JP2017019215A - Coloring laminate and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring laminate having no change of color of a coloring layer and a manufacturing method therefor.SOLUTION: A coloring laminate 1 is manufactured by laminating a coloring layer 10, a metal fine particle-containing layer 25 containing a plurality of metal fine particles 20 having aspect ratio of 2 or more and a dielectric layer 30. In the metal fine particles-containing layer 25, the plurality of metal fine particles 20 are arranged without forming a conductive path, and the metal fine particles 20 are oriented in parallel to a laminate surface. The metal fine particles-containing layer 25 satisfies the following formula 1 of d<λ/10, and a dielectric layer 30 is an outermost layer and satisfies the following formula 2 of M-λ/8<n×d<M+λ/8. In the formulae 1 and 2, λ represents a wavelength of light inhibiting reflection, drepresents physical thickness of the metal fine particles-containing layer, M satisfies the following formula of M=(4m+1)×λ/8, drepresents physical thickness of the dielectric layer, nrepresents a real part of refractive index of the dielectric layer, and m represents an integer of 0 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a colored laminate in which a plurality of layers including a colored layer are laminated and a method for producing the same.

Technology for decorating the surface is used in various applications such as housings for electrical appliances such as mobile phones, personal computers and televisions, vehicle bodies and frames, interior materials for buildings, signboards, packaging materials, and decorative windows. .
Patent Document 1 proposes a decorative film that is a laminated film of a resin layer containing a black component and a colorless and transparent resin layer, and defines the thickness and surface roughness of both resin layers.
Patent Document 2 discloses a pattern in which a moth-eye structure antireflection layer is laminated on a pattern layer in order to display a desired pattern such as characters, figures, and patterns formed on a transparent substrate more clearly. An attached film has been proposed.

  In general, in order to reduce reflection on the surface of an optical member such as a lens, an antireflection layer formed by laminating a plurality of dielectric layers is used as an antireflection layer having a fine uneven layer, such as a moth-eye structure. Are known. In addition, it is desirable that the anti-reflection film provided for preventing a decrease in visibility due to the appearance of an external light source or landscape on the display portion of the display, etc., has an anti-static function as well as an anti-reflection function. It is. Patent Document 3 proposes an antireflection film that is suitable for the display part of such a display, and has an antireflection property and scratch resistance, and includes a visible light wavelength absorption layer composed of a metal fine particle layer in a multilayer film. Has been.

International Publication 2008/099797 Pamphlet JP 2014-71220 A International Publication No. 2004/031813 (Patent No. 4400458)

  Since the film with a pattern described in Patent Document 2 has an antireflection layer on the surface side, the pattern can be displayed very clearly. However, since the antireflection layer having a moth-eye structure is used, There is a problem that the rubbing property is low. The antireflection layer having a moth-eye structure is generally produced using a transfer mold, but the transfer mold is worn by repeated use, and the desired moth-eye structure cannot be obtained. There is a problem that it is not enough.

  Therefore, it is conceivable to apply, for example, an antireflection layer disclosed in Patent Document 3, which has higher abrasion resistance than a moth-eye structure, as an antireflection layer provided on a pattern layer (colored layer) in a film with a pattern.

  However, since the antireflection layer described in Patent Document 3 has a configuration in which the antireflection effect is enhanced by absorbing visible light, the transmittance decreases and the antireflection layer is laminated with a colored layer. If so, there is a problem that the color of the colored layer changes.

  This invention is made | formed in view of the said situation, Comprising: It aims at providing the colored laminated body which does not produce the color change of a colored layer, and its manufacturing method.

The colored laminate of the present invention is formed by laminating a colored layer, a metal fine particle-containing layer containing a plurality of metal fine particles having an aspect ratio of 2 or more, and a dielectric layer in this order,
In the metal fine particle-containing layer, a plurality of metal fine particles are arranged without forming a conductive path, and the metal fine particles are oriented parallel to the laminated surface,
The metal fine particle-containing layer satisfies the following formula 1,
The dielectric layer is the outermost layer, and the dielectric layer satisfies the following formula 2.
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
Here, λ represents the wavelength of light for preventing reflection, d ₂ represents the physical thickness of the metal fine particle-containing layer, M = (4m + 1) × λ / 8, and d ₁ represents the physical thickness of the dielectric layer. represents, n ₁ denotes the real part of the refractive index of the dielectric layer, m represents an integer of 0 or more.

  Whether or not a plurality of metal fine particles are arranged without forming a conductive path is determined based on an image obtained by a scanning electron microscope (SEM). Specifically, the metal fine particle-containing layer of the optical member is observed with a scanning electron microscope in a 2.5 μm × 2.5 μm region, and the fine particles are continuously connected from the left end to the right end of the obtained image. In this case, it is considered that the conductive path is formed, and when the fine particles are separated on the way, it is considered that the conductive path is not formed.

  When the metal fine particles are flat, the major axis length of the metal fine particles is the equivalent circle diameter of the main plane, which is smaller than the wavelength λ of light that prevents reflection, and the aspect ratio is the ratio of the equivalent circle diameter to the plate thickness. It is desirable that the aspect ratio is 3 or more.

  When the metal fine particles are rod-shaped, the major axis length of the metal fine particles is the rod length, which is smaller than the wavelength λ of light that prevents reflection, the aspect ratio is the ratio of the rod length to the equivalent circle diameter, and the aspect ratio Is preferably 2.5 or more.

The colored laminate of the present invention preferably includes a hard coat layer between the colored layer and the metal fine particle-containing layer.
The hard coat layer refers to a layer having higher scratch resistance than the electric layer and the metal fine particle layer.

  In the colored laminate of the present invention, a high refractive index layer having a refractive index of 1.55 or more may be disposed between the colored layer and the metal fine particle-containing layer.

  In addition, when the colored laminate of the present invention includes the hard coat layer and the high refractive index layer, the high refractive index layer is preferably disposed between the metal fine particle-containing layer and the hard coat layer. .

  In the colored laminate of the present invention, a transparent substrate may be disposed between the colored layer and the metal fine particle-containing layer.

  The metal fine particles may be any one of Au (gold), Ag (silver), Pt (platinum), Cu (copper), and Al (aluminum), or Au, Ag, Pt, Cu, and Al. It is preferable to consist of an alloy containing at least one. The metal fine particles are most preferably Ag.

In the first method for producing a colored laminate of the present invention, a metal fine particle-containing layer satisfying the following formula 1 containing a plurality of metal fine particles having an aspect ratio of 2 or more on one surface of a transparent substrate, and the following formula 2 And a dielectric layer satisfying
A colored layer is insert-molded on the other surface of the transparent substrate.
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
Here, λ represents the wavelength of light for preventing reflection, d ₂ represents the physical thickness of the metal fine particle-containing layer, M = (4m + 1) × λ / 8, and d ₁ represents the physical thickness of the dielectric layer. represents, n ₁ denotes the real part of the refractive index of the dielectric layer, m represents an integer of 0 or more.

In the second method for producing a colored laminate of the present invention, a metal fine particle-containing layer satisfying the following formula 1 containing a plurality of metal fine particles having an aspect ratio of 2 or more on one surface of a transparent substrate, and the following formula 2 And a dielectric layer satisfying
Forming a colored layer on the other surface of the transparent substrate;
A resin layer is insert-molded on the exposed surface of the colored layer.
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
Here, λ represents the wavelength of light for preventing reflection, d ₂ represents the physical thickness of the metal fine particle-containing layer, M = (4m + 1) × λ / 8, and d ₁ represents the physical thickness of the dielectric layer. represents, n ₁ denotes the real part of the refractive index of the dielectric layer, m represents an integer of 0 or more.

In the third method for producing a colored laminate of the present invention, the following formula 1 containing a dielectric layer satisfying the following formula 2 and a plurality of metal fine particles having an aspect ratio of 2 or more on one surface of the release substrate. And a metal fine particle-containing layer satisfying the above order,
In-mold molding a colored layer on the exposed surface of the metal fine particle-containing layer,
The release substrate is peeled from the dielectric layer.
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
Here, λ represents the wavelength of light for preventing reflection, d ₂ represents the physical thickness of the metal fine particle-containing layer, M = (4m + 1) × λ / 8, and d ₁ represents the physical thickness of the dielectric layer. represents, n ₁ denotes the real part of the refractive index of the dielectric layer, m represents an integer of 0 or more.

  The colored laminate of the present invention has a configuration in which an antireflection layer (antireflection structure) including a metal fine particle-containing layer and a dielectric layer is laminated on a colored layer, and includes a plurality of metal fine particles having an aspect ratio of 2 or more. Since the antireflection structure includes a layer, absorption in the visible light region can be suppressed, and the color of the colored layer can be clearly seen from the dielectric layer side. The effect of the present invention is particularly remarkable when the color of the colored layer is dark.

It is a cross-sectional schematic diagram which shows the laminated structure of the colored laminated body concerning the 1st Embodiment of this invention. It is a perspective view which shows an example of a flat metal particle. It is a perspective view which shows another example of a flat metal particle. It is a perspective view which shows an example of a rod-shaped metal particle. It is a figure which shows the simulation of the wavelength dependence of the transmittance | permeability for every aspect of a flat metal particle. In the colored laminate of the present invention, it is a schematic cross-sectional view showing the presence state of a metal fine particle-containing layer containing flat metal particles, the metal fine particle-containing layer containing flat metal particles (also parallel to the plane of the substrate) and the flat metal The figure explaining the angle ((theta)) with the main plane (surface which determines the circle equivalent diameter D) of a particle | grain is shown. It is a scanning microscope image of planar view of a metal fine particle content layer. It is a figure which shows the distribution state (100% isolation) of the metal microparticles in a metal microparticle content layer. It is a figure which shows the distribution state (50% isolation) of the metal microparticles in a metal microparticle content layer. It is a figure which shows the distribution state (10% isolation) of the metal microparticles in a metal microparticle content layer. It is a figure which shows the distribution state (2% isolation) of the metal microparticle in a metal microparticle content layer. In the colored laminate of the present invention, it is a schematic cross-sectional view showing the presence state of a metal fine particle-containing layer containing flat metal particles, and the presence region of the flat metal particles in the depth direction of the antireflection structure of the metal fine particle-containing layer FIG. In the colored laminated body of this invention, it is the schematic sectional drawing which showed another example of the presence state of the metal fine particle content layer containing a flat metal particle. It is a cross-sectional schematic diagram which shows the laminated structure of the colored laminated body concerning the 2nd Embodiment of this invention. It is a cross-sectional schematic diagram which shows the laminated structure of the colored laminated body concerning the 3rd Embodiment of this invention. It is a cross-sectional schematic diagram which shows the laminated structure of the colored laminated body concerning the 4th Embodiment of this invention. It is a cross-sectional schematic diagram which shows the laminated structure of the colored laminated body concerning the 5th Embodiment of this invention. It is a cross-sectional schematic diagram which shows the manufacturing process and laminated structure of the colored laminated body concerning the 6th Embodiment of this invention. It is a figure which shows the manufacturing process using the insert molding method of the colored laminated body of this invention. It is a figure which shows the other manufacturing process using the insert molding method of the colored laminated body of this invention. It is a figure which shows the manufacturing process using the in-mold molding method of the colored laminated body of this invention.

