JP2007307893A - Mat-tone film and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mat-tone film being suppressed in the glare characteristic of interference reflection and having a posh metal-tone texture, and to provide a molded article comprising the film. <P>SOLUTION: The mat-tone film comprises a structure formed by laminating a layer (A layer) comprising of a thermoplastic resin A and a layer (B layer) comprising a thermoplastic resin B alternately each in 100 layers or more and has an integration value of ≥10,000 and/or a reflectance of ≥60% in the wavelength λ range [400, 700] (nm) of the spectral reflectance curve R (λ). And, the film comprises at least one layer containing particles which satisfies the relationship of formula (1): 1≤r/t≤300 (1) with respect to the thickness t (nm) of the layer containing particles and the average particle size r (nm) of the particles. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a matte film having a metallic texture in which two kinds of thermoplastic resins are alternately laminated, and a molded article using the matte film.

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

  In addition, a metallic tone film that is suitable for vacuum forming by imparting a metal color by printing or applying an ink component containing glittering powder (aluminum powder) and a thermoplastic resin binder on one side of the thermoplastic resin film. For example, Patent Document 2) has been proposed. In this case as well, a metal-like appearance cannot be obtained unless the metal powder is added at a high concentration, and also a resin film containing a metal at a high concentration. For this reason, there was a problem that the collection was difficult.

  On the other hand, various laminated films that exhibit a metallic tone without using a metal have been proposed. For example, a film that selectively reflects a specific wavelength (for example, by laminating resin layers having different refractive indexes alternately in multiple layers) Patent Documents 3 to 5) are known. Among these, a film that selectively reflects a specific wavelength acts as a filter that transmits or reflects specific light, and is used for a metallic reflector for a backlight such as a liquid crystal display and a reflective polarizer. .

However, this film that selectively reflects a specific wavelength has a strong glossiness, so that it has not only a metal-like texture for decoration applications that require a deep color or a high-class feeling, but also delamination. And formability was not good.
Japanese Patent Publication No. 3-010562 (2nd page) JP-A-8-183057 (2nd page) Japanese Patent Laid-Open No. 3-41401 (2nd page) JP-A-4-295804 (page 2) Japanese translation of PCT publication No. 9-506837 (2nd page)

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue. Therefore, an object of the present invention is to provide a matte film having a high-quality metallic texture and a molded product comprising the same, which suppresses the glare (glossiness) peculiar to interference reflection compared to the conventional art. is there.

In order to achieve the above object, according to the present invention, there is a structure in which layers of thermoplastic resin A (A layer) and layers of thermoplastic resin B (B layer) are alternately laminated by 100 layers or more, and A multilayer laminated film having at least one layer containing particles, wherein the relationship between the thickness t (nm) of the layer containing particles and the number average particle size r (nm) of the particles satisfies the following formula (1) And
1 ≦ r / t ≦ 300 (1)
A matte film satisfying at least one of the following (a) and (b) in the wavelength λ section [400, 700] (nm) of the spectral reflectance curve R (λ) is provided.
(A) The integral value of the spectral reflectance curve R (λ) is 10,000 or more. (B) The reflectance is 60% or more. In the matte film of the present invention,
The relationship between the absolute value X of the refractive index difference between the layer containing the particles and the particles and the number average particle size r (nm) of the particles satisfies the following formula (2):
100 ≦ r × X Formula (2)
The average roughness Ra is 35 nm or more,
The haze value in light with a wavelength of 1500 nm is 10% or more, and the thermoplastic resin A is made of polyethylene terephthalate, and the thermoplastic resin B is a copolymer of 10 mol% or more of each of a spiroglycol component and a cyclohexanedigalbonic acid component. It is preferable to use any polyester that has been prepared.

  Further, the molded product of the present invention is a film insert molded product using the matte film or a vacuum and / or pressure molded product using the matte film.

  According to the present invention, as will be described below, it is possible to collect metal hairline, sandblasting and embossing with reduced environmental load because it can be collected compared to conventional metal-like films, and with excellent releasability and formability. It is possible to obtain a matte film having a high-quality metallic texture as if applied.

The present invention is described in detail below.
The matte tone film of the present invention comprises a structure in which layers of thermoplastic resin A (A layer) and layers of thermoplastic resin B (B layer) are alternately laminated, each having a spectral reflectance curve. Thickness t (nm) of at least one layer comprising particles having an integral value of 10,000 or more and / or a reflectance of 60% or more in a wavelength λ section [400, 700] (nm) of R (λ) and particles The number average particle diameter r (nm) must include a layer satisfying the following formula (1).
1 ≦ r / t ≦ 300 (1)
In the present invention, polyolefins such as polyethylene, polypropylene, and poly (4-methylpentene-1) and cycloolefins are norbornene ring-opening metathesis polymerization, addition polymerization, and addition copolymers with other olefins. Biodegradable polymers such as alicyclic polyolefin, polylactic acid / polybutyl succinate, polyamides such as nylon 6, 11, 12, 66, aramid, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral , Ethylene vinyl acetate copolymer, polyacetal, polyglycolic acid, polystyrene, styrene copolymer polymethyl methacrylate, polycarbonate, polypropylene terephthalate / polyethylene terephthalate / polybutylene terephthalate Polyester such as polyethylene-2,6-naphthalate, polyether sulfone, polyether ether ketone, modified polyphenylene ether, polyphenylene sulfide, polyether imide, polyimide, polyarylate, tetrafluoroethylene resin, trifluorinated ethylene resin A thermoplastic resin such as a trifluoroethylene chloride resin, a tetrafluoroethylene-6-propylene copolymer, or polyvinylidene fluoride can be used. Among these, polyester is particularly preferable from the viewpoint of strength, heat resistance, and transparency. These may be homopolymers, copolymer polymers, or alloy polymers.

  The polyester constituting the matte film of the present invention is preferably a polyester obtained by polymerization from a monomer mainly comprising an aromatic dicarboxylic acid or aliphatic dicarboxylic acid and a diol. Here, as the aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyl Examples include dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, and the like. Examples of the aliphatic dicarboxylic acid include adipic acid, suberic acid, sebacic acid, dimer acid, dodecanedioic acid, cyclohexanedicarboxylic acid and ester derivatives thereof. Of these, terephthalic acid and 2,6 naphthalenedicarboxylic acid are preferred. These acid components may be used alone or in combination of two or more thereof, and further may be partially copolymerized with oxyacids such as hydroxybenzoic acid.

  Examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis (4- Hydroxyethoxyphenyl) propane, isosorbate, spiroglycol and the like. Of these, ethylene glycol is preferably used. These diol components may be used alone or in combination of two or more.

  Of the above polyesters, polyethylene terephthalate and its polymer, polyethylene naphthalate and its copolymer, polybutylene terephthalate and its copolymer, polybutylene naphthalate and its copolymer, and polyhexamethylene terephthalate and its copolymer It is preferable to use a polymer, polyhexamethylene naphthalate and a copolymer thereof.

  In the present invention, the layer made of the thermoplastic resin A (A layer) and the layer made of the thermoplastic resin B (B layer) are layers made of two different thermoplastic resins selected from the above thermoplastic resins. It is. The optimal combination of thermoplastic resins is preferably such that the in-plane refractive index difference between the resins is 0.05 or more from the viewpoint of producing a metal level reflectance by the optical interference phenomenon. More preferably, it is 0.08 or more. More preferably, it is 0.1 or more. The in-plane refractive index here means the refractive index in the in-plane direction of the film. In the case of the matte film of the present invention, the refractive index and the film width in the MD (Machine Direction) direction which is the running direction of the film. This is the average value of the refractive index in the TD (Transverse Direction) direction. The in-plane refractive index difference is the absolute value of the in-plane refractive index difference between the resins. The refractive index can be measured using a known Abbe refractometer.

  The combination of the two types of thermoplastic resins is composed of a layer made of the thermoplastic resin A and a thermoplastic resin B containing the same basic skeleton as the thermoplastic resin A from the viewpoint of easily realizing a laminated structure with high accuracy. It is preferable to have a layer. The basic skeleton here 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. This is because if the thermoplastic resin A and the thermoplastic resin B are resins containing the same basic skeleton, peeling between layers is less likely to occur.

  In the matte film of the present invention, the thermoplastic resin A is preferably polyethylene terephthalate or polyethylene naphthalate from the viewpoint that the in-plane refractive index is increased by orientation crystallization, while the thermoplastic resin B is oriented. A polyester comprising a cyclohexanedimethanol component or a spiroglycol component that is difficult to crystallize is preferred. The polyester comprising a cyclohexanedimethanol component or a spiroglycol component refers to a copolyester obtained by copolymerizing spiroglycol or cyclohexanedimethanol, a homopolyester, or a polyester obtained by blending them. Polyester containing a cyclohexanedimethanol component or a spiroglycol component is preferable because it has a small glass transition temperature difference from polyethylene terephthalate or polyethylene naphthalate, so that it is difficult to be overstretched during molding and is also difficult to delaminate. is there.

  When the thermoplastic resin B contains a cyclohexanedimethanol component, the copolymerization amount is 15 mol from the viewpoint of reducing the in-plane refractive index, hardly causing delamination between layers, and little change in physical properties due to heating or aging. % Or more and 60 mol% or less is preferable.

  From the viewpoint of reducing the in-plane refractive index more than the cyclohexanedimethanol component, the thermoplastic resin B is preferably a polyester comprising a spiroglycol component and a cyclohexanedicarboxylic acid component. When the thermoplastic resin B is a polyester comprising a spiroglycol component and a cyclohexanedicarboxylic acid component, the in-plane refractive index difference from polyethylene terephthalate or polyethylene naphthalate is further increased, so that a high reflectance is easily obtained. Further, since the glass transition temperature difference between polyethylene terephthalate and polyethylene naphthalate is small, it is difficult to be over-stretched during molding, and is also difficult to delaminate.

  In the matte film of the present invention, it is preferable that the thermoplastic resin A is polyethylene terephthalate particularly from the viewpoint of moldability, the in-plane refractive index is lower than that of the cyclohexanedimethanol component, delamination between layers hardly occurs, and heating From the viewpoint of little change in physical properties over time, it is preferable that the thermoplastic resin B is made of a polyester obtained by copolymerizing at least 10 mol% of a spiroglycol component and a cyclohexanedigalbonic acid component. If the amount of copolymerization is excessively increased, the compatibility between the resins will be poor, so that it will be difficult to realize a laminated structure with high accuracy, and from the viewpoint of easy delamination, the amount of copolymerization will be 10 respectively. Combinations within the range of from mol% to 50 mol% are preferred. More preferably, it is 20 mol% or more and 40 mol% or less.

  The matte film of the present invention includes a structure in which layers of thermoplastic resin A (A layer) and layers of thermoplastic resin B (B layer) are alternately laminated in the thickness direction by 100 layers or more. is required. Alternating in the thickness direction means that two types of thermoplastic resins A and B are periodically laminated in a regular arrangement such as A (BA) n (n is a natural number).

  From the viewpoint of achieving high light reflection performance, the number of laminated layers of the matte film of the present invention needs to be 100 or more, preferably 400 or more, more preferably 800 or more. More preferably, it is 1200 or more.

  The laminated structure of 100 layers or more in the matte film of the present invention can be produced by the following method. For example, in the case of a laminated film of A (BA) n, thermoplastic resin is supplied from two units of an extruder A corresponding to the A layer and an extruder B corresponding to the B layer, and the polymer from each flow path is Laminate over 100 layers by using a multi-manifold type feed block and a square mixer, which are known laminating devices, or using only a comb type feed block, and then use the T-type die etc. Examples thereof include a method in which a sheet is melt-extruded and then cooled and solidified on a casting drum to obtain an unstretched film.

