JP2018030234A - Thermoplastic resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin film that has a high chroma and a high angle dependence of color tone and can present various appearances.SOLUTION: The present invention provides a thermoplastic resin film in which: based on spectral reflectances measured at angles of incidence of 0° and 60°, a formula defined in JISZ8781 is used to determine color tone values (L[0°], a[0°], b[0°]), (L[60°], a[60°], b[60°]), and the color tone values satisfy the following formula (i): |√(L[0°]+a[0°]+b[0°])-√(L[60°]+a[60°]+b[60°])|≥5.SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic resin film having high saturation and high angle dependency of color tone and capable of producing various appearances.

Products (parts) such as various home appliances, building components, crafts, and ornaments used for clothing have been used in various decorations such as wood grain and metal to enhance the design. Therefore, a design that can produce various appearances depending on high saturation and the angle of light has been demanded.
The most commonly used technique for imparting various appearances to various molded parts with high saturation and angle 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.
As another method for providing various appearances with high saturation and angle, there are a diffraction grating and vapor deposition. In such a technique, there is a problem that recycling is difficult because of the use of metal, and an alternative is strongly demanded. Furthermore, in the case of a diffraction grating or vapor deposition, the color of the entire design is determined by the metal layer that is the light reflecting layer, and is limited to silver gray, etc. There was an inadequate problem.
On the other hand, a hologram sheet having a high decorative effect that does not require a light reflection layer by using a highly glossy pigment with reflection has been proposed (see, for example, Patent Document 1).
In addition, various films in which thermoplastic resins are laminated in multiple layers have been proposed.For example, a film that selectively interferes and reflects a specific wavelength by laminating resin layers having different refractive indexes alternately in multiple layers is proposed. (For example, refer to Patent Document 2).

JP 2008-32829 A JP 2007-176154 A

Since the method described in Patent Document 1 uses a pigment, it is difficult to keep the haze low. Moreover, since the angle dependency of the color is small, there is a problem that the appearance of various appearances by the angle is not sufficient and the design property is inferior. Further, in the method described in Patent Document 2, although haze is suppressed to a low level, there is a problem that the angle dependency of saturation and color tone is not sufficient, and the design property is inferior. An object of the present invention is to provide a thermoplastic resin film that has high saturation and high angle dependency of color tone and can produce various appearances in view of the above-described problems of the prior art.

In order to solve the above problems, the present invention employs the following means. That is, the color tone values (L ^* [0 °], a ^* [0 °], b ^* [0 °) calculated using the calculation formula stipulated in JISZ8781 for the spectral reflectance measured at incident angles of 0 ° and 60 °. ], (L ^* [60 °], a ^* [60 °], b ^* [60 °]) satisfy the following formula (i).
Formula (i) | √ (L ^* [0 °] ² + a ^* [0 °] ² + b ^* [0 °] ² ) −√ (L ^* [60 °] ² + a ^* [60 °] ² + b ^* [60 °] ² ) | ≧ 5 (Numerical values in [] indicate measurement incident angle)

  According to the present invention, it is possible to obtain a thermoplastic resin film that has high chroma and high angle dependency of color tone and can produce various appearances. More specifically, as a molded body using the same, for example, a casing such as a personal computer or a TV, a decorative molded body such as a member of a home appliance or a building material, an art or craft, a decorative product used for clothing, a decorative thread It can use suitably for etc.

The figure which shows the design layer thickness of Examples 1-6 and Comparative Example 3 The figure which shows the design layer thickness of Examples 7-10 The figure which shows the design layer thickness of the comparative example 1 The figure which shows the design layer thickness of the comparative example 2

The thermoplastic resin film of the present invention has a color tone value ((L ^* [0] calculated using a calculation formula that prescribes the spectral reflectance measured at an incident angle of 0 ° and 60 ° determined by a measuring method described later in JISZ8781 ⁾ . °], a ^* [0 °], b ^* [0 °]), (L ^* [60 °], a ^* [60 °], b ^* [60 °]) satisfy the following formula (i): There is a need.
Formula (i) | √ (L ^* [0 °] ² + a ^* [0 °] ² + b ^* [0 °] ² ) −√ (L ^* [60 °] ² + a ^* [60 °] ² + b ^* [60 °] ² ) | ≧ 5
In the present invention, hereinafter, | √ (L ^* [0 °] ² + a ^* [0 °] ² + b ^* [0 °] ² ) −√ (L ^* [60 °] ² + a ^* [60 °] ² + b ^* [60 °] ² ) | may be referred to as ΔE (angle-dependent color difference). ΔE is an index representing the degree of change in color depending on the viewing angle (angle-dependent color difference). By setting ΔE within the above range, various appearances can be obtained depending on the angle of light, and it is possible to produce colors and high-class feelings that cannot be realized with the existing technology. ΔE is preferably 30 or more, more preferably 50 or more.

The thermoplastic resin film of the present invention preferably satisfies the following (ii) and (iii).
Formula (ii) L ^* [0 °] ≧ 45 and L ^* [60 °] ≧ 45
Formula (iii) √ (a ^* [0 °] ² + b ^* [0 °] ² ) ≧ 5 and √ (a ^* [60 °] ² + b ^* [60 °] ² ) ≧ 5
In the present invention, √ (a ^{* 2} + b ^{* 2} ) may hereinafter be referred to as C ^* (saturation C ^* ). By setting the lightness L ^* and saturation C ^* at the incident angles of 0 ° and 60 ° within the above ranges, various appearances can be produced depending on the angle of light. L ^* [0 °] and L ^* [60 °] are preferably 50 or more. C ^* is preferably 10 or more, more preferably 30 or more.
In the spectral reflectance at a wavelength of 400 nm to 1200 nm measured at an incident angle of 0 °, the thermoplastic resin film of the present invention preferably has a sum of reflection wavelength bands where the reflectance is 30% or more is 150 nm or more and 500 nm or less. With the above configuration, it becomes easy to increase the angle dependency of high saturation and color tone. The sum of the reflection wavelength bands where the reflectance is 30% or more is preferably 150 nm or more and 400 nm or less, and more preferably 200 nm or more and 300 nm or less.