  Embodiments of the present invention will be described below.

FIG. 1 is a schematic cross-sectional view showing the laminated structure of the colored laminate 1 according to the first embodiment of the present invention. As shown in FIG. 1, the colored laminate 1 according to the present embodiment includes a colored layer 10, a metal fine particle-containing layer 25 containing a plurality of metal fine particles 20 having an aspect ratio of 2 or more, and a dielectric that satisfies the following formula 2. The layer 30 is laminated in this order.
In the metal fine particle-containing layer 25, a plurality of metal fine particles 20 are arranged without forming a conductive path, and the metal fine particles 20 are oriented parallel to the laminated surface. The metal fine particle-containing layer 25 satisfies the following formula 1. The dielectric layer 30 is the outermost layer.
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
Here, λ represents the wavelength of light for preventing reflection, d ₂ represents the physical thickness of the metal fine particle-containing layer 25, M = (4m + 1) × λ / 8, and d ₁ represents the physical of the dielectric layer 30. Representing the thickness, n ₁ represents the real part of the refractive index of the dielectric layer 30, and m represents an integer of 0 or more.

The complex refractive index (= n−ik) of an object is divided into a real part n (general object refractive index) and an imaginary part k (extinction coefficient). The complex refractive index of the dielectric layer is expressed as n ₁ -ik _1, and the complex refractive index of the metal fine particle-containing layer is n ₂ -ik ₂ . Hereinafter, when simply referred to as “refractive index”, it means the real part of the complex refractive index.

  The present invention was made for the purpose of making the color of the colored layer clearly visible without changing the color, and the wavelength of light that is desired to prevent reflection in the antireflection structure of the colored laminate of the present invention. Is a wavelength in a visible light region (380 nm to 780 nm) having a visibility of human eyes. Incident light incident on the colored laminate is usually not a single wavelength but light in a certain wavelength range, for example, white light including a visible light region. However, in the present invention, the formulas 1 and 2 do not have to be valid for all wavelengths in the visible light range, and may be valid for specific wavelengths in the visible light range. The specific wavelength can be arbitrarily set, for example, a center wavelength of 580 nm in the visible light region, or a center wavelength of 550 nm in the visible light region having a particularly high visibility of 400 nm to 700 nm, but the wavelength is in the range of 500 to 600 nm. It is preferable. By using the antireflection structure including the metal fine particle containing layer and the dielectric layer satisfying the above formulas 1 and 2 with respect to the arbitrarily set specific wavelength λ, a wide range around the specific wavelength λ (for example, An antireflection effect is exhibited over a bandwidth of 400 to 700 nm, 300 nm, or 400 to 750 nm, 350 nm.

In the colored laminate 1 of the present embodiment shown in FIG. 1, an antireflection structure 40 is constituted by the metal fine particle-containing layer 25 and the dielectric layer 30, and visible light incident from the dielectric layer 30 side is antireflection. The light passes through the structure 40 and enters the colored layer. Since the visible light is hardly reflected by the antireflection structure 40 and the visible light wavelength is incident on the colored layer without being absorbed, the color of the colored layer itself is tinted from the dielectric layer 30 side. It can be clearly recognized without change.
Since the antireflection structure 40 including the metal fine particle-containing layer containing metal fine particles having an aspect ratio of 2 or more can effectively prevent reflection with respect to wavelengths in a wide band of the visible light region, the color of the anti-colored layer Reflection can be effectively prevented without changing the taste. In addition, it is possible to obtain a remarkable effect that the coloring of the colored layer can be emphasized while maintaining the gloss.

The antireflection structure 40, in order to prevent reflection of light incident from the dielectric layer 30, in FIG. 1, the reflected light L _R1 and dielectric layer 30 and the metal fine particle-containing layer 25 on the surface of the dielectric layer 30 With respect to the reflected light _{LR2 at the} interface, the amplitude (magnitude) of reflection is the same, and the phase difference needs to satisfy (2m + 1) · π.

The physical thickness d ₁ of the dielectric layer that satisfies the antireflection condition and the physical thickness d ₂ of the metal fine particle-containing layer are the layers on the colored layer side of the dielectric layer, the metal fine particle-containing layer, and the metal fine particle-containing layer (in FIG. 1). Varies depending on the refractive index of the colored layer 10). When the physical thickness d ₂ of the metal fine particle-containing layer 25 is extremely thin relative to the physical thickness d ₁ of the dielectric layer, the reflected light at the interface between the dielectric layer 30 and the metal fine particle-containing layer 25 and the metal fine particle-containing layer 25 The reflection light at the interface between the colored layer and the colored layer side (colored layer 10 in FIG. 1) is regarded as “reflected light L _R2 ” in FIG. 1, and the above-described antireflection conditions can be applied. .

A range in which a sufficient antireflection effect can be obtained by performing an optical simulation by changing the refractive index and film thickness of the dielectric layer, the metal fine particle containing layer, and the colored layer (or the layer on the colored layer side of the metal fine particle containing layer). Was examined,
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
M = (4m + 1) × λ / 8
I found out that
If Expression 1 is satisfied, reflection of the metal fine particle-containing layer can be suppressed and sufficient cancellation can be achieved.
Further, if Expression 2 is satisfied, the phase shift can be within a certain range, so that sufficient cancellation is possible.
In Equation 2, when m = 0,
0 <n ₁ × d ₁ <λ / 4
Thus, the optical thickness (1 / 4λ) of the dielectric layer of a general antireflection structure formed by laminating a plurality of dielectric layers is thinner.

The usage environment of the colored laminate of the present invention is not particularly limited and varies depending on the application. Examples of the medium that fills the space in which the colored laminate is used include air (n ₀ = 1), water (n ₀ = 1.33), and the like, and the refractive index n ₀ is approximately 1.4 or less. In the present invention, the medium is not limited in any way, and the refractive index of each layer of the colored laminate may be appropriately set depending on the application (medium in the use space).

  Each element of the colored laminate of the present invention will be described in more detail.

<Colored layer>
The colored layer 10 may be a resin layer containing a colored component, or may be formed by screen printing or ink jet printing in addition to a single color colored layer formed using ink, paint, or a metal thin film. It may be a pattern layer such as letters, numbers, figures, patterns, patterns or patterns. The colored layer 10 may be formed on various base materials. That is, in FIG. 1, a colored laminate in which the antireflection structure 40 is formed on the colored layer 10 is illustrated, but in the colored laminate of the present invention, the antireflection structure 40 of the colored layer 10 is formed. Various base materials may be provided on the surface opposite to the surface on which the surface is provided. Examples of the various substrates include glass plates and transparent resin substrates, but the materials are not limited and may be opaque substrates. Moreover, there is no restriction | limiting in the shape of a base material, For example, housing | casings, such as household appliances and miscellaneous goods, etc. other than a film and plate shape etc. are mentioned.

When the colored layer 10 is composed of a resin layer containing a coloring component, a resin as a main component of the resin layer containing a coloring component can be appropriately employed depending on the application. Specific examples include thermoplastic resins, thermosetting resins, photocurable resins, and electron beam curable resins. For example, resins such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, polycarbonate, polystyrene, polyurethane, polyester, polyamide, Teflon (registered trademark), acrylic, and acrylonitrile butadiene styrene can be used, but are not limited thereto. It is not a thing.
The coloring component is not particularly limited and may be either organic or inorganic, and a pigment, dye, or the like having a desired color can be used. For example, as the black component, carbon black, iron trioxide, black titanium pigment, perylene pigment or dye can be used.

<Metal particulate content layer>
The metal fine particle-containing layer 25 includes a plurality of metal fine particles 20 having an aspect ratio of 2 or more in the binder 22. From the viewpoint of haze suppression, the major axis length is preferably smaller than the wavelength λ of light that prevents reflection, and the aspect ratio is preferably less than 40.
The metal fine particles 20 are preferably made of any one of Au, Ag, Pt, Cu, and Al, or an alloy containing at least one of Au, Ag, Pt, Cu, and Al. From the viewpoint of improving the transmittance of visible light, Ag that has particularly small absorption with respect to visible light is most preferable.
The real part n ₂ of the complex refractive index (n ₂ -ik ₂ ) of the metal fine particle-containing layer 25 is preferably less than 1 and the imaginary part k ₂ is preferably 2 or less.

-Metal fine particles-
The metal fine particles 20 are preferably in the form of a flat plate having two opposing main planes as shown in FIGS. 2 and 3, or a rod shape (rod shape) as shown in FIG. In the case of the flat metal particles 20A and 20B shown in FIGS. 2 and 3, the major axis length is the equivalent circle diameter D of the principal plane, and the aspect ratio is the distance between the principal planes opposite to the equivalent circle diameter D, that is, the plate. The ratio D / T with the thickness (plate thickness) T of the metal particles. In the case of the rod-shaped metal particle 20C shown in FIG. 4, the major axis length is the rod length L, and the aspect ratio is the ratio L / φ between the rod length L and the equivalent circle diameter φ of the cross section perpendicular to the rod length direction. is there.

[Flat metal particles]
The flat metal particles are particles having two opposing main planes as shown in FIG. 2 or FIG. Examples of the shape of the main plane include a hexagonal shape, a triangular shape, and a circular shape. Among these, it is preferable that the shape of the main plane is a hexagonal shape as shown in FIG. 2, a polygonal shape equal to or more than a hexagon, or a circular shape as shown in FIG. 3 in terms of high visible light transmittance.