  The multi-manifold type feed block is a known feed block as described in Keiji Sawada “Latest Technology of Plastic Extrusion” (Rubber Digest Co., Ltd.) (1993). That is, before a plurality of resins are fed into the die body, they are merged in the feed block, and then sent to a single manifold of the die to widen and extrude the flow.

Also, the square mixer is a publicly known unit having a merge portion that divides a polymer channel into two channels having a square cross-sectional area, and further joins the branched polymers so that they are stacked again in the thickness direction. It is a cylinder. By repeating this step, it is possible to obtain a multi-layered laminate. For example, an A / B / A3 layered laminate composed of two types of resins becomes a five-layered laminate when branched and merged once. In such a case, the number of layers can be expressed by (initial number of layers−1) × 2 to the nth power + 1. However, n means repeating one branching / merging n times. In addition, since the distribution ratio of the square mixer is usually branched by equal distribution in a flow path having an equal cross-sectional area of 1: 1, the same laminate is periodically formed. On the other hand, if the structure of the initial laminated body is an inclined structure, the laminated body after passing through the square mixer can maintain an inclined structure having a continuous layer thickness by making the distribution ratio non-uniform. The initial inclined structure before the square mixer can be achieved by inclining the pressure loss of each manifold in the multi-manifold type feed block corresponding to each layer having the inclined structure.
From the above, when a multi-manifold type feed block and a square mixer are combined, for example, when a laminated body in 11 layers in a multi-manifold type feed block passes through the square mixer four times, 161 layers Can be obtained. Examples of a method for increasing the number of layers include a method of arranging a plurality of feed blocks in parallel, a method of increasing the number of square mixers, and a method of increasing the number of layers of the laminated flow obtained in the feed block. As the multi-manifold type feed block here, a type II feed block described in JP-A-2006-44212 is exemplified.

  However, when the manifold type feed block described above is used, the size of the apparatus increases, and it is difficult to obtain a multilayer laminated film that maintains high lamination accuracy because it passes through the square mixer a plurality of times. Therefore, in the matte film of the present invention, it is preferable to obtain a laminated structure using a comb type feed block having a large number of fine slits. Details of the comb type feed block are described in Japanese Patent Application Laid-Open No. 2005-352237. This feed block can easily form a laminate of up to 400 layers at a time by increasing the number of slits. Furthermore, if a square mixer is combined, a laminate of 1000 layers or more can be obtained. In order to achieve higher stacking accuracy, a stack of 800 layers or more can be easily obtained by arranging at least two fine slit members in parallel without using a square mixer. Details of the manufacturing method are described in JP-A-2005-352237.

  The matte film of the present invention has a spectral reflectance curve R (λ in the wavelength λ section [400, 700] (nm) of the spectral reflectance curve R (λ) from the viewpoint of obtaining a metallic gloss. ) Integral value of 10,000 or more, and (b) reflectance in the wavelength λ section [400, 700] (nm) needs to satisfy at least one of 60% or more. Conventionally, in order to quantify this glossiness, it is expressed by parameters according to the visual sensitivity such as specular glossiness obtained by the method of measuring the specular gloss described in JIS Z8741 and the color measurement method described in JIS Z8722. It has been. However, in the retroreflector using the interference reflection phenomenon as in the present invention, the spectral reflection curve has a characteristic, so that the spectral reflectance curve R can be used to express the metallic luster in human appearance. It was found that it was appropriate to evaluate that the integral value of the spectral reflectance curve R (λ) in the wavelength λ interval [400, 700] (nm) of (λ) is 10,000 or more ”. is there. The average reflectance is 33.3% or more.

  For (b), the reflectance in the wavelength λ interval [400, 700] (nm) needs to be 60% or more. Although the integrated value as described in (a) can express a rough metallic luster, there are cases where it cannot be expressed. That is, even if the condition (a) is not satisfied, the same glossiness may be realized if a high reflectance is realized at a specific wavelength. Therefore, when the reflectance is 60% or more, it is more preferably 80% or more, and still more preferably 100% or more, from the viewpoint of obtaining the same metallic luster as the condition (a). The reflectance here means the maximum reflectance.

The most preferable condition is to satisfy both the conditions (a) and (b).
The spectral reflectance curve R (λ) is a reflectance distribution at each wavelength obtained by a known spectrophotometer. The reflectance may be a relative reflectance or an absolute reflectance. When the absolute reflectance and the relative reflectance are compared using the same test object, the absolute reflectance is usually lower, and therefore the absolute reflectance is preferable. The wavelength interval Δλ between measurement points is 1 nm. As the integrated value in the visible light region is larger, the metallic luster is increased. Therefore, the integrated value in the wavelength λ section [400, 700] (nm) is more preferably 15000 or more. On the other hand, if the glossiness is higher than that of metal, the integrated value is preferably 32000 or less in order to impair the high-quality feeling.

  The integrated value in the wavelength λ interval [400, 700] (nm) is the spectral reflectance curve R (λ) and wavelength λ in the wavelength λ interval [400, 700] (nm) in the graph of the relationship between wavelength and reflectance. It is the area surrounded by the axis. When the integral value S is expressed by an equation, it is defined by the following equation (3).

  However, it is difficult to integrate an arbitrarily obtained spectral reflectance curve R (λ). Usually, the equation (3) is calculated using the theory of numerical integration methods such as the Simpson method and the trapezoidal method. In the present invention, the reflectance R (λ) data for each wavelength of 1 nm in the wavelength λ section [400, 700] (nm) obtained by the spectrophotometer is used to calculate using the Simpson method for simplicity of calculation. It is preferable. A detailed explanation of the Simpson method is described in “Numerical Calculation Method I for Electronic Computers” (Baifukan) (1965) by Jiro Yamauchi et al.

  Further, from the viewpoint of suppressing the color shift phenomenon depending on the viewing angle of interference reflection and obtaining a metallic luster, in the wavelength λ section [400, 1000] (nm) of the spectral reflectance curve R (λ). The integral value is more preferably 30000 or more. On the other hand, the upper limit of the integral value is preferably 60000 or less.

The reflection performance that produces the glossy feeling of the matte film of the present invention does not use the specular reflection performance of the conventional metal itself, but uses the principle of interference reflection by the laminated structure at the optical wavelength level. Interference reflection is a phenomenon in which a number of different light-transmitting media, that is, thin layers having different refractive indexes, are stacked and the reflected lights on the boundary surfaces interfere with each other and strengthen each other. For example, for a multilayer film in which a large number of two types of thermoplastic resins A and B are alternately stacked, when light is incident perpendicularly to the surface of the film, the wavelength λ that satisfies the following formula (4) is satisfied at the interface of the stack (Nm) of light is reflected.
2 · (nA · dA + nB · dB) = nλ (4)
here,
nA: Refractive index of thermoplastic resin A nB: Refractive index of thermoplastic resin B dA (nm): Thickness of layer of thermoplastic resin A dB (nm): Thickness of layer of thermoplastic resin B n: Order of reflection The natural number to represent. Therefore, the reflection wavelength λ can be arbitrarily set by selecting the thermoplastic resins A and B and adjusting the layer thickness. A characteristic of the obtained spectral reflection curve is a ripple curve. Depending on the layer thickness distribution, a spectral reflection curve in which large peaks (peak values of reflectance) and valleys (minimum values of reflectance) are repeated.

  The layer thickness of each constituent layer is preferably set according to the refractive index of the thermoplastic resin that constitutes each layer. For example, the refractive index of the thermoplastic resin forming the laminated structure in the example as will be described later is in the range of about 1.3 to 1.9, and the thickness of each layer in this case is from the viewpoint of facilitating the use of optical interference. It is preferable to set to a value in the range of 30 to 650 nm. More preferably, it is 50-350 nm.

  Moreover, the target laminated structure is determined according to the required reflection performance. For example, a narrow-band reflection filter having a function of reflecting only light of a specific wavelength and transmitting other light forms a periodic structure in which the thickness of the resin A and the thickness of the resin B are constant in the thickness direction. An edge filter that has a function of transmitting or reflecting all light having a wavelength longer than or equal to a certain wavelength needs to form an inclined structure in which the layer thickness of the resin A and the layer thickness of the resin B change at a constant rate. There is. In addition, in any filter such as a narrow band transmission filter, a wide band transmission filter, and a polarization beam splitter, if an objective function is determined, an optimal structure can be determined by optical calculation. The theory of optical computation is described in Mitsunobu Kohatayama “Basic Theory of Optical Thin Films” (Opttronics) (2003).

  In the matte film of the present invention, the reflective performance in the visible light region is indispensable from the viewpoint of giving a metallic luster, so that it is similar to the laminated structure of the edge filter. That is, the wavelengths λ (for example, 400 nm) and λ ′ (for example, 700 nm) serving as the end of the desired reflection wavelength band are determined, and the layer corresponding to the reflection wavelength λ according to the above equation (4) from the known ejection ratio and refractive index The thicknesses dA and dB and the layer thicknesses dA ′ and dB ′ corresponding to the reflection wavelength λ ′ are obtained. The layer thickness between dA → dA ′ and between dB → dB ′ is such that the layer thickness distribution continuously changes monotonously increasing or decreasing monotonically. It is preferable that the gradient structure of the layer thickness in the thickness direction adopts a relation of an arithmetic progression, a geometric progression, and a quadratic function. In particular, the geometric sequence relationship is preferable. Further, the degree of inclination, which is the ratio of the maximum thickness layer to the minimum thickness layer of the thermoplastic resin A, depends on the refractive index difference between the resin A and the resin B, but achieves a high reflection band in the matte film of the present invention. From the viewpoint, it is preferably 0.7 or less. More preferably, it is 0.5 or less. By achieving the laminated structure as described above, a matte film having a metallic luster can be obtained. Further, the lamination ratio (A / B) of the thermoplastic resins A and B is preferably 0.8 to 3 from the viewpoint of increasing the reflectance and widening the reflection band. More preferably, it is 1-2.

The matte film of the present invention has at least one layer containing particles, and the relationship between the thickness t (nm) of the layer containing particles and the number average particle size r (nm) of the particles is expressed by the following formula (1). Must be satisfied.
1 ≦ r / t ≦ 300 (1)
That is, when at least one layer containing particles satisfies the above formula (1), it is possible to provide a matte film having a high-quality metallic texture. The light diffusibility by particles has a larger scattering cross-sectional area of the particles and the longer the optical path length, the stronger the properties. Therefore, it is preferable that 100 or more layers satisfy the above formula (1). If r / t is less than 1, the particles are buried in the layer, so that the glare caused by specular reflection light is strong and the high-class feeling is impaired. More preferably, it is 5 or more. Furthermore, it is preferably 20 or more. On the other hand, if the r / t exceeds 300, if there are particles in the inner layer of the matte film, the layer is disturbed, so that the metallic luster is easily lost. The feeling of ruggedness will damage the luxury. More preferably, it is 100 or less.

  As the particles of the present invention, any organic or inorganic particles that are inert to the resin can be used. As the shape, particles such as agglomerated particles, true spherical particles, beaded particles, complex particles, and scale particles can be used. The inorganic materials include iron oxide, magnesium oxide, cerium oxide, zinc oxide, barium carbonate, barium titanate, barium chloride, barium hydroxide, barium oxide, alumina, serinite, silicon oxide (silica). Calcium carbonate, titanium oxide, alumina, zirconia, aluminum silicate, mica, pearl mica, wax clay, calcined clay, bentonite, talc, kaolin, other composite oxides, etc. Examples thereof include a modified olefin resin, a crosslinked or non-crosslinked polystyrene resin, a crosslinked or non-crosslinked acrylic resin, a fluorine resin, and a silicon resin. Among these, agglomerated particles that are easy to change in shape without destroying the interface of the layer are preferable.