The thermoplastic resin film of the present invention has a standard deviation of L ^* [0 °] determined by a measurement method described later as ΔL ^* , and a spectral reflectance at a wavelength of 400 nm to 1200 nm measured at the incident angle of 0 ° is 150 nm or more. When the standard deviation of the spectral reflectance in the reflection wavelength band where the reflectance is 30% or more is R (%), it is preferable that 2 ≦ R × ΔL ^* is satisfied. By adopting the above-described configuration, it is possible to develop design properties due to interference unevenness, and it is possible to produce more various appearances. R × ΔL ^* is preferably 5 or more, and more preferably 10 or more. Moreover, it is preferable that it is 30 or less from a viewpoint which will impair the designability, when interference nonuniformity is too strong.

  The thermoplastic resin film of the present invention preferably has a film haze of 0.1% to 2.0%. By setting the film haze to 2.0% or less, it becomes possible to express a transparent design. Moreover, since it becomes easy to impart design properties to the thermoplastic resin film by printing or the like, the width of the design can be widened. On the other hand, when the film haze is 0.1% or more, various appearances can be produced. The film haze is preferably from 0.1% to 1.5%, and more preferably from 0.2% to 1.0%.

The thermoplastic resin film of the present invention has a layer (A layer) mainly composed of the thermoplastic resin A and a layer (B layer) mainly composed of a thermoplastic resin different from the thermoplastic resin A. A thermoplastic resin film having 50 layers is preferred. The A layer and the B layer are preferably adjacent to each other. Here, the fact that the A layer and the B layer are adjacent means that the film has at least one structure in which the A layer and the B layer are directly laminated. Further, if the A layer and the B layer are adjacent to each other, the layer is not particularly limited as long as the effects of the present invention are not impaired. From the viewpoint of giving a phase difference to the film and generating a reflection wavelength band due to interference reflection, the A layer And B layers are preferably located periodically, more preferably alternately in the thickness direction. Here, as an example in which the A layer and the B layer are periodically positioned, when there is a layer (C layer) that does not correspond to the A layer, the B layer, the A layer, and the B layer, these layers are as follows: The aspect laminated | stacked on the thickness direction by the permutation is mentioned.
CA (BA) n
CA (BA) nC
A (BA) nCA (BA) m
(ABC) n
A is the A layer, B is the B layer, C is the C layer, m and n are the number of repetitions.
The A layer and the B layer are alternately positioned in the thickness direction. The thermoplastic resin film is composed of only the A layer and the B layer, and the A layer and the B layer include A (BA) n and A (BA) nB. , B (AB) n, or B (AB) nA in the permutation of the thickness direction, or the C layer is laminated on at least one outermost layer of the thermoplastic resin film represented in this aspect The aspect currently performed is said.

  As an example of the aspect in which the C layer is laminated on at least one outermost layer of the thermoplastic resin film, for example, at least one outermost layer of the thermoplastic resin film is hard-coated within a range that does not impair the effects of the present invention. Layer, colored layer, slippery layer, antistatic layer, anti-abrasion layer, antireflection layer, ultraviolet absorption layer, printing layer, transparent conductive layer, gas barrier layer, hologram layer, release layer, adhesive layer, embossing layer, and adhesion Examples include a functional layer such as a layer.

  In the thermoplastic resin film of the present invention, the total number of the A layer and the B layer is preferably 50 or more and 3,000 or less from the viewpoint of reducing lamination unevenness during production while ensuring a reflection wavelength band. When the total number of A layers and B layers is less than 50, sufficient reflectivity and reflection band cannot be obtained, and the selective wavelength cut performance required in each application may not be satisfied. On the other hand, when the total number of the A layer and the B layer exceeds 3,000, the production apparatus becomes large, and the stacking accuracy may be lowered and the reflection unevenness may be caused. The total number of layers is such that the sum of the reflection wavelength bands in which the reflectance is 30% or more in the spectral reflectance at a wavelength of 400 nm to 1200 nm measured at the incident angle of 0 ° is 150 nm or more, and the reflectance is 30% continuously. From the viewpoint of facilitating the reflection wavelength band to be 150 nm or more, it is preferably 100 or more and 1,000 or less.

  The thermoplastic resin film of the present invention preferably has two or more laminated structures in which the total number of the A layer and the B layer is 50 or more, more preferably 3 or more. By having two or more laminated structures, even if local thickness band loss occurs in one laminated structure, there is a layer thickness region of another laminated structure that complements it. The deviation of the mechanical characteristics and the loss of the reflection wavelength band can be suppressed.

  The resin constituting the thermoplastic resin film of the present invention needs to contain a thermoplastic resin as a main component from the viewpoint of ensuring good moldability. In the present invention, the main component means 50% by weight or more based on the total components.

  Further, the thermoplastic resin film of the present invention preferably has a layer (A layer) containing thermoplastic resin A as a main component and a layer (B layer) containing thermoplastic resin B as a main component. From the viewpoint of adjusting film stability and light transmittance, one of the thermoplastic resin A and the thermoplastic resin B is mainly composed of a crystalline thermoplastic resin, and either one is mainly composed of an amorphous thermoplastic resin. It is preferable to use as a component. For example, it is preferable that the thermoplastic resin A is a crystalline thermoplastic resin and the thermoplastic resin B is an amorphous thermoplastic resin. By setting it as such an aspect, it becomes possible to set it as the film design which has the characteristic of the crystalline thermoplastic resin excellent in dimensional stability and heat resistance, and the characteristic of the amorphous thermoplastic resin excellent in moldability. . In addition, the average in-plane refractive index of the layer mainly composed of crystalline thermoplastic resin is higher than the average in-plane refractive index of the layer mainly composed of amorphous thermoplastic resin, and the average refractive index difference between layers Occurs. Then, by adjusting the average refractive index difference between the layers, it becomes possible to adjust the light transmittance. Furthermore, since one layer is mainly composed of an amorphous thermoplastic resin, crystallization is less likely to occur even at high temperatures, so it is possible to reduce the occurrence of problems such as whitening of the thermoplastic resin film. It becomes.

  The thermoplastic resin referred to in the present invention refers to a resin that has the characteristics of being softened by heating and having plasticity, and solidifying when cooled. Amorphous thermoplastic resin refers to a thermoplastic resin having a heat of crystal melting of less than 0.1 mJ / mg when the temperature is raised at a rate of temperature rise of 5 ° C./min in differential calorimetry (DSC), A crystalline thermoplastic resin refers to a thermoplastic resin that does not correspond to an amorphous thermoplastic resin.

