preferably. Moreover, as extending | stretching temperature, the glass transition temperature-glass transition temperature +120 degreeC of resin which comprises a laminated | multilayer film are preferable.

  The biaxially stretched film is preferably subjected to a heat treatment at a temperature not lower than the stretching temperature and not higher than the melting point in the tenter in order to impart flatness and dimensional stability. In particular, in order to achieve the configuration of the present invention, the heat treatment temperature is preferably 220 ° C. or higher, more preferably 245 ° C. or higher. In particular, when heat treatment is performed at (melting point of crystalline resin−15 ° C.) or more and (melting point of crystalline resin−5 ° C.) or less, Hg / Ha can be more easily achieved from 0.8 times to 1 time. Become. After being heat-treated in this way, it is gradually cooled down uniformly, then cooled to room temperature and wound up. Moreover, you may use a relaxation process etc. together in the case of annealing from heat processing as needed.

  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.

  The film thus biaxially stretched 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 impart flatness and dimensional stability. 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.

The laminated film of the present invention can reflect light, but the reflectance is controlled by the refractive index difference between the layer made of the resin A and the layer made of the resin B and the number of layers.
2 × (na · da + nb · db) = λ Equation 1
na: In-plane average refractive index of the layer made of resin A nb: In-plane average refractive index of the layer made of resin B da: Layer thickness (nm) of the layer made of resin A
db: Layer thickness of the layer made of resin B (nm)
λ: main reflection wavelength (primary reflection wavelength)
Next, a colored layer and / or a binder layer is applied to the laminated film thus obtained by coating or printing. As a coating method, gravure printing, screen printing, offset printing, and the like are preferable, and screen printing is more preferable. Further, it is preferable to apply a colored layer and / or a binder layer of 5 μm or more by screen printing, and the ink for forming the colored layer is preferably a two-component curable ink. In this case, it becomes easy to suppress the ink flow at the time of injection molding, and it becomes possible to suppress discoloration due to a change in the ink film thickness. The residual solvent ratio contained in the colored layer and the binder layer is preferably 0.0001 ppm or more and 3% or less. This is because, when the residual solvent ratio is 0.0001 ppm or more and 3% or less, the colored layer or the binder layer does not foam or the like even when the molded body is subjected to a thermal cycle test.

  Next, it is preferable to pre-mold the laminated film on which the colored layer and / or the binder layer are formed as necessary. As the pre-molding method, vacuum molding, vacuum pressure molding, plug assist vacuum pressure molding, in-mold molding, insert molding, cold molding, press molding, drawing molding, pressure molding, etc. are preferable, and Hg / Ha is 0. In order to easily achieve from 0.7 to 1.05, it is more preferable that the film temperature at the time of forming is 230 ° C. or less by a method such as pressure forming, vacuum pressure forming or press forming. Here, the ratio (Tf / Tc) between the thickness Tc of the laminated film coated in the vicinity of the corner of the molded body and the thickness Tf of the laminated film coated on the flat part of the molded body is 0.8 or more and 3 or less. In order to achieve this, after preheating at 130 ° C. or higher and 200 ° C. or lower in advance, press molding or pressure molding is preferably performed using a mold temperature-controlled to a lower temperature.

  The laminated film thus obtained or the pre-formed laminated film is preferably coated and integrated with the substrate by in-mold molding or insert molding. At this time, the gate structure may be any of a gate structure such as a pin gate, a side gate, a film gate, a tunnel gate, and a disk gate, but a side gate and a film gate are particularly preferable. When the material that becomes the base material flows in parallel to the film surface like a side gate or a film gate, thermal damage to the film is reduced, and Hg / Ha is 0.7 or more and 1.05 or less. Can be easily achieved. In addition, ink flow can be suppressed.