The layer containing particles means that the matte film of the present invention has 100 layers or more, and therefore means at least one of these layers containing particles. That is, when particles are present in all layers, it means that at least one layer should satisfy the above formula (1). Conversely, if all layers except one layer are non-particle layers, this one layer must satisfy the above formula (1).
The layer thickness can be measured by a known TEM or SEM observation of a cross section of the matte film. The magnification may be appropriately adjusted to the layer thickness to be observed. For example, a layer thickness of 1 μm or less can be observed at 20,000 times or more by TEM observation. On the other hand, from 1 to 10 μm, observation at about 20,000 to 1000 times by SEM observation is preferable.
The average particle diameter of the particles in the present invention is the number average particle diameter. The number average particle diameter D can be determined according to the following formula (5).

N is the number of particles. di is a particle diameter (nm). The particle diameter di is the major axis diameter when the particles are observed.

In addition, even the average particle size obtained from the particle size distribution may be adopted from the viewpoint of showing the same tendency. As a method for measuring the particle size distribution curve, it can be measured using a known sieving method, a microscope method, a light scattering method, a sedimentation method, a centrifugal force method and the like. Methods for obtaining various average particle sizes are described in “Powder” (Maruzen) (Showa 37) by Keiichiro Kubo. In recent years, the average particle size can be obtained from the obtained microphotographs using image processing software.
In the matte film of the present invention, from the viewpoint of imparting high diffuse reflection performance, the absolute value X of the refractive index difference between the particle-containing layer and the particle and the average particle diameter r (nm) of the particle It is preferable that the relationship satisfies the following formula (2).
100 ≦ r × X Formula (2)
In order to impart diffusion performance, the above formula (2) may have a large difference in refractive index when the average particle size of the contained particles is small, and conversely, a difference in refractive index may be small when the average particle size is large. It was derived by finding. From the viewpoint of imparting higher diffusibility, r × X is more preferably 500 or more. The layer containing particles is a resin layer containing particles, and may be any one of thermoplastic, thermosetting, and electron beam curable resins. The absolute value X of the difference in refractive index between the particle-containing layer and the particle is the absolute value of the difference between the refractive index of the resin layer and the refractive index of the particle. The refractive index can be measured by JIS K7142 (1996) A method and B method. Adjustment of the value of r × X can be easily achieved by adjusting the selection of resin and particles.

  Light scattering is roughly classified into light scattering (including Mie scattering and Rayleigh scattering) that occurs between the above-described particles and a medium having a different refractive index, and light scattering depending on the surface shape (for example, ground glass). ). The matte film of the present invention preferably has an average roughness Ra of 35 nm or more from the viewpoint of imparting moderate slipperiness and more light diffusibility. More preferably, it is 100 nm or more. Here, Ra is the center line average roughness. Ra takes a measurement length L portion from the roughness curve in the direction of the center, the extraction center line is X-axis, the vertical axis is Y, and the roughness curve is represented by Y = f (x). It is given by the following equation (6).

  Further, if Ra is too high, the surface becomes too rough and, on the contrary, the high-quality texture is impaired. Therefore, Ra is preferably 1000 nm or less. The method of controlling Ra to the above-mentioned value is not particularly limited, but can be achieved by appropriately adjusting the average particle diameter and outermost layer thickness of the particles contained in the outermost layer and the particle concentration. In addition, it can also be achieved by roughening the surface of the matte film by embossing.

  In the matte film of the present invention, the haze value in light having a wavelength of 1500 nm is preferably 10% or more. If the haze value is less than 10%, the light diffusibility is small, and a high-quality metallic texture cannot be obtained. More preferably, it is 20% or more. Conversely, if the haze is too high, the haze value is preferably less than 50% from the viewpoint of impairing the sense of quality. The method of adjusting to the above-described haze range with a wavelength of light that is not in the visible light range is that the relationship between the average roughness Ra and r (nm) / t (nm) in the formula (1) is the formula (1) and (2) Adjusting the value of r × X in the equation.

  Since the mat-like film of the present invention and the molded product are integrally formed, a molded product having a high-quality metallic texture can be obtained, so that the film insert molded product uses the mat-like film of the present invention. preferable. A film insert molding product is manufactured by inserting a special film that has undergone design printing into a plastic molding mold, and then pouring the heat-fluidized molding material (injection resin) into the mold. This is an injection-molded product with an integrated design film. The matte film of the present invention preferably has a film thickness of 50 μm or more and 350 μm or less from the viewpoint of easy insert molding. More preferably, they are 80 micrometers or more and 200 micrometers or less. It can be adjusted by changing the casting speed, extrusion amount, etc. in the film production process. Furthermore, in order to improve the adhesion to the insert resin, an easy-adhesion layer such as an acrylic, urethane, polyester, or polyvinyl chloride vinyl acetate copolymer resin is previously formed on the matte film of the present invention. You can keep it. As the conditions for film insert molding, the injection temperature of the molding resin is the melting temperature of the resin, and is generally about 240 ° C. for acrylic, about 280 ° C. for polyester, and about 200 ° C. for polyamide. It has been. In addition, polystyrene, polycarbonate, etc. are around 270 ° C., and may be determined according to the resin to be used. The mold temperature is preferably 80 ° C. or higher and 150 ° C. or lower from the viewpoint of moldability and adhesiveness of the matte film of the present invention. In order to make the matte film of the present invention stand out, it is preferable that carbon black is added to the resin to be inserted. The addition amount is suitably 1% by weight or more.

  The molded product is preferably a vacuum and / or pressure molded product using the matte film of the present invention. In vacuum molding, first, a thermoplastic resin sheet is sandwiched between clamp metal frames and heated and softened with a heater, and then a male or female mold provided with a vacuum hole in the mold corner in advance is pushed up and vacuum-sucked. The sheet is molded by adhering it to the mold at atmospheric pressure, and the molded product is cooled and cured before being taken out. In addition to the above steps, vacuum / pressure forming is a method in which the pressure box is lowered at the same time as the die is pushed up, and pressure is added to the sheet to form the sheet in close contact with the mold with a large forming pressure instead of atmospheric pressure. is there. A molded product produced by this method is a vacuum / pressure molded product. The heating temperature of the heater is preferably a temperature at which the resin is thermally deformed. In the case of the matte film of the present invention, if it is less than 150 ° C., high moldability cannot be obtained, and if it exceeds 250 ° C., color unevenness and flatness of the molded product are deteriorated. It is below ℃. On the other hand, the same applies to the mold temperature, and is preferably from the glass transition point to the crystal melting temperature. In the matte film of this invention, it is preferable that it is 80 to 150 degreeC. If the air pressure is too high, it will lead to film breakage, and if it is too low, the moldability will be sweetened, so about 0.5 MPa to 5 MPa is preferable. The term “sweet” as used herein means that there are no corners compared to unstretched sheets such as acrylic (PMMA) and polycarbonate (PC) used for ordinary insert molding materials. For the same reason, the degree of vacuum is preferably 100 mmHg or less in terms of differential pressure. In addition, when a molded product having a high molding ratio is used, the mat-like film according to the present invention and the insert molding mat bonded to the PMMA, PC, acrylonitrile-butadiene-styrene copolymer (ABS) resin sheet, and the like. It is also preferable to use a tone film. The thickness of the unstretched sheet is preferably about 100 to 500 μm from the viewpoint of moldability.

  Specific embodiments for achieving the matte film of the present invention will be described below.

  In the production method of the multi-layer laminated matte film of the present invention, in the case of a laminated film of A (BA) n, each thermoplastic resin is an extruder A corresponding to the A layer and an extruder B corresponding to the B layer. The melt from which the polymer from each flow path was laminated using a multi-manifold die, feed block, square mixer or static mixer is melt-extruded into a sheet using a T-type die, etc. Then, it obtains by the method of cooling and solidifying on a casting drum and obtaining an unstretched film. The laminated structure of the matte film of the present invention is preferably an inclined structure composed of 100 layers or more. An inclined structure of 100 layers or more can be manufactured by using a comb-type feed block. The number of layers can be determined by adjusting the number of slits of the slit plate constituting the comb type feed block. From the viewpoint of achieving high reflection performance in the wavelength λ section [400, 700] (nm), the number of layers of the present invention is preferably 500 or more, more preferably 800 or more. . More preferably, it is 1600 layers. Since the maximum number of slits attached to one slit plate is about 300 from the viewpoint of increasing the size of the apparatus, in order to achieve 800 layers or more, a method using one slit plate and a square mixer, or There is a method of arranging several slit plates in parallel. In order to achieve higher stacking accuracy, the latter is most preferable. Moreover, as a method of obtaining an inclined structure, it is achieved by inclining the gap and length of the slit inside the feed block. On the other hand, when a square mixer is used, the distribution ratio is usually equally divided and branched in a flow path having an equal cross-sectional area of 1: 1. Therefore, if the structure of the initial laminate is an inclined structure, the thickness The inclined structure is periodically and repeatedly arranged in the direction by the number of branches. However, by setting the distribution ratio to unequal distribution, it is possible to maintain an inclined structure in which the polymer laminate after passing through the square mixer is continuous. That is, when the graph of the layer number and the layer thickness is plotted, an approximate curve or an approximate straight line represented by a geometric sequence or a quadratic function that continuously rises to the right is obtained.

  If only the outermost layer of these laminated structures wants to have different characteristics, it is also possible to join a new third component resin supplied from the extruder C using pinol to form a cover layer It is. The known pinol can be used only on one surface layer or on both surface layers. Other than the above-mentioned coextrusion method, the third component resin can be laminated on the surface layer by a coating method. The different properties include slipperiness, light diffusibility, easy adhesion, moisture resistance, and the like.

In the matte film of the present invention, adding particles to the outermost layer is very effective from the viewpoint of imparting light diffusibility for exhibiting a metallic tone having a high quality texture.
FIG. 1 shows an example of a feed block which is an embodiment of the present invention. The feed block is a laminating apparatus for laminating two types of thermoplastic resins A and thermoplastic resins B, and will be described in detail below. In FIG. 1, member plates 1 to 9 are stacked in this order to form a feed block 10.

  The feed block 10 in FIG. 1 has four resin inlets derived from the resin introduction plates 2, 4, 6, and 8. For example, the thermoplastic resin A is supplied from the introduction ports 11 of the resin introduction plates 2 and 6. Then, the thermoplastic resin B is supplied from the introduction port 11 of the resin introduction plates 4 and 8. Then, the slit plate 3 receives the thermoplastic resin A from the resin introduction plate 2 and the thermoplastic resin B from the resin introduction plate 4, and the slit plate 5 receives the thermoplastic resin A and the resin introduction plate 4 from the resin introduction plate 6. The slit plate 7 receives the thermoplastic resin A from the resin introduction plate 6 and the thermoplastic resin B from the resin introduction plate 8.

  Here, the type of the thermoplastic resin introduced into each slit plate is determined by the positional relationship between the bottom surface of the liquid reservoir 12 in the resin introduction plates 2, 4, 6, and 8 and the end of each slit in the slit plate. The That is, as shown in FIG. 3, the ridge line 13 at the top of each slit in the slit plate is inclined with respect to the thickness direction of the slit plate (FIGS. 2B and 2C). However, as shown in FIG. 2 (a), the slit width for forming the thick film layer positioned at both ends of each slit plate is the same as the slit width for forming another thin film layer from the viewpoint of preventing the thin film layer from being destroyed. It is necessary to be twice or more. Here, the slit width for forming the other thin film layer is the width of the slit portion for forming the thin film layer adjacent to the slit for forming the thick film layer. More preferably, it is 3 times or more.