  Moreover, the thermoplastic resin A in the A layer of the thermoplastic resin film of the present invention and the thermoplastic resin B in the B layer may be one type or plural types. Here, when there are a plurality of types of thermoplastic resins A in the A layer, the content of the thermoplastic resin A is calculated by adding up the resins corresponding to the thermoplastic resin A. The same applies to the thermoplastic resin B in the B layer.

  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・ Fluorine resin such as ethylene tetrafluoride-6-propylene copolymer / vinylidene fluoride resin, acrylic resin, methacrylic resin, polyacetal resin, It can be used polyglycolic acid resin, polylactic acid resin, and the like. Among these, a polyester resin is particularly preferable from the viewpoint of strength, heat resistance, and transparency.

  In the thermoplastic resin film of the present invention, the polyester resin refers to a polycondensate of a dicarboxylic acid component and a diol component. Each of the dicarboxylic acid component and the diol component may be a single component or a plurality of types of components. Here, the polyester resin in which both the dicarboxylic acid component and the diol component are single components is referred to as a homopolyester resin, and the polyester resin in which any one of the dicarboxylic acid component and the diol component is a plurality of components is referred to as a copolyester resin.

  Examples of the homopolyester resin in the present invention include the above-mentioned polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate, as well as poly-1,4-cyclohexanedimethylene terephthalate, polyethylene diphenylate, and the like. Can be mentioned.

  The copolyester resin in the present invention is preferably a copolyester resin comprising at least three or more components selected from the following 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, 4,4 Examples include '-diphenylsulfone dicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexane dicarboxylic acid, and ester derivatives thereof. Examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, 2,2-bis (4 ′ -Β-hydroxyethoxyphenyl) propane, isosorbate, 1,4-cyclohexanedimethanol, spiroglycol and the like.

  In the thermoplastic resin film of the present invention, when the thermoplastic resin A is a crystalline thermoplastic resin and the thermoplastic resin B is an amorphous thermoplastic resin, the in-plane average refractive index of the A layer is B layer. It is relatively higher than the in-plane average refractive index. 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. If the difference in refractive index 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.

  In the thermoplastic resin film of the present invention, the absolute value of the difference in the HSP value (Hansen solubility parameter) between resins, the strength, heat resistance, and transparency of the film, the manufacturing cost, and the stability of film formation From the viewpoint, it is preferable that the crystalline thermoplastic resin A is a crystalline polyester and the amorphous thermoplastic resin B is an amorphous polyester. Furthermore, from the viewpoints of improving reflection performance, suppressing changes in optical properties due to heating and aging, and reducing peeling between layers, the crystalline polyester is crystalline polyethylene terephthalate, and the amorphous polyester is spiroglycol copolymer polyethylene terephthalate. And / or cyclohexanedimethanol copolymerized polyethylene terephthalate is more preferable.

  As long as the effects of the present invention are not impaired, the A layer and the B layer in the present invention may contain particles such as colloidal silica, titanium oxide, and crosslinked polystyrene in order to impart functions such as winding characteristics, rigidity, and optical characteristics. it can. The content of these resins and particles in the A layer or B layer is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 10% by weight or less when the entire layer is taken as 100% by weight.

  Further, the A layer and the B layer in the present invention are various additives, for example, an antioxidant, an antistatic agent, a crystal nucleating agent, an inorganic particle, an organic particle, a thinning agent, a heat, unless the effects of the present invention are impaired. It may contain a stabilizer, a lubricant, an infrared absorber, an ultraviolet absorber, a dopant for adjusting the refractive index, and the like.

  The thermoplastic resin film of the present invention is preferably a uniaxial or biaxially oriented film from the viewpoint of increasing the average refractive index difference between the A layer and the B layer. Here, the uniaxial or biaxially oriented film refers to a film in which molecular chains are oriented and crystallized in a uniaxial or biaxial direction at least in the A layer. Although it does not specifically limit as a method of making a film into a uniaxial or biaxially oriented film, unless the effect of this invention is impaired, The method of extending | stretching to a uniaxial or biaxial direction is mentioned.

  In the thermoplastic resin film of the present invention, the molecular chain is oriented and crystallized by uniaxial or biaxial stretching, and the dimensional stability and heat resistance can be improved. Moreover, when a crystalline thermoplastic resin is contained in the A layer, it is oriented and crystallized in the longitudinal direction and its refractive index increases. On the other hand, when the amorphous thermoplastic resin B is contained in the B layer, even if it is uniaxially or biaxially stretched, it does not crystallize as easily as the A layer. Thus, an average refractive index difference occurs between the layers, and the light transmittance can be adjusted. More specifically, by increasing the draw ratio, the average refractive index difference between the layers increases, so that the light transmittance can be controlled low.

  The figure which shows the design layer thickness is demonstrated as an example of the preferable layer structure of the thermoplastic resin film in this invention. FIG. 1 is a diagram in which the A layer and the B layer are plotted with respect to each layer order (hereinafter referred to as a layer number). The layer thickness corresponds only to the integer layer number in the figure, the A layer corresponds to the odd number, and the B layer corresponds to the even number. In order to prevent the film from being fused to a stretching roll or the like, the outermost thick film layer is preferably formed of an A layer.

  In the thermoplastic resin film of the present invention, as shown in FIGS. 1 to 4, the layer structure may have a layer structure that decreases after the layer thickness increases as it goes from one surface to the opposite surface. preferable. By setting it as such a structure, the performance which reflects the optical wavelength of the reflection wavelength band with sufficient width | variety can be given to a film. Further, even if a stacking fault occurs in a part of the pole and deviates from the design value, since the same layer thickness exists in the other part, it is possible to suppress the loss of the reflection wavelength band. In the order of FIG. 4, FIG. 1, FIG. 2, and FIG. 3, the width of the layer thickness distribution of the A layer and the B layer in the stacked structure is designed to be small.