  In the present specification, the circular shape means a shape in which the number of sides having a length of 50% or more of the average equivalent circle diameter of flat metal particles described later is 0 per flat metal particle. . The circular flat metal particles are not particularly limited as long as the flat metal particles are round and have no corners when the flat metal particles are observed from above the main plane with a transmission electron microscope (TEM).

  In the present specification, the hexagonal shape means a shape in which the number of sides having a length of 20% or more of the average equivalent circle diameter of the flat metal particles described later is 6 per flat metal particle. The hexagonal flat metal particles are not particularly limited as long as the flat metal particles are hexagonal when the flat metal particles are observed from above the main plane with a transmission electron microscope (TEM), and can be appropriately selected according to the purpose. For example, the hexagonal corners may be sharp or dull, but the corners are preferably dull in that the absorption in the visible light region can be reduced. There is no restriction | limiting in particular as a grade of the dullness of an angle | corner, According to the objective, it can select suitably.

(Average circle equivalent diameter and coefficient of variation of flat metal particles)
The equivalent circle diameter D, which is the major axis length of the flat metal particles, is represented by the diameter of a circle having an area equal to the projected area of each particle. The projected area of each particle can be obtained by a known method in which the area on an electron micrograph is measured and corrected with the photographing magnification. The average equivalent circle diameter D _AV is an arithmetic average value obtained by obtaining a particle size distribution (particle size distribution) from statistics of the equivalent circle diameter D of 200 flat metal particles and calculating from the particle size distribution. The coefficient of variation in the particle size distribution of the flat metal particles is a value (%) obtained by dividing the standard deviation of the particle size distribution by the average equivalent circle diameter.

In the colored laminate of the present invention, the coefficient of variation in the particle size distribution of the flat metal particles is preferably 35% or less, more preferably 30% or less, and particularly preferably 20% or less. The coefficient of variation is preferably 35% or less from the viewpoint of reducing absorption of visible light in the antireflection structure.
The equivalent circle diameter D of the flat metal particles is smaller than the wavelength λ of light for preventing reflection, preferably 0.5 times or less of λ, more preferably 0.4 times or less, and 0.3 It is particularly preferable that the ratio is not more than twice. Specifically, the equivalent circle diameter D is preferably 10 to 500 nm, more preferably 20 to 300 nm, and even more preferably 50 to 200 nm.

(Thickness and aspect ratio of flat metal particles)
In the colored laminate of the present invention, the thickness T of the flat metal particles is preferably 20 nm or less, more preferably 2 to 15 nm, and particularly preferably 4 to 12 nm.
The particle thickness T can be measured by an atomic force microscope (AFM) or a transmission electron microscope (TEM).

Examples of the method for measuring the average particle thickness by AFM include a method in which a particle dispersion containing flat metal particles is dropped on a glass substrate and dried to measure the thickness of one particle.
As a method of measuring the average particle thickness by TEM, for example, a particle dispersion containing flat metal particles is dropped on a silicon substrate, dried, and then subjected to a coating process by carbon vapor deposition or metal vapor deposition, and a focused ion beam ( FIB) A method of measuring the thickness of a particle by preparing a cross section by processing and observing the cross section with a TEM can be used.

  When the metal fine particles are flat metal particles, the ratio D / T (aspect ratio) of the diameter (equivalent circle diameter) D to the thickness T of the flat metal particles is preferably 3 or more. Although it can select suitably according to the objective, 3-40 are preferable and 5-40 are more preferable from a viewpoint of reducing absorption and haze of visible light. If the aspect ratio is 3 or more, visible light absorption can be suppressed, and if it is less than 40, haze in the visible region can also be suppressed.

  FIG. 5 shows a simulation result of the wavelength dependence of the transmittance when the aspect ratio of the circular flat metal particles is changed. As circular flat metal particles, the case where the thickness T was 10 nm and the major axis length (diameter) D was changed to 80 nm, 120 nm, 160 nm, 200 nm, and 240 nm was examined. As shown in FIG. 5, the absorption peak (bottom of transmittance) generated at the plasmon resonance wavelength shifts to the long wavelength side as the aspect ratio increases, and the absorption peak shifts to the short wavelength side as the aspect ratio decreases. Although not shown, when the aspect ratio is less than 3, the absorption peak is close to the visible range, and when the aspect ratio is 1, the absorption peak is in the visible range. Thus, if the aspect ratio is 3 or more, the transmittance for visible light can be improved. In particular, the aspect ratio is preferably 5 or more.

  The plasmon resonance wavelength λ (absorption peak wavelength in FIG. 5) of the flat metal particles in the metal fine particle-containing layer is not limited as long as it is longer than the predetermined wavelength to be prevented from being reflected, and can be appropriately selected according to the purpose. Although it is possible, in order to shield heat rays, it is preferably 700 nm to 2,500 nm. The reason why the plasmon resonance wavelength λ is 700 nm is when the aspect ratio of the flat metal particles is about 5.

(Method for synthesizing flat metal particles)
The method for synthesizing the flat metal particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, liquid phase methods such as a chemical reduction method, a photochemical reduction method, and an electrochemical reduction method are hexagonal or circular. It is mentioned as what can synthesize the shape flat metal particle. Among these, a liquid phase method such as a chemical reduction method or a photochemical reduction method is particularly preferable in terms of shape and size controllability. After synthesizing hexagonal to triangular tabular metal particles, hexagonal to triangular tabular metal particles are obtained by, for example, etching treatment with a dissolved species that dissolves silver such as nitric acid and sodium sulfite, and aging treatment by heating. The flat metal particles having a hexagonal shape or a circular shape may be obtained by blunting the corners.

  As another method for synthesizing flat metal particles, a seed crystal may be previously fixed on the surface of a transparent substrate such as a film or glass, and then metal particles (for example, Ag) may be grown on the flat plate.

  In the colored laminated body of this invention, in order to provide a desired characteristic to a flat metal particle, you may give a further process. Examples of the further treatment include formation of a high refractive index shell layer, addition of various additives such as a dispersant and an antioxidant.

[Bar-shaped metal particles]
The rod-like metal particles are particles having a shape extending in a uniaxial direction as shown in FIG.

(Bar length of rod-shaped metal particles)
The rod length L, which is the long axis length of the rod-shaped metal particles, is the length of the rod in the uniaxial direction described above, and the rod length L of each particle is the same on the electron micrograph as in the case of the flat metal particles described above. It can be obtained by photographing the length and correcting with the photographing magnification.
The rod length L, which is the major axis length of the rod-like metal particles, is smaller than the wavelength λ of light for preventing reflection, preferably 0.8 times or less of λ, and more preferably 0.6 times or less. It is particularly preferably 0.5 times or less. The lower limit of the bar length is not particularly limited, but is preferably 1 nm or more, more preferably 2 nm or more, and particularly preferably 5 nm or more. Specifically, the rod length L is preferably 50 nm or more and 300 nm or less.

(The diameter and aspect ratio of rod-shaped metal particles)
The diameter (equivalent circle diameter) φ of the rod-shaped metal particle is obtained from an image of a cross section perpendicular to the length direction of the rod obtained by acquiring an AFM or TEM image by the same method as the method of measuring the thickness of the flat metal particle. The equivalent circle diameter may be calculated by a known method in which the area of the cross section is measured and corrected by the photographing magnification.
The diameter φ of the rod-shaped metal particles is smaller than 0.5 times the wavelength λ of light for preventing reflection, preferably 0 or 4 times or less of λ, more preferably 0.3 or less, It is particularly preferable that the ratio is 1 time or less.

  When the metal fine particles are rod-shaped metal particles, the ratio L / φ (aspect ratio) of the rod length L to the equivalent circle diameter φ is preferably 2.5 or more. The aspect ratio can be appropriately selected depending on the purpose, but from the viewpoint of reducing absorption of visible light and haze, 3 to 40 is preferable, and 5 to 40 is more preferable. If the aspect ratio is 3 or more, visible light absorption can be suppressed, and if it is less than 40, haze in the visible region can also be suppressed.

[Disposition and distribution of metal fine particles]
The arrangement and distribution state of the metal fine particles in the metal fine particle-containing layer will be described.
(Plane orientation)
In the metal fine particle-containing layer 25, the metal fine particles 20 are oriented parallel to the laminated surface. The fact that the metal fine particles 20 are oriented parallel to the laminated surface means that the major axis length of the metal fine particles 20 is parallel to the surface of the metal fine particle-containing layer 25. In this specification, not only the case where the angle θ between the major axis length and the surface is 0 °, but also the range where the angle θ between the major axis length and the surface is ± 30 ° is parallel. That is, in FIG. 6, the surface 25S of the metal fine particle-containing layer 25 and the extended line of the major axis of the metal fine particle 20 (on the main plane in the case of flat metal particles, the axis in the rod length direction in the case of rod-like metal particles). The formed angle (± θ) is 0 ° to 30 °. In addition, it is more preferable that the angle (± θ) is plane-aligned in the range of 0 ° to 20 °, and it is particularly preferable that the plane is aligned in the range of 0 ° to 10 °. When the cross section of the colored laminate is observed, the metal fine particles 20 are more preferably oriented in a state where the tilt angle (± θ) shown in FIG. 6 is small.
Further, the metal fine particles whose plane orientation is in the parallel range where the angle θ is 0 ° to ± 30 ° is preferably 50% or more of the total number of metal fine particles, and more preferably 70% or more. More preferably, it is 90% or more.

  Whether or not the metal fine particles 20 are oriented with respect to the surface 25S of the metal fine particle-containing layer 25 is evaluated by, for example, preparing an appropriate cross-sectional slice of the colored laminate and observing the metal fine particle-containing layer 25 in this slice. The method can be taken. Specifically, a cross-section sample or a cross-section sample of a colored laminate is prepared using a microtome or a focused ion beam (FIB), and this is used for various microscopes (for example, a field emission scanning electron microscope (FE-SEM), And a method of evaluating from an image obtained by observation using a transmission electron microscope (TEM) or the like.

  As a method for observing the cross-section sample or cross-section sample prepared as described above, whether the main plane of the flat metal particles is plane-oriented with respect to one surface of the metal fine particle-containing layer in the sample, or the long axis of the rod-like metal particles There is no particular limitation as long as it can be confirmed whether or not the film is plane-oriented. For example, a method using FE-SEM, TEM, or the like can be given. In the case of a cross-section sample, observation may be performed by FE-SEM, and in the case of a cross-section sample, observation may be performed by TEM. When evaluating by FE-SEM, it is preferable to have a spatial resolution that can clearly determine the shape and tilt angle (± θ in FIG. 6) of the metal fine particles.