  As shown in FIG. 3, the height of the bottom surface of the liquid reservoir 12 in the resin introduction plates 2, 4, 6, 8 (8 is omitted from FIG. 3 because it is a repetitive structure) is the upper end of the ridge line 13. It is located at a height between the part 14 and the lower end part 15. As a result, the thermoplastic resin is introduced from the liquid reservoir 12 of the resin introduction plates 2, 4, 6 and 8 from the side where the ridge line 13 is raised (16 in FIG. 3), but the ridge line 13 is lowered. From the side, the slit is sealed and the thermoplastic resin is not introduced. Thus, since the thermoplastic resin A or B is selectively introduced for each slit, the flow of the thermoplastic resin having a laminated structure is omitted from FIG. ) And flows out from the outlet 17 below the slit plates 3, 5, 7.

  As the shape of the slit, it is preferable that the slit area on the side where the thermoplastic resin is introduced is not the same as the slit area on the side where the thermoplastic resin is not introduced. With such a structure, the flow rate distribution on the side where the thermoplastic resin is introduced and the side where the thermoplastic resin is not introduced can be reduced, so that the laminating accuracy in the width direction is improved. Further, (slit area on the side where the thermoplastic resin is not introduced) / (slit area on the side where the thermoplastic resin is introduced) is preferably 0.2 or more and 0.9 or less. More preferably, it is 0.5 or less. Moreover, it is preferable that the pressure loss in a feed block will be 1 Mpa or more. Moreover, it is preferable that the slit length (the longer one of the Z-direction slit lengths in FIG. 1) is 20 mm or more. On the other hand, the slit gap is preferably 0.1 mm or more, more preferably from the viewpoint of processing accuracy. It is 0.5 mm or more and 2 mm or less. Thus, the thickness of each layer can be controlled by adjusting the gap and length of the slit. Note that the slit is preferably manufactured by wire electric discharge machining from the viewpoint of requiring high machining accuracy by finely adjusting the gap and length.

  It is also preferable to have a manifold portion corresponding to each slit plate. Because the manifold part makes the flow velocity distribution in the width direction (Y direction in FIG. 1) inside the slit plate uniform, the lamination ratio in the width direction of the laminated films can be made uniform, and a large area film However, it becomes possible to laminate with high accuracy, and the reflectance in the film width direction can be controlled with high accuracy.

  More preferably, the thermoplastic resin is supplied from one liquid reservoir to two or more slit plates. In this way, even if the flow distribution is slightly generated in the width direction inside the slit plate, since it is further laminated by the confluence apparatus described below, the lamination ratio is made uniform in total. It is possible to reduce unevenness of the higher-order reflection band.

  As shown in FIG. 1, the outlet 17 below the slit plates 3, 5, 7 is arranged in a positional relationship in which the laminated structures of the three thermoplastic resin flows are arranged in parallel. They are separated from each other. The shape of the outlet 17 preferably has an aspect ratio of 1 or more from the viewpoint of increasing the lamination accuracy. The aspect ratio here is the ratio of the length in the lamination direction (X-axis direction in FIG. 1) to the length in the film width direction (Y-axis direction in FIG. 1).

The laminated film of the present invention is preferably manufactured using a merging device 18 as shown in FIG. 4 (a) arranged just below the feed block 10 in FIG. 1 (Z direction). 4B, 4C, and 4D are XY cross-sectional views taken along lines LL ′, MM ′, and NN ′ in FIG. 4A, respectively. Hereinafter, three thermoplastic resin flows after the slit plate will be described. As can be understood from the cross-sectional views of FIGS. 4B and 4C from the middle LL ′ to the MM ′ by the merging device 18 shown in FIG. Conversion takes place and the configuration of the three thermoplastic resin streams changes from parallel to serial. Here, the cross-sectional area of the resin flow path from LL ′ to MM ′ in FIG. 4A is preferably all constant from the viewpoint of increasing the lamination accuracy. Also, the area of the cross-sectional shape at the position MM ′ should be as wide as possible from the viewpoint of adjusting the flow rate of the polymer and controlling the stacking disorder. Specifically, the discharge amount of the alternately laminated thermoplastic resin passing through the cross-sectional area within a unit time is preferably 40 kg / hr / cm ² or less. More preferably, it is 30 kg / hr / cm ² or less, and further preferably 20 kg / hr / cm ² or less. Further, the thermoplastic resin flow is widened from MM ′ to NN ′ in FIG. 4A, and flows into the base portion downstream from NN ′ in FIG. Thereafter, the molten thermoplastic resin flow is filled in the manifold portion inside the T die, further widened, then extruded into a sheet form from the die slit, and solidified on a cooling roll having a glass transition temperature or lower of the thermoplastic resin. Thus, an unstretched laminated film is obtained. The laminated film which is an unstretched film thus obtained has high lamination accuracy.

  Furthermore, it can also obtain by the method of extending | stretching this unstretched laminated film at the temperature more than the glass transition point (Tg) of a resin composition. The stretching method at this time is preferably stretched in at least one direction from the viewpoint of thermal dimensional stability. In particular, biaxial stretching is preferably performed by a known sequential biaxial stretching method or simultaneous biaxial stretching method. The known biaxial stretching method may be a method of stretching in the width direction after stretching in the longitudinal direction, a method of stretching in the longitudinal direction after stretching in the width direction, and a plurality of stretching in the longitudinal direction and stretching in the width direction. You may carry out in combination. For example, in the case of a stretched film composed of polyester, the stretching temperature and the stretching ratio may be any amount, but in the case of a normal polyester film, the stretching temperature is 80 ° C. or more and 130 ° C. or less, and the stretching ratio is 2 times. It is preferably 7 times or more. The stretching method in the longitudinal direction is performed by utilizing the change in the speed between the rolls. Moreover, the well-known tenter method is utilized for the extending | stretching method of the width direction. That is, the film is conveyed while being held at both ends by a clip and stretched in the width direction.

  The stretched film is then subsequently heat treated in a tenter. This heat treatment is generally performed at a temperature higher than the stretching temperature and lower than the melting point. In the case of ordinary polyester, it is preferably performed in the range of 130 ° C. to 250 ° C., but more preferably in the range of 200 ° C. to 240 ° C. from the viewpoint of suppressing the heat shrinkage rate. Furthermore, it is also preferable to perform a relaxation heat treatment of about 2 to 10% in the width direction or the longitudinal direction in order to impart thermal dimensional stability of the film.

  Next, the simultaneous biaxial stretching method will be described. The unstretched film cast on the cooling roll is guided to a simultaneous biaxial tenter, and conveyed while holding both ends of the film with clips, and stretched simultaneously and / or stepwise in the longitudinal direction and the width direction. Stretching in the longitudinal direction is achieved by increasing the distance between the clips of the tenter and in the width direction by increasing the distance between the rails on which the clips run. The tenter clip subjected to stretching and heat treatment in the present invention is preferably driven by a linear motor system. In addition, there are a pantograph method, a screw method, etc. Among them, the linear motor method is excellent in that the stretching ratio can be freely changed because the degree of freedom of each clip is high. When the film is a normal polyester, the stretching ratio, stretching temperature, and heat treatment temperature are similar to the conditions for sequential biaxial stretching. That is, the stretching temperature is preferably 80 ° C. or higher and 130 ° C. or lower, and the stretching magnification is preferably 8 to 30 times as the area magnification.

  The thickness of the matte film of the present invention is determined from the balance between the thickness of each layer and the total number of laminated layers, and is usually 50 μm to 200 μm.

  The matte film of the present invention has an outermost layer made of at least one of a polyester resin, an acrylic resin, and a urethane resin, from the viewpoint of enhancing the easy adhesion with the insert resin and / or the diffuse reflection performance by adding high concentration particles. There is preferably a primer layer comprising a selected resin. These resins may be used alone or in combination of a plurality of types.

  The urethane resin used as a constituent component of the primer layer may be any water-soluble or water-dispersible one having an anionic group, and its main constituent component is obtained by copolymerizing a polyol compound and a polyisocyanate compound. It is what

  Examples of the polyol compound used for the urethane resin include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, and triethylene. Examples include glycol, polycaprolactone, polyhexamethylene adipate, polytetramethylene adipate, trimethylolpropane, trimethylolethane, glycerin, and acrylic polyol.

  Examples of the polyisocyanate compound used for the urethane resin include tolylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, an adduct of tolylene diisocyanate and trimethylolpropane, an adduct of hexamethylene diisocyanate and trimethylolethane, and the like. Can be mentioned.

  The anionic group in the urethane resin contributes to the improvement of the affinity for water. For example, sulfonic acid group, carboxylic acid group, sulfuric acid half ester group and their ammonium salts, lithium salts, sodium salts, potassium salts, A magnesium salt can be mentioned. Particularly preferred is a sulfonate group.

As content with respect to the urethane resin of an anionic group, 0.5-15 mass% is preferable.
As content of the anionic group with respect to a polyurethane resin, 0.05-8 mass% is preferable. The effect of improving the water dispersibility of the urethane resin can be obtained when the content is 0.05% by mass or more, and the water resistance of the resin is deteriorated or the resin layer is fixed to each other when the content is 8% by mass or less. Occurrence of the phenomenon can be suppressed.

  The urethane resin preferably contains a chain extender or a crosslinking agent in addition to the above components. As the chain extender or crosslinking agent, ethylene glycol, propylene glycol, butanediol, diethylene glycol, ethylenediamine, diethylenetriamine, or the like can be used.

The molecular weight of the urethane resin is preferably 300 to 20000 in terms of number average molecular weight.
Regarding the acrylic resin used as the constituent component of the primer layer, examples of the monomer component constituting the acrylic resin include alkyl acrylate, alkyl methacrylate (the alkyl group is methyl, ethyl, n-propyl, isopropyl, n- Butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, lauryl group, stearyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.), 2-hydroxyethyl acrylate, 2-hydroxy Hydroxy group-containing monomers such as ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-meth Amide group-containing monomers such as roll acrylamide, N-methylol methacrylamide, N, N-dimethylol acrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-phenyl acrylamide, N, N-diethylaminoethyl acrylate, N Amino group-containing monomers such as N, diethylaminoethyl methacrylate, epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, acrylic acid, methacrylic acid or salts thereof (including lithium salts, sodium salts, potassium salts, etc.) A monomer containing a carboxyl group or a salt thereof can be used. These may be used by polymerizing one kind alone, or two or more kinds may be copolymerized and used.

  In particular, those containing a polymerization component selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylol acrylamide, and acrylic acid are preferable.

  Further, other types of monomers may be copolymerized as long as the effect of the acrylic resin as a primer layer is not impaired. Examples of other types of monomers that can be copolymerized include monomers containing an epoxy group such as allyl glycidyl ether, monomers containing a sulfonic acid group such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof, or salts thereof, crotonic acid, Monomers containing carboxyl groups such as itaconic acid, maleic acid, fumaric acid and their salts or salts thereof, monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride, vinyl isocyanate, allyl isocyanate, styrene, vinyl Methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkylmaleic acid monoester, alkyl fumaric acid monoester, acrylonitrile, methacrylonitrile, alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate It can be used vinyl chloride and the like. Examples of the salt with a sulfonic acid group or a carboxyl group include lithium salt, sodium salt, potassium salt, ammonium salt and the like.