  Moreover, as a material used as a base material, it is preferable that it is a thermoplastic resin. In particular, in the case of polymethyl methacrylate (PMMA), acrylonitrile / butadiene styrene copolymer (ABS), acrylonitrile / ethylene-propylene rubber / styrene copolymer (AES), an alloy of polycarbonate (PC) and ABS, Hg / It becomes easier for Ha to achieve 0.7 or more and 1.05 or less. Further, when the melt flow rate (temperature: vicinity of the injection molding temperature) of the resin is 15 or more, it becomes easier to achieve Hg / Ha of 0.7 or more and 1.05 or less. The injection speed is preferably 50 mm / sec or more, and more preferably 100 mm / sec or more. In this case, the ink flow can be suppressed and thermal damage to the film can be greatly suppressed.

An evaluation method of physical property values used in the present invention will be described.
(Method for evaluating physical properties)
(1) Layer structure Hg, Ha
The gate part of the molded body and the part 3 cm away from the gate part of the molded body were each cut out with a knife. Each cut-out part was obtained using a microtome to obtain a cross-sectional thin film section. When the base material of the molded body was thick and it was difficult to obtain a thin film slice, the thin film slice was obtained using a microtome after mechanically peeling the base material without destroying the film.

  Next, the layer structure was observed by electron microscope observation. That is, using a transmission electron microscope H-7100FA type (manufactured by Hitachi, Ltd.), the cross section of the film was magnified 40000 times at an acceleration voltage of 75 kV, a cross-sectional photograph was taken, the layer configuration, and the thickness of each layer were measured. . In this example, in order to obtain high contrast, staining was performed using known RuO4.

  In order to clarify the layer structure, the following treatment was performed, and the number of layers and the layer thickness were counted. First, a TEM photograph image of about 40,000 times was captured at an image size of 720 dpi using a CanonScan D123U. The image is saved in the JPEG format, and then image processing software Image-Pro Plus ver. 4 (sales company Planetron Co., Ltd.) was used to open this JPG file and perform image analysis. In the image analysis process, the relationship between the thickness in the thickness direction and the average brightness of the area sandwiched between the two lines in the width direction was read as numerical data in the vertical thick profile mode. Using the spreadsheet software (Excel2000), the position (nm) and brightness data were subjected to numerical processing of sampling step 6 (decimation 6) and 3-point moving average. Furthermore, the obtained data with periodically changing brightness was differentiated, the maximum value and the minimum value of the differential curve were read, and the layer thickness was calculated with the interval between these adjacent ones as the layer thickness. This operation was performed for each photograph, and the number of layers and the layer thickness of all layers were calculated. The number of layers of the laminated film obtained from the gate portion was Hg, and the number of layers of the laminated film at a site 3 cm away from the gate portion was Ha.

(2) Laminated film thickness Tf, Tc
A corner portion of the molded body and a flat portion of the molded body were cut out with a knife. A flat cross section was obtained by a microtome for each cut out part. Next, the cross section was observed at a magnification of 500 times with a scanning electron microscope ABT-32 manufactured by Topcon Corporation, and the film thickness was measured. The film thickness of the thinnest part of the laminated film coated on the corner of the molded body was Tc, and the thickness of the laminated film coated on the flat part of the molded body was Tf.

(3) Intrinsic viscosity Calculated from the solution viscosity measured at 25 ° C in orthochlorophenol. The solution viscosity was measured using an Ostwald viscometer. The unit is [dl / g]. The n number was 3, and the average value was adopted.

(4) Heat of fusion The heat of fusion was measured and calculated according to JIS-K-7122 (1987) using differential calorimetry (DSC) for the laminated film separated from the molded body. Measurement conditions are as follows.
Equipment: “Robot DSC-RDC220” manufactured by Seiko Electronics Industry Co., Ltd.
Data analysis "Disc Session SSC / 5200"
Sample mass: 5mg
Temperature rising condition: 25 ° C. to 300 ° C. 10 ° C./min. , Then held at 300 ° C. for 5 minutes and then rapidly cooled to 25 ° C.

(5) Calorific value of exothermic peak (cold crystallization calorific value)
About the laminated | multilayer film isolate | separated from the molded object, the calorie | heat amount (cold crystallization calorie | heat amount) of the exothermic peak was measured and calculated according to JIS-K-7122 (1987) using differential calorimetry (DSC). Measurement conditions are as follows.
Equipment: “Robot DSC-RDC220” manufactured by Seiko Electronics Industry Co., Ltd.
Data analysis "Disc Session SSC / 5200"
Sample mass: 5mg
Temperature rising condition: 25 ° C. to 300 ° C. 10 ° C./min. , Then held at 300 ° C. for 5 minutes and then rapidly cooled to 25 ° C.