(Distribution of fine metal particles)
FIG. 7 is a scanning microscope image in plan view of an example of the metal fine particle-containing layer 25. In the example shown in FIG. 7, flat metal particles are included as the metal fine particles. As shown in FIG. 7, the metal fine particles are preferably arranged randomly (non-periodically) in the layer and dispersedly arranged so as not to form a conductive path.

The distribution state of the metal fine particles 20 is not particularly limited as long as a conductive path is not formed by a plurality of metal fine particles.
8A to 8D are plan views schematically showing the distribution state of the metal fine particles 20 in the metal fine particle-containing layer 25. FIG. The white portions in the figure are the metal fine particles 20. In FIG. 8A, the plurality of metal fine particles 20 are all distributed in a plane direction (100%) in isolation. FIG. 8B shows a state where 50% of the plurality of metal fine particles 20 are isolated and the other 50% are in contact with adjacent particles and distributed in a partially connected state 24. FIG. 8C shows a state in which only 10% of the plurality of metal fine particles 20 are present in isolation, and the others are in contact with adjacent particles and distributed in a partially connected state 24. As shown in FIG. 8A, it is most preferable that the metal fine particles 20 are isolated from each other. However, if 10% or more are arranged in isolation, a sufficient antireflection effect can be obtained. On the other hand, FIG. 8D shows the distribution of the metal fine particles when only 2% of the plurality of metal fine particles 20 are isolated. In FIG. 8D, the metal fine particles are connected from one end to the other end in the image to be conductive. A path 26 is formed. When the conductive path 26 is formed in this way, the absorption factor of the visible light wavelength by the metal fine particles increases, and the reflectance also increases. Therefore, the present invention requires that the conductive path is not formed by at least the metal particles as shown in FIGS. 8A to 8C.

  Regarding the presence / absence of conductive path formation, a conductive path is formed when metal fine particles are continuously connected from one end of the region to the other opposite end in a 2.5 μm × 2.5 μm region observed by SEM. If the metal fine particles are separated on the way, it is determined that a conductive path is not formed.

  The distribution of metal fine particles in the metal fine particle-containing layer is preferably uniform. Uniform distribution here means that when the distance to the nearest particle for each particle (distance between nearest particles) is quantified by the distance between the centers of the particles, the distance between the nearest particles of each particle is changed. The coefficient (= standard deviation ÷ average value) is small. The variation coefficient of the closest interparticle distance is preferably as small as possible, preferably 30% or less, more preferably 20% or less, more preferably 10% or less, and ideally 0%. When the variation coefficient of the distance between the closest particles is large, the metal fine particles are densely formed or the particles are aggregated in the metal fine particle-containing layer, and the haze tends to deteriorate. The distance between the closest particles can be measured by observing the coated surface of the metal fine particle-containing layer with an SEM or the like.

  When the metal fine particles 20 in the metal fine particle-containing layer 25 are rod-like metal particles, a plurality of rod-like metal particles are dispersed so that the major axis is in a random direction rather than being arranged in one direction in the plane. This is preferable because generation of polarization characteristics can be suppressed.

(Area ratio of metal fine particles)
The total value B of the area of the metal fine particles relative to the area A of the base material when the colored laminate is viewed from above (the total projected area A of the metal fine particle-containing layer when viewed from the direction perpendicular to the metal fine particle-containing layer) The area ratio [(B / A) × 100] as a ratio is preferably 5% or more, and more preferably 10% or more and less than 70%. If the area ratio is 5% or more, a sufficient antireflection effect can be obtained. If the area ratio is less than 70%, a conductive path is not formed, and absorption and reflection of visible light can be suppressed and a decrease in transmittance can be suppressed.

When the metal fine particle is a flat metal particle, the area ratio should be an optimum value according to the thickness T of the flat metal particle and the refractive index n ₁ of the dielectric layer in order to obtain a low reflectance in a wide wavelength range. preferable. Consider a case where all the metal fine particles are flat metal particles, and the medium of the use space is air (n ₀ = 1). For example, when the thickness of the flat metal particles is 4 nm and the refractive index of the dielectric layer is 1.4, the area ratio is preferably 40% or more and less than 70%, and more preferably 50% or more and less than 65%. For example, when the thickness of the flat metal particles is 8 nm and the refractive index of the dielectric layer is 1.4, the area ratio is preferably 5% or more and less than 40%, more preferably 6% or more and less than 30%. For example, when the thickness of the flat metal particles is 18 nm and the refractive index of the dielectric layer is 1.4, the area ratio is preferably 5% or more and less than 30%, more preferably 5% or more and less than 25%.

  Here, the area ratio can be measured, for example, by image processing an image obtained by SEM observation of the colored laminate from above or an image obtained by AFM (Atomic Force Microscope) observation.

(Thickness of metal fine particle-containing layer, existence range of metal fine particles in thickness direction)
The boundary between the metal fine particle-containing layer and the dielectric layer can be determined by observing the like similarly SEM, it is possible to determine the thickness d ₂ of the metal particle-containing layer. Even when the dielectric layer is formed on the metal fine particle-containing layer using the same type of polymer as the polymer contained in the metal fine particle-containing layer, the metal fine particle-containing layer is generally boundaries can be discriminated, it is possible to determine the thickness d ₂ of the metal particle-containing layer. If the boundary is not clear, the surface of the metal fine particle that is located farthest from the substrate is regarded as the boundary.

FIG. 9 and FIG. 10 are schematic cross-sectional views showing the existence state of the metal fine particles 20 in the metal fine particle-containing layer 25 in the colored laminate of the present invention.
Physical thickness d ₂ of the metal particle-containing layer 25 in the colored laminate of the present invention, as the thickness is small, makes the angle range of the plane orientation of the fine metal particles tends approaches 0 °, since it can reduce the absorption of visible light The thickness is preferably 100 nm or less, more preferably 3 to 50 nm, and particularly preferably 5 to 40 nm.

When the metal fine particle 20 is a flat metal particle, when the physical thickness d ₂ of the metal fine particle-containing layer 25 is d ₂ > D _AV / 2 with respect to the average equivalent circle diameter D _AV of the flat metal particle, 80 of the flat metal particle. or number percent, is preferably present in a range from the surface of d _2/2 of the metal particle-containing layer, more preferably present in the range of d _2/3, 60% by number or more metal particles of flat metal particles More preferably, it is exposed on one surface of the containing layer. That tabular metal particles to be present in a range of d _2/2 from the surface of the metal fine particle-containing layer, at least a portion of the tabular metal particles are included in a range from the surface of d _2/2 of the metal particle-containing layer means. FIG. 9 is a schematic diagram showing the case where the thickness d ₂ of the metal fine particle-containing layer is d ₂ > D _AV / 2, and in particular, 80% by number or more of the flat metal particles are included in the range f. It is a figure showing that it is f <d < ₂ > / 2.
Further, the fact that the flat metal particles are exposed on one surface of the metal fine particle-containing layer means that a part of one surface of the flat metal particles is an interface position with the dielectric layer. FIG. 10 is a diagram showing a case where one surface of the flat metal particle coincides with the interface with the dielectric layer.

Here, the flat metal particle presence distribution in the metal fine particle-containing layer can be measured, for example, from an image obtained by SEM observation of the cross section of the colored laminate.
The colored laminate of the present invention, the physical thickness d ₂ of the metal particle-containing layer to an average equivalent-circle diameter D _AV of the tabular metal particles, preferably when the d 2 _{<D AV} / 2, more preferably d _{2 <D AV} / 4 and d ₂ <D _AV / 8 is more preferable. Lowering the coating thickness of the metal fine particle-containing layer is preferable because the plane orientation angle range of the flat metal particles tends to approach 0 ° and absorption of visible light can be reduced.

-Binder-
The binder 22 in the metal fine particle-containing layer 25 preferably includes a polymer, and more preferably includes a transparent polymer. Examples of the polymer include natural materials such as polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, polyurethane resin, gelatin, and cellulose. Examples thereof include polymers such as polymers. Among them, the main polymer is preferably a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl chloride resin, a (saturated) polyester resin, or a polyurethane resin, and more preferably a polyester resin or a polyurethane resin. You may use a binder in combination of 2 or more types of polymers.

  Among polyester resins, a saturated polyester resin is more particularly preferable from the viewpoint of imparting excellent weather resistance since it does not contain a double bond. Moreover, it is more preferable to have a hydroxyl group or a carboxyl group at the molecular terminal from the viewpoint of obtaining high hardness, durability and heat resistance by curing with a water-soluble or water-dispersible curing agent or the like.

A commercially available polymer can also be preferably used as the polymer, and examples thereof include Plus Coat Z-687, which is a water-soluble polyester resin manufactured by Kyoyo Chemical Industry Co., Ltd.
Moreover, in this specification, the main polymer contained in a metal fine particle content layer means the polymer component which occupies 50 mass% or more of the polymer contained in a metal fine particle content layer.
The content of the polyester resin and the polyurethane resin with respect to the metal fine particles contained in the metal fine particle-containing layer is preferably 1 to 10000% by mass, more preferably 10 to 1000% by mass, and 20 to 500% by mass. Is particularly preferred.
The refractive index n of the binder is preferably 1.4 to 1.7.

<Dielectric layer>
The dielectric layer 30 constitutes the outermost layer of the colored laminate 1. As described above, the optical thickness (n ₁ × d ₁ , also referred to as optical path length) of the dielectric layer 30 is such that the reflected light L _R1 of the incident light from the surface of the dielectric layer 30 is incident light. is the thickness to be canceled by the interference between the reflected light L _R2 at the metal fine particle-containing layer 25. Here, “the reflected light L _R1 is canceled by interference with the reflected light L _R2 in the metal fine particle containing layer 25 of incident light” means that the reflected light L _R1 and the reflected light L _R2 interfere with each other as a whole. This means that the reflected light is reduced, and is not limited to the case where the reflected light is completely eliminated.