  The acrylic resin may be a modified acrylic copolymer such as a block copolymer or a graft copolymer modified with polyester, urethane, epoxy, or the like.

Polyester resin is preferable in terms of adhesiveness among resins constituting the primer layer.
As the acid component constituting the polyester resin, aromatic, aliphatic, and alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids can be used.

  As aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2 -Bisphenoxyethane-p, p'-dicarboxylic acid, phenylindanedicarboxylic acid, etc. can be used. From the viewpoint of the strength and heat resistance of the primer layer, these aromatic dicarboxylic acids preferably account for 30 mol% or more of the total dicarboxylic acid component, more preferably 35 mol% or more, and even more preferably 40 mol%. That's it.

  Examples of the aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, and ester-forming derivatives thereof can be used.

  As the glycol component of the polyester resin used as a constituent component of the primer layer, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2 -Ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1, 5-pentanediol, 2,2,4-trimethyl 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4 , 4'-thiodiphenol, bisphenol A, 4,4'-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p- Use dihydroxybenzene, 4,4′-isopropylidenephenol, 4,4′-isopropylidenebindiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, etc. Can do.

  The polyester resin used as a constituent component of the primer layer is preferably an aqueous liquid and used as a coating liquid. In this case, in order to facilitate water-solubilization or water-dispersion of the polyester resin, a carboxylic acid group, a carboxylic acid It is preferable to copolymerize a compound containing a base, a sulfonic acid group or a sulfonic acid group.

  Examples of the compound containing a carboxylic acid group or a carboxylate group include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 5- (2,5-dioxo Tetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-cyclohexene-1,2-dicarboxylic acid, cyclopentanetetracarboxylic acid 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol Bis-trimellitate, 2,2 ′, 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, etc., or alkali metal salts or alkaline earth metals thereof Examples thereof include salts and ammonium salts.

  Examples of the compound containing a sulfonic acid group or a sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and sulfo-p-xylyl. Ren glycol, 2-sulfo-1,4-bis (hydroxyethoxy) benzene, or alkali metal salts, alkaline earth metal salts, and ammonium salts thereof can be used.

  The preferred polyester resin used in the primer layer is selected from terephthalic acid, isophthalic acid, sebacic acid, 5-sodium sulfoisophthalic acid as the acid component, and ethylene glycol, diethylene glycol, 1,4-butanediol, and neopentyl glycol as the glycol component. And the like. When water resistance is required for the primer layer, a copolymer containing trimellitic acid as a copolymer component thereof can be suitably used instead of 5-sodium sulfoisophthalic acid.

  The polyester resin used for the primer layer may be a modified polyester copolymer such as a block copolymer or a graft copolymer modified with acrylic, urethane, epoxy or the like.

  The intrinsic viscosity of the polyester resin used in the primer layer according to the present invention is preferably 0.3 dl / g or more in terms of adhesiveness, more preferably 0.35 dl / g or more, and still more preferably 0.4 dl / g. g or more.

  In addition, the glass transition temperature (Tg) of the polyester resin is preferably 130 ° C. or less, more preferably 80 ° C. or less, in order to obtain the stability and water dispersibility of the resin. On the other hand, in order to maintain heat-resistant adhesiveness and prevent the occurrence of a blocking phenomenon in which the resin layers adhere to each other, the temperature is preferably set to 0 ° C. or higher.

  The primer layer may be composed of a single layer or a plurality of layers.

  The thickness of the primer layer is preferably 0.001 to 5 μm, preferably 0.005 to 1 μm, and more preferably 0.01 to 0.1 μm. By setting the thickness to 0.001 μm or more, the effect of improving the adhesiveness can be obtained.

  As a method for producing a urethane resin having an anionic group which is one of preferred resins for forming a primer layer, for example, a polyol, a polyisocyanate, a chain extender and the like are mixed with a compound having an anionic group, A method of performing polymerization of urethane resin and addition of an anionic group in the same process, a method of reacting and fixing a compound having an anionic group to an isocyanate group of a urethane resin produced in advance, or a urethane resin produced in advance And a method of reacting a specific compound with a group having active hydrogen.

  In addition, acrylic resin, which is another preferable resin for forming the primer layer, is dissolved, emulsified, or suspended in water and used as an aqueous acrylic resin solution from the viewpoint of environmental protection and explosion-proof properties during application. preferable. Water-based acrylic resins are copolymerized with monomers having a hydrophilic group (such as acrylic acid, methacrylic acid, acrylamide, vinyl sulfonic acid and salts thereof), and emulsion polymerization and suspension polymerization using reactive emulsifiers and surfactants. It can be produced by a method such as soap-free polymerization.

  In addition, as a method for producing a polyester resin which is another preferable resin for forming the primer layer, for example, a dicarboxylic acid component and a glycol component may be directly esterified, or ester may be used as a first step. After the exchange reaction, a polycondensation reaction may be performed as the second stage. As the reaction catalyst at this time, for example, compounds such as alkali metals, alkaline earth metals, manganese, cobalt, zinc, antimony, germanium, titanium, and the like can be used.

  Polyester resins having a large amount of carboxylic acid at the terminal and / or side chain are preferably used. Examples of methods for obtaining these are JP-A-54-46294 and JP-A-60-209073. JP-A-62-240318, JP-A-53-26828, JP-A-53-26829, JP-A-53-98336, JP-A-56-116718, JP-A-61-124684 And a method of copolymerizing a trivalent or higher polyvalent carboxylic acid described in JP-A-62-240318.

  The method of providing the primer layer on the matte film of the present invention may be a method of applying after the production of the matte film, but it is applied during the production process of the matte film which is a stretched film and is a base material. A method of stretching together with a matte film is preferable in terms of cost. For example, the coating liquid may be continuously applied to a polyester film uniaxially stretched in the longitudinal direction. The coated film is dried while passing through a zone heated stepwise and stretched in the width direction. Furthermore, it is continuously guided to a heating zone of 150 to 240 ° C., and the polyethylene terephthalate layer of the two thermoplastic resins completes the crystal orientation. The coating solution used in this case is preferably an aqueous solution in terms of environmental pollution and explosion-proof properties. In the present invention, before applying the coating solution, the surface of the base film (in the case of the above example, a uniaxially stretched film) is subjected to a corona discharge treatment or the like, and the wetting tension of the base film surface is preferably 47 mN. / M or more, more preferably 50 mN / m or more from the viewpoint of improving the adhesion of the primer layer to the substrate film. Various coating methods such as a reverse coating method, a gravure coating method, a rod coating method, a barcode method, a Mayer barcode method, a die coating method, a spray coating, and the like can be used as a method for coating on the base film. .

  Also, in the matte film of the present invention, various additives such as antioxidants, heat stabilizers, lubricants, pigments, dyes, antistatic agents, fillers, nucleating agents, etc. do not deteriorate the properties. It may be added to the extent. In particular, it is preferable to add an easy lubricant from the viewpoint of imparting slipperiness. As an easy-lubricant, you may serve as the particle | grains which give light diffusibility. Easy lubricants can be broadly classified into organic and inorganic lubricants. As the shape, shape particles such as aggregated particles, spherical particles, beaded particles, complex particles, and scale-like particles can be used. In addition, the inorganic materials include silicon oxide, calcium carbonate, titanium oxide, alumina, zirconia, aluminum silicate, mica, clay, talc, barium sulfate, etc., and the organic materials include polyimide resin, olefin or Modified olefin resins, cross-linked or non-cross-linked polystyrene resins, cross-linked or non-cross-linked acrylic resins, fluororesins, silicone resins, and other organic lubricants such as stearamide, oleic amide, and fumaric amide Mention may be made of amide compounds. In particular, the matte film of the present invention has a number average particle diameter of 1 μm or more and a particle concentration of 0.1% by weight or more from the viewpoint of a high light scattering effect that exhibits a high-grade metallic texture. preferable. Here, the particle concentration refers to the concentration in the resin layer to which particles are added, not in the entire film. More preferably, the particle concentration is 3 μm or more and 0.2% by weight or more. The particle type is determined from the viewpoint of satisfying the above formula (1) and / or formula (2). From the viewpoint of cost and high light diffusibility, it is preferable that 0.1% by weight or more of aggregated silica having an average particle diameter of 4 μm or more is added. FIG. 5 shows a schematic diagram of a cross section of the matte film of an example showing the relationship between suitable particles and the layer thickness of the matte film of the present invention. As shown in FIG. 5, the matte film of the present invention has a characteristic that the layer interface is difficult to be destroyed even if the particle diameter 22 of the contained particles extends over a dozen layers. Satisfies the high-quality texture of

  The matte film of the present invention is preferably calendered at a temperature not lower than the glass transition temperature (Tg) and not higher than the melting point (Tm) of the constituent resin from the viewpoint of imparting light diffusion performance utilizing the surface shape. For example, in the case of polyester, calendering is preferably performed under conditions of 100 ° C. or more and less than 200 ° C. and a linear pressure of 30 kg / cm or more. More preferably, it is 120 ° C. or higher and lower than 180 ° C., and the linear pressure is 100 kg / cm or higher. From the viewpoint of uniformly applying pressure to the roll material at that time, it is effective that the upper roll is a metal roll having a surface roughness of 1S or more, and the lower roll is an ultra-hard rubber roll. Here, the linear pressure is a value obtained by dividing the load applied to the roll by a hydraulic system or the like by the surface length of the roll. From the viewpoint of imparting high light diffusibility, it is more preferably 3.2S or more, and still more preferably 12.5S or more. Furthermore, it is also preferable to use a roll whose surface has been embossed. The embossing (unevenness) pattern in this case may be one using fine grain surfaces # 350, 1000, sandblasting No. 60, etc. from the viewpoint of imparting light diffusibility to the film surface. The groove depth of the rolls of various embossed patterns is preferably 0.009 mm or more. More preferably, it is 0.03 mm or more.

The high-quality metallic texture that is the effect of the present invention will be described. In the present invention, the high-quality metallic texture is less glossy than that obtained by finishing the metal itself with a mirror finish, that is, the regular reflection component is suppressed while the reflectance in the visible light region is comparable to that of metal. And exhibiting a reflected color in which the color shift phenomenon peculiar to the interference reflection phenomenon is suppressed. The color shift phenomenon is a phenomenon in which color changes as the incident angle of light becomes deeper. Specifically, it is known that the expression (5) is expanded to be expressed by the expression (7) in which the incident angle of light is considered. That is, this expression indicates that the reflection wavelength λ shifts to the lower wavelength side as the incident angle becomes deeper.
2 · (nA · dA · cos θA + nB · dB · cos θB) = nλ (7)
Note that n represents the refractive index, d represents the layer thickness, θ represents the incident angle (the angle between the incident vector and the interface normal vector), and the subscript represents the A layer and the B layer. Even if this color shift occurs, it is preferable that the spectral reflectance curve in the wavelength range of 400 to 700 nm does not change so much that it becomes a completely pseudo metal reflector. In addition, even if there is a slight color change, it is a color that cannot be produced with metal, so a unique texture leads to a high-class feeling.

  In order to evaluate this high-quality metallic texture, it is preferable to make a judgment based on the glossiness (brightness), the color of the regular reflection light and diffuse reflection light, and the like.

  Hereinafter, the matte film of the present invention will be described with reference to examples.

[Methods for measuring physical properties and methods for evaluating effects]
The characteristic value evaluation method and the effect evaluation method are as follows.