(6) Glossiness The glossiness of the molded product was measured using a handy gloss meter PG-1M manufactured by Nippon Denshoku Industries Co., Ltd. The measurement conditions are as follows.
Measurement site: Laminated film surface angle: 20 °
(7) Electromagnetic wave shielding property In accordance with ASTM D4935, 45 M to 3 GHz electromagnetic wave permeability was measured with a coaxial tube type shielding effect measuring system manufactured by Keycom Corporation. About the Example and the comparative example, the loss of 2.4 GHz was described.

(8) The discolored molded article was visually observed under a fluorescent lamp. The case where there was almost no partial discoloration was evaluated as ◯, the case where there was a slight discoloration, and the case where there was a clear discoloration as x.

(9) The color-change molded article at the corners was visually observed under a fluorescent lamp. When almost no partial color change was observed, it was marked with ◯, and when the color change was clear, x.

(Examples 1-4)
<Production method of resin A polyethylene terephthalate (PET)>
100 parts by weight of dimethyl terephthalate (hereinafter referred to as DMT) and 62 parts by weight of ethylene glycol (hereinafter referred to as EG) were charged into a transesterification (hereinafter referred to as EI reaction) apparatus and melted at 150 ° C. Subsequently, 0.05 part by weight of magnesium acetate tetrahydrate was added, and methanol was distilled while raising the temperature of the reaction product to 235 ° C. over 3 hours, thereby carrying out EI reaction. After a predetermined amount of methanol was distilled and the EI reaction was completed, 0.02 part by weight of trimethyl phosphoric acid (hereinafter referred to as TMPA) was added.

  Five minutes after adding TMPA, 0.03 part by weight of antimony trioxide was added. Thereafter, the reaction product was transferred to a polycondensation apparatus.

  While stirring the low polymer, the temperature inside the polymerization apparatus was gradually raised from 235 ° C. to 285 ° C., and the pressure was lowered to 130 Pa. The time to reach the final temperature and final pressure was both 90 minutes. When the predetermined stirring torque was reached, the inside of the polymerization apparatus was returned to normal pressure with nitrogen gas, the polycondensation reaction was stopped, the polymer was discharged into cold water in a strand form, and immediately cut to obtain a polyester chip.

    The intrinsic viscosity of the obtained polyester chip was 0.65.

<Resin B: Production method of 30 mol% cyclohexanedicarboxylic acid and 25 mol% spiroglycol copolymerized PET (PE / SPG / T / CHDC):>
First, a synthesis method of a titanium catalyst citrate chelate titanium compound will be described. Citric acid monohydrate (532 g, 2.52 mol) was dissolved in warm water (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. To this stirred solution was slowly added titanium tetraisopropoxide (284 g, 1.0 mol) from the addition funnel. The mixture was heated to reflux for 1 hour to produce a cloudy solution, from which the isopropanol / water mixture was distilled and distilled under reduced pressure. The product was cooled to a temperature below 70 ° C., and 380 g of a 32 wt% aqueous solution of NaOH was slowly added via a dropping funnel while stirring the solution. The resulting product was filtered and then mixed with ethylene glycol (504 g, 8.1 mol) and heated under vacuum to remove isopropanol / water and a slightly cloudy, pale yellow product (Ti-containing) Amount 3.85% by weight).

  Next, the manufacturing method of resin B is described. 53.4 parts by weight of DMT, 23.6 parts by weight of dimethyl cyclohexanedicarboxylate (hereinafter referred to as CHDC), 44 parts by weight of EG, and 30 parts by weight of spiroglycol (hereinafter referred to as SPG) were charged into an EI reactor. An EG solution containing 0.06 parts by weight of a water salt was charged, an EG solution containing 0.01 parts by weight of potassium hydroxide was added, and the contents were dissolved at 150 ° C. and stirred.