The dielectric layer 30 only needs to satisfy the above-described formula 2. In principle, the optical thickness of the dielectric layer 30 is optimally (4m + 1) × λ / 8. Depending on the conditions, the optimum value changes in the range of about λ / 16 to λ / 4, and therefore, it may be set as appropriate according to the layer configuration.
It is more preferable that the dielectric layer 30 satisfies the following formula 2A.
M−λ / 12 <n ₁ × d ₁ <M + λ / 12 Formula 2A
It is particularly preferable that the dielectric layer 30 satisfies the following formula 2B.
M−λ / 16 <n ₁ × d ₁ <M + λ / 16 (Formula 2A)

Physical thickness d ₁ of the dielectric layer 30 is specifically, it is preferably 400nm or less, it may be appropriately set according to the material of the dielectric layer.

Although the real part n ₁ of the refractive index of the dielectric layer 30 is not particularly limited, the refractive index is smaller than or similar to the refractive index of the layer disposed on the side opposite to the surface of the dielectric layer 30 of the antireflection structure 40. It is preferable from the viewpoint of reducing the reflected light as a whole. Moreover, it is desirable that it is larger than the refractive index of the medium (for example, air) which fills the space where the colored laminate is used.
Specifically, the real part n ₁ of the refractive index of the dielectric layer 30 is preferably 1.2 to 2.0.

The imaginary part k ₁ of the refractive index of the dielectric layer 30 is preferably 0.3 or less, more preferably 0.1 or less, and 0 from the viewpoint of reducing absorption and increasing transmittance. Particularly preferred.

The constituent material of the dielectric layer 30 is not particularly limited. As the dielectric layer, for example, a composition containing a thermoplastic polymer, a thermosetting polymer, an energy radiation curable polymer, an energy radiation curable monomer, or the like as a binder is cured by thermal drying or irradiation with energy radiation. A layer in which low refractive index particles having a low refractive index are dispersed in a binder, a layer in which low refractive index particles having a low refractive index are polycondensed or cross-linked with a monomer and a polymerization initiator, and a layer containing a binder having a low refractive index And so on.
Examples of the energy radiation curable polymer include, but are not limited to, Unidic EKS-675 (an ultraviolet curable resin manufactured by DIC). Although it does not specifically limit as an energy radiation-curable monomer, A fluorine-containing polyfunctional monomer etc. are preferable.

  The colored laminate of the present invention may include a layer other than the above layers. Hereinafter, the structure of the colored laminated body of embodiment provided with the other layer is demonstrated.

  FIG. 11 is a schematic cross-sectional view showing a laminated structure of the colored laminate 2 according to the second embodiment of the present invention. As shown in FIG. 11, the colored laminate of the present invention includes a high refractive index layer 32 having a refractive index higher than that of the colored layer 10 between the colored layer 10 and the metal fine particle-containing layer 25. May be. In the colored laminate 2 shown in FIG. 11, constituent elements other than the high refractive index layer 32 are the same as those in the first embodiment, and equivalent elements are denoted by the same reference numerals. The same applies to the following drawings.

  In the colored laminate 2, the antireflection structure 40 is configured by the metal fine particle-containing layer 25, the dielectric layer 30, and the high refractive index layer 32. By providing the high refractive index layer 32, the antireflection effect can be further enhanced.

<High refractive index layer>
The refractive index of the high refractive index layer 32 may be larger than the refractive index of the layer opposite to the metal fine particle-containing layer 25 of the high refractive index layer 32 (colored layer 10 in the example of FIG. 11). In particular, it is preferably 1.6 or more. The upper limit of the refractive index of the high refractive index layer 32 is not particularly limited, but is preferably 2.6 or less, more preferably 2.0 or less, and particularly preferably 1.8 or less.
The constituent material of the high refractive index layer 32 is not particularly limited as long as the refractive index is 1.55 or more. For example, it contains a binder, metal oxide fine particles, a matting agent, and a surfactant, and further contains other components as necessary. The binder is not particularly limited and can be appropriately selected depending on the purpose. For example, a thermosetting type such as an acrylic resin, a silicone resin, a melamine resin, a urethane resin, an alkyd resin, or a fluorine resin. Or a photocurable resin etc. are mentioned.
The material of the metal oxide fine particles is not particularly limited as long as the metal fine particles having a refractive index larger than that of the binder is used, and can be appropriately selected according to the purpose. For example, tin-doped indium oxide (hereinafter, Abbreviated as “ITO”), zinc oxide, titanium oxide, zirconia oxide and the like.

  FIG. 12 is a schematic cross-sectional view showing the layer configuration of the colored laminate 3 according to the third embodiment of the present invention. As shown in FIG. 12, the colored laminate of the present invention may include a hard coat layer 34 between the colored layer 10 and the metal fine particle-containing layer 25.

<Hard coat layer>
By providing the hard coat layer 34, the scratch resistance can be enhanced. The hard coat layer may contain metal oxide particles and an ultraviolet absorber.
There is no restriction | limiting in particular as the hard-coat layer 34, The material and a formation method can be selected suitably according to the objective, For example, acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin And thermosetting or photocurable resins such as fluorine-based resins. A sol-gel cured product obtained by hydrolysis and polycondensation of at least one alkoxide compound of an element selected from the group consisting of Si, Ti, Zr and Al can also be used. There is no restriction | limiting in particular as thickness of a hard-coat layer, Although it can select suitably according to the objective, 1 micrometer-50 micrometers are preferable.

  FIG. 13: is a schematic cross section which shows the layer structure of the colored laminated body 4 of the 4th Embodiment of this invention. As shown in FIG. 13, the colored laminate of the present invention may include a high refractive index layer 32 and a hard coat layer 34 between the colored layer 10 and the metal fine particle-containing layer 25. With this configuration, the antireflection performance can be improved and the scratch resistance can be enhanced.

  When the high refractive index layer 32 and the hard coat layer 34 are provided, a configuration in which the high refractive index layer 32 is disposed between the metal fine particle-containing layer 25 and the hard coat layer 34 as shown in FIG. The hard coat layer 34 may be disposed between the metal fine particle-containing layer 25 and the high refractive index layer 32.

When the high refractive index layer 32 is disposed between the metal fine particle-containing layer 25 and the hard coat layer 34, the optical film thickness of the high refractive index layer 32 is preferably λ / 4 or less. At this time, the physical film thickness of the high refractive index layer 32 is specifically preferably 200 nm or less.
On the other hand, when the hard coat layer 34 is disposed between the metal fine particle-containing layer 25 and the high refractive index layer 32, the optical film thickness of the high refractive index layer 32 is preferably λ / 2 or less. At this time, the physical film thickness of the high refractive index layer 32 is specifically preferably 300 nm or less.

  FIG. 14 is a schematic cross-sectional view showing the layer configuration of the colored laminate 5 according to the fifth embodiment of the present invention. As shown in FIG. 14, the colored laminate of the present invention may include a transparent substrate 35 and a high refractive index layer 32 between the colored layer 10 and the metal fine particle-containing layer 25. At this time, the high refractive index layer 32 has a refractive index larger than the refractive index of the transparent substrate 35 which is the layer on the opposite side of the metal fine particle containing layer 25 of the high refractive index layer 32. Further, the transparent substrate 35 and the colored layer 10 may be laminated with the adhesive layer 36 interposed therebetween. The colored layer 10 may be formed by direct application or the like on the surface side of the transparent substrate 35 on which the antireflection structure 40 is not laminated, and in that case, the layer structure without the adhesive layer 36 in FIG. Become.

<Transparent substrate>
The transparent substrate 35 preferably has a visible light transmittance of 70% or more, more preferably 80% or more.

The shape, structure, size, material and the like of the transparent substrate 35 are not particularly limited and can be appropriately selected depending on the purpose.
Examples of the shape include a film shape and a flat plate shape, and the structure may be a single layer structure or a laminated structure, and the size may be determined according to the application.
Examples of the transparent base material include polyolefin resins such as glass, polyethylene, polypropylene, poly-4-methylpentene-1 and polybutene-1; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins and polychlorinated resins. Vinyl resins, polyphenylene sulfide resins, polyether sulfone resins, polyethylene sulfide resins, polyphenylene ether resins, styrene resins, acrylic resins, polyamide resins, polyimide resins, cellulose resins such as cellulose acetate, etc. Or a laminated film of these. Among these, a triacetyl cellulose (TAC) film and a polyethylene terephthalate (PET) film are particularly preferable.

  When the transparent substrate 35 is in the form of a flat plate or a film, the thickness thereof is not particularly limited and can be appropriately selected according to the purpose of use for preventing reflection. When it is a film, it is usually about 10 μm to 500 μm. The thickness of the transparent substrate 35 is preferably 10 μm to 300 μm, more preferably 20 to 200 μm, and particularly preferably 35 to 100 μm.

<Adhesive layer>
The adhesive layer 36 can contain an ultraviolet absorber.
There is no restriction | limiting in particular as a material which can be utilized for formation of the adhesion layer 36, According to the objective, it can select suitably, For example, a polyvinyl butyral (PVB) resin, an acrylic resin, a styrene / acrylic resin, a urethane resin, polyester Examples thereof include resins and silicone resins. These may be used individually by 1 type and may use 2 or more types together. An adhesive layer made of these materials can be formed by coating or laminating.
Furthermore, an antistatic agent, a lubricant, an antiblocking agent, or the like may be added to the adhesive layer 36.
The thickness of the adhesive layer 36 is preferably 0.1 μm to 100 μm.

  In addition, since the adhesion layer 36 is interposed when the layers are attached, the adhesive layer 36 is provided not only between the colored layer 10 and the transparent substrate 35 but also between other layers. Also good.

<Other layers and ingredients>
The colored laminate of the present invention may further include an infrared absorbing compound-containing layer containing an infrared absorbing compound, an ultraviolet absorber-containing layer containing an ultraviolet absorber, and the like. An infrared absorbing compound-containing layer or an ultraviolet absorber-containing layer may be provided separately. However, an infrared absorbing compound-containing layer or an ultraviolet absorbing layer containing an infrared absorbing compound or an ultraviolet absorber in the hard coat layer or the adhesive layer described above. It is good also as an agent content layer.

  Next, a method for forming each layer will be described.

<Method for forming metal fine particle-containing layer>
There is no restriction | limiting in particular in the formation method of the metal fine particle content layer 25. FIG. For example, a dispersion containing metal fine particles (metal fine particle dispersion) is applied to the surface of an arbitrary layer such as the substrate or the dielectric layer 30 using a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like. Examples thereof include a method of aligning the surface by a method such as a method, an LB (Langmuir Blodgett) film method, a self-assembly method, and spray coating.