(1) Layer thickness, number of layers, layered structure The layer structure of the film was determined by observation with a transmission electron microscope (TEM) for a sample obtained by cutting a cross section using a microtome. That is, using a transmission electron microscope H-7100FA type (manufactured by Hitachi, Ltd.), the cross section of the film was magnified 40000 times under the condition of an acceleration voltage of 75 kV, a cross-sectional photograph was taken, and the layer configuration and each layer thickness were measured. did. In some cases, in order to obtain high contrast, a staining technique using known RuO ₄ or OsO ₄ was used.

  (2) A method for calculating the particle-containing layer thickness “t”.

The TEM photograph image of about 40,000 times obtained in the item (1) was captured with CanonScanD123U at an image size of 720 dpi. Save the image to a personal computer as a bitmap file (BMP) or compressed image file (JPEG), and then use the image processing software Image-Pro Plus ver.4 (distributor Planetron Co., Ltd.) Was opened and image analysis was performed. 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 data of the position (nm) and the brightness was adopted in the sampling step 6 (decimation 6), and then numerical processing of a three-point moving average was performed. Furthermore, the data obtained by periodically changing the brightness is differentiated, and the maximum value and the minimum value of the differential curve are read by the VBA program. Calculated. This operation was performed for each photograph, and the layer thicknesses of all layers were calculated.
Here, in order to uniquely determine the value of r / t, among the thermoplastic resin layers including the particles, the average layer thickness for 100 layers is obtained from the thin layer thickness in the permutation of the layer thicknesses. Was the particle-containing layer thickness “t”. However, when the particle-containing layer is less than 100 layers, the average layer thickness value of the number of layers is defined as the particle-containing layer thickness “t”. When the particles contain only one layer, the layer thickness is defined as the particle-containing layer thickness “t”.

(3) Spectral reflectivity and integration value calculation method A spectrophotometer (U-3410 Spectrophotometer) manufactured by Hitachi, Ltd. was fitted with a φ60 integrating sphere 130-0632 (Hitachi, Ltd.) and a 10 ° inclined spacer, and the reflectivity was measured. . The bandpass is set to 2 nm / servo, the gain is set to 3, and the range from 250 nm to 2600 nm is set to 120 nm / min. And a spectral reflectance curve R (λ) was obtained. In order to standardize the reflectance, an aluminum oxide plate attached to the apparatus was used as a standard reflecting plate, and at the time of sample measurement, black paint was applied with magic ink to eliminate interference caused by reflection from the back surface. Further, the reflectance is the maximum value of the reflectance curve at a wavelength of 400 to 700 nm, and the wavelength was taken as the reflection wavelength. The output data was collected every 1 nm step.

  Next, the integrated value in the wavelength λ section [400, 700] (nm) was obtained using the reflectance data obtained every 1 nm in the wavelength range of 250 to 2600 nm. The integration value was calculated by VBA (Visual Basic Application) on the Excel 2000 worksheet using the Simpson 1/3 formula. The equidistant minute points h for calculation were calculated as 1 nm.

(4) Average particle diameter: r (μm)
The matte film was cut using a microtome to produce a cross section. Using a field emission scanning electron microscope JSM-6700F (manufactured by Jeol Co., Ltd.), select a magnification at which the particles can be sufficiently observed within a magnification range of 5000 to 40000 times. The particles were observed. By changing the observation location, the particle diameter was measured for 50 or more particles, and the number average particle diameter was determined based on Equation (5). The particle diameter to be measured is the major axis particle diameter of the particles.

  When the particles are agglomerated particles, only a part of the agglomerated particles can be confirmed by cross-sectional observation. Therefore, the surface of the film is exposed by plasma ion etching, and then Pt ion plating is performed on the surface. Agglomerated particles were observed. As the particle diameter 22, the major axis of a circle or ellipse 26 circumscribing a lump of aggregated particles as shown in FIG. 6 was measured.

  In addition, the particle diameter φ (μm) of the particles used for coating is measured using a centrifugal sedimentation type particle size distribution measuring apparatus (5A-Cp2 type, manufactured by Takatsuki Seisakusho) with inert particles as ethylene glycol or water slurry, and the formula ( Based on 5), the average particle size was determined.

(5) Particle Concentration A solvent that dissolves the polyester but does not dissolve the inert particles was selected, the inert particles were centrifuged from the polyester, and the ratio (% by weight) to the total weight of the particles was defined as the particle concentration.

(6) Absolute value ΔN of the difference between the refractive index of the matrix resin layer and the refractive index of the particles contained in the resin layer
In the case of the matrix resin layer obtained by the coextrusion method, a single film was formed under the same film forming conditions as the matte film (no particles). In this case, the unstretched film was formed by the same method up to casting. Next, a sample is cut out from the unstretched film to a size of 10 cm × 10 cm, stretched using a biaxial stretching apparatus (Toyo Seiki Co., Ltd.), and the obtained stretched film is attached to a 20 cm × 20 cm metal frame. Then, heat treatment was performed using a tunnel oven (manufactured by Taishin Manufacturing Co., Ltd.) to obtain a single film. In addition, when the heat treatment temperature at the time of film formation was a temperature at which the thermoplastic resin was melted, it was sandwiched by a support such as a polyimide film and subjected to heat treatment in a tunnel oven. A sample was cut out from the center of the obtained single film in the width direction of the film in a dimension of 4 × length 3.5 cm, and the refractive index of MD and TD was measured using an Abbe refractometer 4T (manufactured by Atago Co., Ltd.). Asked. As a light source, a sodium D line wavelength of 589 nm was used. The average refractive index of MD and TD was taken as the refractive index of the matrix resin layer. As the immersion liquid, methylene iodide and a test piece having a refractive index of 1.74 were used.

  In the case of the matrix resin layer obtained by the coating method, both the thermoplastic resins A and B are made of polyethylene terephthalate resin to form a matte film, and the refractive index of the matrix resin layer formed on the surface layer is the same as above. Was measured according to JIS K7142 (1996) A method.

On the other hand, the refractive index of the particles was measured according to JIS K7142 (1996) B method.
The absolute value of the difference between the two obtained refractive indexes was obtained.

(7) Surface roughness Samples cut from the center in the film width direction to a length of 4.0 x 3.5 cm in width were used as samples, and the surface roughness (centerline average roughness Ra) was manufactured by Kosaka Laboratory. The three-dimensional roughness meter SE-3AK was used. The measurement conditions are shown below. Z. magnification: 20000, Y. drive. Pitch: 10 μm, X. magnification: 200, X. drive: 100 μm / s, X. measure length: 2000 μm
(8) Haze at a wavelength of 1500 nm Using a spectrophotometer U-3410 manufactured by Hitachi, Ltd. at a specific wavelength, a sample having a length 4.0 × width 3.5 cm cut from the center in the film width direction is used as a sample. The total light transmittance when an integrating sphere was used on the light receiver side at 1500 nm and the linear transmittance when no integrating sphere was used were measured. Haze was determined by dividing these differences by the total light transmittance and multiplying by 100. In addition, the model 210-2112 used for the attachment apparatus made from Hitachi, Ltd. which measures linear transmittance with parallel light. The measurement conditions were the same as in item (3).
(9) Judgment of high-quality metallic texture The sample is cut out from the center in the width direction of the film at 5 cm x 5 cm, then the back of the sample is painted black with magic ink (name), and CM-3600d manufactured by Konica Minolta Co., Ltd. is used. Using the target mask (CM-A106) with a measurement diameter of φ8mm, L *, a *, and b * values were measured using the SCE method with the regular reflected light removed and the SCI method with the regular reflected light, respectively. And the average value of n number 5 was calculated | required. The white calibration plate and zero calibration box were calibrated using the following. Furthermore, with respect to the obtained value, a matte film that simultaneously satisfies the following formulas (8) and (9) was evaluated as “◯”, and a matte film that satisfied only the formula (9) as “Δ” was determined as acceptable. . In addition, the thing which is not satisfied with Formula (8) and Formula (9) was set as x, and it was made disqualified. In addition, among the ◯, the matte film that satisfies the expressions (10) and (11) at the same time exhibits a metal-like texture with a high-class feeling. Note that D65 was selected as the light source used for calculation of the colorimetric values.
White calibration plate: CM-A103
Zero calibration box: CM-A104

(Note that Δa is the absolute value of the difference between the chromaticness coefficients a * obtained by the SCI method and the SCE method. The same applies to Δb. L * (SCE) is also obtained by the SCE method. L * value.)
(10) Peel test result A sample was cut out in a 5 cm square from the center in the film width direction and evaluated according to JIS K5600. 5 × 5 25 square cuts were made at a cut interval of 2 mm, and detachment was performed using a Sekisero tape (product number 252), and the number of peeled squares was counted. The number of trials was 5, and the average value was obtained. The evaluation criteria were determined as follows.
○: Number of peels 3 or less Δ: Number of peels 4-6 or less ×: Number of peels 7 or more [Example 1]
Polyethylene terephthalate having IV = 0.63 was used as thermoplastic resin A (0.2% by weight of agglomerated silica having an average particle size of 4 μm was added to thermoplastic resin A), and IV = 0 as thermoplastic resin B. .55 polyethylene terephthalate copolymer (polyethylene terephthalate copolymerized with 20 mol% of spiroglycol component and 30 mol% of cyclohexanedicarboxylic acid component) was used (thermoplastic resin B has no particles).
Thermoplastic resins A and B are melted at 280 ° C. in each extruder, passed through 5 sheets of FSS type leaf disk filters, and the discharge ratio is thermoplastic resin A composition / thermoplastic resin B with a gear pump. While weighing so that the composition = 1.2 / 1, two slit plates with 267 slits were combined in a 801-layer feed block with a total of three, one with 269 slit plates. Thus, a stacked body in which 801 layers were alternately stacked in the thickness direction was obtained. However, in each of the slit plates used, the slit width for forming the thick film layer positioned at both ends is designed to be at least twice the slit width for forming the other thin film layer, and the minimum for forming the thin film layer The degree of inclination, which is the ratio of the layer thickness to the maximum layer thickness, was set to 0.3 design. Here, the slit width (gap) was all constant, and only the length was changed. The breakdown of the laminated structure is a laminated body having an inclined structure in which 401 layers of thermoplastic resin A and 400 layers of thermoplastic resin B are alternately laminated in the thickness direction.

Next, the cross-sectional shape of the polymer flow path through which the 801-layer laminated flow in which the laminated flow from each slit plate merges from the feed block passes through the polymer tube (the position of MM ′ in FIG. 4A) ), A square shape having an aspect ratio (length in the width direction / length in the thickness direction) of 1.5 was used. Further, the discharge amount of the thermoplastic resin which is 801 layers laminated passing through the cross-sectional area in a unit time of the polymer tube was 20kg / hr / cm ^2. The laminate was supplied to a T-die and formed into a sheet shape, and then rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. while applying an electrostatic applied voltage of 8 kV with a wire to obtain an unstretched film. .

  This unstretched film is longitudinally stretched at 100 ° C. and a stretching ratio of 3.5 times, led to a tenter that holds both ends with clips, 110 ° C. and 4.3 times laterally stretched, and then subjected to heat treatment at 235 ° C., TD relaxation of about 5% was performed at 120 ° C. to obtain a matte film having a thickness of 97 μm. The cross section in the thickness direction of the obtained matte film was observed with a TEM at a magnification of 40,000, and the layer thickness distribution was determined by image processing. The layer thickness of layer number 1 as the outermost layer is 1.7 μm, the layer thickness of layer number 267 is 3.3 μm, the layer thickness of layer number 535 is 3.7 μm, and the layer thickness of layer number 801 as the outermost layer The thickness of the four layers was a thick film layer of the thermoplastic resin A. On the other hand, the thicknesses of the thin film layers of the obtained thermoplastic resins A and B were all in the range of 44 nm to 199 nm, and both the A layer and the B layer realized an inclined structure. Table 1 shows the physical properties of the resulting matte film.