  In the thermoplastic resin film of the present invention, it is preferable that an easy-adhesion layer comprising an acrylic / urethane copolymer resin and two or more kinds of crosslinking agents is provided on at least one surface of the thermoplastic resin film. When a print layer or a hard coat layer is applied to a thermoplastic resin film, the adhesion at the interface may be reduced if an easy adhesion layer is not provided on the treated surface. Moreover, when applying a printing layer and a hard-coat layer on both surfaces of a thermoplastic resin film, it is preferable that the easily bonding layer is provided in both surfaces.

  As the acrylic / urethane copolymer resin constituting the easy-adhesion layer preferably used in the present invention, an acrylic monomer is, for example, an alkyl acrylate (the alkyl group is methyl, ethyl, n-propyl, n-butyl, isobutyl, t- Butyl, 2-ethylhexyl, cyclohexyl, etc.), 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and other hydroxy group-containing monomers, acrylamide, methacrylamide, N-methyl methacrylamide N-methylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate Amino group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and other glycidyl group-containing monomers, acrylic acid, methacrylic acid and their salts (sodium salts, potassium salts, ammonium salts, etc.) carboxyl groups or monomers containing such salts, etc. Can be used. Moreover, as the urethane component in the present invention, a resin obtained by reacting a polyhydroxy compound and a polyisocyanate compound by a known urethane resin polymerization method such as emulsion polymerization or suspension polymerization can be used. Examples of the polyhydroxy compound constituting the urethane component include polyethylene glycol, polypropylene glycol, polyethylene / polypropylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, poly Caprolactone, polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythritol, polycarbonate diol, glycerin and the like can be used.

  As the crosslinking agent constituting the easy-adhesion layer in the present invention, it is preferable to copolymerize a crosslinkable functional group, for example, a melamine crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, an epoxy crosslinking agent, or a methylolation. Alternatively, alkylolized urea crosslinking agents, acrylamide crosslinking agents, polyamide crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, various silane coupling agents, various titanate coupling agents, and the like can be used. Further, from the viewpoint of heat-and-moisture resistance to the hard coat layer and the silicone-based adhesive layer, it is preferable to use two or more types of crosslinking agents. Specifically, at least one of the crosslinking agents is an oxazoline-based crosslinking agent or a carbodiimide. It is preferable to use a system crosslinking agent.

  Furthermore, since only the components of the easy-adhesion layer are easily charged, foreign matters may be mixed in various film processing steps, causing a problem of appearance defects. Therefore, it is preferable that the component of the easily adhesive layer contains a conductive polymer from the viewpoint of antistatic. As the conductive polymer, polypyrrole, polyaniline, polyacetylene, polythiophene vinylene, polyphenylene sulfide, poly-p-phenylene, polyheterocycle vinylene, particularly preferably (3,4-ethylenedioxythiophene) (PEDOT) is there.

  When the thermoplastic resin film of the present invention is used for a molded body, the molded body is made of a resin base material, the thermoplastic resin film of the present invention integrally laminated on the surface of the base material, and colored as necessary. Preferably it comprises a 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 the resin molding and the thermoplastic resin film, a decorative molding sheet or film on which a pattern or the like is printed is used, and the sheet is integrated with the substrate surface of the molded body by in-mold 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.

  The manufacturing method of the thermoplastic resin film of this invention can be illustrated as follows. For example, first, two types of resins A and B are prepared in the form of pellets. The pellets are dried in hot air or under vacuum as necessary, and then supplied to each of two extruders. In each extruder, the resin melted by heating to a temperature equal to or higher than the melting point makes the amount of resin extruded uniform with a gear pump or the like, and removes foreign matter or modified resin through a filter or the like. Resin A and resin B sent out from different flow paths using two extruders are sent 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 desirable to use a feed block including at least one. When such a feed block is used, the apparatus does not become extremely large, so that foreign matter due to thermal deterioration is small, and even when the number of layers is extremely large, it is possible to stack with high accuracy. 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 slit shape (length, width, gap), an arbitrary layer thickness can be achieved. For this reason, the layer structure which is the characteristic of this invention can be achieved easily. On the other hand, in a 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 system. In addition, it is difficult to achieve an arbitrary layer thickness.

Next, in the thermoplastic resin film of the present invention, in the spectral reflectance at a wavelength of 400 nm to 1200 nm measured at an incident angle of 0 °, the sum of the reflection wavelength bands where the reflectance is 30% or more is set to 150 nm or more and 500 nm or less. Therefore, it is necessary to design the layer thickness of each layer based on the following formulas (iv) and (v).
In addition, when a wavelength light in the near-ultraviolet to infrared wavelength region is irradiated onto a normal film, a part of the film is absorbed by the film without being transmitted or reflected. However, in the thermoplastic resin exemplified above, the absorptance with respect to light in the wavelength range from near ultraviolet to infrared is sufficiently smaller than the reflectance and transmittance. Therefore, the absorptivity is treated as 0% in the equation (v). And
Equation _{(iv) 2 × (n a} · d a + n b · d b) = λ
Formula ^{_{(v) [1 - {(}} n a L -n b L) / (n a L + n b L)} 2] × 100 = T
n _a : In-plane average refractive index of the A layer n _b : In-plane average refractive index of the B layer d _a : Layer thickness (nm) of the A layer
d _b : Layer thickness of the B layer (nm)
λ: main reflection wavelength (primary reflection wavelength)
L: Number of layers A and B corresponding to the main reflection wavelength λ T: Light transmittance of each wavelength (%)
The in-plane average refractive index (n _a , n _b ) of the A layer and the B layer is 5 mm (width direction) × 20 mm (longitudinal direction) × 0.5 mm (thickness direction) of a single film oriented film. It is obtained by measuring the refractive index of the film at a temperature of 23 ° C. and a wavelength of 589 nm five times with an Abbe refractometer, and calculating the average value.

The values of the layer thicknesses (d _a , d _b ) of the A layer and the B layer can be determined by cutting the film along a plane perpendicular to the thickness direction using a microtome and observing the cross section with a transmission electron microscope. . Specifically, the amorphous thermoplastic resin B is stained with RuO ₄ , a cross-sectional image magnified 40,000 times with a transmission electron microscope is taken, and analysis is performed with image processing software.