While stirring, methanol was distilled while slowly raising the temperature of the reaction contents to 235 ° C. over 4 hours. A predetermined amount of methanol was distilled off to complete the EI reaction. Thereafter, an EG solution containing 0.01 part by weight of TMPA and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite) (hereinafter referred to as PEP36) manufactured by Asahi Denka Kogyo Co., Ltd. EG slurry containing 0.12 parts by weight was added. After adding TMPA or the like, excess EG was distilled while stirring for 30 minutes, and after adding 30 ppm of titanium catalyst as a titanium element, excess EG was distilled while stirring for 10 minutes. Thereafter, the EI reactant was transferred to a polycondensation reactor. Next, the content of the polymerization reactor was stirred and the pressure was reduced and the temperature was increased, and a polycondensation reaction was performed while distilling EG. Note that the pressure was reduced from normal pressure to 133 Pa or less over 120 minutes, and the temperature was raised from 235 ° C. to 285 ° C. over 90 minutes. When the stirring torque reached a predetermined value, the inside of the polymerization reactor was returned to normal pressure with nitrogen gas, the valve at the bottom of the polymerization reactor was opened, and the gut-like polymer was discharged into the water tank. The polyester gut cooled in the water tank was cut with a cutter to form chips. It was 0.72 of the obtained polyester B, and was an amorphous resin.
<Method for producing laminated film>
Resin A and Resin B were prepared as two types of thermoplastic resins. The prepared resins A and B were each melted at 280 ° C. with a vented twin-screw extruder, and then merged in a 901-layer feed block via a gear pump and a filter. Both the surface layer portions were made of resin A, and the layer thicknesses of the layer made of resin A and the layer made of resin B were made substantially the same. Subsequently, after being merged by a 901-layer feed block, guided to a T-die and 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 to obtain a cast film. . The discharge amount was adjusted so that the weight ratio of the resin A and the resin B was about 1, so that the thickness ratio of the adjacent layers was about 1.
The obtained cast film was heated in a roll group set at 75 ° C., and then stretched 3.3 times in the longitudinal direction while rapidly heating from both sides of the film with a radiation heater between 100 mm in the stretch section length, and then temporarily Cooled down. Subsequently, both sides of this uniaxially stretched film were subjected to corona discharge treatment in air, the wetting tension of the base film was set to 55 mN / m, and the treated surface (polyester resin having a glass transition temperature of 18 ° C.) / (Glass transition) Polyester resin having a temperature of 82 ° C.) / Laminate-forming film coating liquid composed of silica particles having an average particle diameter of 100 nm was applied to form a transparent, easy-sliding, and easy-adhesion layer.

This uniaxially stretched film was guided to a tenter, preheated with hot air at 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 in a tenter with hot air of 248 ° C., then subjected to a relaxation treatment of 7% in the width direction at the same temperature, and then gradually cooled to room temperature and wound up. The thickness of the obtained film was 100 μm. The design layer thickness of this film is as shown in FIG.
Next, a two-component curable ink was applied to one side of the obtained film by screen printing to form a colored layer, and then a binder layer was formed. The printing conditions are as follows.
<Colored layer>
Ink: Teikoku Ink Manufacturing Co., Ltd. IPX971
Solvent: F-003 (10% dilution) manufactured by Teikoku Ink Manufacturing Co., Ltd.
Curing agent: Teikoku Ink Manufacturing Co., Ltd. 240 curing agent (10% mixed)
Screen mesh: T-225
Drying: 80 ° C x 10 minutes (box drying)
<Binder>
Binder: IMB-003 manufactured by Teikoku Ink Manufacturing Co., Ltd.
Screen mesh: T-225
Drying: 90 ° C x 60 minutes (box drying)
Next, the film on which the colored layer and the binder layer were formed was cut into predetermined dimensions, set in a mold, and insert molded under the following conditions.
Clamping pressure: 60ton
Mold temperature: Table 1
Molded resin: Sumitomo Dow Co., Ltd. PC / ABS alloy SD polycarbonate IM6011
Molding resin temperature: 260 ° C
Injection speed: Table 1
Molded product dimensions (L x W x H): 60 x 60 x 3 mm
Gate: φ2 mm pin gate The results obtained are shown in Table 1.