  In order to promote surface orientation, the metal fine particle dispersion may be applied and then passed through a pressure roller such as a calender roller or a lami roller.

<Method for forming dielectric layer, high refractive index layer, hard coat layer>
The dielectric layer 30, the high refractive index layer 32, and the hard coat layer 34 are preferably formed by coating. The coating method at this time is not particularly limited, and a known method can be used. For example, each prepared coating solution is applied by a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like. The method etc. are mentioned.

<Method for forming adhesive layer>
The adhesive layer 36 is preferably formed by coating. For example, it can be laminated on the surface of a lower layer such as a substrate, a metal fine particle-containing layer, or an ultraviolet absorbing layer. There is no limitation in particular as the coating method at this time, A well-known method can be used.
A film in which the pressure-sensitive adhesive is previously applied and dried on a release film is prepared, and the film is left in a dry state by laminating the pressure-sensitive adhesive surface of the film and the antireflection structure surface of the present invention. It is possible to laminate an adhesive layer. The laminating method at this time is not particularly limited, and a known method can be used.

  Hereinafter, the manufacturing method of the colored laminated body of this invention is demonstrated. In the following manufacturing method, the method for forming each layer is as described above.

  The colored laminate 1 shown in FIG. 1 can be manufactured by forming the metal fine particle-containing layer 25 and the dielectric layer 30 in this order on the colored layer 10.

  Further, as shown in FIG. 15, a colored layer 10 in which a dielectric layer 30 and a metal fine particle-containing layer 25 are laminated in this order on one surface of a release substrate 15 and an adhesive layer 36 is formed on the surface. The upper adhesive layer 36 and the metal fine particle-containing layer 25 are bonded together, and then the release substrate 15 is peeled off, whereby the colored layer 1 shown in FIG. The colored laminated body 6 shown in FIG. 15 provided with an adhesive layer 36 therebetween can be manufactured.

  In the colored laminate 5 shown in FIG. 14, the metal fine particle-containing layer 25 and the dielectric layer 30 are formed in this order on one surface of the transparent substrate 35, and then, on the other surface of the transparent substrate 35. It can be manufactured by bonding the colored layer 10 through the adhesive layer 36.

  Further, the metal fine particle-containing layer 25 and the dielectric layer 30 are formed in this order on one surface of the transparent substrate 35, and then the colored layer 10 is directly formed on the other surface of the transparent substrate 35. Thereby, the colored laminated body of the structure which is not provided with the adhesion layer 36 in the colored laminated body 5 shown in FIG. 14 can be manufactured.

FIG. 16 is a diagram schematically showing a manufacturing process and a layer structure for explaining a method for manufacturing a colored laminate of the present invention using insert molding. In FIG. 16, the lower part is a cross-sectional view of the laminated body in each process of the upper part.
The laminated film 11 in which the high refractive index layer 32, the metal fine particle-containing layer 25, and the dielectric layer 30 are laminated in this order on one surface of the transparent substrate 35 is disposed along the concave portion in the cavity of the molding die 80. Then, after closing the mold 80, a resin composition 10A for forming a colored layer is injected from the resin injection hole 82, and the colored layer 10 is insert-molded on the surface of the laminated film 11 on the transparent substrate 35 side. The colored laminated body of the structure which is not provided with the adhesion layer 36 in the colored laminated body 5 shown in FIG. 14 can be manufactured.

FIG. 17 is a diagram schematically showing a manufacturing process and a layer structure for explaining another manufacturing method of the colored laminate of the present invention using insert molding. In FIG. 17, the lower part is a cross-sectional view of the laminated body in each process of the upper part.
A laminated film 12 produced by laminating and forming the metal fine particle-containing layer 25 and the dielectric layer 30 in this order on one surface of the transparent substrate 35 and forming the colored layer 10 on the other surface of the transparent substrate 35. The resin composition 60A for forming the resin layer 60 is injected from the resin injection hole 82 after being disposed along the concave portion in the cavity of the molding die 80 and closed, and the colored layer of the laminated film 12 is injected. The colored layered product provided with the resin layer 60 on the surface side where the antireflection structure 40 of the colored layer 10 is not formed can be manufactured by insert-molding the resin layer 60 on the surface of 10. By using a mold having a desired shape, a colored laminate including a resin layer 60 having a wide variety of shapes can be obtained.

FIG. 18 is a diagram schematically showing a manufacturing process and a layer structure for explaining a method for manufacturing a colored laminate according to the present invention using in-mold molding. In FIG. 17, the lower part is a cross-sectional view of the laminated body in each process of the upper part.
A laminated film prepared by laminating the dielectric layer 30 and the metal fine particle-containing layer 25 in this order on one surface of the film-like release substrate 15 is such that the metal fine particle-containing layer 25 side is the resin injection hole 82 side. Thus, it arrange | positions in the cavity of the shaping die 80. FIG. After closing the mold 80, a resin composition 10A for forming the colored layer 10 is injected from the resin injection hole 82, and the colored layer 10 is in-mold molded on the surface (exposed surface) of the metal fine particle-containing layer 25. The colored laminated body 1 having a laminated structure shown in FIG. 1 can be manufactured by peeling from the release substrate 15 when taking out from the mold 80.

  In general, an antireflection layer having a laminated structure of a plurality of dielectric layers needs to be manufactured with high accuracy because the antireflection function greatly changes as the thickness of each layer changes. When a laminated body is produced by integrating a resin layer with a film having an antireflection structure by insert molding or in-mold molding, since the film having the antireflection structure is stretched during molding, a plurality of dielectric layers The antireflection film having the laminated structure is not suitable for producing a laminate by insert molding or in-mold molding. However, the antireflection structure including the metal fine particle-containing layer has a small change in the antireflection function as compared with the conventional antireflection layer having a laminated structure of a plurality of dielectric layers even if the film thickness changes. Therefore, even if elongation occurs due to insert molding or in-mold molding and the film thickness changes somewhat, the antireflection function by the antireflection structure can be sufficiently maintained.

  The colored laminate of the present invention can achieve high productivity because each layer can be formed by a coating method. In addition, because of the versatility of film, a wide variety of housings such as electrical appliances, vehicle bodies and frames, dashboard materials, building interior materials, signs (advertisements, signs, etc.), packaging materials, decorative windows, etc. It can be used for

Examples of the present invention and comparative examples will be described below.
First, the preparation and evaluation of various coating solutions used in the production of each example and comparative example will be described.

-Preparation of flat silver particle dispersion A1-
Ion exchange water 13L was weighed in a reaction vessel made of NTKR-4 (manufactured by Nippon Metal Industry Co., Ltd.), and four NTKR-4 propellers and four NTKR-4 paddles were attached to a SUS316L shaft. While stirring using a chamber equipped with an agitator, 1.0 L of a 10 g / L aqueous solution of trisodium citrate (anhydrous) was added and kept at 35 ° C. 0.68 L of 8.0 g / L polystyrene sulfonic acid aqueous solution was added, and 0.041 L of sodium borohydride aqueous solution prepared to 23 g / L using 0.04 N sodium hydroxide aqueous solution was further added. 13 L of 0.10 g / L silver nitrate aqueous solution was added at 5.0 L / min.

  1.0 L of 10 g / L trisodium citrate (anhydride) aqueous solution and 11 L of ion exchange water were added, and 0.68 L of 80 g / L potassium hydroquinone sulfonate aqueous solution was further added. Stirring was increased to 800 rpm, 8.1 L of a 0.10 g / L silver nitrate aqueous solution was added at 0.95 L / min, and then the temperature was lowered to 30 ° C.

  A 44 g / L methylhydroquinone aqueous solution (8.0 L) was added, and then a 40 ° C. gelatin aqueous solution described later was added in its entirety. The stirring was increased to 1200 rpm, and the whole amount of a silver sulfite white precipitate mixture described later was added.

  When the pH change of the preparation solution stopped, 5.0 L of 1N NaOH aqueous solution was added at 0.33 L / min. Thereafter, 2.0 g / L of 1- (m-sulfophenyl) -5-mercaptotetrazole sodium aqueous solution (NaOH and citric acid (anhydride) was used to adjust to pH = 7.0 ± 1.0 and dissolve 0.18 L) was added, and 0.078 L of 70 g / L 1,2-benzisothiazolin-3-one (the aqueous solution was adjusted to be alkaline with NaOH) was added. In this way, a flat silver particle dispersion A1 was prepared.

-Preparation of gelatin aqueous solution-
16.7 L of ion-exchanged water was weighed in a dissolution tank made of SUS316L. 1.4 kg of alkali-treated beef bone gelatin (GPC weight average molecular weight 200,000) subjected to deionization treatment was added while stirring at low speed with an agitator made of SUS316L. Furthermore, 0.91 kg of alkali-treated beef bone gelatin (GPC weight average molecular weight 21,000) subjected to deionization treatment, proteolytic enzyme treatment, and oxidation treatment with hydrogen peroxide was added. Thereafter, the temperature was raised to 40 ° C., and gelatin was swollen and dissolved simultaneously to completely dissolve it.

-Preparation of silver sulfite white precipitate mixture-
In a dissolution tank made of SUS316L, 8.2 L of ion-exchanged water was weighed, and 8.2 L of a 100 g / L silver nitrate aqueous solution was added. While stirring at a high speed with an agitator made of SUS316L, 2.7 L of 140 g / L sodium sulfite aqueous solution was added in a short time to prepare a mixed solution containing a silver sulfite white precipitate. This mixture was prepared immediately before use.