  Next, an image analysis method will be described. First, after processing by a low-pass filter (size: 7 × 7 strength: 10 times: 10), numerical data of position and brightness is obtained in the vertical thick profile mode. The position is previously scaled by spatial calibration. Then, every 6 pieces of data are extracted from the numerical data of the position and brightness by using spreadsheet software, and a three-point moving average process is further performed. The numerical value data of luminance thus obtained is differentiated by the numerical value data of the position, and the maximum value and the minimum value of the differential curve are calculated. The interval between adjacent local maximum and local minimum values is defined as the thickness of each layer. At this time, a fixed threshold is set for the differential value so as not to detect noise of the differential curve.

The image processing software and the spreadsheet software are not particularly limited as long as they have a function required for analysis. As image processing software, for example, Image-ProPlus ver. For example, “EXCEL” (registered trademark) 2000 (manufactured by Microsoft) can be used as the spreadsheet software.
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 rotary cooling bodies, such as a casting drum, and is cooled and solidified, and a casting film (non-stretched film) is obtained. At this time, it is preferable to use a wire-like, tape-like, wire-like, or knife-like electrode to be brought into close contact with a rotating 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 rotating cooling body such as a casting drum and rapidly cooled and solidified, or brought into close contact with a rotating cooling body with a nip roll and rapidly cooled and solidified.

The casting film (unstretched film) thus obtained is preferably biaxially stretched as necessary. Biaxial stretching refers to stretching in the longitudinal direction and the width direction. Stretching may be performed sequentially in biaxial directions or simultaneously in two directions. Further, the film may be re-stretched in the longitudinal direction and / or the width direction.
First, the case of sequential biaxial stretching will be described. Here, the stretching in the longitudinal direction refers to stretching for imparting molecular orientation to the film in the longitudinal direction. Usually, the stretching is performed by a difference in the peripheral speed of the roll. You may carry out in multiple steps using a roll pair of books. The stretching ratio varies depending on the type of resin, but usually 2 to 15 times is preferable. When polyethylene terephthalate is used as one of the resins constituting the thermoplastic resin film, 2 to 7 times is particularly preferably used. It is done. Moreover, as extending | stretching temperature, the glass transition temperature of the resin which comprises a thermoplastic resin film-glass transition temperature +100 degreeC is preferable.

When providing an easily bonding layer in the thermoplastic resin film of this invention, the method of coating and laminating | coating a coating agent is preferable. As a method for coating the coating agent, the coating is performed in a process separate from the thermoplastic resin film manufacturing process in the present invention, that is, the so-called off-line coating method, and the coating is performed during the thermoplastic resin film manufacturing process in the present invention. Thus, there is a so-called in-line coating method in which easy-adhesion layers are laminated at once. It is preferable to adopt an in-line coating method from the viewpoint of cost and uniform coating thickness, and the solvent of the coating liquid used in that case is preferably an aqueous system from the viewpoint of environmental pollution and explosion-proof property, and water is used. It is the most preferred embodiment to use.
When laminating the easy-adhesion layer by in-line coating, a coating material that forms the easy-adhesion layer is continuously applied to the uniaxially stretched thermoplastic resin film. As a coating method of a coating (water-based coating) using water as a solvent, for example, a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method, or the like can be used.
Before applying the aqueous coating agent, it is preferable to subject the surface of the thermoplastic resin film to a corona discharge treatment or the like. This is because the adhesiveness between the thermoplastic resin film and the coating material is improved and the coating property is also improved.
The easy-adhesive layer has a crosslinking agent, antioxidant, heat-resistant stabilizer, anti-glare stabilizer, ultraviolet absorber, organic easy-to-lubricant, pigment, dye, organic or inorganic as long as the effect of the invention is not impaired. You may mix | blend particle | grains, a filler, surfactant, etc.
Subsequent stretching in the width direction refers to stretching for imparting molecular orientation in the width direction of the film, usually using a tenter, transporting the film while holding both ends with clips, and applying heat to the film. After preheating, the film is stretched in the width direction. The aqueous coating applied just before the tenter is dried during this preheating. Although it changes with kinds of resin as a magnification of extending | stretching, 2 to 15 times is preferable normally, When polyethylene terephthalate is used for either of the resin which comprises the thermoplastic resin film in this invention, it is 2 to 7 times. Particularly preferred. Moreover, as extending | stretching temperature, the glass transition temperature-glass transition temperature +120 degreeC of resin which comprises the thermoplastic resin film in this invention are preferable. The biaxially stretched thermoplastic resin film is preferably 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. After being heat-treated in this way, it is gradually cooled gradually, cooled to room temperature, and wound up by a winder. 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 coating material which comprises an easily bonding layer is apply | coated continuously to the obtained cast film. As a coating method of a coating (water-based coating) using water as a solvent, for example, a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method, or the like can be used.
Before applying the aqueous coating material, it is preferable to subject the surface of the thermoplastic resin film in the present invention to corona discharge treatment or the like. This is because the adhesiveness between the thermoplastic resin film and the coating material is improved and the coating property is also improved. Next, the cast film (non-stretched film) coated with the coating agent is guided to the simultaneous biaxial tenter, and conveyed while holding both ends of the film with clips, and stretched in the longitudinal and width directions simultaneously and / or stepwise. To do. 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. The stretching magnification varies depending on the type of resin, but usually, the area magnification is preferably 6 to 50 times, and the area magnification is particularly preferably 8 to 30 times. Moreover, as extending | stretching temperature, the glass transition temperature-glass transition temperature +120 degreeC of resin which comprises a thermoplastic resin film is preferable. 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 impart flatness and dimensional stability. In this heat treatment, in order to suppress the distribution of the main orientation axis in the width direction, it is preferable to perform a relaxation treatment instantaneously 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 gradually, cooled to room temperature, and wound up by a winder. 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. It is preferable to perform relaxation treatment in the longitudinal direction immediately before and / or immediately after entering the heat treatment zone.

EXAMPLES Hereinafter, although this invention is demonstrated along an Example, this invention is not restrict | limited by these Examples.
(material)
(Resin A)
To a mixture of 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, 0.09 parts by weight of magnesium acetate and 0.03 parts by weight of antimony trioxide are added with respect to the amount of dimethyl terephthalate, and the temperature is raised by a conventional method. Then, a transesterification reaction is performed. Subsequently, 0.020 part by weight of 85% aqueous solution of phosphoric acid is added to the transesterification reaction product with respect to the amount of dimethyl terephthalate, and then transferred to a polycondensation reaction tank. Further, the reaction system was gradually reduced in pressure while heating and heated, and a polycondensation reaction was performed at 290 ° C. under a reduced pressure of 1 mmHg to obtain polyethylene terephthalate (hereinafter sometimes referred to as PET).