(Example 5)
A molded body was obtained in the same manner as in Example 3 except that the amount of discharge was adjusted and a laminated film having a ratio of adjacent layer thicknesses of 2 was obtained. The obtained results are shown in Table 1.

(Example 6)
As the resin A, polyethylene naphthalate (PEN) having an intrinsic viscosity of 0.72 was used. This resin A was a crystalline resin. As resin B, ethylene terephthalate (PET / I) copolymerized with 12 mol% of isophthalic acid was used. In addition, this resin B had an intrinsic viscosity of 0.67 and was a crystalline resin. About other conditions, it formed into a film similarly to Example 4 and the molded object was obtained. The obtained results are shown in Table 1.

(Comparative Example 1)
A molded body was prepared in the same manner as in Example 2 except that the molding conditions were changed as shown in Table 2. The obtained results are shown in Table 1.

(Comparative Examples 2-3)
A molded product was obtained in the same manner as in Example 1 except that ethylene terephthalate (PET / I) copolymerized with 12 mol% of isophthalic acid having an intrinsic viscosity of 0.67 was used as the resin B, and the molding conditions were changed as shown in Table 2. Created. The obtained results are shown in Table 2.

(Example 7)
A molded body was obtained under the same conditions as in Example 1 except that pre-molding and insert molding were performed as described below. The obtained results are shown in Table 2.
<Pre-molding>
Preheating (film temperature): 180 ° C
Pre-molding method: Press molding Pre-molded product dimensions by press molding (L x W x H): Convex mold of 60 x 80 x 6 mm, corner R = 2.1 mm
Press mold temperature: 70 ° C
<Insert molding>
Clamping pressure: 60ton
Mold temperature: Table 2
Molded resin: Sumitomo Dow Co., Ltd. PC / ABS alloy SD polycarbonate IM6011
Molding resin temperature: 260 ° C
Injection speed: Table 2
Molded product external dimensions (L x W x H): 60 x 80 x 6 mm (wall thickness 2.5 mm), corner R = 2.1 mm
(Example 8)
A molded body was obtained under the same conditions as in Example 7 except that pre-molding and insert molding were performed as described below. The obtained results are shown in Table 2.
<Pre-molding>
Preheating (film temperature): 80 ° C
Pre-molding method: Press molding Pre-molded product dimensions by press molding (L x W x H): Convex mold of 60 x 80 x 6 mm, corner R = 2.1 mm
Press mold temperature: 50 ° C
<Insert molding>
Clamping pressure: 60ton
Mold temperature: Table 2
Molded resin: Sumitomo Dow Co., Ltd. PC / ABS alloy SD polycarbonate IM6011
Molding resin temperature: 260 ° C
Injection speed: Table 2
Molded product external dimensions (L x W x H): 60 x 80 x 6 mm (wall thickness 2.5 mm), corner R = 2.1 mm

  Although the use of this invention is not specifically limited, It can use especially suitably for a mirror, a metallic decoration material, the optical member for a display, etc.

Claims (3)

A molded body obtained by coating a base material with a laminated film having at least 30 layers comprising a layer comprising resin A and a layer comprising resin B, wherein the laminated film is coated at a position close to the gate portion. a number of layers of Hg, the ratio of the number of layers Ha of the laminated film coated at a site distant from the gate portion (Hg / Ha) is Ri der 0.7 to 1.05 and covers the molded body The molded body characterized in that the calorific value of an exothermic peak observed in a range of 100 ° C. to 200 ° C. in DSC measurement of the laminated film is 0 J / g or more and 5 J / g or less . The molded article according to claim 1 , wherein the molded article has a portion having a glossiness of 500 or more. The ratio (Tf / Tc) between the thickness Tc of the laminated film coated in the vicinity of the corner of the molded body and the thickness Tf of the laminated film coated on the flat part of the molded body is 0.8 or more and 3 or less. molded body according to claim 1 or 2, characterized in.