-Preparation of flat silver particle dispersion B1-
800 g of the above-mentioned flat silver particle dispersion A1 was collected in a centrifuge tube and adjusted to pH = 9.2 ± 0.2 at 25 ° C. using 1N NaOH and / or 1N sulfuric acid. Using a centrifuge (HimacCR22GIII, angle rotor R9A, manufactured by Hitachi Koki Co., Ltd.), centrifugation was performed at 9000 rpm for 60 minutes at 35 ° C., and 784 g of the supernatant was discarded. A 0.2 mM NaOH aqueous solution was added to the precipitated tabular silver particles to make a total of 400 g, and the mixture was hand-stirred with a stir bar to obtain a coarse dispersion. In the same manner, a crude dispersion for 24 centrifuge tubes was prepared to a total of 9600 g, and added to a SUS316L tank and mixed. Furthermore, 10 cc of a 10 g / L solution of Pluronic 31R1 (manufactured by BASF) (diluted with a mixed solution of methanol: ion exchange water = 1: 1 (volume ratio)) was added. Using an automixer type 20 (manufactured by homomixer MARKII) manufactured by Primix Co., Ltd., the batch dispersion treatment was performed at 9000 rpm for 120 minutes on the crude dispersion mixture in the tank. The liquid temperature during dispersion was kept at 50 ° C. After dispersion, the temperature was lowered to 25 ° C., and single-pass filtration was performed using a profile II filter (manufactured by Nippon Pole Co., Ltd., product type MCY1001Y030H13).
In this manner, the dispersion A1 was subjected to a desalting treatment and a redispersion treatment to prepare a flat silver particle dispersion B1.

-Evaluation of flat metal particles-
It was confirmed that hexagonal to circular and triangular tabular grains were formed in the tabular silver particle dispersion A1. In the dispersion A1, all the metal fine particles were flat metal particles. An image obtained by TEM observation of the flat silver particle dispersion A1 was taken into image processing software ImageJ and subjected to image processing. Image analysis was performed on 500 particles arbitrarily extracted from TEM images of several fields of view, and the equivalent circle diameter was calculated. As a result of statistical processing based on these populations, the average diameter was 120 nm.

The flat silver particle dispersion B1 was measured in the same manner, and almost the same result as the flat silver particle dispersion A1 was obtained including the shape of the particle size distribution.
The flat silver particle dispersion B1 was dropped on a silicon substrate and dried, and the individual thickness of the flat silver particles was measured by the FIB-TEM method. Ten flat silver particles in the flat silver particle dispersion B1 were measured, and the average thickness was 8 nm.
That is, the aspect ratio of the tabular fine particles used in the following examples is 120/8 = 15.

-Preparation of rod-shaped silver particle dispersion-
After forming a silver twin twin seed crystal by the method described in CHEMISTRY OF MATERIALS (Vol. 20, Issue 16, P5186-5190, 2008), ACS NANO (Vol.3, No.1, P21-26, 2009) The bar-shaped silver particle dispersions C1 to C3 were prepared by controlling the amount of the aqueous silver nitrate solution added by the method described in (1).

  An ultrafiltration module SIP1013 (trade name, manufactured by Asahi Kasei Co., Ltd., molecular weight cut off: 6,000), a magnet pump, and a stainless steel cup were connected with a silicone tube to obtain an ultrafiltration device.

  The dispersion liquid of C1 to C3 was put in a stainless cup of an ultrafiltration device, and ultrafiltration was performed by operating a pump. When the filtrate from the ultrafiltration module reached 50 mL, 950 mL of distilled water was added to the stainless steel cup for washing. The above washing was repeated until the electric conductivity (measured with CM-25R manufactured by Toa DKK Co., Ltd.) was 50 μS / cm or less, followed by concentration, and 0.95% by mass of rod-shaped silver particle dispersions D1 to D3. Got.

-Evaluation of rod-shaped metal particles-
In the rod-like silver particle dispersions C1 to C3, it was confirmed that rod-like particles having a uniform shape were formed. When the images obtained by TEM observation of the rod-shaped silver particle dispersions C1 to C3 were measured in the same manner as the flat silver particles, the average major axis length was 70 to 220 nm as shown in Table 1 below.
Further, gelatin was added to each of the rod-shaped silver particle dispersions D1 to D3 so as to be 2% by mass, applied onto a TAC film (Fujitack, 80 μm), and dried. When a cross-sectional image of the rod-like silver particles obtained by TEM observation of this film was measured in the same manner as the flat silver particles, the average diameter (equivalent circle diameter) was 40 nm. Table 1 below collectively shows the average major axis length, average diameter, and aspect ratio of the rod-like silver particle dispersions C1 to C3 (D1 to D3).

-Preparation of coating liquids E1, F1 to F3 for metal fine particle-containing layer, coating liquid G1 for dielectric layer and coating liquid H1 for high refractive index layer-
The coating solutions E1, F1, F2, and F3 for the metal fine particle-containing layer, the coating solution G1 for the dielectric layer, and the coating solution H1 for the high refractive index layer were prepared at the composition ratios of the materials shown in Table 2, respectively.
In Table 2, the unit of each value is part by mass.

-Preparation of coating liquid I1 for hard coat layer-
With the formulation shown in Table 3, a hard coat layer coating solution I1 was prepared.

  The hard coat layer coating solution I1 was prepared by the following method. While stirring the aqueous acetic acid solution vigorously, 3-glycidoxypropyltrimethoxysilane was dropped into the aqueous acetic acid solution over 3 minutes. Next, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added to the acetic acid aqueous solution over 3 minutes with vigorous stirring. Next, tetraethoxysilane was added to the acetic acid aqueous solution over 5 minutes with vigorous stirring, and then stirring was continued for 2 hours. Next, colloidal silica, a curing agent, and surfactants A and B were sequentially added to prepare a hard coat layer coating solution I1.

-Preparation of coating liquid J1 for colored (black) layer-
<Preparation of white inorganic fine particle dispersion>
The components having the composition shown in Table 4 were mixed, and the mixture was subjected to a dispersion treatment with a dynomill type disperser to obtain a white inorganic fine particle dispersion 1 having a solid content of 49.0%.

<Preparation of coating liquid J1 for colored (black) layer>
The components having the composition shown in Table 5 were mixed to obtain a colored layer coating solution J1.

Using the coating liquids E1, F1, F2, F3, G1, H1, I1 and J1 prepared as described above, Examples and Comparative Examples of the colored laminates of the present invention were prepared. Table 6 summarizes the layer structure of each example and comparative example.

  A method for producing a colored laminate of each example and comparative example will be described.

[Example 1]
Using a black polyethylene terephthalate film (black PET: Lumirror X30: manufactured by Toray Industries, Inc.) having a thickness of 250 μm as the colored layer 10, the coating liquid E1 for the metal fine particle-containing layer is dried on the surface using a wire bar. It apply | coated so that latter average thickness might be set to 20 nm. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and the metal fine particle content layer 25 was formed.
On the formed metal fine particle containing layer 25, the coating liquid G1 for dielectric layers was applied using a wire bar so that the average thickness after drying was 60 nm. Then, it heated at 130 degreeC for 1 minute, dried and solidified, the dielectric material layer 30 was formed, and the colored laminated body of Example 1 of the layer structure shown in FIG. 1 was obtained.

[Example 2]
Using black PET having a thickness of 250 μm as in Example 1 as the colored layer 10, the coating liquid H1 for the high refractive index layer is formed on the surface thereof using a wire bar so that the average thickness after drying is 55 nm. It was applied to. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and the high refractive index layer 32 was formed.
On the formed high refractive index layer 32, in the same manner as in Example 1, the metal fine particle-containing layer 25 and the dielectric layer 30 are formed in this order so that the average thickness after drying becomes 20 nm and 60 nm, respectively. The colored laminated body of Example 2 of the layer structure shown in FIG. 11 was obtained.

[Example 3]
Using black PET having a thickness of 250 μm as in Example 1 as the colored layer 10, the coating liquid I1 for hard coating is applied on the surface using a wire bar so that the average thickness after drying becomes 1 μm. did. Then, it heated at 130 degreeC for 3 minute (s), dried and solidified, and the hard-coat layer 34 was formed.
On the formed hard coat layer 34, in the same manner as in Example 2, the high refractive index layer 32, the metal fine particle-containing layer 25, and the dielectric layer 30 were sequentially dried in this order with an average thickness of 55 nm, 20 nm, It formed so that it might become 60 nm, and the colored laminated body of Example 3 of the layer structure shown in FIG. 13 was obtained.

[Example 4]
Using a transparent polyethylene terephthalate film (transparent PET: Lumirror U34: manufactured by Toray Industries, Inc.) having a thickness of 50 μm as the transparent substrate 35, a coating liquid H1 for a high refractive index layer is formed on the surface using a wire bar, It was applied so that the average thickness after drying was 55 nm. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and the high refractive index layer 32 was formed.
On the formed high refractive index layer 32, in the same manner as in Example 1, the metal fine particle-containing layer 25 and the dielectric layer 30 were formed in this order so that the average thickness after drying was 20 nm and 60 nm, respectively. . Furthermore, after sticking the adhesion layer (8172CL: product made from 3M) 36 on the surface where the high refractive index layer 32 of the transparent base material 35 is not apply | coated, the black polyethylene terephthalate which is the colored layer 10 through the adhesion layer 36 It bonded on the surface of a film (Lumirror X30: Toray Industries, Inc.), and obtained the colored laminated body of Example 4 of the layer structure shown in FIG.

[Example 5]
Using a transparent PET having a thickness of 50 μm as in Example 4 as the transparent substrate 35, the coating liquid H1 for the high refractive index layer is formed on the surface thereof using a wire bar, and the average thickness after drying becomes 55 nm. It was applied as follows. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and the high refractive index layer 32 was formed.
On the formed high refractive index layer 32, in the same manner as in Example 1, the metal fine particle-containing layer 25 and the dielectric layer 30 were formed in this order so that the average thickness after drying was 20 nm and 60 nm, respectively. .
Furthermore, on the surface of the transparent substrate 35 on which the high refractive index layer 32 is not applied, the colored layer coating liquid J1 was applied using an applicator so that the average thickness after drying was 10 μm. Then, it heated at 130 degreeC for 1 minute, dried and solidified, the colored layer 10 was formed, and the colored laminated body of Example 5 which has the layer structure which is not equipped with the adhesion layer 36 in the colored laminated body 5 shown in FIG. Got.

[Example 6]
A colored laminate of Example 6 was obtained in the same manner as in Example 2 except that the coating solution E1 for the metal fine particle-containing layer was changed to F2.

[Example 7]
A colored laminate of Example 7 was obtained in the same manner as in Example 2 except that the coating solution E1 for the metal fine particle-containing layer was changed to F3.

[Comparative Example 1]
A colored laminate of Comparative Example 1 was obtained in the same manner as in Example 2 except that the coating solution E1 for the metal fine particle-containing layer was changed to F1.