(Resin B-1)
Resin A and copolymer polyethylene terephthalate obtained by copolymerizing 21 mol% of spiroglycol (SPG) with respect to the total glycol component and 24 mol% of cyclohexanedicarboxylic acid (CHDC) with respect to the total dicarboxylic acid component were 15:85 (weight ratio). Copolymerized polyethylene terephthalate mixed in

(Resin B-2)
Copolymerized polyethylene terephthalate obtained by mixing resin A and polyethylene terephthalate obtained by copolymerizing 32 mol% of cyclohexanedimethanol (CHDM) with respect to all glycol components at a weight ratio of 18:82.

(Resin B-3)
Copolymerized polyethylene terephthalate obtained by mixing resin A and polyethylene terephthalate obtained by copolymerizing 32 mol% of cyclohexanedimethanol (CHDM) with respect to all glycol components at a weight ratio of 38:62.
(Resin B-4)
Copolyethylene terephthalate obtained by mixing resin A and polyethylene terephthalate obtained by copolymerizing 32 mol% of cyclohexanedimethanol (CHDM) with respect to the total glycol component at a weight ratio of 49:51.
(Pigment resin)
Resin A and pearl pigment (PEAL GLAZE MM-100R manufactured by Nihon Koken Co., Ltd.) are mixed at a weight ratio of 80:20, kneaded at 280 ° C. using a vent type twin screw extruder, and contains 20% by weight of pearl pigment. A pigment resin was obtained.
(Composition of easy adhesion layer)
-Aqueous dispersion of acrylic / urethane copolymer resin (a): Sannaron WG658 (solid content concentration 30% by weight), manufactured by Sannan Synthetic Chemical Co., Ltd.
-Aqueous dispersion of isocyanate compound (b): “Elastoron” (registered trademark) E-37 (solid content concentration: 28% by weight) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
-Aqueous dispersion of epoxy compound (c): manufactured by DIC Corporation, CR-5L (solid content concentration: 100% by weight)
An aqueous dispersion of the composition (d) comprising a compound having a polythiophene structure and a compound having an anion structure (solid content concentration: 1.3% by weight)
-Aqueous dispersion of oxazoline compound (e): Nippon Shokubai Co., Ltd., "Epocross" (registered trademark) WS-500 (solid content concentration 40 wt%)
-Aqueous dispersion of carbodiimide compound (f): "Carbodilite" (registered trademark) V-04 manufactured by Nisshinbo Co., Ltd. (solid content concentration 40%)
Acetylene diol-based surfactant (g): manufactured by Nissin Chemical Co., Ltd., Olphine EXP4051 (solid content concentration 50%)
Silica particles (h): JGC Catalysts & Chemicals, Spherica slurry 140 (solid content 40%)
-Aqueous solvent (i): pure water The above-mentioned (a) to (h) in terms of solids weight ratio (a) / (b) / (c) / (d) / (e) / (f) / ( g) / (h) = 100/100/75/25/60/60/15/10, and the aqueous coating material ((a) to (g)) has a solid content concentration of 3% by weight. (I) was mixed to adjust the concentration.

  Hereinafter, evaluation methods of physical property values used in the present invention will be described.

(Method for evaluating physical properties)
(1) Thermoplastic resin film overall thickness About the obtained thermoplastic resin film, the film thickness of arbitrary 10 points | pieces was measured using the digital micrometer micromate M-30 by Sony Precision Technology, The average value was defined as the total thickness of the thermoplastic resin film.
(2) Spectral reflectivity A 5 cm square sample was cut out from the center of the thermoplastic resin film, and the back side of the measurement surface of the sample was painted black with oil-based ink. Next, the absolute reflectance at an incident angle of 0 ° and 60 ° was measured using a spectrophotometer (manufactured by Hitachi, Ltd., U-4100 Spectrophotometer). The inner wall of the attached integrating sphere is barium sulfate, and the standard plate is aluminum oxide. In addition, an angle variable absolute reflectance attachment device was used for measurement at an incident angle of 60 °. The measurement wavelength was 400 nm to 1200 nm, the slit was 2 nm (visible) / automatic control (infrared), the gain was set to 2, and the measurement was performed at a scanning speed of 600 nm / min.

(3) Reflection wavelength band of spectral waveform From the spectral reflectance data obtained in (2), a wavelength region having a reflectance of less than 30% continuously at a pitch of 2 nm or more is defined as a reflection wavelength band, Reflect the wavelength threshold at which the reflectivity is 30% or more in the range where the reflectivity is increased at the lower wavelength end of the reflection wavelength band, and reflect the wavelength threshold at which the reflectivity is 30% or less in the range where the reflectivity is decreased relative to the wavelength. The high wavelength end of the wavelength band was taken, and the absolute value of the wavelength difference between the low wavelength end and the high wavelength end was taken as the reflection wavelength bandwidth. When the reflection wavelength band is in the vicinity of the measurement wavelength range (400 to 1,200 nm) and the upper and lower limits of the measurement wavelength do not exceed 30%, the upper and lower limits of the measurement wavelength are regarded as the high / low wavelength ends, respectively. It was. When there are a plurality of reflection wavelength bands, the low wavelength end that is the lowest wavelength in each wavelength band is the low wavelength end, the high wavelength end that is the highest wavelength is the high wavelength end, and the reflected wavelength in each wavelength band is The sum of the bandwidths was taken as the reflection wavelength bandwidth.