  Next, the matte film thus obtained was preheated at a temperature of 230 ° C. using a mold made of aluminum with a depth of 1 mm, 3 mm and 5 mm marked “Lumirror TORAY”. Vacuum / pressure forming was performed under the conditions of 90 ° C., pressure of 1 MPa, and ultimate vacuum of 300 mmHg or less in terms of differential pressure. By coating the back surface of the obtained molded product with a black spray, it was possible to obtain a molded product having a high-class metallic texture with less glare peculiar to interference reflection than in the past.

  Moreover, the film insert molded product was produced using the obtained matte film. Molding conditions were as follows. A pellet-like resin in which 5% by weight of carbon black was added to polybutylene terephthalate (Toraycon type 1200S) manufactured by Toray Industries, Inc. was charged into an injection molding extruder, and molding was performed at an extrusion temperature of 250 degrees. . Note that a mold for molding a rear piece of a mobile phone was used as the mold. The obtained molded product of the rear piece of the mobile phone was able to obtain a molded product having a high-class metallic texture with less glare peculiar to interference reflection than in the past.

[Example 2]
Polyethylene terephthalate having IV = 0.63 was used as thermoplastic resin A (0.5% by weight of titanium oxide having an average particle size of 0.3 μm was added to thermoplastic resin A), and IV was used as thermoplastic resin B. = 0.75 Polyethylene terephthalate copolymer (polyethylene terephthalate copolymerized with 30 mol% of cyclohexanedimethanol component) was used (thermoplastic resin B is particle-free). Further, a mat-like film having a thickness of 78 μm was obtained in the same manner as in Example 1 except that the design value of the slope was changed to 0.7. Table 1 shows the physical properties of the resulting matte film. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.

[Example 3]
Polyethylene terephthalate having IV = 0.63 was used as thermoplastic resin A (0.2% by weight of aggregated silica having an average particle size of 1.2 μm was added to thermoplastic resin A), and IV was used as thermoplastic resin B. = 0.55 polyethylene terephthalate copolymer (polyethylene terephthalate copolymerized with 10 mol% of spiroglycol component and 10 mol% of cyclohexanedicarboxylic acid component) was used (thermoplastic resin B has no particles). Others were the same as in Example 1, and a matte film having a thickness of 93 μm was obtained. Table 1 shows the physical properties of the resulting matte film. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.

[Example 4]
Polyethylene terephthalate having IV = 0.63 is used as thermoplastic resin A (0.2% by weight of colloidal silica having an average particle size of 0.55 μm (KE-P50 manufactured by Nippon Shokubai Co., Ltd. was added to thermoplastic resin A)). It was. Others were the same as in Example 2, and a matte film having a thickness of 75 μm was obtained. Table 1 shows the physical properties of the resulting matte film. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.
[Example 5]
Polyethylene terephthalate having IV = 0.63 is used as the thermoplastic resin A, and a copolymer of polyethylene terephthalate having IV = 0.55 is used as the thermoplastic resin B (polyethylene terephthalate copolymerized with 30 mol% of cyclohexanedimethanol component). Used (no particles of thermoplastic resins A and B). A mat-like film having a thickness of 75 μm was obtained in the same manner as in Example 1 except that the design value of the degree of inclination was changed to 0.7. Table 1 shows the physical properties of the resulting matte film.
Furthermore, using methyl ethyl ketone as the diluent, the hard component (Nippon Kayaku DPHA), the soft component (Toagosei M350), the thermal cross-linking agent (Nippon Cytec Cymel 303), and the particles (Sekisui Chemical SBX8) are stirred. A coating agent was prepared, applied to a film with a metabar, and then dried and solidified at 200 ° C. The particle concentration was adjusted so that the concentration was 5% by weight with respect to the solid component of the coating composition. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.
[Example 6]
A mat-like film having a thickness of 73 μm was obtained in the same manner as in Example 2 except that the thermoplastic resin A to which 5% by weight of barium sulfate having an average particle diameter of 2 μm was added was used. Table 1 shows the physical properties of the resulting matte film. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.

[Example 7]
Polyethylene terephthalate with IV = 0.63 was used as thermoplastic resin A (no particles), and polyethylene terephthalate copolymer with IV = 0.75 as thermoplastic resin B (30 mol% of cyclohexanedimethanol component was copolymerized). (Polyethylene terephthalate) was used (0.2% by weight of aggregated silica having an average particle size of 1.2 μm was added to the thermoplastic resin B).
Others were the same as in Example 2, and a matte film having a thickness of 75 μm was obtained. Table 1 shows the physical properties of the resulting matte film. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.

[Example 8]
Polyethylene terephthalate having IV = 0.63 was used as thermoplastic resin A (0.2% by weight of agglomerated silica having an average particle size of 4 μm was added to thermoplastic resin A), and IV = 0 as thermoplastic resin B. .55 polyethylene terephthalate copolymer (polyethylene terephthalate copolymerized with 25 mol% of spiroglycol component and 40 mol% of cyclohexanedicarboxylic acid component) was used (thermoplastic resin B is particle-free). Thermoplastic resins A and B are melted at 280 ° C. in each extruder, passed through 5 sheets of FSS type leaf disk filters, and the discharge ratio is thermoplastic resin A composition / thermoplastic resin B with a gear pump. While weighing so that the composition = 1.2 / 1, two slit plates with 267 slits were combined in a 801-layer feed block with a total of three, one with 269 slit plates. Thus, a stacked body in which 801 layers were alternately stacked in the thickness direction was obtained. However, in each of the slit plates used, the slit width for forming the thick film layer positioned at both ends is designed to be at least twice the slit width for forming the other thin film layer, and the minimum for forming the thin film layer The degree of inclination, which is the ratio of the layer thickness to the maximum layer thickness, was set to 0.5 design. Here, the slit width (gap) was all constant, and only the length was changed. The breakdown of the laminated structure is a laminated body having an inclined structure in which 401 layers of thermoplastic resin A and 400 layers of thermoplastic resin B are alternately laminated in the thickness direction.
Next, the cross-sectional shape of the polymer flow path through which the 801-layer laminated flow in which the laminated flow from each slit plate merges from the feed block passes through the polymer tube (the position of MM ′ in FIG. 4A) ) Used was a square shape with an aspect ratio (length in the width direction / length in the thickness direction) of 1.5. Moreover, the discharge amount of the 801 layers of laminated thermoplastic resin passing within the cross-sectional area of the polymer tube within a unit time was 20 kg / hr / cm ² . The laminate was supplied to a T-die and formed into a sheet shape, and then rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. while applying an electrostatic applied voltage of 8 kV with a wire to obtain an unstretched film. .

This unstretched film was longitudinally stretched at 100 ° C. and a stretch ratio of 3.5 times, and then subjected to corona treatment on the surface of the plate under conditions of a plate voltage of 3.4 V and a plate current of 0.15 A, and easy adhesion with a metabar. Water-based coating agent (vinyl acetate / acrylic resin / crosslinking agent: melamine resin / surfactant formulation) as a primer layer after heat drying on one side of the film so as to have a thickness of 0.5 μm Then, the film was guided to a tenter that grips both ends with clips at 110 ° C. and transversely stretched 4.3 times, then heat treated at 235 ° C., and subjected to TD relaxation of about 5% at 120 ° C., with a thickness of 87 μm. A matte film was obtained. The cross section in the thickness direction of the obtained matte film was observed with a TEM at a magnification of 40,000, and the layer thickness distribution was determined by image processing. The layer thickness of layer number 1 that is the outermost layer is 1.7 μm, the layer thickness of layer number 267 is 3.3 μm, the layer thickness of layer number 535 is 3.5 μm, and the layer thickness of layer number 801 that is the outermost layer The thickness of the four layers was a thick film layer of the thermoplastic resin A. On the other hand, the thicknesses of the thin film layers of the obtained thermoplastic resins A and B were all in the range of 44 nm to 155 nm, and an inclined structure was realized. Table 1 shows the physical properties of the resulting matte film. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.
Moreover, the film insert molded product was produced using the obtained matte film. Compared with Example 1, it is a molded product in which the interface between the insert film and the resin molded product is difficult to peel off, and has a high-class metallic texture with less glare peculiar to interference reflection than in the past. It was also confirmed that this was a molded product.

[Example 9]
Polyethylene terephthalate having IV = 0.63 was used as thermoplastic resin A (0.2% by weight of agglomerated silica having an average particle size of 4 μm was added to thermoplastic resin A), and IV = 0 as thermoplastic resin B. .55 polyethylene terephthalate copolymer (polyethylene terephthalate copolymerized with 15 mol% of spiroglycol component and 20 mol% of cyclohexanedicarboxylic acid component) was used (thermoplastic resin B is particle-free). Thermoplastic resins A and B are melted at 280 ° C. in each extruder, passed through 5 sheets of FSS type leaf disk filters, and the discharge ratio is thermoplastic resin A composition / thermoplastic resin B with a gear pump. While weighing so that the composition = 2/1, 201 layers were combined in a 201-layer feed block having a configuration using only one slit plate having 201 slits, and 201 layers were alternately stacked in the thickness direction. A laminated body was obtained. However, in the slit plate used, the slit width for forming the thick film layers positioned at both ends is designed to be twice or more the slit width for forming the other thin film layers, and the minimum thickness for forming the thin film layers The slope, which is the ratio of the layer thickness to the maximum layer thickness, was set to 0.915 design. Here, the slit width (gap) was all constant, and only the length was changed. Also, the breakdown of the laminated structure is a laminated body having an inclined structure in which the thermoplastic resin A is composed of 101 layers and the thermoplastic resin B is laminated alternately in the thickness direction.

Next, from this feed block, 201 layers passing through the cross-sectional area of the polymer tube within a unit time through a rectangular polymer tube having an aspect ratio (length in the width direction / length in the thickness direction) of 1.5 The discharge amount of the laminated thermoplastic resin was 20 kg / hr / cm ^2. ) After supplying the laminate to a T-die and forming it into a sheet, an electrostatic application voltage of 8 kV was applied with a wire. However, it was rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. to obtain an unstretched film.

  This unstretched film is longitudinally stretched at 92 ° C and a stretch ratio of 3.5 times, and then both ends are led to a tenter gripped by clips, and 100 ° C and 4.3 times laterally stretched, followed by heat treatment at 230 ° C. Then, TD relaxation of about 5% was performed at 120 ° C. to obtain a matte film having a thickness of 15 μm. The cross section in the thickness direction of the obtained matte film was observed with a TEM at a magnification of 40,000, and the layer thickness distribution was determined by image processing. The layer thicknesses of layer numbers 1 and 201 which are the outermost layers were 1.5 μm, and both layers were thick film layers of the thermoplastic resin A. On the other hand, the thicknesses of the thin film layers of the obtained thermoplastic resins A and B were all in the range of 34 nm to 108 nm, and both the A layer and the B layer realized a slight inclined structure. Table 1 shows the physical properties of the resulting matte film. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.