[Comparative Example 2]
Comparative Example 2 was prepared by providing no coating layer on the surface of 250 μm thick black PET used as the colored layer in Example 1. That is, the comparative example 2 is black PET itself in which the antireflection structure is not laminated.

[Example 8]
On the surface of a release film (therapeutic: manufactured by Toray Film Processing Co., Ltd.) 15 as a release substrate, the dielectric layer coating liquid G1 is dried to an average thickness of 60 nm using a wire bar. It applied so that it might become. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and the dielectric material layer 30 was formed.
On the formed dielectric layer 30, the coating liquid E1 for metal fine particle content layer was apply | coated so that the average thickness after drying might be set to 20 nm using the wire bar. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and the metal fine particle content layer 25 was formed.
As the colored layer 10, black PET having a thickness of 250 μm similar to that in Example 1 was used, and an adhesive layer (8172CL: manufactured by 3M) 36 was bonded onto the surface thereof. The surface of the adhesive layer 36 opposite to the surface where the black PET is applied is bonded to the metal fine particle-containing layer 25 laminated on the release film 15, and then the release film 15 is peeled off. 8 colored laminates were obtained.

[Example 9]
Using a transparent PET having a thickness of 50 μm as in Example 4 as the transparent substrate 35, the coating liquid H1 for the high refractive index layer is formed on the surface thereof using a wire bar, and the average thickness after drying becomes 55 nm. It was applied as follows. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and the high refractive index layer 32 was formed.
On the formed high refractive index layer 32, in the same manner as in Example 1, the metal fine particle-containing layer 25 and the dielectric layer 30 were formed in this order so that the average thickness after drying was 20 nm and 60 nm, respectively. .
This film was placed in a molding die and hot press-molded into a dish shape so that the surface of the transparent substrate 35 coated with the high refractive index layer 32 was convex. After cutting unnecessary portions of the molded film, the molded product is placed in a mold, and a black PET chip is used as a molding material on the surface of the transparent substrate 35 on which the high refractive index layer 32 is not applied. The colored layer 10 was insert-molded and integrated to obtain a colored laminate of Example 9 (see FIG. 16).

[Example 10]
On the surface of a release film (therapeutic: manufactured by Toray Film Processing Co., Ltd.) 15 as a release substrate, the dielectric layer coating liquid G1 is dried to an average thickness of 60 nm using a wire bar. It applied so that it might become. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and the dielectric material layer 30 was formed.
On the formed dielectric layer 30, the coating liquid E1 for metal fine particle content layer was apply | coated so that the average thickness after drying might be set to 20 nm using the wire bar. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and the metal fine particle content layer 25 was formed.
After this film is placed in a molding die, the colored layer 10 is in-molded and integrated on the surface of the metal fine particle-containing layer 25 laminated on the release film 15 using a black PET chip as a molding material. The release film 15 was peeled off to obtain a colored laminate of Example 10 (see FIG. 18).

-Evaluation method-
The following evaluation was performed about the colored laminated body of the said Example and comparative example.

[Reflectance]
Using a reflective film thickness spectrometer (FE3000: manufactured by Otsuka Electronics Co., Ltd.), measurement of the reflectance at a wavelength of 550 nm when light is incident on the colored laminate of each example and comparative example from the dielectric layer 30 side. went. For Comparative Example 2, “dielectric layer 30” is read as “one side of black PET” (the same applies hereinafter).

[Blackness, color]
Color evaluation Pure color fluorescent lamps (FL20SN-EDL: manufactured by Toshiba Corporation) are lit, and the colored laminates of the examples and comparative examples are placed and white blurring is observed when the fluorescent lamps are observed from the reflected position. Sensory evaluation was performed on the following criteria, and the average value of five observers was shown.

<White blur>
A: No white blur B: Small white blur C: Medium white blur D: Large white blur <color>
A: No color change B: Color change appears weak C: Color change appears strong

[surface hardness]
Using a pencil scratch hardness tester (533M: manufactured by Yasuda Seiki Seisakusyo Co., Ltd.), the surface of the dielectric layer 30 of the colored laminate of each example and comparative example was evaluated under the conditions of a pencil angle of 45 ° and a load of 750 g. . Ten scratch tests were performed with pencils having the same hardness, and the surface hardness was defined as a pencil hardness having 3 or less scratches.

[Temperature rise]
When the flood beam lamp (BRF110V120W: manufactured by Toshiba Corporation) was placed at a distance of 50 cm from the surface immediately above the dielectric layer 30 side of the colored laminate of each example and comparative example, and was lit, 3 The surface temperature after minutes was measured with a radiation thermometer (IR-TA: manufactured by Chino Corporation). (Measuring environment 25 ° C., no wind) The temperature difference before lighting and after 3 minutes was evaluated according to the following criteria.
A: Less than 20 ° C B: 20 ° C or more and less than 25 ° C C: 25 ° C or more and 30 ° C or less D: 30 ° C or more

Table 7 shows the measurement results and evaluation results for each example and comparative example.

  The colored laminates of Examples 1 to 10 all have a reflectance of less than 0.5%, which is better than that of Comparative Example 2 that does not have the antireflection structure. Since the comparative example 1 contains silver particles with a low aspect ratio, it has absorption in the visible light region and the reflectance is lowered, but the yellowish color appears strongly, resulting in poor jetness. Since Examples 6 and 7 having rod-like silver particles as in Comparative Example 1 have a higher aspect ratio than that of Comparative Example 1 and are 2.5 or more, absorption in the visible light region can be suppressed, and jetness is a comparative example. It is thought that it was better than 1. In addition, the plate-like metal particles were superior to the rod-like metal particles in terms of suppressing the color tone and temperature rise.

1, 2, 3, 4, 5, 6 Colored laminate 10 Colored layer 20 Metal fine particles 20A, 20B Flat metal particles 20C Bar-shaped metal particles 22 Binder 25 Metal fine particle-containing layer 30 Dielectric layer 32 High refractive index layer 34 Hard coat layer 35 Transparent base material 40 Antireflection structure

Claims (11)

A colored layer, a metal fine particle-containing layer containing a plurality of metal fine particles having an aspect ratio of 2 or more, and a dielectric layer are laminated in this order,
In the metal fine particle-containing layer, the plurality of metal fine particles are arranged without forming a conductive path, and the metal fine particles are oriented parallel to the laminated surface,
The metal fine particle-containing layer satisfies the following formula 1,
A colored laminate in which the dielectric layer is an outermost layer, and the dielectric layer satisfies the following formula 2.
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
Here, λ represents the wavelength of light for preventing reflection, d ₂ represents the physical thickness of the metal fine particle-containing layer, M = (4m + 1) × λ / 8, and d ₁ represents the physical of the dielectric layer. Representing the thickness, n ₁ represents the real part of the refractive index of the dielectric layer, and m represents an integer of 0 or more. The metal fine particles are flat,
The major axis length of the metal fine particle is a circle equivalent diameter of the main plane, which is smaller than the wavelength λ of the light for preventing reflection, and the aspect ratio is a ratio of the circle equivalent diameter to the plate thickness, which is 3 or more. The colored laminate according to claim 1. The metal fine particles are rod-shaped,
The major axis length of the metal fine particles is a rod length, which is smaller than a wavelength λ of light for preventing reflection, and the aspect ratio is a ratio of the rod length to a circle-equivalent diameter, which is 2.5 or more. The colored laminate according to 1.   The colored laminate according to any one of claims 1 to 3, further comprising a hard coat layer between the colored layer and the metal fine particle-containing layer.   The colored laminate according to any one of claims 1 to 4, wherein a high refractive index layer having a refractive index of 1.55 or more is disposed between the colored layer and the metal fine particle-containing layer.   The colored laminate according to claim 4, wherein a high refractive index layer having a refractive index of 1.55 or more is disposed between the metal fine particle-containing layer and the hard coat layer.   The colored laminate according to any one of claims 1 to 6, wherein a transparent substrate is disposed between the colored layer and the metal fine particle-containing layer.   The metal fine particles are made of any one of Au, Ag, Pt, Cu and Al, or an alloy containing at least one of Au, Ag, Pt, Cu and Al. The colored laminate according to claim 1. On one surface of the transparent substrate, a metal fine particle-containing layer satisfying the following formula 1 containing a plurality of metal fine particles having an aspect ratio of 2 or more and a dielectric layer satisfying the following formula 2 are laminated in this order,
The manufacturing method of the colored laminated body which insert-molds a colored layer in the other surface of the said transparent base material.
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
Here, λ represents the wavelength of light for preventing reflection, d ₂ represents the physical thickness of the metal fine particle-containing layer, M = (4m + 1) × λ / 8, and d ₁ represents the physical of the dielectric layer. Representing the thickness, n ₁ represents the real part of the refractive index of the dielectric layer, and m represents an integer of 0 or more. On one surface of the transparent substrate, a metal fine particle-containing layer satisfying the following formula 1 containing a plurality of metal fine particles having an aspect ratio of 2 or more and a dielectric layer satisfying the following formula 2 are laminated in this order,
Forming a colored layer on the other surface of the transparent substrate;
The manufacturing method of the colored laminated body which insert-molds a resin layer on the exposed surface of the said colored layer.
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
Here, λ represents the wavelength of light for preventing reflection, d ₂ represents the physical thickness of the metal fine particle-containing layer, M = (4m + 1) × λ / 8, and d ₁ represents the physical of the dielectric layer. Representing the thickness, n ₁ represents the real part of the refractive index of the dielectric layer, and m represents an integer of 0 or more. On one surface of the release substrate, a dielectric layer satisfying the following formula 2 and a metal fine particle-containing layer satisfying the following formula 1 containing a plurality of metal fine particles having an aspect ratio of 2 or more are laminated in this order,
In-mold molding a colored layer on the exposed surface of the metal fine particle-containing layer,
The manufacturing method of the colored laminated body which peels the said mold release base material from the said dielectric material layer.
d ₂ <λ / 10 Equation 1
M−λ / 8 <n ₁ × d ₁ <M + λ / 8 Equation 2
Here, λ represents the wavelength of light for preventing reflection, d ₂ represents the physical thickness of the metal fine particle-containing layer, M = (4m + 1) × λ / 8, and d ₁ represents the physical of the dielectric layer. Representing the thickness, n ₁ represents the real part of the refractive index of the dielectric layer, and m represents an integer of 0 or more.