(4) Color tone (L ^* [0 °], a ^* [0 °], b ^* [0 °]), (L ^* [60 °], a ^* [60 °], b ^* [60 °])
From the spectral reflectance data obtained in (2), a spectral reflection curve obtained by averaging the P wave and S wave of the respective spectral reflection curves at incident angles of 0 ° and 60 ° was obtained. Next, from the average spectral reflection curve at each angle, L ^* [0 °], a ^* [0 °], b ^* [0 °], L ^* [60 °], L ^* [0 °], a ^* [0 °], L ^* [60 °], a ^* [60 °] and b ^* [60 °] were calculated, and the angle-dependent color difference ΔE and the saturation C ^* for each incident angle were obtained from the following equations.
Formula (vi) ΔE = | √ (L ^{* 2} + a ^{* 2} + b ^{* 2} ) [0 °] −√ (L ^{* 2} + a ^{* 2} + b ^{* 2} ) [60 °] |
Formula (vii) C ^* = √ (a ^{* 2} + b ^{* 2} )
(5) R × ΔL ^*
A total of four 5 cm square samples were cut from the four corners of the A4 size thermoplastic resin film, and the reflection in the reflection wavelength band of each sample was obtained from the spectral reflectance data at an incident angle of 0 ° obtained by the same method as in (3). The average value R of the standard deviation of the rate and the standard deviation ΔL ^* of the lightness L ^* in each sample were calculated.

(6) The haze was 23 ° C. and the relative humidity was 65%, using a turbidimeter NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd. The average value measured three times was taken as the haze value.

(7) Ornamental design properties The obtained thermoplastic resin film is decorated to two men each in their 20s, women, men in their 30s, women, men in their 40s, women, men in their 50s (16 people in total). Each of the design properties (color variety, luxury) was evaluated with a maximum of 10 points, and the average score was expressed by the following criteria to obtain an evaluation result.
A: 8 or more points.
○: 6 to less than 8 points.
Δ: Less than 4 to 6 points.
X: Less than 4 points.

Example 1
After the resin A and the resin B-1 are set to a discharge amount ratio (discharge amount of the resin A / discharge amount of the resin B-1) of 1.1, each is melted at 280 ° C. with a separate twin-screw extruder with a vent. 1 and the 549-layer feed block having two slit plates having 275 slits having a second manifold having a length twice as long as the slit width through the gear pump and the filter. I let you. At this time, the temperature of the feed block was 280 ° C. The outermost layers on both sides are resin A, resin A and resin B-1 are alternately laminated, and the layer thicknesses of the adjacent resin A and resin B layers in the thin film layer are substantially the same. (Outermost layer (A layer) / B layer / A layer / B layer /... B layer / outermost layer (A layer)). Thereafter, the molten resin flow was filled in the manifold portion inside the T die and further widened, and then extruded into a sheet form from the die slit. Next, it was brought into close contact with a casting drum maintained at a surface temperature of 25 ° C. by electrostatic application, and rapidly cooled and solidified to obtain a cast film.

  The obtained cast film was heated with a roll group set at 75 ° C., then stretched 3.3 times in the longitudinal direction while rapidly heating from both sides of the stretch section with a radiation heater between 100 mm in length, and then cooled once. Thus, a uniaxially stretched film was obtained. Next, both surfaces of the uniaxially stretched film were subjected to corona discharge treatment in the air, the coating tension of the film was 55 mN / m, and the composition of the easy adhesion layer was applied to both surfaces of the film with a # 4 metabar.

  The obtained uniaxially stretched film was guided to a tenter, and after preheating with 100 ° C hot air, it was stretched 3.6 times in the transverse direction at a temperature of 110 ° C. The stretched film is directly heat-treated in a tenter with hot air of 230 ° C., then subjected to a relaxation treatment of 7% in the width direction at the same temperature, and then cooled to room temperature and wound with a winder. An axially stretched film was obtained. The total film thickness of the obtained biaxially stretched thermoplastic resin film was 48 μm. The layer design of this thermoplastic resin film is as shown in FIG. 1, and the layer thickness of each layer was controlled by adjusting the slit gap. A cross section in the thickness direction of the thermoplastic resin film was observed with a TEM, and a layer thickness distribution was determined by image processing. The layer thickness distributions (3 and 4 in FIG. 1) of the A layer and the B layer in the laminated structure were 60 nm to 101 nm and 52 nm to 84 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 1.

(Example 2)
A thermoplastic resin film having a thickness of 48 μm was obtained in the same manner as in Example 1 except that the resin B-1 in Example 1 was changed to the resin B-2. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 59 nm to 99 nm and 50 nm to 80 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 1.

(Example 3)
A thermoplastic resin film having a thickness of 65 μm was obtained in the same manner as in Example 1 except that the thickness was adjusted by changing the line speed in Example 1. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 82 nm to 138 nm and 72 nm to 115 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 1.

Example 4
A thermoplastic resin film having a thickness of 48 μm was obtained in the same manner as in Example 3 except that the resin B-1 in Example 3 was changed to the resin B-2. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 82 nm to 134 nm and 72 nm to 112 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 1.

(Example 5)
A thermoplastic resin film having a thickness of 38 μm was obtained in the same manner as in Example 1 except that the resin B-1 of Example 1 was changed to Resin B-3 and the thickness was adjusted by changing the line speed. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 46 nm to 78 nm and 41 nm to 65 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 1.

(Example 6)
A thermoplastic resin film having a thickness of 37 μm was obtained in the same manner as in Example 1 except that the resin B-3 in Example 5 was changed to the resin B-4. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 45 nm to 77 nm and 40 nm to 65 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 1.

(Example 7)
In Example 2, the layer design is changed to FIG. 2 by adjusting the number of slits and the slit width of the feed block, and the thickness is 37 μm in the same manner as in Example 2 except that the thickness is adjusted by changing the line speed. A thermoplastic resin film was obtained. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 22 nm to 116 nm and 16 nm to 76 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 1.

(Example 8)
A thermoplastic resin film having a thickness of 92 μm was obtained in the same manner as in Example 7 except that the resin B-2 of Example 7 was changed to resin B-1 and the thickness was adjusted by changing the line speed. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 55 nm to 291 nm and 39 nm to 192 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 1.

Example 9
A thermoplastic resin film having a thickness of 94 μm was obtained in the same manner as in Example 8 except that the resin B-1 in Example 8 was changed to the resin B-2. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 61 nm to 288 nm and 41 nm to 192 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 2.

(Example 10)
A thermoplastic resin film having a thickness of 93 μm was obtained in the same manner as in Example 8 except that the resin B-1 in Example 8 was changed to the resin B-3. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 57 nm to 282 nm and 45 nm to 184 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 2.

(Example 11)
On the surface of a thermoplastic resin film obtained in the same manner as in Example 1, a binder IMB-003 manufactured by Teikoku Ink Manufacturing Co., Ltd. was formed to 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. The obtained decorative molded body had high chroma and high angle dependency of tone, and was excellent in appearance.