[Example 10]
Polyethylene terephthalate having IV = 0.65 was used as thermoplastic resin A (12% by weight of MERCK Xirallic® T60-24 WNT Stellar Green (TiO2 coated interference green) was added to thermoplastic resin A). Further, as the thermoplastic resin B, a copolymer of polyethylene terephthalate having IV = 0.75 (polyethylene terephthalate copolymerized with 30 mol% of cyclohexanedimethanol component) was used (thermoplastic resin B has no particles). Others were the same as in Example 9, and a matte film having a thickness of 16 μm was obtained. The cross section in the thickness direction of the obtained matte film was observed with a TEM at a magnification of 40,000, and the layer thickness distribution was determined by image processing. The layer thicknesses of layer numbers 1 and 201 which are the outermost layers were 1.5 μm, and both layers were thick film layers of the thermoplastic resin A. On the other hand, the thicknesses of the thin film layers of the obtained thermoplastic resins A and B were all in the range of 44 nm to 122 nm, and both the A layer and the B layer realized a slight inclined structure. Table 1 shows the physical properties of the resulting matte film. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.
[Example 11]
Polyethylene terephthalate having IV = 0.63 was used as thermoplastic resin A (1.0 weight% of aggregated silica having an average particle size of 4 μm was added to thermoplastic resin A), and IV = 0 as thermoplastic resin B. .55 polyethylene terephthalate copolymer (polyethylene terephthalate copolymerized with 15 mol% of spiroglycol component and 20 mol% of cyclohexanedicarboxylic acid component) was used (thermoplastic resin B is particle-free). Further, a film having a thickness of 110 μm was obtained in the same manner as in Example 1 except that the design value of the inclination degree was changed to 0.5. Further, the casting speed as the film forming condition was changed to obtain a film having a thickness of 90 μm. A mat-like film was obtained by bonding two films having different thicknesses with an adhesive. The physical properties of the matte film are shown in Table 1. By making the back side black by spraying, it was confirmed that it was a matte film with a high-quality metallic texture.

[Comparative Example 1]
Polyethylene terephthalate with IV = 0.63 is used as thermoplastic resin A, and polyethylene terephthalate copolymer with IV = 0.75 (polyethylene terephthalate copolymerized with 30 mol% of cyclohexanedimethanol component) is used as thermoplastic resin B. Used (no particles of thermoplastic resins A and B).
Thermoplastic resins A and B are melted at 280 ° C. in each extruder, passed through 5 sheets of FSS type leaf disk filters, and the discharge ratio is thermoplastic resin A composition / thermoplastic resin B with a gear pump. While weighing so that the composition = 1/1, two slit plates with 267 slits were joined together in a 801-layer feed block, which was a total of three, one with 269 slit plates. A laminate in which 801 layers were alternately laminated in the thickness direction was obtained. However, in each slit plate used, there is no slit width for forming the thick film layer located at both ends, and the inclination degree which is the ratio of the minimum layer thickness to the maximum layer thickness and the design of 0.7 is the design. did. Here, the slit width (gap) was all constant, and only the length was changed. The breakdown of the laminated structure is a laminated body having an inclined structure in which 401 layers of thermoplastic resin A and 400 layers of thermoplastic resin B are alternately laminated in the thickness direction.

Next, the cross-sectional shape of the polymer flow path through which the 801-layer laminated flow in which the laminated flow from each slit plate merges from the feed block passes through the polymer tube (the position of MM ′ in FIG. 4A) ) Used was a square shape with an aspect ratio (length in the width direction / length in the thickness direction) of 1.5. Moreover, the discharge amount of the 801 layers of laminated thermoplastic resin passing within the cross-sectional area of the polymer tube within a unit time was 20 kg / hr / cm ² .

  Further, the thermoplastic resin C obtained by adding 0.05% by weight of synthetic calcium carbonate having an average particle diameter of 1.1 μm to the thermoplastic resin A from the extruder C is joined from the pinol under the feed block so as to come to the outermost layer portion. Thus, a laminate composed of a total of 803 layers was obtained.

  The laminate was supplied to a T-die and formed into a sheet shape, and then rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. while applying an electrostatic applied voltage of 8 kV with a wire to obtain an unstretched film. .

  This unstretched film is longitudinally stretched at 100 ° C. and a stretching ratio of 3.5 times, led to a tenter that holds both ends with clips, 110 ° C. and 4.3 times laterally stretched, and then subjected to heat treatment at 235 ° C., About 5% TD relaxation was performed at 120 ° C. to obtain a film having a thickness of 75 μm. The cross section in the thickness direction of the obtained film was observed with a TEM at a magnification of 40,000, and the layer thickness distribution was determined by image processing. The outermost layer No. 1 had a layer thickness of 1.5 μm, the outermost layer No. 803 had a layer thickness of 1.5 μm, and these two layers were both thick layers of the thermoplastic resin C. On the other hand, the thicknesses of the thin film layers of the obtained thermoplastic resins A and B were all in the range of 54 nm to 125 nm, and an inclined structure was realized. Table 1 shows the physical property results of the obtained film. The obtained film had a strong specular reflection, so the glare was severe, and it did not have a high-quality metallic texture.

[Comparative Example 2]
Polyethylene terephthalate having IV = 0.63 was used as the thermoplastic resin A, and a copolymer of polyethylene terephthalate having IV = 0.67 (polyethylene terephthalate copolymerized with 25 mol% of isophthalic acid) was used as the thermoplastic resin B. (Non-particles in thermoplastic resins A and B).

  Thermoplastic resins A and B are melted at 280 ° C. in each extruder, passed through 5 sheets of FSS type leaf disk filters, and the discharge ratio is thermoplastic resin A composition / thermoplastic resin B with a gear pump. Laminating 533 layers alternately in the thickness direction by combining them in a 533-layer feed block having a configuration using two slit plates with 268 slits while measuring so that the composition = 1/1. The body. However, in each slit plate used, there is no slit width for forming the thick film layer located at both ends, and the inclination degree which is the ratio of the minimum layer thickness to the maximum layer thickness and the design of 0.7 is the design. did. Here, the slit width (gap) was all constant, and only the length was changed. The breakdown of the laminated structure is a laminated body having an inclined structure in which the thermoplastic resin A is alternately laminated in the thickness direction including 267 layers and the thermoplastic resin B is 266 layers.

Next, a cross-sectional shape of a polymer flow path through which a 533-layer laminated flow in which the laminated flow from each slit plate merges from this feed block passes through a polymer pipe (the position of MM ′ in FIG. 4A) ) Used was a square shape with an aspect ratio (length in the width direction / length in the thickness direction) of 1.5. Further, the discharge amount of the 533 layers laminated thermoplastic resin passing through the cross-sectional area of the polymer tube within a unit time was 20 kg / hr / cm ² .

Further, the thermoplastic resin C obtained by adding 0.04% by weight of synthetic calcium carbonate having an average particle size of 0.4 μm to the thermoplastic resin A from the extruder C is joined from the pinol under the feed block so as to come to the outermost layer. Thus, a laminate composed of a total of 535 layers was obtained.
Thereafter, a film having a thickness of 50 μm was obtained in the same manner as in Comparative Example 1. Table 1 shows the physical property results of the obtained film. Since the obtained film had a low reflectance, it was not glossy and did not have a metallic texture.

[Comparative Example 3]
The thermoplastic resin A was changed to polyethylene terephthalate to which 0.05% by weight of crosslinked polystyrene having an average particle size of 0.3 μm was added, and the thermoplastic resin B was changed to a polyethylene terephthalate copolymer (17.5 mol% of the isophthalic component was added). Polymerized polyethylene terephthalate) and a laminate comprising a total of 801 layers in the same manner as in Comparative Example 1 without using pinol.
Thereafter, a film having a thickness of 68 μm was obtained in the same manner as in Comparative Example 1. Table 1 shows the physical property results of the obtained film. Since the obtained film had a low reflectance, it was not glossy and did not have a metallic texture.

[Comparative Example 4]
The thermoplastic resin C is the outermost layer portion in the same manner as in Comparative Example 1, except that the thermoplastic resin C is changed to the thermoplastic resin A to which 0.02% by weight of agglomerated silica having an average particle diameter of 1.2 μm is added. From the pinol under the feed block, the laminate was composed of a total of 803 layers. Table 1 shows the physical property results of the obtained film. The obtained film had a strong specular reflection, so the glare was severe, and it did not have a high-quality metallic texture.
[Comparative Example 5]
Other than using polyethylene terephthalate with IV = 0.63 as thermoplastic resin A (polyethylene terephthalate with 0.5 wt% of colloidal silica having an average particle size of 0.03 μm added to thermoplastic resin A). Obtained a mat-like film having a thickness of 97 μm in the same manner as in Example 1. Table 1 shows the physical properties of the resulting matte film. The obtained film had a strong specular reflection and did not have a high-quality metallic texture.

The matte film of the present invention is retrievable compared to conventional metal film, so the environmental load is reduced, and metal hairline sandblasting and embossing with excellent peelability and formability are applied. Because it has a high-quality metallic texture, it is used as a metallic decorative material, especially reflective design materials used for building materials, packaging, automobile interior and exterior, and anti-counterfeiting materials such as holograms used in securities. It can be preferably used.

An example of a configuration diagram of a feed block used in the present invention Configuration diagram of slit plate and slit Cross-sectional configuration diagram of slit Schematic diagram of merging device Schematic diagram of cross section of matte tone film Lump of agglomerated particles

Explanation of symbols

1: member plate 2: resin introduction plate 3: slit plate 4: resin introduction plate 5: slit plate 6: resin introduction plate 7: slit plate 8: resin introduction plate 9: member plate 10: feed block 11: introduction port 12: Liquid reservoir 13: Ridge line at the top of each slit 14: Upper end part of the ridgeline at the top part of each slit 15: Lower end part of the ridgeline at the top part of each slit 16: Resin introduced into the slit 17: Outlet 18: Junction device 19L : Outlet 20L of the slit plate 3: Outlet 21L of the slit plate 5: Outlet 19M of the slit plate 7: Cross section shape 20M of the flow path rearranged from the outflow port of the slit plate 3 by restriction of the flow path 20: Slit plate Cross-sectional shape 21M of the flow path rearranged by restriction of the flow path from the outlet of 5: Cross-sectional shape 19N of the flow path rearranged by restriction of the flow path from the outlet of the slit plate 7: of the widened flow path Cross-sectional shape 20N: Width flow paths of the cross-sectional shape 21N: the cross section of the widened flow path configuration 22: particle size 23: resin layer 24: Film Thickness Direction 25: aggregated particles 26: circle or ellipse circumscribing the agglomerated particles a mass

Claims (7)

A multilayer laminate having a structure in which layers of thermoplastic resin A (A layer) and layers of thermoplastic resin B (B layer) are alternately laminated at least 100 layers, and at least one layer containing particles The relationship between the thickness t (nm) of the layer containing the particles and the number average particle size r (nm) of the particles satisfies the following formula (1):
1 ≦ r / t ≦ 300 (1)
A matte film satisfying at least one of the following (a) and (b) in a wavelength λ section [400, 700] (nm) of a spectral reflectance curve R (λ).
(A) The integral value of the spectral reflectance curve R (λ) is 10,000 or more. (B) The reflectance is 60% or more. The relationship between the absolute value X of the refractive index difference between the layer containing the particles and the particles and the number average particle size r (nm) of the particles satisfies the following formula (2). Matte film.
100 ≦ r × X Formula (2) The matte film according to claim 1 or 2, wherein the average roughness Ra is 35 nm or more. The matte film according to any one of claims 1 to 3, wherein a haze value in light having a wavelength of 1500 nm is 10% or more. The thermoplastic resin A is made of polyethylene terephthalate, and the thermoplastic resin B is made of a polyester obtained by copolymerizing at least 10 mol% of a spiroglycol component and a cyclohexanedigalbonic acid component, respectively. Matte film. A film insert molded article using the matte film according to any one of claims 1 to 5. A vacuum and / or compressed air molded product using the matte film according to any one of claims 1 to 5.

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