Mold temperature: 80 ℃
Molding resin temperature: 260 ° C
Molding resin: SD polycarbonate (IM6011)
Clamping pressure: 60ton
Molded case: PC (Example 12)
On both surfaces of the thermoplastic resin film obtained in the same manner as in Example 1, 100 parts (weight, hereinafter the same) of acrylic polyol (number average molecular weight 10,000, OH value 20), aliphatic diisocyanate curing agent (isocyanurate of hexane diisocyanate) (Cyclized product) A coating solution consisting of 30 parts and 18.2 parts of methyl ethyl ketone was applied, followed by drying and curing at 180 ° C. for 30 seconds and further at 90 ° C. for 12 hours to form a resin layer having a dry film thickness of 2 μm. The resulting thermoplastic resin film for decorative yarns on which the resin layer was formed was slit to a width of 0.5 mm, and decorative yarns were obtained without any locations where the metallic glitter was impaired. The obtained decorative yarn had high chroma and high angle dependency of color tone, and was excellent in appearance.

(Comparative Example 1)
A thermoplastic resin film having a thickness of 95 μm was obtained in the same manner as in Example 8 except that the layer design was changed to FIG. 3 by adjusting the slit width of the feed block in Example 8. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 31 nm to 345 nm and 8 nm to 265 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 2.

(Comparative Example 2)
A thermoplastic resin film having a thickness of 46 μm was obtained in the same manner as in Example 1 except that the layer design was changed to FIG. 4 by adjusting the number of slits and the slit width of the feed block in Example 1. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 59 nm to 62 nm and 50 nm to 54 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 2.

(Comparative Example 3)
A thermoplastic resin film having a thickness of 48 μm was obtained in the same manner as in Example 1 except that the resin B-1 in Example 1 was changed to the resin B-5. The layer thickness distributions of the A layer and the B layer in the laminated structure of the thermoplastic resin film were 61 nm to 100 nm and 53 nm to 81 nm, respectively. The properties and evaluation results of this thermoplastic resin film are shown in Table 2.

(Comparative Example 4)
In Example 1, the feed block is changed to pinole having three slits, resin B-1 is changed to pigment resin, and the discharge amount ratio (discharge amount of resin A / discharge amount of pigment resin) is changed to 8. A three-layer film having a thickness of 48 μm was obtained in the same manner as in Example 1 except that 2. The properties and evaluation results of this three-layer film are shown in Table 2.

(Comparative Example 5)
In Example 1, a single film film having a thickness of 49 μm was obtained in the same manner as in Example 1 except that the feed block was changed to a single layer pinol and only resin A was discharged. After providing the metal thin film layer by aluminum vapor deposition on one surface of this single layer film, the fine uneven | corrugated shape was provided in the surface by the embossing method, and the vapor deposition film with a thickness of 50 micrometers was obtained. Table 2 shows the properties and evaluation results of this deposited film.

  The present invention provides a thermoplastic resin film that has high saturation and high angle dependency of color tone, and can produce various appearances. More specifically, as a molded body using the same, for example, a casing such as a personal computer or a TV, a decorative molded body such as a member of a home appliance or a building material, an art or craft, a decorative product used for clothing, a decorative thread It can use suitably for etc.

1: Layer number 2: Layer thickness 3: Layer thickness distribution of layer A 4: Layer thickness distribution of layer B

Claims (11)

Color tone values (L ^* [0 °], a ^* [0 °], b ^* [0 °]) calculated using a calculation formula stipulated in JISZ8781 for spectral reflectance measured at least at an incident angle of 0 ° and 60 ° ), (L ^* [60 °], a ^* [60 °], b ^* [60 °]) satisfy the following formula (i).
Formula (i) | √ (L ^* [0 °] ² + a ^* [0 °] ² + b ^* [0 °] ² ) −√ (L ^* [60 °] ² + a ^* [60 °] ² + b ^* [60 °] ² ) | ≧ 5 The color tone values (L ^* [0 °], a ^* [0 °], b ^* [0 °]), (L ^* [60 °], a ^* [60 °], b ^* [60 °]) The thermoplastic resin film according to claim 1, which satisfies the following formulas (ii) and (iii).
Formula (ii) L ^* [0 °] ≧ 45 and L ^* [60 °] ≧ 45
Formula (iii) √ (a ^* [0 °] ² + b ^* [0 °] ² ) ≧ 5 and √ (a ^* [60 °] ² + b ^* [60 °] ² ) ≧ 5 3. The spectral reflectance at a wavelength of 400 nm to 1200 nm measured at an incident angle of 0 °, wherein the sum of the reflection wavelength bands at which the reflectance is 30% or more is 150 nm or more and 500 nm or less. Thermoplastic resin film. The standard deviation of L ^* [0 °] is ΔL ^* , and the spectral reflectance in the reflection wavelength band in which the reflectance is continuously 30% or more at 150 nm or more in the spectral reflectance at the wavelength of 400 nm to 1200 nm measured at the incident angle of 0 °. 4. The thermoplastic resin film according to claim 3, wherein 2 ≦ R × ΔL ^* is satisfied, where R (%) is a standard deviation of. The thermoplastic resin film according to any one of claims 1 to 4, wherein the haze is 0.1% or more and 2.0% or less. A layer having a thermoplastic resin A as a main component (A layer) and a layer having a thermoplastic resin B as a main component (B layer), wherein the A layer and the B layer are adjacent to each other; 6. The thermoplastic resin film according to claim 1, wherein the total number of the B layers is 50 or more and 3000 or less. The thermoplastic resin film according to claim 6, wherein the thermoplastic resin A is a crystalline thermoplastic resin, and the thermoplastic resin B is an amorphous thermoplastic resin. The crystalline thermoplastic resin is crystalline polyethylene terephthalate, and the amorphous thermoplastic resin is spiroglycol copolymerized polyethylene terephthalate and / or cyclohexanedimethanol copolymerized polyethylene terephthalate, Item 8. The thermoplastic resin film according to Item 7. A decorative molded body using the thermoplastic resin film according to claim 1. The ornament using the thermoplastic resin film in any one of Claims 1-8. A decorative yarn using the thermoplastic resin film according to any one of claims 1 to 8.

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